Fischer-Tropsch catalyst passivation and activation

Abstract

The present disclosure relates generally to compositions and methods for producing Fischer-Tropsch catalysts. In particular, the present application relates to a process for preparing a catalyst material for use in a Fischer-Tropsch synthesis reactor comprising providing a first catalyst material comprising cobalt supported on a support; contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material; the reduced catalyst material is then contacted with carbon monoxide, thereby forming a passivated catalyst material comprising cobalt carbide.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority from European patent application No. 22211100.7, filed on December 2, 2022, which is hereby incorporated by reference in its entirety.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] field

[0005] The present disclosure relates to compositions and methods for the passivation and subsequent activation of Fischer-Tropsch catalysts, and the use of such catalysts in the synthesis of oxygenated and non-oxygenated hydrocarbons. Technical Background

[0006] The conversion of synthesis gas to hydrocarbons by the Fischer-Tropsch process has been known for many years.The growing importance of alternative energy sources has led to renewed interest in the Fischer-Tropsch (FT) process as it allows a direct and environmentally acceptable route to high quality fuels and feedstock chemicals.

[0007] The FT process is known for producing straight-chain hydrocarbons used in fuels and oxygenates used as valuable feedstock chemicals. Hydrocarbon fuels derived from the FT process are better able to meet increasingly stringent environmental regulations than fuels produced by conventional refining because FT-derived fuels generally have lower levels of sulfur, nitrogen, and aromatic compounds that contribute to potent pollutants such as SO2, NO x The FT process reduces the emission of fuel oil and particulate matter. Alcohols derived from the FT process generally have a higher octane rating than hydrocarbons and therefore burn more completely, thereby reducing the environmental impact of such fuels. The alcohols and other oxygenates obtained can also be used as reagents in other processes, such as in the synthesis of lubricants.

[0008] A variety of transition metals have been identified as catalytically active in the conversion of synthesis gas to hydrocarbons and their oxygenated derivatives. In particular, cobalt, nickel, ruthenium, and iron have been studied, usually in combination with support materials, the most common of which are alumina, silica, and carbon.

[0009] In a typical preparation of a supported cobalt-containing FT synthesis catalyst, a solid support material is contacted with a solution of a soluble cobalt compound (e.g., cobalt nitrate). The impregnated support is then calcined and / or oxidized to form cobalt oxide, typically one or more of CoO, Co2O3, or Co3O4. However, such oxides generally have poor FT catalytic activity and must be reduced to form the preferred catalytically active species of cobalt metal. During calcination, cobalt oxide crystallites form on the support material. The properties of these crystallites, which serve as precursors to the active catalyst, are known to have an impact on both the activity and selectivity of the final FT catalyst.

[0010] However, reduced forms of FT catalysts (e.g., cobalt metal) are susceptible to reoxidation upon exposure to the atmosphere. Furthermore, the reduction conditions required to convert the oxides to active metal catalysts are generally more severe than those of a typical FT process, and current industry trends favor smaller, decentralized FT reactors placed in close proximity to the synthesis gas feedstock. Consequently, catalysts are typically produced on a large scale in dedicated reactors and then transported to the FT reactors. During such storage and transport, the catalyst (especially if reduced) must be carefully handled to reduce accidental exposure to oxygen, which could reduce catalyst activity, yield, and / or lifetime.

[0011] A common solution is to encapsulate the reduced catalyst in wax to form a physical barrier to oxygen ingress. The wax-encapsulated catalyst is then loaded into the reactor and the wax is melted. However, any remaining wax residue may carbonize during the subsequent high-temperature treatment, resulting in undesirable deposits that are harmful to the catalyst function. A second solution is to incompletely reduce the catalyst material to retain an oxide layer on the catalyst surface. Once placed in the reactor, the oxide layer can be reduced. However, this method suffers from the fact that if hydrogen is used as a reducing agent, byproduct water is produced, which may be harmful to the reactor and catalyst. In addition, as mentioned above, oxide reduction conditions are generally more severe than FT process conditions, requiring temperatures of at least 300°C, at least 400°C or even at least 500°C. Such high temperatures require the reactor to be constructed with a higher grade of steel than would otherwise be necessary, which makes some reactors unsuitable for this purpose and increases the cost of reactors designed to adapt to harsh reduction schemes.

[0012] Therefore, there is a need to develop new methods for producing passivated catalyst materials that allow for convenient production and handling of reduced catalyst materials.

[0013] Overview

[0014] The present inventors have discovered a method for producing highly active catalyst compositions for FT synthesis. This method and the compositions derived therefrom allow for the production of catalyst materials that are resistant to environmental oxidation, yet can be advantageously reduced to an active form under mild conditions, along with inert byproducts. Notably, this method allows for the ex situ preparation of passivated catalysts that can subsequently be stored, transported, and introduced into Fischer-Tropsch reactors. Due to the mild activation conditions, the Fischer-Tropsch reactor does not need to be capable of reaching exceptionally high pressures and temperatures, reducing equipment costs during use.

[0015] Thus, in one aspect, the present disclosure provides a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, the method comprising:

[0016] providing a first catalyst material comprising cobalt (e.g., in oxide form) supported on a support;

[0017] contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material; and then

[0018] The reduced catalyst material is contacted with carbon monoxide to form a passivated catalyst material comprising cobalt carbide.

[0019] In another aspect, the present disclosure provides a passivated catalyst material for use in the Fischer-Tropsch synthesis of a hydrocarbon composition from a gas feed comprising carbon monoxide and hydrogen, the passivated catalyst material comprising cobalt supported on a carrier, at least 5 wt. % (e.g., at least 25%, at least 50%, or even at least 75%) of the cobalt of the passivated catalyst material being in the form of cobalt carbide.

[0020] In another aspect, the present disclosure provides a passivated catalyst material prepared by the method as otherwise described herein.

[0021] In another aspect, the present disclosure provides a method for converting a mixture of hydrogen and carbon monoxide into a hydrocarbon composition comprising one or more optionally oxygenated hydrocarbons, the method comprising:

[0022] providing a reactor zone having a passivated catalyst material as otherwise described herein disposed therein;

[0023] The passivated catalyst material is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, wherein the activated catalyst material comprises less metal carbide than the passivated catalyst material.

[0024] In certain embodiments as otherwise described herein, the activated catalyst material as otherwise described herein comprises hcp cobalt metal in a ratio to fcc cobalt metal of at least 50:50 as measured by x-ray diffraction. In certain desirable embodiments as otherwise described herein, the hcp metal is present in a ratio to fcc cobalt metal of at least 75:25 (e.g., at least 80:20 or at least 85:15) as measured by x-ray diffraction.

[0025] In certain embodiments, the methods as otherwise described herein further comprise contacting the activated catalyst material in the reaction zone with a gas mixture comprising carbon monoxide and hydrogen to form a hydrocarbon composition.

[0026] In another aspect, the present disclosure provides a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, comprising:

[0027] providing a first catalyst material comprising cobalt oxide supported on a carrier;

[0028] contacting a first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material, wherein the first catalyst material comprises cobalt metal;

[0029] contacting the reduced catalyst material with carbon monoxide to form a passivated catalyst material comprising cobalt carbide; and

[0030] contacting the passivated catalyst material with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, wherein the activated catalyst material comprises less metal carbides than the passivated catalyst material,

[0031] wherein the ratio of hcp cobalt metal to fcc cobalt metal of the activated catalyst material has an hcp ratio that is at least 10 points greater than the ratio of hcp cobalt metal to fcc cobalt metal of the reduced catalyst material.

[0032] In certain such embodiments, the reduced catalyst material comprises hcp cobalt metal and fcc cobalt metal in a ratio ranging from 25:75 and 75:25; and the activated catalyst material comprises hcp cobalt metal to fcc cobalt metal in a ratio of at least 75:25.

[0033] Other aspects of the present disclosure will be apparent to those skilled in the art in view of the following description.

[0034] BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a graph of the relative proportions of certain cobalt species during processing according to example embodiments.

[0036] Figure 2 is a representative x-ray diffraction pattern showing the various species present, according to an example embodiment.

[0037] Figure 3 is a graph of the relative proportions of certain cobalt species during processing according to example embodiments.

[0038] Figure 4 is a graph of the formation of cobalt metal and cobalt carbide when subjected to various gases, according to an example embodiment.

[0039] Figure 5 is a graph of relative carbide concentration over time under various conditions, according to example embodiments.

[0040] Figure 6 Data for an exemplary Fischer-Tropsch synthesis are provided.

[0041] Detailed description

[0042] The present disclosure relates to methods of preparing catalyst materials for use in Fischer-Tropsch synthesis processes, as well as the catalyst materials themselves and methods of using the same.

[0043] The present inventors have found that treating the reduced catalyst material with carbon monoxide can form metal carbides (e.g., cobalt carbide), which produce a passivated catalyst material. Advantageously, this transformation causes the catalyst passivation material to resist atmospheric oxidation or other degradation during storage or transportation because the metal carbide cannot be further oxidized by molecular oxygen or other common oxidants. In addition, metal carbides are known for their excellent hardness, resulting in mechanically stronger passivated catalyst materials that can better withstand the mechanical stress during transportation and processing between sites (e.g., during loading into the reactor). In addition, the present inventors have found that the passivated catalyst material containing cobalt carbide can be easily converted into an activated catalyst material under relatively mild conditions, producing methane as the main by-product. This generation of methane is superior to traditional activation methods, such as using hydrogen to reduce from oxides, which produces undesirable by-products (e.g., water). Under these conditions, water can be a potent oxidant, inhibiting reduction, promoting cobalt sintering and being harmful to catalyst and reactor function. Furthermore, because the conditions for activation according to the present disclosure are mild, high pressure hydrogen equipment may not be necessary for activation, simplifying equipment capital requirements. In fact, in many cases, the carbide material can itself be converted into an activated catalyst under Fischer-Tropsch reaction conditions.

[0044] Such a method allows for the physical separation of catalyst preparation and Fischer-Tropsch synthesis, wherein a stable, passivated catalyst is prepared at a first location and transported to a Fischer-Tropsch reactor (in some cases over many miles), where the catalyst is depassivated by activation under relatively mild conditions and then used for Fischer-Tropsch synthesis. This is particularly advantageous because the reactor requirements for the two methods are generally quite different. In addition, the method allows for the use of a dispersed Fischer-Tropsch reactor that does not require conventional high-temperature, high-pressure catalyst activation. Thus, for many Fischer-Tropsch reactors, far fewer high-temperature, high-pressure reactors can be used to activate the catalyst, and the Fischer-Tropsch reactor can have lower temperature and / or lower pressure capabilities.

[0045] The cobalt metal typically formed in the activated form of a Fischer-Tropsch catalyst material (e.g., by reduction of cobalt oxide) typically consists of a mixture of two metallic phases: hexagonal close-packed (hcp) cobalt and face-centered cubic (fcc) cobalt. Due to the small energy difference between the two phases, both phases are typically present in significant amounts. The present inventors have noted that hcp cobalt is more active for the FT process than typical mixed-phase cobalt. See, for example, Journal of Catalysis 277, 14-26 (2011). Advantageously, while the reduction of cobalt oxide provides a mixture of hcp cobalt and fcc cobalt, the reduction of a passivated catalyst based on cobalt carbide surprisingly produces a catalyst comprising almost exclusively cobalt metal in the hcp phase. Therefore, the present method can be used not only to produce an excellent passivated catalyst material for transportation and processing, but also to form a catalyst composition upon activation that is superior to the reduced catalyst material before passivation and superior to the reduced catalyst material prepared by conventional direct reduction of cobalt oxide.

[0046] Thus, one aspect of the present disclosure provides a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, the method comprising:

[0047] providing a first catalyst material comprising cobalt supported on a support;

[0048] contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material; and then

[0049] The reduced catalyst material is contacted with carbon monoxide to form a passivated catalyst material comprising cobalt carbide.

[0050] The catalyst materials described herein include various forms of cobalt, a support, and optionally other metals or reaction modifiers.Supported cobalt-based materials are well known in the art and can generally be adapted for use in the methods and materials described herein.

[0051] In certain embodiments as further described herein, the catalyst materials as described herein include cobalt in the range of 5% to 35% by weight on an elemental basis. For example, in certain embodiments as further described herein, cobalt may be present in the range of 7-35% by weight, or 10-35% by weight, or 5-25% by weight, or 7-25% by weight, or 10-25% by weight, or 5-20% by weight, or 7-20% by weight, or 10-20% by weight.

[0052] The catalyst materials as described herein may include other metal species, for example as promoters. For example, in certain embodiments as otherwise described herein, the catalyst material includes manganese, for example, in an amount ranging from up to 15 wt%, such as up to 12 wt%, or up to 10 wt%, or up to 7 wt%, or up to 5 wt%, or up to 3 wt%, or up to 2 wt%, calculated on an elemental basis; typically, when manganese is present, it will be present in an amount of at least 0.1 wt%, or at least 0.2 wt%, or at least 0.3 wt%, or at least 0.5 wt%, or at least 0.5 wt%, calculated on an elemental basis. In certain such embodiments, the catalyst material comprises 0.1-15 wt%, for example 0.2-15 wt%, or 0.3-15 wt%, or 0.4-15 wt%, or 0.5-15 wt%, or 0.1-12 wt%, or 0.2-12 wt%, or 0.3-12 wt%, or 0.4-12 wt%, or 0.5-12 wt%, or 0.1-10 wt%, or 0.2-10 wt%, or 0.3-10 wt%, or 0.4-10 wt%, or 0.5-10 wt%, or 0.1-7 wt%, or 0. %. Manganese is preferably in an amount in the range of 0.2-7 wt%, or 0.3-7 wt%, or 0.4-7 wt%, or 0.5-7 wt%, or 0.1-5 wt%, or 0.2-5 wt%, or 0.3-5 wt%, or 0.4-5 wt%, or 0.5-5 wt%, or 0.1-3 wt%, or 0.2-3 wt%, or 0.3-3 wt%, or 0.4-3 wt%, or 0.5-3 wt%, or 0.1-2 wt%, or 0.2-2 wt%, or 0.3-2 wt%, or 0.4-2 wt%, or 0.5-2 wt%. In some embodiments, manganese is present in relatively larger amounts, such as 2-15 wt %, such as 3-15 wt %, or 4-15 wt %, or 2-12 wt %, or 3-12 wt %, or 4-12 wt %, or 2-10 wt %, or 3-10 wt %, or 4-10 wt %, or 2-7 wt %, or 3-7 wt %, or 4-7 wt %. Of course, in other embodiments, manganese is substantially absent (e.g., less than 0.1 wt % or less than 0.5 wt % manganese is present). Other metals may be present, for example, as additives.

[0053] Various support materials are known in the art and can be selected based on the precise requirements of the FT reactor or other chemical, mechanical or economic requirements. In certain embodiments as otherwise described herein, the support comprises at least one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide. In specific embodiments, the support comprises exactly one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide.

[0054] The first catalyst material can be prepared using traditional methods in the art. In certain embodiments, cobalt is introduced onto a carrier by introducing a solution containing a soluble cobalt salt (e.g., cobalt nitrate) onto the carrier and calcining and / or oxidizing the composition to form insoluble cobalt particles (e.g., as cobalt oxide) on the carrier. In certain embodiments, the first catalyst material comprises a composition of a calcined metal (e.g., including calcined cobalt) adhered to the carrier. In specific embodiments, the cobalt of the first catalyst material (i.e., as at least a portion of cobalt, at most all cobalt, such as at least 50%, at least 75% or at least 90%) is in the form of at least one of cobalt oxide and cobalt hydroxide. For example, the cobalt can be cobalt oxide (e.g., CoO, Co3O4 or Co2O3 or a combination thereof) or cobalt hydroxide (e.g., Co(OH)2 or Co(OH)3 or a combination thereof) or a combination of cobalt oxide and cobalt hydroxide. In certain embodiments, the first catalyst material comprising cobalt oxide supported on a support is at least partially oxidized, wherein at least 10% of the cobalt is in oxidized form, e.g., at least 20% of the cobalt is in oxidized form, or at least 30% is in oxidized form, or at least 50% is in oxidized form; this can be in the form of fully oxidized cobalt or a passivated material having an oxide layer and a metal core.

[0055] After providing the first catalyst material, the cobalt species supported thereon, for example in the form of one or more cobalt oxides / cobalt hydroxides as described above, is substantially reduced to produce a reduced catalyst material. The method causes at least a portion of the cobalt to be converted into cobalt metal. Desirably, the reduction causes at least 50 mol % of the cobalt of the reduced catalyst material to be in the form of cobalt metal, for example, at least 75 mol % or at least 90 mol % of the cobalt to be in the form of cobalt metal. For example, in a specific embodiment, at least 95 mol % of the cobalt is in the form of cobalt metal. Those of ordinary skill in the art can use conventional methods to reduce the cobalt catalyst material (for example, a material based on cobalt oxide or cobalt hydroxide) to a metallic form. In certain embodiments as described herein, the first reducing agent is hydrogen, H2. Hydrogen can be mixed with other gases such as an inert carrier gas. Examples of such inert carrier gases include nitrogen, carbon dioxide, argon or helium. Hydrogen can also be mixed with carbon monoxide, with or without one or more additional carrier gases. In certain embodiments, the first reducing gas comprises carbon monoxide, wherein carbon monoxide is present in an amount ranging from 0.1 to 10 volume %, for example, from 0.1 to 5 volume % or from 0.1 to 1 volume %. However, in other embodiments, carbon monoxide is substantially absent (i.e., no more than 0.1 volume %). In certain embodiments, reduction is achieved by contacting the first catalyst material with the first reducing gas, wherein the first reducing gas comprises a first reductant, wherein the first reducing gas comprises at least 50 volume % H2 (e.g., at least 60 volume %, or at least 70 volume %, or at least 80 volume %, or at least 90 volume %, or at least 95 volume %, or substantially 100 volume % H2).

[0056] The reduction of the first catalyst material is carried out at a first temperature to provide a reduced catalyst material. In certain embodiments as described herein, the first temperature is in the range of 200°C to 500°C. For example, in certain embodiments, the first temperature is in the range of 250°C to 400°C, or in the range of 260°C to 350°C, or in the range of 270°C to 330°C, or in the range of 280°C to 320°C, or in the range of 290°C to 310°C. In certain embodiments, the first temperature is about 300°C. The reduction of the first catalyst material to a reduced catalyst material occurs at a first pressure. In certain embodiments as described herein, the first pressure is in the range of 0.5 bara to 5 bara, for example, 0.7 bara to 3 bara. Reduction can be carried out under conditions sufficient to provide the desired degree of reduction as described above (for example, up to 48 hours, for example 2-48 hours or 8-30 hours).

[0057] As described herein, treating the first catalyst material with the first reducing agent produces a reduced catalyst material comprising cobalt as the cobalt metal (e.g., in an amount of at least 50 mol%, such as at least 75 mol%, or at least 90 mol%, or at least 95 mol% of the cobalt as described above). In certain embodiments, as further described herein, the cobalt metal of the reduced catalyst material comprises a significant amount of fcc cobalt metal as well as hcp cobalt metal. In specific embodiments, the cobalt metal comprises fcc cobalt metal and hcp cobalt metal in a ratio ranging from 25:75 to 75:25.

[0058] In a typical Fischer-Tropsch process, this reduced catalyst material itself would be suitable as a catalyst. However, the present inventors have determined that converting this reduced catalyst material to a carbide form can provide a passivated catalyst material that is stable for transport and handling over relatively long distances and times, and that is also substantially converted to HCP cobalt metal by subsequent reduction, which the present inventors have noted is more active in the Fischer-Tropsch process than the FCC form.

[0059] By making the catalyst material through reduction be contacted with carbon monoxide to form the catalyst material through passivation.Advantageously, the catalyst material through passivation comprises cobalt carbide.As further described in the following examples, the relative proportion of metal species can be determined by fitting x-ray diffraction pattern.In certain embodiments as described in addition herein, by x-ray diffraction survey, at least 25 mol % or at least 50 mol % of cobalt of the catalyst material through passivation is in the form of cobalt carbide.For example, in some embodiments, at least 75 mol % or even at least 90 mol % of cobalt of the catalyst material through passivation is in the form of cobalt carbide.Of course, in other embodiments, even when the conversion to carbide is lower (for example, when the surface carbide of catalyst particles is enough to protect the cobalt metal inside the particle), passivation can be effective.

[0060] The reaction of the reduced catalyst material to the passivated catalyst material is carried out at a passivation pressure and a passivation temperature. In certain embodiments as further described herein, the passivation pressure is in the range of >0 bara to 30 bara, for example, 0.2-30 bara or 0.2-20 bara or 0.2-10 bara or 0.5-30 bara or 0.5-21 bara or 0.5-10 bara. In certain specific embodiments, the passivation pressure is less than 10 bara. Carbon monoxide can be provided in various concentrations in the process gas, for example, at least 25% by volume, at least 50% by volume, or at least 75% by volume; the process gas may further include, for example, an inert gas such as nitrogen. In certain embodiments, the passivation temperature is in the range of 25°C to 250°C, for example, 50°C to 225°C. For example, in specific embodiments, the passivation temperature is in the range of 25°C to 200°C, or 75°C to 200°C, or 100°C to 200°C, or 125°C to 200°C. In specific embodiments, the passivation temperature is about 200° C. In other embodiments, the passivation temperature does not exceed 150° C., or does not exceed 100° C. For example, in certain embodiments, the passivation temperature is in the range of 25° C. to 150° C. (e.g., 50° C. to 125° C., or 50° C. to 100° C.). One of ordinary skill in the art will perform passivation with carbon monoxide under conditions (e.g., temperature, pressure, time) that provide the desired degree of carbide conversion.

[0061] A particular advantage of the process according to the present disclosure is the formation of a passivated catalyst material having improved atmospheric oxidation resistance. This is effected by chemically protecting at least a portion of the cobalt metal as a carbide. As described elsewhere, this carbide can then be converted into an activated catalyst material. A benefit of the process is that the passivated catalyst material can be formed in one reactor, which may be particularly suitable or optimized for catalyst passivation, and then transported to another reactor for use in the FT process, where the risk of forming undesirable metal oxides is minimized. Given the industry trend towards decentralization of FT reactors, it is beneficial to be able to geographically separate catalyst production and catalyst use in the FT process.

[0062] Therefore, in certain embodiments, the method as described in addition herein also includes packaging the passivated catalyst material. The passivated catalyst material can be packaged in a closed container such as a drum, bag, box, tank or modular catalyst container. Similarly, in certain embodiments as described in addition herein, the method further includes transporting the passivated catalyst material to a position away from the reactor where it is passivated. In specific embodiments, transportation is to different reactors, or to different buildings, different locations, different facilities or different factories. In some such embodiments, the position away from the reactor where the passivated catalyst material is passivated is at least one mile from the reactor, for example, at least ten miles from the reactor, at least twenty miles from the reactor, at least fifty miles from the reactor or at least one hundred miles from the reactor.

[0063] For example, the passivated catalyst material can be produced in a first reactor, optionally packaged, and then transported to a second reactor. In specific embodiments, the first and second reactors are not equivalent (e.g., the first reactor can be optimized for producing the passivated catalyst material, and the second reactor can be optimized for the FT process). Notably, the second reactor need not be constructed to the same specifications as the first reactor; since the FT process is typically conducted under less stringent conditions than those used for the initial reduction, lower grade materials can be used in the FT reactor where the passivated catalyst is activated and used than in the reactors where the initial reduction is performed.

[0064] Advantageously, the passivation techniques and passivated catalysts described herein can allow reactor specialization, wherein a first reactor can be efficiently constructed, scaled, and operated to produce the passivated catalyst material, while a second reactor can be efficiently constructed, scaled, and operated for relatively mild activation of the passivated material and subsequent Fischer-Tropsch synthesis. For example, the emerging field of biomass conversion is amenable to the use of relatively smaller Fischer-Tropsch reactors that can be placed close to the site of biomass generation (e.g., municipal waste or agricultural or agricultural waste).

[0065] The packaging and transportation of the passivated catalyst also allows for lower risk in the catalyst production process, since standardized passivated catalysts can be produced and quality checked before being transported to the Fischer-Tropsch reactor site. This can allow for optimization and standardization of passivation protocols in ways that would be unavailable to a Fischer-Tropsch reactor. In addition, offsite catalyst production allows for identification of catalyst batches that do not meet specific specifications, and eliminates the reliance on the Fischer-Tropsch reactor and its operator to continuously produce highly active catalyst materials. Since synthesis reactor downtime can be costly, any method step that reduces the risk of reactor downtime (e.g., due to inappropriate catalyst preparation) or accelerates catalyst preparation (e.g., those in the present disclosure) is very valuable.

[0066] Thus, another aspect of the present disclosure is a passivated catalyst material for use in the synthesis of a hydrocarbon composition from a Fischer-Tropsch feed comprising carbon monoxide and hydrogen, the passivated catalyst material comprising cobalt supported on a carrier, wherein at least 25 mol % (e.g., at least 50 mol %) of the cobalt of the passivated catalyst material as measured by x-ray diffraction is in the form of cobalt carbide. In certain desirable embodiments, at least 75 mol % (e.g., at least 90 mol %) of the cobalt of the passivated catalyst material as measured by x-ray diffraction is in the form of cobalt carbide. The amount of cobalt and the amount and identity of any other metals, the carrier, and other specific features of the passivated catalyst material may be as described above. The passivated catalyst material may be prepared as described herein and may be packaged as described above.

[0067] As described above, the passivated catalyst material can be treated to convert at least a portion of the cobalt carbide to cobalt metal, making it suitable for use in the FT process. Accordingly, another aspect of the present disclosure provides a method for preparing an activated catalyst material suitable for use in Fischer-Tropsch synthesis, the method comprising contacting a passivated catalyst material as described herein with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, such that the activated catalyst material comprises less cobalt carbide and more cobalt metal than the passivated catalyst material.

[0068] In cases where the passivated catalyst material is shipped from elsewhere, the method may include unpacking the passivated catalyst material (eg, from a closed container in which it is packaged, such as a drum, bag, box, canister, or modular catalyst container).

[0069] It is noteworthy that the second reducing agent can be selected to effectively convert the desired part or all of cobalt carbide into cobalt metal.In certain embodiments, the amount of the cobalt carbide in the activated catalyst material (i.e., by the fraction of cobalt total amount) is no more than 50 mol of the amount of the cobalt carbide in the passivated catalyst material (i.e., by the fraction of cobalt total amount).For example, in certain embodiments as described in addition herein, the amount of the cobalt carbide in the activated catalyst material (i.e., by the fraction of cobalt total amount) is no more than 25 mol of the amount of the cobalt carbide in the passivated catalyst material (i.e., by the fraction of cobalt total amount), for example, no more than 10 mol%, or no more than 5 mol%, or no more than 1 mol%.In addition, it is possible that some cobalt metals remain in the formation of the reduced catalyst material, and these cobalt metals are not converted into carbide, and are not further oxidized in the treatment process of the passivated catalyst material.In certain embodiments as described in addition herein, in the activated catalyst material, at least 50 mol of cobalt is cobalt metal form, and for example, at least 75 mol of or at least 90 mol of, or at least 95 mol of, or at least 99 mol of cobalt is cobalt metal form. The proportion of cobalt species is determined by x-ray diffraction methods well known in the art (see Examples).

[0070] A surprising effect of the methods and materials described herein is that the cobalt metal formed as part of the activated catalyst material has unexpectedly been found to have a greater proportion of hcp cobalt metal and less of the other common cobalt metal phase, fcc cobalt metal, than cobalt metal formed by conventional reduction of metal oxides (e.g., formed during the production of reduced catalyst materials as described elsewhere herein and in conventional reduction of cobalt oxide / cobalt hydroxide-based catalyst materials for the FT process). This is advantageous because hcp cobalt metal has been found to exhibit higher FT process activity than fcc cobalt metal. The higher activity of hcp cobalt metal means that less catalyst can be used to achieve the same production volume as conventional catalysts, and / or the reactor can be operated at a lower temperature. Both of these effects can result in significant cost savings. Thus, in certain embodiments as described elsewhere herein, the activated catalyst material comprises cobalt metal, wherein the cobalt metal comprises hcp cobalt metal in a ratio of at least 50:50 (e.g., at least 60:40 or at least 70:30) to fcc cobalt metal as measured by x-ray diffraction. For example, in certain embodiments as further described herein, the cobalt metal comprises hcp cobalt metal in a ratio of at least 75:25 (e.g., at least 80:20 or at least 85:15) to fcc cobalt metal. This contrasts with the lower ratios (typically 50:50 or less) found in conventional materials. As further described in the Examples, the amounts of hcp and fcc cobalt can be determined using x-ray diffraction.

[0071] In certain embodiments, the second reducing agent is identical with the first reducing agent. In other embodiments, the second reducing agent is different from the first reducing agent. In a specific embodiment, the second reducing agent is hydrogen, H . Hydrogen can be mixed with other gases (such as inert carrier gases). The example of such inert carrier gases includes nitrogen, carbon dioxide, argon or helium. Hydrogen can also be mixed with carbon monoxide, with or without one or more other carrier gases. In certain embodiments, reduction is achieved by contacting the passivated catalyst material with the second reducing gas, wherein the second reducing gas comprises the second reducing agent, wherein the second reducing gas comprises at least 50 volume % H (for example, at least 60 volume % or at least 70 volume % or at least 80 volume % or at least 90 volume % or at least 95 volume % or substantially 100 volume % H ).

[0072] In certain embodiments, reduction is achieved by contacting the passivated catalyst material with a second reducing gas, wherein the second reducing gas comprises hydrogen and carbon monoxide. In certain embodiments, the second reducing gas is a mixture of hydrogen and carbon monoxide, i.e., synthesis gas. When the second reducing gas is synthesis gas, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the second reducing gas is generally at least 1:1, preferably at least 1.1:1, more preferably at least 1.2:1, more preferably at least 1.3:1, more preferably at least 1.4:1, more preferably at least 1.5:1, or even at least 1.6:1. When the second reducing gas is synthesis gas, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the second reducing gas is at most 10:1, preferably at most 5:1, most preferably at most 3:1. Examples of suitable volume ratios of hydrogen to carbon monoxide (H2:CO) in the second reducing gas include the following ranges: 1:1 to 5:1; 1.1:1 to 3:1; 1.2:1 to 3:1; 1.3:1 to 2.2:1; 1.4:1 to 5:1; 1.4:1 to 3:1; 1.4:1 to 2.2:1; 1.5:1 to 3:1; 1.5:1 to 2.2:1; and 1.6:1 to 2.2:1.

[0073] The reduction of the passivated catalyst material to the activated catalyst material is carried out at a second temperature and a second pressure. In certain embodiments as further described herein, the second temperature is in the range of 120°C to 250°C. It is worth noting that the reduction of the carbide can be carried out at a lower temperature than the reduction of the cobalt oxide / cobalt hydroxide based material, which is typically carried out in the range of 260°C to 400°C or even up to 500°C. For example, in certain embodiments, the second temperature is in the range of 135-250°C, or 150-250°C, or 120-235°C, or 135-235°C, or 150-235°C, or 120-220°C, or 135-220°C, or 150-220°C. In certain embodiments, the second temperature is in the range of 120-195°C, for example, 135-195°C or 150-195°C. In specific embodiments, the second temperature is about 175°C. In certain embodiments as described in addition herein, the second pressure is in the range of 0.5 bara to 5 bara. Reduction can be carried out under the time and conditions sufficient to provide the desired reduction degree as described above. For example, the catalyst material through passivation is reduced to the time in the range of the activated catalyst material that can be continued for 2 hours to 48 hours, or 2 hours to 36 hours, or 2 hours to 24 hours, or 2 hours to 12 hours, or 2 hours to 8 hours. For example, reduction can be carried out in the range of 3 hours to 48 hours, or 4 hours to 48 hours, or 5 hours to 48 hours, or 5 hours to 36 hours, or 5 hours to 24 hours.

[0074] In certain embodiments, the reduction of the passivated catalyst material to the activated catalyst material is carried out at a second temperature of at least 180° C., for example, the second temperature can be in the range of 200-250° C., or 200-240° C., or 200-235° C., or 200-230° C., or 200-220° C. In certain embodiments, the second pressure is greater than 5 bara, for example, greater than 10 bara; the second pressure can be in the range of 10-50 bara, or 10-40 bara, or 10-35 bara, or 15-50 bara, or 15-40 bara, or 15-30 bara, or 20-50 bara, or 20-40 bara, or 20-35 bara. The reduction can be carried out for a time and under conditions sufficient to provide the desired degree of reduction as described above. For example, the reduction of the passivated catalyst material to the activated catalyst material can be carried out for a time in the range of 2 hours to 48 hours, or 2 hours to 36 hours, or 2 hours to 24 hours, or 2 hours to 12 hours, or 2 hours to 8 hours. For example, the reduction can be carried out for a time in the range of 3 hours to 48 hours, or 4 hours to 48 hours, or 5 hours to 48 hours, or 5 hours to 36 hours, or 5 hours to 24 hours.

[0075] In certain embodiments, the reduction of the passivated catalyst material to the activated catalyst material is carried out using syngas as the second reducing gas at a second temperature of at least 180°C and a second pressure greater than 5 bara.

[0076] In certain embodiments, the conditions of the Fischer-Tropsch process are suitable for activating the passivated catalyst material, and therefore separate conditions are not required.

[0077] In certain embodiments, the gas feed comprising carbon monoxide and hydrogen used in Fischer-Tropsch synthesis may be used as the second reducing gas, and the temperature and pressure used in Fischer-Tropsch synthesis may be used as the second temperature and second pressure, respectively.

[0078] Another aspect of the present disclosure is an activated catalyst material for synthesizing a Fischer-Tropsch hydrocarbon composition (optionally containing oxygen) from a gas feed comprising carbon monoxide and hydrogen, the activated catalyst material comprising cobalt supported on a support, wherein the cobalt metal comprises hcp cobalt metal in a ratio of at least 50:50 to fcc cobalt metal. For example, in certain embodiments, the hcp cobalt metal is present in a ratio of at least 75:25, e.g., at least 80:20 or at least 85:15. The activated catalyst material according to this aspect of the present disclosure can be as described above with respect to the above method for reducing carbides.

[0079] Another aspect of the present disclosure is a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, comprising:

[0080] providing a first catalyst material comprising cobalt oxide supported on a carrier;

[0081] contacting a first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material, wherein the first catalyst material comprises cobalt metal;

[0082] contacting the reduced catalyst material with carbon monoxide to form a passivated catalyst material comprising cobalt carbide; and

[0083] The passivated catalyst material is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, wherein the activated catalyst material comprises less metal carbides than the passivated catalyst material, wherein the activated catalyst material comprises cobalt metal.

[0084] Process operations and various catalyst materials may be as otherwise described herein.

[0085] In certain desirable embodiments, the proportion of hcp metal in the activated catalyst material is significantly greater than its proportion in the reduced catalyst material. For example, in certain embodiments as further described herein, the ratio of hcp cobalt metal to fcc cobalt metal in the activated catalyst material is at least 10 points greater than the ratio of hcp cobalt metal to fcc cobalt metal in the reduced catalyst material. As used herein, the difference between a 50:50 ratio and a 60:40 ratio is 10 points. In certain such embodiments, the ratio of hcp cobalt metal to fcc cobalt metal in the activated catalyst material is at least 15 points greater than the ratio of hcp cobalt metal to fcc cobalt metal in the reduced catalyst material, e.g., at least 20 points or at least 25 points. For example, in certain embodiments, the reduced catalyst material comprises hcp cobalt metal and fcc cobalt metal in a ratio ranging from 25:75 to 75:25; and the activated catalyst material comprises hcp cobalt metal in a ratio of at least 75:25 to fcc cobalt metal.

[0086] Once produced, the activated catalyst material is suitable for use in a FT process. Accordingly, another aspect of the present disclosure provides a method for converting a mixture of hydrogen and carbon monoxide into a hydrocarbon composition comprising one or more optionally oxygenated hydrocarbons, the method comprising:

[0087] providing an activated catalyst material according to any one of claims 30 to 40 in a reactor zone (e.g. in a Fischer-Tropsch reactor); and

[0088] The activated catalyst material in the reactor zone is contacted with a gas mixture comprising carbon monoxide and hydrogen to form a hydrocarbon composition.

[0089] One of ordinary skill in the art can adapt a conventional FT process to use the catalyst materials described herein. In certain embodiments of the Fischer-Tropsch process of the present disclosure, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the gaseous reactant mixture is typically at least 1:1, preferably at least 1.1:1, more preferably at least 1.2:1, more preferably at least 1.3:1, more preferably at least 1.4:1, more preferably at least 1.5:1 or even at least 1.6:1. In some or all embodiments of the present invention, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the gaseous reactant mixture is at most 5:1, preferably at most 3:1, and most preferably at most 2.2:1. Examples of suitable volume ratios of hydrogen to carbon monoxide (H2:CO) in the gaseous reactant mixture include the following ranges: from 1:1 to 5:1; from 1.1:1 to 3:1; from 1.2:1 to 3:1; from 1.3:1 to 2.2:1; from 1.4:1 to 5:1; from 1.4:1 to 3:1; from 1.4:1 to 2.2:1; from 1.5:1 to 3:1; from 1.5:1 to 2.2:1; and from 1.6:1 to 2.2: 1. The gaseous reactant stream may also contain other gaseous components, such as nitrogen, carbon dioxide, water, methane, and other saturated and / or unsaturated light hydrocarbons, each preferably present at a concentration of less than 30% by volume.

[0090] According to the present disclosure, conventional Fischer-Tropsch temperatures may be used to produce optionally oxygenated hydrocarbons. For example, the temperature of the reaction may suitably be in the range of 100 to 400° C., such as 150 to 350° C., or 150 to 250° C. The pressure of the reaction may suitably be in the range of 10 to 100 bar (1 to 10 MPa), such as 15 to 75 bar (1.5 to 7.5 MPa), or 20 to 50 bar (2.0 to 5.0 MPa).

[0091] In a preferred embodiment, the temperature of the Fischer-Tropsch reaction is in the range of 150 to 350° C., more preferably 180 to 300° C., and most preferably 200 to 260° C. In a preferred embodiment, the pressure of the Fischer-Tropsch reaction is in the range of 10 to 100 bar (1 to 10 MPa), more preferably 10 to 60 bar (1 to 6 MPa), and most preferably 20 to 45 bar (2 to 4.5 MPa).

[0092] The Fischer-Tropsch synthesis reaction can be carried out in the reactor of any suitable type, and for example, the reaction can be carried out in a fixed-bed reactor, a slurry bed reactor or a CANS reactor. Specifically with respect to the CANS reactor, the catalyst material through passivation as described herein can be packaged in a modular catalyst container (for example, in a different place and then transported to a reactor site) in the reactor tube applicable to the CANS reactor. CANS can be loaded with catalyst and put into a device (plant) for redistribution. The CANS design means that it is easier to process, transport and store catalyst (in CANS), and this becomes very useful for the method. Catalyst can be loaded in CAN and reduced and passivated before storage, transport and subsequent loading into the Fischer-Tropsch device, and in the Fischer-Tropsch device, catalyst can be reactivated. The CANS reactor and associated containers applicable to the methods described herein are described in WO 2011 / 048361, which is hereby incorporated by reference in its entirety for its disclosure of this tank and its purposes.

[0093] It may be desirable to introduce the passivated catalyst material into the reactor zone before the activated catalyst material is formed, that is, so that activation of the catalyst occurs in situ in the reactor zone. The method allows the passivated catalyst material to be loaded from the first reactor or from another site (e.g., by unpacking it from a container, or by connecting a tank to the reactor zone). Subsequently, before forming the activated catalyst material, the second reactor can be purged of undesirable components, such as atmospheric oxygen or moisture, allowing a highly active catalyst to be provided under carefully controlled conditions. Therefore, in certain embodiments as further described herein, the method further comprises introducing the passivated catalyst material into the reactor zone.

[0094] In some cases, the passivated catalyst material can replace a previous catalyst material. For example, the previous catalyst material can be a spent catalyst material that has lost activity or selectivity due to accidental degradation. As another example, the spent catalyst material can be a material optimized for a specific process or product distribution, and different catalysts with different optimizations are desired. Therefore, in certain embodiments as further described herein, the method further includes removing the spent catalyst material from the reactor zone before introducing the passivated catalyst material into the reactor zone.

[0095] The hydrocarbon composition can vary based on changes in process conditions as known in the art. In certain embodiments, the hydrocarbon composition comprises hydrocarbons (e.g., straight-chain hydrocarbons, branched-chain hydrocarbons, saturated or unsaturated hydrocarbons) and oxygenated derivatives thereof. Examples of oxygenated derivatives thereof include hydrocarbons having one or more functional groups of alcohols, aldehydes, ketones, carboxylic acids, esters, and combinations thereof. In certain embodiments as further described herein, the hydrocarbon composition comprises at least one of alkanes, olefins, and alcohols. Example

[0096] The following examples illustrate specific embodiments of the methods of the present disclosure and various uses thereof. They are set forth for illustrative purposes only and should not be considered to limit the scope of the present disclosure.

[0097] X-ray fitting scheme

[0098] X-ray diffraction data were collected using CuKα radiation at 10.5 kW (for reference, conventional laboratory sources are typically 1.5 kW), using a Bruker D8 ultrafast source and a LynxEye detector over an angular range of 15-90 degrees 2θ with a fixed divergence slit. The instrument features an Anton Parr XRK900 reaction chamber capable of collecting data at temperatures up to 900°C and 10 barg. This was equipped with an open sample holder to ensure gas flow through the sample, reducing reliance on diffusion through the powder alone. TOPAS software was used for line fitting and peak analysis. The in-situ XRD cell was set up to feed CO, H2, inert gas, or synthesis gas as required, at pressures up to 10 barg. Once the sample was loaded (~100 μL of catalyst) into the XRD cell, analytes were collected for 30 minutes at 5°C ramps between room temperature and 300°C. This was done to provide a very slow ramp to observe the transformation of the cobalt species.

[0099] The grain size was calculated from the integrated widths of all peaks collected in the diffraction pattern and Rietveld refinement. The broadening from strain contributed negligible amounts to the refinement and was therefore not used. Therefore, all broadening of the spinel and monoxide peaks was attributed to changes in grain size.

[0100] Example 1: In-situ control of catalyst composition

[0101] In order to evaluate the transformation of the catalyst material from cobalt oxide to cobalt carbide to hcp cobalt, in situ x-ray diffraction was used to monitor a 10% cobalt catalyst (with 1% manganese) on a titania support during treatment under various conditions. The results are shown in Figure 1 and Figure 2 In. Figure 1 In FIG, three reaction steps are shown, with the weight % of various cobalt species determined by XRD fitting shown. In an initial treatment with H2 at 300°C and 1 bar, the cobalt oxide in the first catalyst material is converted to cobalt metal in the reduced catalyst material. Treatment with 50% carbon monoxide gas (with an inert carrier gas) at 200°C converts the cobalt metal to cobalt carbide in the passivated catalyst material. Then in the final step, pure hydrogen treatment alone at 180°C, about the same temperature as a typical Fischer-Tropsch reaction, decomposes the carbide to cobalt metal to provide an activated catalyst material. Figure 2XRD patterns of the materials resulting from the three reaction steps are shown; in particular, only hcp cobalt metal is observed in the activated catalyst material.

[0102] Example 2: Air Stability of Passivated Catalyst Materials

[0103] To explore the stability of the passivated catalyst material under atmospheric conditions, a passivated catalyst comprising cobalt carbide was formed as described above. After the cobalt carbide was formed with carbon monoxide, the catalyst was cooled and the gas feed was changed to air. The temperature was slowly raised to 100°C under a stream of air until the carbide began to disappear, as observed by x-ray diffraction. It was then held in air at elevated temperatures up to about 100°C. The results are shown in FIG. Figure 3 Cobalt carbide was found to be stable in air to about 60°C. As mentioned above, under 100% hydrogen, the carbide was converted to cobalt metal at 180°C.

[0104] Thus, these data indicate that the methods and materials described herein can allow the formation of a passivated catalyst material in which cobalt is present primarily in the form of carbides, and the storage and transport of this material to various locations for loading into a reactor. Notably, the carbides can be converted to active metal using relatively mild hydrogen treatment, for example at temperatures similar to those used in conventional Fischer-Tropsch reactions. Thus, the Fischer-Tropsch reaction system does not require extensive modification or additional heating equipment to utilize the catalysts described herein.

[0105] Example 3: Formation of cobalt carbide under various conditions

[0106] The kinetics of cobalt carbide formation under various gas compositions were studied and measured by X-ray diffraction as described above. A 10% cobalt, 1% manganese catalyst on a titania support was reduced with 100% H2 at 300°C and 1 bar. The temperature was then maintained at 200°C and various carbon monoxide feeds were introduced (5% CO, 25% CO and 50% CO, the balance being inert gases), with brief treatments with a helium / hydrogen mixture between each CO feed to reduce any carbides that formed. The data are shown in Figure 4 and Figure 5 The yield of carbides increases with increasing CO concentration, with 50% CO being able to convert all cobalt metal into carbides within about 18 hours of operation. Figure 5 As shown in , increasing pressure is provided for faster conversion.

[0107] Example 4: Reactivity in Fischer-Tropsch synthesis

[0108] A 10% cobalt, 1% manganese catalyst on a titanium dioxide support was reduced in 100% H2 at 300°C for 15 hours. The catalyst was then passivated with 50% CO in N2 at 200°C. 3 mL of the catalyst was loaded into a Fischer-Tropsch reactor for the synthesis reaction. The Fischer-Tropsch reaction was carried out at 42 barg and 1250 GHSV with a 1.8:1 H2:CO molar ratio (containing 20% ​​inert carrier gas). Data are available at Figure 6 The run time is shown in FIG and summarized in the table below, and lasts for about 100 hours.

[0109]

[0110] Various exemplary embodiments of the present disclosure include, but are not limited to, the enumerated embodiments listed below, which may be combined in any number and in any combination that is not technically or logically conflicting.

[0111] Embodiment 1 provides a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, the method comprising:

[0112] providing a first catalyst material comprising cobalt oxide supported on a carrier;

[0113] contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material; and then

[0114] The reduced catalyst material is contacted with carbon monoxide to form a passivated catalyst material comprising cobalt carbide.

[0115] Embodiment 2 provides the method of embodiment 1, wherein each catalyst material comprises cobalt in the range of 5 wt% to 35 wt% on an elemental basis.

[0116] Embodiment 3 provides the method of embodiment 1, wherein each catalyst material comprises cobalt in the range of 7-35 wt%, or 10-35 wt%, or 5-25 wt%, or 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt% on an elemental basis.

[0117] Embodiment 4 provides the method of any one of Embodiments 1-3, wherein each catalyst material further comprises manganese, such as in the range of up to 15 wt. % on an elemental basis.

[0118] Embodiment 5 provides the method of any of Embodiments 1-3, wherein each catalyst material further comprises manganese in an amount in the range of 2-15 wt. % on an elemental basis, for example, in an amount in the range of 3-15 wt. %, or 4-15 wt. %, or 2-12 wt. %, or 3-12 wt. %, or 4-12 wt. %, or 2-10 wt. %, or 3-10 wt. %, or 4-10 wt. %, or 2-7 wt. %, or 3-7 wt. %, or 4-7 wt.

[0119] Embodiment 6 provides the method of any one of Embodiments 1-5, wherein the support comprises at least one of titania, zirconia, ceria, alumina, silica, and zinc oxide.

[0120] Embodiment 7 provides the method of any one of Embodiments 1-6, wherein the cobalt of the first catalyst material (e.g., at least 50 mol%, at least 75 mol%, or at least 90 mol%) is in the form of at least one of cobalt oxide and cobalt hydroxide.

[0121] Embodiment 8 provides the method of any one of Embodiments 1-7, wherein the first reducing agent is hydrogen.

[0122] Embodiment 9 provides the method of embodiment 8, wherein the first temperature is in the range of 250-350°C, and the first pressure is in the range of 0.7 bara to 3 bara.

[0123] Embodiment 10 provides the method of any one of Embodiments 1-9, wherein the reduced catalyst material comprises cobalt metal as measured by x-ray diffraction, wherein the cobalt metal comprises hcp cobalt metal and fcc cobalt metal in a ratio ranging from 25:75 and 75:25.

[0124] Embodiment 11 provides the method of any one of Embodiments 1-10, wherein at least 25 mol% (e.g., at least 50 mol%) of the cobalt of the passivated catalyst material is in the form of cobalt carbide as measured by x-ray diffraction.

[0125] Embodiment 12 provides the method of any one of Embodiments 1-10, wherein at least 75 mol% (e.g., at least 90 mol%) of the cobalt of the passivated catalyst material is in the form of cobalt carbide as measured by x-ray diffraction.

[0126] Embodiment 13 provides the method of any of Embodiments 1-12, further comprising packaging the passivated catalyst material, for example, in a closed container such as a drum, bag, box, canister, or modular catalyst container.

[0127] Embodiment 14 provides the method of any one of Embodiments 1-13, further comprising transporting the passivated catalyst material to a location remote from the reactor in which it was passivated (eg, to a different reactor, building, site, or facility).

[0128] Embodiment 15 provides the method of embodiment 14, wherein the location remote from the reactor where the passivated catalyst material is passivated is at least one mile from the reactor, e.g., at least ten miles from the reactor, at least twenty miles from the reactor, at least fifty miles from the reactor, or at least one hundred miles from the reactor.

[0129] Embodiment 16 provides a passivated catalyst material for synthesizing a Fischer-Tropsch hydrocarbon composition from a gas feed comprising carbon monoxide and hydrogen, the passivated catalyst material comprising cobalt supported on a carrier, wherein at least 25 mol% (e.g., at least 50%) of the cobalt in the passivated catalyst material is in the form of cobalt carbide as measured by x-ray diffraction.

[0130] Embodiment 17 provides a passivated catalyst material according to embodiment 16, wherein at least 75 mol% (e.g., at least 90 mol%) of the cobalt of the passivated catalyst material is in the form of cobalt carbide as measured by x-ray diffraction.

[0131] Embodiment 18 provides passivated catalyst materials according to Embodiment 16 or Embodiment 17, wherein each catalyst material comprises cobalt in the range of 5 wt% to 35 wt% on an elemental basis.

[0132] Embodiment 19 provides passivated catalyst materials according to embodiment 16 or embodiment 17, wherein each catalyst material comprises cobalt in the range of 7-35 wt%, or 10-35 wt%, or 5-25 wt%, or 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt% on an elemental basis.

[0133] Embodiment 20 provides a passivated catalyst material according to any one of Embodiments 16-19, wherein each catalyst material further comprises manganese, for example, in the range of up to 15 weight percent on an elemental basis.

[0134] Embodiment 21 provides a passivated catalyst material according to any of Embodiments 16-19, wherein each catalyst material further comprises manganese in an amount in the range of 2-15 wt. % on an elemental basis, for example, in an amount in the range of 3-15 wt. %, or 4-15 wt. %, or 2-12 wt. %, or 3-12 wt. %, or 4-12 wt. %, or 2-10 wt. %, or 3-10 wt. %, or 4-10 wt. %, or 2-7 wt. %, or 3-7 wt. %, or 4-7 wt.

[0135] Embodiment 22 provides a passivated catalyst material according to any one of Embodiments 16-21, wherein the support comprises at least one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide.

[0136] Embodiment 23 provides a passivated catalyst material prepared by the method according to any one of embodiments 1-15 (eg, according to any one of embodiments 16-22).

[0137] Embodiment 24 provides the passivated catalyst material of any of Embodiments 16-23 packaged in a closed container, such as, for example, a drum, bag, box, canister, or modular catalyst container.

[0138] Embodiment 25 provides a method for providing an activated catalyst material suitable for Fischer-Tropsch synthesis, the method comprising:

[0139] The passivated catalyst material of any of embodiments 16-24 is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material comprising cobalt metal, such that the activated catalyst material comprises less cobalt carbide and more cobalt metal than the passivated catalyst material.

[0140] Embodiment 26 provides the method of Embodiment 25, further comprising unpacking the passivated catalyst material (e.g., from a closed container in which it is packaged, such as a drum, bag, box, canister, or modular catalyst container).

[0141] Embodiment 27 provides the method of Embodiment 26, wherein at least 50 mole percent of the cobalt of the activated catalyst material is in the form of cobalt metal.

[0142] Embodiment 28 provides the method of Embodiment 26, wherein at least 75 mol% (e.g., at least 90 mol%, at least 95 mol%, or at least 99 mol%) of the cobalt of the activated catalyst material is in the form of cobalt metal.

[0143] Embodiment 29 provides the method of any one of Embodiments 26-28, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 50:50 (e.g., at least 60:40 or at least 70:30) to fcc cobalt metal as measured by x-ray diffraction.

[0144] Embodiment 30 provides the method of any one of Embodiments 26-29, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 75:25 to fcc cobalt metal as measured by x-ray diffraction.

[0145] Embodiment 31 provides the method of any one of Embodiments 26-29, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 80:20 (e.g., at least 85:15) to fcc cobalt metal as measured by x-ray diffraction.

[0146] Embodiment 32 provides the method of any one of Embodiments 26-31, wherein the contacting with the second reducing agent is contacting with hydrogen, and the second temperature is in the range of 120°C to 250°C.

[0147] Embodiment 33 provides the method of embodiment 32, wherein the second temperature is in the range of 120°C to 195°C.

[0148] Embodiment 34 provides an activated catalyst material for synthesizing a Fischer-Tropsch hydrocarbon composition from a gas feed comprising carbon monoxide and hydrogen, the activated catalyst material comprising cobalt supported on a carrier, wherein the cobalt comprises hcp cobalt metal in a ratio of at least 50:50 to fcc cobalt metal.

[0149] Embodiment 35 provides the activated catalyst material of Embodiment 34, wherein at least 50 mole percent of the cobalt of the activated catalyst material is in the form of cobalt metal.

[0150] Embodiment 36 provides the activated catalyst material of Embodiment 34, wherein the cobalt comprises hcp cobalt metal in a ratio of at least 75:25 (e.g., at least 80:20 or at least 85:15) to fcc cobalt metal.

[0151] Embodiment 37 provides the activated catalyst material of any one of Embodiments 34-36, comprising cobalt in the range of 5 wt% to 35 wt% on an elemental basis.

[0152] Embodiment 38 provides the activated catalyst material of any of Embodiments 34-36, comprising cobalt in the range of 7-35 wt%, or 10-35 wt%, or 5-25 wt%, or 7-25 wt%, or 10-25 wt%, or 5-20 wt%, or 7-20 wt%, or 10-20 wt% on an elemental basis.

[0153] Embodiment 39 provides the activated catalyst material of any one of Embodiments 34-38, further comprising manganese, eg, in the range of up to 15 weight percent on an elemental basis.

[0154] Embodiment 40 provides an activated catalyst material according to any of Embodiments 34-39, further comprising manganese in an amount in the range of 2-15 wt. % on an elemental basis, for example, in an amount in the range of 3-15 wt. %, or 4-15 wt. %, or 2-12 wt. %, or 3-12 wt. %, or 4-12 wt. %, or 2-10 wt. %, or 3-10 wt. %, or 4-10 wt. %, or 2-7 wt. %, or 3-7 wt. %, or 4-7 wt.

[0155] Embodiment 41 provides an activated catalyst material according to any one of Embodiments 34-40, wherein the support comprises at least one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide.

[0156] Embodiment 42 provides an activated catalyst material (eg, according to any one of Embodiments 34-41) prepared by the method according to any one of Embodiments 25-33.

[0157] Embodiment 43 provides a method for converting a mixture of hydrogen and carbon monoxide into a hydrocarbon composition comprising one or more optionally oxygenated hydrocarbons, the method comprising:

[0158] providing an activated catalyst material according to any one of embodiments 34-42 in a reactor zone (e.g., in a Fischer-Tropsch reactor), or performing the method of any one of embodiments 25-33; and

[0159] The activated catalyst material in the reactor zone is contacted with a gas mixture comprising carbon monoxide and hydrogen to form a hydrocarbon composition.

[0160] Embodiment 44 provides the method of Embodiment 43, wherein providing the activated catalyst material comprises performing an activation method according to any one of Embodiments 25-33.

[0161] Embodiment 45 provides the method of embodiment 44, wherein the activation method is performed in situ in the reactor zone.

[0162] Embodiment 46 provides the method of Embodiment 45, wherein the passivated catalyst material is introduced into the reactor zone prior to performing the activation method.

[0163] Embodiment 47 provides the method of Embodiment 46, further comprising removing spent catalyst material from the reactor zone before introducing the passivated catalyst material into the reactor zone.

[0164] Embodiment 48 provides the method of any one of Embodiments 43-47, wherein the hydrocarbon composition comprises at least one of an alkane, an alkene, and an alcohol.

[0165] Embodiment 49 provides a method for preparing a catalyst material for use in Fischer-Tropsch synthesis, comprising:

[0166] providing a first catalyst material comprising cobalt oxide supported on a carrier;

[0167] contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material, wherein the first catalyst material comprises cobalt metal;

[0168] contacting the reduced catalyst material with carbon monoxide to form a passivated catalyst material comprising cobalt carbide; and

[0169] The passivated catalyst material is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, wherein the activated catalyst material comprises less metal carbides than the passivated catalyst material, wherein the activated catalyst material comprises cobalt metal.

[0170] Embodiment 50 provides the method of Embodiment 49, wherein the hcp ratio in the ratio of hcp cobalt metal to fcc cobalt metal of the activated catalyst material is at least 10 points greater than the hcp ratio in the ratio of hcp cobalt metal to fcc cobalt metal of the reduced catalyst material.

[0171] Embodiment 51 provides the method of Embodiment 49, wherein the hcp ratio in the ratio of hcp cobalt metal to fcc cobalt metal of the activated catalyst material is at least 15 points (e.g., at least 20 points, or even at least 25 points) greater than the hcp ratio in the ratio of hcp cobalt metal to fcc cobalt metal of the reduced catalyst material.

[0172] Embodiment 52 provides the method of any one of Embodiments 49-51, wherein the reduced catalyst material comprises hcp cobalt metal and fcc cobalt metal in a ratio ranging from 25:75 and 75:25; and the activated catalyst material comprises hcp cobalt metal in a ratio to fcc cobalt metal of at least 75:25.

[0173] Embodiment 53 provides the method of any one of Embodiments 49-52, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 50:50 (e.g., at least 60:40 or at least 70:30) to fcc cobalt metal as measured by x-ray diffraction.

[0174] Embodiment 54 provides the method of any one of Embodiments 49-52, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 75:25 to fcc cobalt metal as measured by x-ray diffraction.

[0175] Embodiment 55 provides the method of any one of Embodiments 49-52, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 80:20 (e.g., at least 85:15) to fcc cobalt metal as measured by x-ray diffraction.

[0176] Embodiment 56 provides the method of any of Embodiments 49-55, further comprising packaging the passivated catalyst material, for example, in a closed container such as a drum, bag, box, canister, or modular catalyst container.

[0177] Embodiment 57 provides the method of any of Embodiments 49-56, further comprising transporting the passivated catalyst material to a location remote from the reactor in which it was passivated (eg, to a different reactor, building, site, or facility).

[0178] Embodiment 58 provides the method of embodiment 57, wherein the location remote from the reactor where the passivated catalyst material is passivated is at least one mile from the reactor, e.g., at least ten miles from the reactor, at least twenty miles from the reactor, at least fifty miles from the reactor, or at least one hundred miles from the reactor.

[0179] The details shown herein are presented as examples and only for the purpose of illustrative discussion of certain embodiments of the present disclosure, and are presented in order to provide the most useful and easily understood description of the principles and concepts of the various embodiments of the present disclosure. In this regard, no attempt is made to show the details associated with the method of the present disclosure in more detail than is necessary for a basic understanding of the methods described herein, and the descriptions taken by these embodiments make it clear to those skilled in the art how several forms of the method of the present disclosure can be embodied in practice. Therefore, before describing the disclosed methods and apparatus, it should be understood that the aspects described herein are not limited to specific embodiments, equipment or configurations, and therefore can certainly vary. It should also be understood that the terms used herein are only used for the purpose of describing specific aspects, and unless specifically defined herein, are not intended to be restrictive.

[0180] The terms "a," "an," "the," and similar referents used in the context of describing the methods of the present disclosure (especially in the context of the following embodiments and claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0181] All methods described herein can be performed in any suitable order of steps, unless otherwise indicated herein or otherwise clearly contradictory to the context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the methods of the present disclosure and does not limit the scope of the present disclosure. The language in the specification should not be interpreted as indicating any unclaimed elements that are essential to the practice of the methods of the present disclosure.

[0182] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise," "comprising," and the like are to be construed in an inclusive sense, rather than an exclusive or exhaustive sense; that is, in the sense of "including but not limited to." Words using the singular or plural number also include the plural and singular, respectively. Furthermore, when used in this application, the words "herein," "above," and "below," and words of similar import shall refer to this application as a whole and not to any particular portions of this application.

[0183] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of the elements, steps, ingredients, or components specifically stated thereof. As used herein, the transitional terms "comprise" or "comprises" are meant to include, but are not limited to, and permit the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase "consisting of does not include any unspecified elements, steps, ingredients, or components. The transitional phrase "consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those elements, steps, ingredients, or components that do not materially affect the embodiment.

[0184] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0185] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure 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.

[0186] The grouping of alternative elements or embodiments of the present disclosure should not be construed as limiting. Each group member can quote and claim protection individually or in any combination with other members of the group or other elements found herein. For convenience and / or patentability reasons, it is contemplated that one or more members of a group can be included in the group or deleted from the group. When any such inclusion or deletion occurs, specification sheets are considered to comprise the group through modification, thereby realizing the written description of all Markush groups used in the appended claims.

[0187] Some embodiments of various aspects of the present disclosure are described herein, including the best mode known to the inventors for performing the methods described herein. Of course, upon reading the foregoing description, variations of these described embodiments will become apparent to those of ordinary skill in the art. Such persons will appropriately adopt such variations, and therefore may implement the methods of the present disclosure in a manner different from that specifically described herein. Therefore, the scope of the present disclosure includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. In addition, the present disclosure encompasses any combination of the above-mentioned elements in all their possible variations, unless otherwise indicated herein or clearly contradicted by other context.

[0188] As used herein, the phrase "at least a portion" is used to mean at least a portion of the desired amount, up to the entire possible amount.

[0189] Finally, it should be understood that the various embodiments herein are illustrative of the disclosed method. Other modifications that may be employed are within the scope of the present disclosure. Thus, by way of example and not limitation, alternative configurations of the method may be employed according to the teachings herein. Therefore, the disclosed method is not limited to what is precisely shown and described.

Claims

1. A method for preparing a catalyst material for use in Fischer-Tropsch synthesis, the method comprising: providing a first catalyst material comprising cobalt oxide supported on a carrier; contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material; Then The reduced catalyst material is contacted with carbon monoxide to form a passivated catalyst material comprising cobalt carbide.

2. The process of claim 1 wherein each catalyst material comprises cobalt in the range of 5 wt% to 35 wt% on an elemental basis.

3. The method of claim 1 wherein each catalyst material further comprises manganese, ruthenium or rhenium, for example in the range of up to 15 wt% on an elemental basis.

4. The method of claim 1, wherein the first reducing agent is hydrogen, and the first temperature is in the range of 250-350°C, and the first pressure is in the range of 0.7 bara to 8 bara.

5. The method of claim 1, wherein the reduced catalyst material comprises cobalt metal, wherein the cobalt metal comprises hcp cobalt metal and fcc cobalt metal in a ratio ranging from 25:75 to 75:

25.

6. The process of claim 1 wherein at least 20 mole percent of the cobalt of the passivated catalyst material is in the form of cobalt carbide as determined by x-ray diffraction.

7. The method of claim 1, further comprising packaging the passivated catalyst material, for example in a closed container such as a drum, bag, box, canister, or modular catalyst container.

8. The method of claim 1, further comprising transporting the passivated catalyst material to a location remote from the reactor in which it was passivated (e.g., to a different reactor, building, site, or facility).

9. The method of claim 8, wherein the location remote from the reactor in which the passivated catalyst material is passivated is at least 10 miles from the reactor.

10. A passivated catalyst material for the synthesis of a hydrocarbon composition from a Fischer-Tropsch feed comprising carbon monoxide and hydrogen, the passivated catalyst material comprising cobalt supported on a carrier, wherein at least 20 mol% of the cobalt of the passivated catalyst material is in the form of cobalt carbide as determined by x-ray diffraction.

11. The passivated catalyst material of claim 10, wherein each catalyst material comprises cobalt in the range of 5 wt% to 35 wt% on an elemental basis.

12. The passivated catalyst material according to claim 10, which is packaged in a closed container such as a drum, bag, box, can or modular catalyst container.

13. A method for providing an activated catalyst material suitable for Fischer-Tropsch synthesis, the method comprising: The passivated catalyst material according to claim 10 is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material comprising cobalt metal, such that the activated catalyst material comprises less cobalt carbide and more cobalt metal than the passivated catalyst material.

14. The method of claim 13, wherein at least 75 mole percent of the cobalt of the activated catalyst material is in the form of cobalt metal.

15. The method of claim 12, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 75:25 to fcc cobalt metal as measured by x-ray diffraction.

16. The method of claim 12, wherein the contacting with the second reducing agent is contacting with hydrogen, and the second temperature is in the range of 120°C to 250°C.

17. An activated catalyst material for the synthesis of a Fischer-Tropsch hydrocarbon composition from a gas feed comprising carbon monoxide and hydrogen, the activated catalyst material comprising cobalt supported on a carrier, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 50:50 to fcc cobalt metal as determined by x-ray diffraction.

18. The activated catalyst material of claim 17, wherein the cobalt metal of the activated catalyst material comprises hcp cobalt metal in a ratio of at least 75:25 to fcc cobalt metal as measured by x-ray diffraction.

19. A process for converting a mixture of hydrogen and carbon monoxide into a hydrocarbon composition comprising one or more optionally oxygenated hydrocarbons, the process comprising: providing an activated catalyst material according to claim 17 in a reactor zone; and The activated catalyst material in the reactor zone is contacted with a gas mixture comprising carbon monoxide and hydrogen to form the hydrocarbon composition.

20. The method of claim 19, wherein providing the activated catalyst material comprises performing an activation process, wherein the activation process is performed in situ in a reactor zone.

21. A method for preparing a catalyst material for use in Fischer-Tropsch synthesis, comprising: providing a first catalyst material comprising cobalt oxide supported on a carrier; contacting the first catalyst material with a first reducing agent at a first temperature and a first pressure to form a reduced catalyst material, wherein the first catalyst material comprises cobalt metal; contacting the reduced catalyst material with carbon monoxide to form a passivated catalyst material comprising cobalt carbide; and The passivated catalyst material is contacted with a second reducing agent at a second temperature and a second pressure to form an activated catalyst material, wherein the activated catalyst material comprises less metal carbides than the passivated catalyst material, wherein the activated catalyst material comprises cobalt metal.

22. The method of claim 21, wherein the ratio of hcp cobalt metal to fcc cobalt metal of the activated catalyst material has an hcp ratio that is at least 10 points greater than the ratio of hcp cobalt metal to fcc cobalt metal of the reduced catalyst material.

23. The method of claim 21, further comprising transporting the passivated catalyst material to a location remote from the reactor in which it was passivated (e.g., to a different reactor, building, site, or facility).

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