In situ treatment of fischer-tropsch catalysts

Abstract

A process for converting a mixture of hydrogen and carbon monoxide to a hydrocarbon composition comprising one or more optionally oxygen-containing hydrocarbons, the process comprising the steps of: (a) providing a catalyst material comprising cobalt supported on a support; (b) reducing the catalyst material at a temperature of less than 300 DEG C to form a first activated catalyst; (c) contacting the first activated catalyst with a mixture of hydrogen and carbon monoxide at a first reaction temperature (TR1) of at least 180 DEG C and a first reaction pressure (PR1) of at least 10 bara to produce hydrocarbons for a first reaction period of at least 24 hours; (d) after the first reaction period, contacting the first activated catalyst with a carbon monoxide rich stream at a first pressure (P1) and a first temperature (T1) to provide a treated catalyst wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300 DEG C; (e) contacting the treated catalyst with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst, wherein P2 is at least 10 bara and wherein T2 is less than 300 DEG C; and (f) contacting the second activated catalyst with a mixture of hydrogen and carbon monoxide at a second reaction temperature (TR2) of at least 180 DEG C and a second reaction pressure (PR2) of at least 10 bara to produce hydrocarbons.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to European patent application No. 22211255.9 filed on December 2, 2022, European patent application No. 22211252.6 filed on December 2, 2022, European patent application No. 22211242.7 filed on December 2, 2022, European patent application No. 22211105.6 filed on December 2, 2022, European patent application No. 22211100.7 filed on December 2, 2022, European patent application No. 22211257.5 filed on December 2, 2022, and European patent application No. 22211256.7 filed on December 2, 2022, each of which is hereby incorporated by reference in its entirety.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] field

[0005] The present disclosure relates to methods for treating a Fischer-Tropsch catalyst during a Fischer-Tropsch process, and methods for improving at least one aspect of the performance of a Fischer-Tropsch catalyst. 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, such as 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.

[0010] Subjecting the Fischer-Tropsch catalyst to controlled treatments and conditions (e.g. the process by which the FT catalyst is activated) is known to have an impact on the performance of the Fischer-Tropsch reaction and is therefore typically carried out under conditions that differ from those of the Fischer-Tropsch reaction.

[0011] Therefore, there is a need to develop new methods for treating FT catalysts.

[0012] Overview

[0013] The present inventors have found that in situ treatment of a Fischer-Tropsch catalyst, which may be carried out during operation of a Fischer-Tropsch synthesis reaction, may result in an improvement in at least one aspect of the performance of the Fischer-Tropsch catalyst.

[0014] Thus, in one aspect, the present disclosure provides 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 the steps of:

[0015] (a) providing a catalyst material comprising cobalt supported on a carrier;

[0016] (b) reducing the catalyst material at a temperature below 300° C. to form a first activated catalyst;

[0017] (c) reacting a first activated catalyst with a mixture of hydrogen and carbon monoxide at a first reaction temperature (T R 1) and a first reaction pressure (P R 1) to produce hydrocarbons over a first reaction period lasting at least 24 hours;

[0018] (d) after the first reaction period, contacting the first activated catalyst with a carbon monoxide-rich stream at a first pressure (P1) and a first temperature (T1) to provide a treated catalyst, wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300° C.;

[0019] (e) contacting the treated catalyst with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst, wherein P2 is at least 10 bara and wherein T2 is less than 300° C.; and

[0020] (f) reacting a second activated catalyst with a mixture of hydrogen and carbon monoxide at a second reaction temperature (T R 2) and a second reaction pressure (P R 2) contacting to produce hydrocarbons.

[0021] Another aspect of the present disclosure is the use of an in situ catalyst treatment process as described herein to increase the selectivity of carbon monoxide and hydrogen to hydrocarbons having five or more carbon atoms (C5+) compared to a catalyst not subjected to such in situ treatment.

[0022] Another aspect of the present disclosure is the use of the in situ catalyst treatment method as described herein to increase the conversion of carbon monoxide and hydrogen to hydrocarbons (compared to a catalyst that has not been subjected to such in situ treatment).

[0023] Another aspect of the present disclosure is the use of the in situ catalyst treatment method as described herein to increase the catalyst life of a catalyst.

[0024] Other aspects of the present disclosure will be apparent to those skilled in the art in view of the following description.

[0025] Detailed description

[0026] The present disclosure relates to Fischer-Tropsch synthesis processes and methods of improving the performance of Fischer-Tropsch synthesis processes using cobalt-based catalysts.

[0027] The present inventors have found that in situ treatment of an activated cobalt-containing catalyst material with a carbon monoxide-rich stream can form cobalt carbide, and that subsequent treatment of the cobalt carbide-containing catalyst material with a hydrogen-rich stream can then be used to convert hydrogen and carbon monoxide into hydrocarbon compositions. The present inventors have surprisingly found that carrying out such in situ treatment of the catalyst after it has undergone a hydrocarbon synthesis stage can have a significant effect on the performance of the catalyst in a Fischer-Tropsch synthesis reaction.

[0028] Cobalt metal, typically formed in the activated form of Fischer-Tropsch catalyst materials (e.g., from 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 these 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, reduction of a passivated catalyst based on cobalt carbide surprisingly produces a catalyst comprising almost exclusively cobalt metal in the hcp phase.

[0029] Thus, one aspect of the present disclosure provides 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 the steps of:

[0030] (a) providing a catalyst material comprising cobalt supported on a carrier;

[0031] (b) reducing the catalyst material at a temperature below 300° C. to form a first activated catalyst;

[0032] (c) reacting a first activated catalyst with a mixture of hydrogen and carbon monoxide at a first reaction temperature (T R 1) and a first reaction pressure (P R 1) contacting to produce hydrocarbons over a first reaction period lasting at least 24 hours;

[0033] (d) after the first reaction period, contacting the first activated catalyst with a carbon monoxide-rich stream at a first pressure (P1) and a first temperature (T1) to provide a treated catalyst, wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300° C.;

[0034] (e) contacting the treated catalyst with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst, wherein P2 is at least 10 bara and wherein T2 is less than 300° C.; and

[0035] (f) reacting a second activated catalyst with a mixture of hydrogen and carbon monoxide at a second reaction temperature (T R 2) and a second reaction pressure (P R 2) contacting to produce hydrocarbons.

[0036] 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.

[0037] 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.

[0038] 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% 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%, 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 within 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.

[0039] 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 further described herein, the support comprises at least one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide. In specific embodiments, as further described herein, the support comprises exactly one of titanium oxide, zirconium oxide, ceria, aluminum oxide, silicon oxide, and zinc oxide. In another specific embodiment, as further described herein, the support comprises titanium oxide. In another specific embodiment, as further described herein, the support is titanium oxide.

[0040] The catalyst material can be prepared using conventional methods in the art. In certain embodiments, cobalt is introduced onto a support by introducing a solution containing a soluble cobalt salt (e.g., cobalt nitrate) onto the support and calcining and / or oxidizing the composition to form insoluble cobalt particles (e.g., as cobalt oxide) on the support. In certain embodiments, the catalyst material comprises a composition of a calcined metal (e.g., including calcined cobalt) adhered to the support. In a specific embodiment, the cobalt (i.e., at least a portion of cobalt, up to all cobalt, e.g., at least 50%, at least 75%, or at least 90%) of the catalyst material is in the form of at least one of cobalt oxide and cobalt hydroxide. For example, the cobalt in the catalyst material 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.

[0041] In certain embodiments of the present invention, the catalyst material may be reduced and passivated before being charged to the reactor, in which case the catalyst material may comprise cobalt in a passivated form, for example, by converting at least a portion of the cobalt into a cobalt carbide form or a cobalt oxide form. In specific embodiments, the cobalt of the catalyst material is in a passivated form and comprises at least a portion in the form of cobalt carbide (i.e., at least a portion of the cobalt, up to all of the cobalt, such as at least 40%, at least 50%, or at least 60%). In other specific embodiments, the cobalt of the catalyst material is in a passivated form and comprises at least a portion in the form of cobalt oxide (i.e., for example, at least 10% and up to 40% in the form of cobalt oxide). In some or all embodiments, the catalyst material comprises cobalt in the form of cobalt oxide or cobalt hydroxide or cobalt carbide, or a combination of two or more of cobalt oxide and cobalt hydroxide and cobalt carbide.

[0042] After providing the catalyst material, the cobalt species supported thereon, for example, comprising one or more cobalt in the form of cobalt oxide / cobalt hydroxide / cobalt carbide as described above, is substantially reduced to produce a first activated catalyst. This method results in at least a portion of the cobalt being converted into cobalt metal. Desirably, the reduction results in at least 50 mol% of the cobalt in the first activated catalyst material being in the form of cobalt metal, for example, at least 75 mol% or at least 90 mol% of the cobalt being 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. One of ordinary skill in the art can use conventional methods to reduce the cobalt on the catalyst material to a metallic form. In certain embodiments as further described herein, hydrogen, H2, is used as a reducing agent to reduce the cobalt on the catalyst material. The 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. The hydrogen can also be mixed with carbon monoxide, with or without one or more additional carrier gases. In certain embodiments, the cobalt on the catalyst material is reduced using a reducing agent comprising 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 %. In other embodiments, however, carbon monoxide is substantially absent (i.e., no more than 0.1 volume %). In certain embodiments, reduction is achieved by contacting the catalyst material with a reducing gas, wherein the 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).

[0043] The catalyst material is reduced to provide a first activated catalyst at a temperature of less than 300°C. Suitable reduction temperatures will be known to those skilled in the art. In certain embodiments as further described herein, the reduction temperature is in the range of 200°C to less than 300°C, or in the range of 210°C to less than 300°C, or in the range of 210°C to 290°C, or in the range of 220°C to less than 300°C, or in the range of 220°C to 290°C, or in the range of 220°C to 280°C, or in the range of 230°C to 280°C, or in the range of 240°C to 280°C. The catalyst material is reduced to the first activated catalyst at a suitable reduction pressure. Suitable reduction pressures will be known to those skilled in the art. In certain embodiments as further described herein, the reduction pressure is in the range of 0.5 bara to 5 bara, for example, 0.7 bara to 3 bara. The reduction can be carried out for a time (eg, up to 48 hours, eg, 2-48 hours or 8-30 hours) and under conditions sufficient to provide the desired degree of reduction as described above.

[0044] As described herein, treating the catalyst material with a reducing gas produces an activated catalyst that includes cobalt as the cobalt metal (e.g., cobalt in an amount of at least 50 mol%, e.g., at least 75 mol%, or at least 90 mol%, or at least 95 mol% as described above).

[0045] As described herein, reduction of the catalyst material produces a first activated catalyst comprising cobalt as the cobalt metal (e.g., cobalt in an amount of at least 50 mol%, such as at least 75 mol%, or at least 90 mol%, or at least 95 mol%, as described above). In certain embodiments, as further described herein, the cobalt metal of the first activated catalyst comprises a significant amount of fcc cobalt metal and 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.

[0046] The first activated catalyst is reacted with a mixture of hydrogen and carbon monoxide (first gaseous reactant mixture) at a first reaction temperature (T R 1) and a first reaction pressure (P R 1) Contacting to produce hydrocarbons.

[0047] Those of ordinary skill in the art can adapt conventional Fischer-Tropsch process conditions for the methods described herein. In certain embodiments of the Fischer-Tropsch methods of the present disclosure, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the first 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 invention, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the first 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 first gaseous reactant mixture 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. 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.

[0048] The first reaction temperature (T R1) is at least 180°C, however, one of ordinary skill in the art can adjust conventional Fischer-Tropsch temperatures for use in order to produce hydrocarbons according to the present disclosure. For example, the first reaction temperature can suitably be in the range of 180 to 400°C, such as 180 to 350°C, 180 to 300°C, or 180 to 250°C.

[0049] The first reaction pressure (P R 1) is at least 10 bara (bar absolute pressure) (1 MPa), however one of ordinary skill in the art may adjust conventional Fischer-Tropsch pressures for use in order to produce hydrocarbons according to the present disclosure. For example, the first reaction pressure may suitably be in the range of 10 to 100 bara (1 to 10 MPa), such as 15 to 75 bara (1.5 to 7.5 MPa), or 20 to 50 bara (2.0 to 5.0 MPa).

[0050] In a preferred embodiment, the first reaction temperature is in the range of 180 to 350° C., more preferably 180 to 300° C., and most preferably 200 to 260° C. In a preferred embodiment, the first reaction pressure is in the range of 10 to 100 bara (1 to 10 MPa), more preferably 10 to 60 bara (1 to 6 MPa), and most preferably 20 to 45 bara (2 to 4.5 MPa).

[0051] The first reaction period is a period of at least 24 hours. The first reaction period can be up to six months, or even up to one year; typically, the first reaction period will be at least 24 hours and at most 30 days, more typically at most 28 days, for example at most 21 days. In some or all embodiments, the first reaction period is in the range of 24 hours to 360 hours, for example, 24 to 240 hours, or 24 to 168 hours.

[0052] The Fischer-Tropsch synthesis reaction can be carried out in any suitable type of reactor, for example the reaction can be carried out in a fixed bed reactor, a slurry bed reactor or a CANS reactor. CANS reactors and related containers suitable for use in the methods described herein are described in WO 2011 / 048361, which is hereby incorporated by reference in its entirety for its disclosure of such tanks and their uses.

[0053] In a typical Fischer-Tropsch process, after in-situ hydrocarbon production begins, the first activated catalyst will not be subjected to a multi-step treatment. Instead, in a typical Fischer-Tropsch process, the process will be stopped, and before the process will start again, the first activated catalyst will be subjected to a decoking step (e.g., such as by steam or oxidation treatment). Advantageously, the inventors have found that shutting down the process and oxidizing the first activated catalyst is not necessary. Instead, in-situ treatment of the catalyst can be used. Therefore, the inventors have determined that in-situ treatment of the catalyst can improve at least one aspect of catalyst performance. In some or all embodiments of the present invention, contact of the first activated catalyst with the carbon monoxide-rich stream occurs when the catalyst is not exposed to oxidizing conditions and the temperature of the reactor has not dropped below the first temperature (T1).

[0054] The treated catalyst is formed by contacting the first activated catalyst after the first reaction period with a carbon monoxide-rich stream at a first temperature (T1) and a first pressure (P1).The treated catalyst will comprise cobalt in the form of cobalt carbide.

[0055] In certain embodiments as described in addition herein, the stream rich in carbon monoxide is carbon monoxide gas, CO. Carbon monoxide gas can be mixed with other gases, such as an inert carrier gas. The example of this inert carrier gas includes nitrogen, carbon dioxide, argon or helium. Carbon monoxide gas can also be mixed with hydrogen, with or without one or more other carrier gases. In certain embodiments, the stream rich in carbon monoxide comprises hydrogen, wherein hydrogen exists in an amount within the range of 0.1-10 volume %, for example 0.1-5 volume % or 0.1-1 volume %. But in other embodiments, there is substantially no hydrogen (that is, no more than 0.1 volume %). In certain embodiments, the formation of treated catalyst is carried out by contacting treated catalyst with a stream rich in carbon monoxide, wherein the stream rich in carbon monoxide comprises at least 50 volume %CO (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 %CO). In specific embodiments, the carbon monoxide-rich stream comprises at least 50 vol% CO (e.g., at least 60 vol%, or at least 70 vol%, or at least 80 vol%, or at least 90 vol%, or at least 95 vol%) and less than 10 vol% H2 (e.g., in the range of 0.1-10 vol%, or in the range of 0.1-5 vol%, or in the range of 0.1-1 vol%, or not greater than 0.1 vol%).

[0056] In certain other embodiments as described herein, the carbon monoxide-rich stream is synthesis gas, i.e., a mixture of carbon monoxide and hydrogen. In some embodiments, the carbon monoxide-rich stream is synthesis gas, wherein the volume ratio of hydrogen to carbon monoxide (H2:CO) in this synthesis gas is lower than that of the first gaseous reactant mixture, i.e., the volume ratio comprises more carbon monoxide than that of the first gaseous reactant mixture. For example, the synthesis gas that can be used as the carbon monoxide-rich stream can have a volume ratio of hydrogen to carbon monoxide (H2:CO) of at most 1.5:1, such as at most 1.4:1, or at most 1.3:1, or at most 1.2:1, or at most 1.1:1, or at most 1:1. Examples of suitable volume ratios of hydrogen to carbon monoxide (H2:CO) in the first gaseous reactant mixture include the following ranges: 0.5:1 to 1.5:1; 0.5:1 to 1.4:1; 0.5:1 to 1.3:1; 0.5:1 to 1.2:1; 0.5:1 to 1.1:1; 0.5:1 to 1:1; 0.7:1 to 1.5:1; 0.7:1 to 1.4:1; 0.7:1 to 1.3:1; 0.7:1 to 1.2:1; 0.7:1 to 1.1:1; 0.7:1 to 1:1; 0.8:1 to 1.5:1; 0.8:1 to 1.4:1; 0.8:1 to 1.3:1; 0.8:1 to 1.2:1; 0.8:1 to 1.1:1; 0.8:1 to 1:1; 0.9:1 to 1.5:1; 0.9:1 to 1.4:1; 0.9:1 to 1.3:1; 0.9:1 to 1.2:1; 0.9:1 to 1.1:1; 0.9:1 to 1:1.

[0057] Formation of the treated catalyst is carried out at a first pressure (P1) and a first temperature (T1), wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300° C. In certain embodiments as otherwise described herein, P1 is in the range of 1 bara to at most 10 bara, and in other embodiments as otherwise described herein, P1 is at least 5 bara, preferably in the range of 5 bara to 50 bara. Examples of suitable ranges for P1 include 1-10 bara, or 2-10 bara, or 2-10 bara, or 3-10 bara, or 4-10 bara, or 5-10 bara, or 5-30 bara, or 5-25 bara, or 7-50 bara, or 7-30 bara, or 7-25 bara, or 10-50 bara, or 7-30 bara, or 7-25 bara, or 10-50 bara, or 10-30 bara, or 10-25 bara. The carbon monoxide-rich stream can be provided in the process gas with various concentrations, for example, at least 5 volume %, for example, at least 25 volume %, at least 50 volume % or at least 75 volume %; the process gas can further include, for example, an inert gas, such as nitrogen. In certain embodiments, T1 is in the range of 25° C. to 250° C., for example, 50° C. to 225° C. For example, in specific embodiments, T1 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, T1 is about 200°C. In other embodiments, T1 does not exceed 150°C, or does not exceed 100°C. For example, in certain embodiments, T1 is in the range of 25°C to 150°C, such as 50°C to 125°C, or 50°C to 100°C. Advantageously, the inventors have found that the formation of the treated catalyst can be carried out in situ and without shutting down the Fischer-Tropsch process. By forming the first treated catalyst in situ, the temperature of the process can be maintained. For example, in some or all embodiments as described herein, the first temperature (T1) is at the first reaction temperature (T R 1) within 100°C, for example, at the first reaction temperature (T R 1) within 50°C, or at the first reaction temperature (T R 1). In some or all embodiments, the first pressure (P1) is within 25°C of the first reaction pressure (P R 1) within 30 bara, for example, at the first reaction pressure (P R 1) within 20 bara, or at the first reaction pressure (P R 1) within 10 bara.

[0058] The first activated catalyst is contacted with a stream rich in carbon monoxide at a first temperature (T1) and a first pressure (P1) for a period of time sufficient to form at least some of the cobalt on the first activated catalyst into cobalt carbide to provide a treated catalyst. In some or all embodiments, the treated catalyst is substantially free of cobalt oxide (e.g., CoO, Co2O3, or Co3O4) and / or cobalt hydroxide (e.g., Co(OH)2 or Co(OH)3). The first activated catalyst is contacted with carbon monoxide for a period of time typically of at least 1 hour, typically for a period of time of at most 168 hours. Typically, the first activated catalyst is contacted with carbon monoxide for a period of time of at least 1 hour and at most 168 hours, more typically at least 2 hours and at most 96 hours, such as at least 2 hours and at most 48 hours, or at least 2 hours and at most 36 hours, or at least 2 hours and at most 24 hours, or at least 2 hours and at most 12 hours, or at least 2 hours and at most 8 hours.

[0059] The treated catalyst is then contacted with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst.

[0060] Notably, the hydrogen-rich stream may be selected to effectively convert some or all of the cobalt carbide formed during formation of the treated catalyst to cobalt metal.

[0061] In certain embodiments as described in addition herein, the hydrogen-rich logistics is hydrogen H .Hydrogen can be mixed with other gases, such as an inert carrier gas.The example of this inert carrier gas 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, the hydrogen-rich logistics comprises carbon monoxide, wherein carbon monoxide exists in an amount within the range of 0.1-10 volume %, such as 0.1-5 volume % or 0.1-1 volume %.But in other embodiments, there is substantially no carbon monoxide (that is, no more than 0.1 volume %).In certain embodiments, the formation of the second activated catalyst is carried out by contacting the treated catalyst with a hydrogen-rich logistics, wherein the hydrogen-rich logistics 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 ). In specific embodiments, formation of the second activated catalyst is carried out by contacting the treated catalyst with a hydrogen-rich stream, wherein the hydrogen-rich stream comprises at least 50 vol% H2 (e.g., at least 60 vol%, or at least 70 vol%, or at least 80 vol%, or at least 90 vol%, or at least 95 vol%) and less than 10 vol% CO (e.g., in the range of 0.1-10 vol%, or in the range of 0.1-5 vol%, or in the range of 0.1-1 vol%, or not greater than 0.1 vol%).

[0062] The formation of the second activated catalyst is carried out at a second temperature (T2) and a second pressure (P2). The second temperature is less than 300°C. In certain embodiments as otherwise described herein, the second temperature is in the range of 150°C to less than 300°C. In certain embodiments, the second temperature is in the range of 150-290°C, or 150-280°C, or 150-270°C, or 180-300°C, or 180-290°C, or 180-280°C, or 180-270°C, or 200-300°C, or 200-290°C, or 200-280°C, or 200-270°C. The formation of the second activated catalyst can advantageously be completed in situ, and the temperature and pressure of the previous step of the process can be maintained. For example, in some or all embodiments as described herein, the second temperature (T2) is within 100° C. of the first temperature (T1), such as within 50° C. of the first temperature (T1), or within 25° C. of the first temperature (T1). In some or all embodiments, T2 is at most 100° C. greater than T1, such as at most 90° C. greater than T1, or at most 70° C. greater than T1.

[0063] In some embodiments, the second pressure (P2) is at least 10 bara (1MPa). In some embodiments as described in addition herein, P2 is at least 1 bara and in the scope of 50 bara at the most. In some embodiments as described in addition herein, P2 is at least 5 bara, preferably in the scope of 10 bara to 50 bara, for example, 10-30 bara, or 10-25 bara, or 12-50 bara, or 12-30 bara, or 12-25 bara, or 15-50 bara, or 15-30 bara, or 15-25 bara, or 15-50 bara, or 15-30 bara, or 15-25 bara. In some or all embodiments, the second pressure (P2) is in the 30 bara of the first pressure (P1), for example, in the 20 bara of the first pressure (P1), or in the 10 bara of the first pressure (P1).

[0064] The formation of the second activated catalyst can be carried out under the time and conditions that are enough to provide the desired reduction degree as above.The contact of treated catalyst with the logistics that is rich in hydrogen will usually occur the time period that continues at least 1 hour, usually, the time period that treated catalyst contacts with the logistics that is rich in hydrogen will be at the most 168 hours.Usually, the time period that treated catalyst contacts with the logistics that is rich in hydrogen will be at least 1 hour and at the most 168 hours, more usually at least 2 hours and at the most 96 hours, for example at least 2 hours and at the most 48 hours, or at least 2 hours and at the most 36 hours, or at least 2 hours and at the most 24 hours, or at least 2 hours and at the most 12 hours, or at least 2 hours and at the most 8 hours.

[0065] In some or all embodiments, the second activated catalyst is substantially free of cobalt oxide (eg, CoO, Co2O3, or Co3O4) and / or cobalt hydroxide (eg, Co(OH)2 or Co(OH)3).

[0066] Once formed, the second activated catalyst is reacted with a mixture of hydrogen and carbon monoxide (a second gaseous reactant mixture) at a second reaction temperature (T R 2) and a second reaction pressure (P R 2) contacting to produce hydrocarbons.

[0067] Similar to the first reaction time period, one of ordinary skill in the art can adjust conventional Fischer-Tropsch process conditions for the methods as described herein. In certain embodiments of the Fischer-Tropsch methods of the present disclosure, the volume ratio of hydrogen to carbon monoxide (H2:CO) in the second 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 second 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 second gaseous reactant mixture 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. 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.

[0068] The second reaction temperature (T R 2) is at least 180°C, however, one of ordinary skill in the art may adjust the conventional Fischer-Tropsch temperature used to produce hydrocarbons in accordance with the present disclosure. For example, the second temperature of the reaction may suitably be in the range of 180 to 400°C, such as 180 to 350°C, 180 to 300°C, or 180 to 250°C. As described above, the inventors have discovered that the treatment step can be performed in situ and the temperature of the process can be maintained. For example, in some or all embodiments as described herein, the second reaction temperature (T R 2) within 100° C. of the second temperature (T2), for example, within 50° C. of the second temperature (T2), or within 25° C. of the second temperature (T2).

[0069] The second reaction pressure (P R 2) is at least 10 bara (bar absolute pressure) (1 MPa), however, one of ordinary skill in the art can adjust the conventional Fischer-Tropsch pressure used to produce hydrocarbons according to the present disclosure. For example, the second reaction pressure can suitably be in the range of 10 to 100 bara (1 to 10 MPa), such as 15 to 75 bara (1.5 to 7.5 MPa), or 20 to 50 bara (2.0 to 5.0 MPa). As with the temperature, the second reaction pressure can be maintained from the previous step. In some or all embodiments, the second reaction pressure (P R2) within 30 bara of the second pressure (P2), for example, within 20 bara of the second pressure (P2), or within 10 bara of the second pressure (P2).

[0070] In a preferred embodiment, the second reaction temperature is in the range of 180 to 350° C., more preferably 180 to 300° C., and most preferably 200 to 260° C. In a preferred embodiment, the second reaction pressure is in the range of 10 to 100 bara (1 to 10 MPa), more preferably 10 to 60 bara (1 to 6 MPa), and most preferably 20 to 45 bara (2 to 4.5 MPa).

[0071] A person of ordinary skill in the art can adapt a conventional FT process for use with 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 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: 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. 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.

[0072] Conventional Fischer-Tropsch temperatures may be used to prepare the optionally oxygenated hydrocarbons according to the present disclosure. 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).

[0073] 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).

[0074] The method as described herein is performed sequentially.

[0075] In another embodiment of the present invention, there is provided 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 the steps of:

[0076] (a) providing a catalyst material comprising cobalt supported on a carrier;

[0077] (b) reducing the catalyst material at a temperature of up to 300° C. to form a first activated catalyst;

[0078] (c) reacting a first activated catalyst with a mixture of hydrogen and carbon monoxide at a first reaction temperature (T R 1) and a first reaction pressure (P R 1) contacting to produce hydrocarbons over a first reaction period lasting at least 24 hours;

[0079] (d) after the first reaction period, contacting the first activated catalyst with a carbon monoxide-rich stream at a first pressure (P1) and a first temperature (T1) to provide a treated catalyst, wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300° C.;

[0080] (e) contacting the treated catalyst with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst, wherein P2 is at least 10 bara and wherein T2 is less than 300° C.; and

[0081] (f) reacting a second activated catalyst with a mixture of hydrogen and carbon monoxide at a second reaction temperature (T R 2) and a second reaction pressure (P R 2) contacting to produce hydrocarbons.

[0082] The hydrocarbon composition produced by the mixture of hydrogen and carbon monoxide can vary based on variations in process conditions 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 oxygen-containing derivatives thereof. Examples of oxygen-containing 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 an alkane, an alkene, and an alcohol.

[0083] Another aspect of the present disclosure is the use of an in situ catalyst treatment process as described herein to increase the selectivity of carbon monoxide and hydrogen to hydrocarbons having five or more carbon atoms (C5+) compared to a catalyst not subjected to such in situ catalyst treatment process.

[0084] Another aspect of the present disclosure is the use of an in situ catalyst treatment process as described herein to increase the conversion of carbon monoxide and hydrogen to hydrocarbons compared to a catalyst that has not been subjected to such an in situ catalyst treatment process.

[0085] Because the use of the in situ catalyst treatment method as described herein increases the productivity of the catalyst in the Fischer-Tropsch reaction, this enables one of ordinary skill in the art to lower the reaction temperature to achieve the same conversion of carbon monoxide and hydrogen to hydrocarbons compared to a catalyst that has not been subjected to such an in situ catalyst treatment method, and therefore another aspect of the present disclosure is to increase the catalyst life of the catalyst using the catalyst treatment method as described herein. Example

[0086] 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.

[0087] The Fischer-Tropsch catalyst was prepared by impregnating a titanium dioxide support with cobalt nitrate hexahydrate, manganese acetate tetrahydrate, followed by drying and calcining at 300° C. After reduction, the catalyst contained cobalt in an amount of 10% by weight and manganese in an amount of 1% by weight.

[0088] The catalysts were activated and treated according to the appropriate listed H2 and CO conditions as detailed below. The catalysts were activated and treated by reacting the corresponding catalysts with 1.8 H2:CO in N2 at 30 barg and 8795 hr. -1 The Fischer-Tropsch reaction was carried out by contacting the catalyst with a 100 μg syngas hourly space velocity. Testing was completed on a high-throughput multichannel reactor with 1 g of catalyst at different applied temperatures, using a common gas feed and pressure. Prior to initial activation, the catalyst was first dried at 120°C in nitrogen.

[0089] Table 1.

[0090]

[0091] *-at 100% H2, 0 barg, 5000 hr -1 , initial activation is performed within 24 hours.

[0092] **-Comparative Example.

[0093] ***-The reaction temperature was adjusted to provide approximately the same conversion as the catalyst before treatment.

[0094] Table 2.

[0095]

[0096] *-50% H2 in N2, 16 barg, 4300 hr -1 , initial activation was performed at 24 hours. **-Comparative Example.

[0097] Table 3.

[0098]

[0099] *-50% H2 in N2, 16 barg, 4300 hr -1 , initial activation was performed at 24 hours. **-Comparative Example.

[0100] As can be seen from the results presented in Table 1 above, the embodiments comprising the treatment resulted in significantly improved CO conversion performance at a given applied temperature, and improved selectivity to C5+ hydrocarbons when the temperature was adjusted to provide a CO conversion comparable to the CO conversion before the treatment was applied.

[0101] As can be seen from the results presented in Table 2 above, the conversion of CO after treatment was greater when a lower initial reduction temperature was applied.

[0102] As can be seen from the results presented in Table 3 above, merely treating the catalyst with a carbon monoxide-rich stream without subsequent treatment with a hydrogen-rich stream does not result in an increase in the conversion of CO after treatment.

[0103] 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 methods 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 methods 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, apparatus 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 limiting.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] All percentages, ratios and proportions herein are by weight unless otherwise specified.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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 process for converting a mixture of hydrogen and carbon monoxide into a hydrocarbon composition comprising one or more optionally oxygenated hydrocarbons, said process comprising the steps of: (a) providing a catalyst material comprising cobalt supported on a carrier; (b) reducing the catalyst material at a temperature below 300° C. to form a first activated catalyst; (c) reacting a first activated catalyst with a mixture of hydrogen and carbon monoxide at a first reaction temperature (T R 1) and a first reaction pressure (P R 1) contacting to produce hydrocarbons over a first reaction period lasting at least 24 hours; (d) after the first reaction period, contacting the first activated catalyst with a carbon monoxide-rich stream at a first pressure (P1) and a first temperature (T1) to provide a treated catalyst, wherein P1 is at least 1 bara and at most 50 bara, and T1 is at most 300° C.; (e) contacting the treated catalyst with a hydrogen-rich stream at a second temperature (T2) and a second pressure (P2) to form a second activated catalyst, wherein P2 is at least 10 bara and wherein T2 is less than 300° C.; and (f) reacting a second activated catalyst with a mixture of hydrogen and carbon monoxide at a second reaction temperature (T R 2) and a second reaction pressure (P R 2) contacting to produce hydrocarbons.

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

3. A method according to claim 1 or claim 2, wherein the catalyst material further comprises manganese, ruthenium or rhenium, for example in the range of up to 15 wt% on an elemental basis.

4. The process according to any one of claims 1 to 3, wherein reducing the catalyst material to form a first activated catalyst in step (b) is carried out using a reducing gas comprising at least 50% by volume of H2.

5. The process according to any one of claims 1 to 3, wherein reducing the catalyst material to form a first activated catalyst in step (b) is carried out at a temperature in the range of 200°C to 300°C.

6. Method according to any one of claims 1 to 5, wherein the first pressure (P1) is in the range of 1 bara to 10 bara.

7. The method according to any one of claims 1 to 5, wherein the first pressure (P1) is in the range of 5 bara to 30 bara.

8. The method according to any one of claims 1 to 7, wherein the first temperature (T1) is in the range of 25°C to 260°C.

9. The process according to any one of claims 1 to 8, wherein the carbon monoxide-rich stream comprises at least 50% by volume of CO and less than 10% by volume of H2.

10. The process according to any one of claims 1 to 8, wherein the carbon monoxide-rich stream is a synthesis gas having a volume ratio of hydrogen to carbon monoxide (H2:CO) of at most 1.5:

1.

11. The process of claim 10, wherein the volume ratio of hydrogen to carbon monoxide (H2:CO) in the synthesis gas is lower than the volume ratio of hydrogen to carbon monoxide in the mixture of hydrogen and carbon monoxide used in step (c).

12. A process according to claim 10 or claim 11, wherein reducing the catalyst material to form a first activated catalyst in step (b) is carried out at a temperature in the range of 220°C to 280°C.

13. The method according to any one of claims 1 to 12, wherein the second temperature (T2) is in the range of 180°C to 290°C.

14. The process according to any one of claims 1 to 13, wherein the hydrogen-rich stream comprises at least 50% by volume of H2 and less than 10% by volume of CO.

15. The method according to any one of claims 1 to 14, wherein the first reaction time period is in the range of 24 hours to 360 hours.

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