Fischer-Tropsch process for increasing the production of alcohols

Abstract

This disclosure generally relates to compositions and methods for producing Fischer-Tropsch catalysts. In particular, this disclosure provides a method for producing a product composition comprising an alcohol and a liquid hydrocarbon via a Fischer-Tropsch synthesis reaction, the method comprising: contacting a mixture of hydrogen and gaseous carbon oxides and an olefin co-feed with a supported cobalt-manganese Fischer-Tropsch synthesis catalyst to provide the product composition, wherein the gaseous carbon oxides are carbon monoxide, carbon dioxide, or a combination thereof; wherein the olefin co-feed comprises at least one C2-C... 14 Olefins are present in an amount of 0.001% to 40% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins; wherein, based on elements, the manganese / cobalt weight ratio in the catalyst is at least 0.05.

Description

[0001] Public background

[0002] field

[0003] This disclosure relates to the Fischer-Tropsch process for producing a product with an increased amount of alcohol from a mixture of hydrogen and carbon monoxide and / or carbon dioxide gases. Technical Background

[0004] The conversion of syngas into hydrocarbons via the Fischer-Tropsch process has been known for many years. The growing importance of alternative energy sources has led to a renewed interest in the Fischer-Tropsch (FT) process, as it enables the direct and environmentally acceptable production of high-quality fuels and feedstock chemicals through the use of bio-derived carbon sources.

[0005] The fuel-to-hydrocarbon (FT) process is known to typically produce straight-chain hydrocarbons for fuel use, as well as oxygenated compounds that serve as valuable feedstock chemicals. Compared to fuels produced by conventional refineries, FT-derived hydrocarbon fuels are better able to meet increasingly stringent environmental regulations because they generally have lower levels of sulfur, nitrogen, and aromatic compounds, which contribute to potent pollutants such as SO2 and NO. x And particulate matter emissions. Alcohols derived from the FT process typically have higher octane numbers than hydrocarbons, resulting in more complete combustion and thus reducing the environmental impact of this fuel. The resulting alcohols and other oxygenated compounds can also be used as reagents in other methods, such as in the synthesis of lubricants.

[0006] Various transition metals have been identified as having catalytic activity for the conversion of syngas into hydrocarbons and their oxygenated derivatives. In particular, cobalt, nickel, and iron have been studied, often in combination with support materials, the most common of which are alumina, silicon dioxide, and carbon.

[0007] Typically, the main focus in the production of Fischer-Tropsch synthesis catalysts is improving activity and C20. 5+ Selectivity of hydrocarbons (e.g., alkanes). Although they are industrially important products in themselves, alcohols are often produced only as byproducts of the Fischer-Tropsch process in much lower yields.

[0008] Therefore, it is necessary to improve the activity and selectivity of the Fischer-Tropsch process for producing increased amounts of alcohol.

[0009] Overview

[0010] The inventors have discovered a method for selectively producing high amounts of olefins and alcohols in a Fischer-Tropsch synthesis reaction.

[0011] Therefore, one aspect of this disclosure provides a method for converting a mixture of hydrogen and gaseous carbon oxides into a product composition comprising an alcohol and a liquid hydrocarbon via a Fischer-Tropsch synthesis reaction, wherein the gaseous carbon oxides are carbon monoxide, carbon dioxide, or a combination thereof, the method comprising:

[0012] A mixture of hydrogen and gaseous carbon oxides (e.g., in the form of a syngas mixture) and an olefin co-feed are contacted with a supported cobalt-manganese Fischer-Tropsch synthesis catalyst to provide a product composition;

[0013] The olefin co-feed contains at least one C2-C 14 Olefins, present in an amount of 0.001% to 40% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins;

[0014] Based on elemental analysis, the manganese / cobalt weight ratio in the catalyst is at least 0.05; and

[0015] In the mixture of hydrogen and gaseous carbon oxides, the molar ratio of hydrogen to gaseous carbon oxides is at least 0.5.

[0016] Other aspects of this disclosure will be apparent to those skilled in the art based on the following description.

[0017] Detailed Explanation

[0018] This disclosure relates to a method for improving alcohol selectivity in the Fischer-Tropsch process. As described in International Patent Application Publication No. 2019 / 154885 and James Paterson et al., “Manipulation of Fischer-Tropsch Synthesis for Production of Higher Alcohols Using Manganese Promoters,” ChemCatChem, 10(22), 5154-5163 (2018) (each in its entirety incorporated herein by reference), the use of a catalyst including manganese can provide a slightly increased amount of alcohol in the product stream. The inventors have now discovered, as demonstrated in the examples below, that the use of an olefin co-feed in the Fischer-Tropsch reaction (i.e., together with gaseous carbon oxides and hydrogen) advantageously leads to an increase in alcohol selectivity. Surprisingly, the increase in alcohol yield can exceed the amount of olefin added.

[0019] Therefore, one aspect of this disclosure provides a method for converting a mixture of hydrogen and gaseous carbon oxides into a product composition comprising an alcohol and a liquid hydrocarbon via a Fischer-Tropsch synthesis reaction, the method comprising:

[0020] A mixture of hydrogen and gaseous carbon oxides (e.g., in the form of a syngas mixture) and an olefin co-feed are contacted with a supported cobalt-manganese Fischer-Tropsch synthesis catalyst to provide a product composition, wherein the gaseous carbon oxides are carbon monoxide, carbon dioxide, or a combination thereof.

[0021] The olefin co-feed contains at least one C2-C 14 Olefins, present in an amount of 0.001% to 40% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins;

[0022] Based on elemental analysis, the manganese / cobalt weight ratio in the catalyst is at least 0.05; and

[0023] In the mixture of hydrogen and gaseous carbon oxides, the molar ratio of hydrogen to gaseous carbon oxides is at least 0.5.

[0024] Therefore, this disclosure provides a method for converting a mixture of hydrogen and gaseous carbon oxides into a composition comprising alcohols and liquid hydrocarbons via a Fischer-Tropsch synthesis reaction, the method comprising contacting the mixture of hydrogen and gaseous carbon oxides, preferably in the form of a syngas mixture, with a supported Co-Mn Fischer-Tropsch synthesis catalyst. The product composition obtained by the Fischer-Tropsch synthesis reaction will also contain other components, such as longer-chain hydrocarbons (e.g., waxes) and other oxygen-containing compounds. However, crucially, the method of this disclosure can exhibit improved selectivity for alcohols compared to conventional Fischer-Tropsch processes using cobalt-based catalysts, and even compared to the Fischer-Tropsch process using cobalt-manganese catalysts described in International Patent Application Publication No. 2019 / 154885 and the paper by Paterson et al.

[0025] In this article, the term "liquid hydrocarbon" used to refer to the products of the Fischer-Tropsch reaction refers to C4 to C6 hydrocarbons. 24 Hydrocarbons. In some embodiments as further described herein, the liquid hydrocarbons are primarily straight-chain hydrocarbons, such as at least 50% by weight, at least 75% by weight, or even at least 90% by weight of straight-chain hydrocarbons.

[0026] The inventors have noted that the use of a cobalt-manganese catalyst can provide a degree of olefinic character to the liquid hydrocarbon. In some embodiments, as further described herein, the liquid hydrocarbon contains at least 1 wt% olefin, for example, at least 2 wt% olefin or at least 3 wt% olefin. In some such embodiments, the liquid hydrocarbon contains at least 5 wt% olefin, for example, at least 10 wt% olefin or at least 20 wt% olefin. In some preferred embodiments, the olefin of the liquid hydrocarbon contains straight-chain α-olefins, for example, at least 50 wt% straight-chain α-olefins, or even at least 70 wt% straight-chain α-olefins. However, other products are also possible. In some embodiments, the olefin of the liquid hydrocarbon contains cyclic olefins. In some embodiments, as further described herein, the olefin of the liquid hydrocarbon contains branched olefins, wherein the branched olefins are terminal olefins within the chain (e.g., for the formula H₂C=C(R)). A (R) B ) of olefins, R A and R B Neither of them are H).

[0027] As used herein with respect to the products of the Fischer-Tropsch reaction, the term "alcohol" refers to an alcohol having any number of carbon atoms. For example, in some embodiments, the alcohol of the Fischer-Tropsch product has 1 to 30 carbon atoms. The alcohol is typically acyclic and can be straight-chain or branched, preferably straight-chain. In some embodiments further described herein, the alcohol comprises at least 50% by weight of a straight-chain α-alcohol, such as at least 70% by weight or at least 80% by weight of a straight-chain α-alcohol.

[0028] The methods described herein can provide alcohols with a variety of carbon numbers. In some embodiments, as further described, the alcohols prepared by the methods of this disclosure comprise a major proportion (at least 50% by weight) of short-chain and medium-chain length C1 to C8 alcohols, such as at least 75% by weight of C1 to C8 alcohols or even at least 90% by weight of C1 to C8 alcohols. However, in other embodiments, the alcohols prepared by the methods of this disclosure comprise a major proportion (more than 50% by weight) of long-chain length C9 to C8 alcohols. 25 Alcohols. In some embodiments, the alcohol composition may depend on the nature of the olefin co-feed as otherwise described herein. For example, in some embodiments, the alcohol contains an increased proportion of the carbonylated product of the olefin co-feed. For example, in an olefin co-feed containing C n H 2n In embodiments of the olefin, the alcohol product composition comprises an increased proportion of C n+1 H 2n+1 OH alcohols (e.g., butanol in the case of propylene co-feed). However, the inventors have noted that various other alcohols are also produced. The amount and relative proportions of alcohols produced by the Fischer-Tropsch reaction are determined by GC mass spectrometry; where conventional GC does not provide sufficient resolution, a two-dimensional GCxGC technique can be used, for example, using different columns.

[0029] In some embodiments as further described herein, the method disclosed herein has at least 10%, for example, at least 15%, of the alcohol (e.g., C1-C1). 24 The selectivity is for alcohols (or C1-C8 alcohols). In some embodiments as further described herein, the method of this disclosure, as further described herein, has at least 20%, for example, at least 25%, selectivity for alcohols (e.g., C1-C8 alcohols). 24 Selectivity for alcohols (or C1-C8 alcohols). In some such embodiments, selectivity is achieved for alcohols (e.g., C1-C8 alcohols). 24 The selectivity for alcohols (or C1-C8 alcohols) is at least 40%, for example at least 50%, at least 60%, or greater than 70%. As used herein, “selectivity” to a given component is measured as the mole fraction of gaseous carbon oxides that react in the method (i.e., excluding any unreacted portion of the gaseous carbon oxides) and are converted into the product. For example, in an embodiment where the gaseous carbon oxide is carbon monoxide, “selectivity” to a given component is defined as the mole fraction of carbon monoxide that reacts in the method and is converted into the relevant product, excluding any unreacted carbon monoxide.

[0030] It is worth noting that the use of a cobalt-manganese catalyst in the Fischer-Tropsch synthesis as described herein can also provide longer-chain alcohols. For example, in some embodiments further described herein, at least 10 wt% (e.g., at least 15 wt%) of the product having 8 to 24 carbon atoms is an alcohol. For example, in some embodiments, at least 20 wt% (e.g., at least 25 wt%) of the product having 1 to 24 carbon atoms is an alcohol. In some such embodiments, no more than 90 wt%, for example, no more than 80 wt%, of the product having 8 to 24 carbon atoms is an alcohol.

[0031] Although the measurement of C1-C8 alcohols is common in the art, due to methodological limitations, in many cases, the yield of C1-C8 alcohols in the Fischer-Tropsch process often represents the total alcohol yield (e.g., C1-C8). 24 (Alcohol yield). Therefore, experimental results regarding C1-C8 alcohol yields can usually be extrapolated to provide total C1-C8 alcohol yields. 24 Indication of alcohol production (see Examples).

[0032] While not wishing to be bound by theory, it is believed that by impregnating a catalyst containing at least 0.5 wt% manganese and a manganese / cobalt weight ratio of at least 0.05 based on elemental weight, the resulting supported Co-Mn Fischer-Tropsch synthesis catalyst will have a cobalt oxide crystallite size that provides or contributes to the benefits when the catalyst is used in the Fischer-Tropsch reaction. In some embodiments of this disclosure, the cobalt oxide crystallites (e.g., Co3O4) resulting from the combination of total manganese and manganese / cobalt weight ratio as described herein have a particle size of less than 150 Å (15 nm), for example less than 100 Å (10 nm), preferably less than 80 Å (8 nm). Once the Co-Mn Fischer-Tropsch synthesis catalyst is activated and used in the Fischer-Tropsch reaction, the productivity and selectivity for alcohols can be significantly enhanced compared to cobalt-containing synthesis catalysts containing no manganese or insufficient manganese. Furthermore, without being bound by theory, it is believed that the productivity and selectivity for olefins can be significantly enhanced compared to cobalt-containing synthesis catalysts containing no manganese or insufficient manganese.

[0033] While not bound by any particular theory, it is believed that the presence of manganese contributes to surface effects on solid supports, influencing the development and dispersion of cobalt oxide crystallites on the surface. This can stem from the activity of cobalt-containing precursor compounds (one or more) suspended or dissolved in an impregnation solution in the presence of manganese-containing precursor compounds during catalyst preparation. Therefore, catalysts particularly suitable for this paper may involve applying one or more cobalt-containing precursor compounds and one or more manganese-containing precursor compounds to a support material so that they form a mobile mixture on the surface of the support during preparation.

[0034] As described above, the inventors have found that FT catalysts containing a mixture of cobalt and manganese are particularly suitable for increasing alcohol yield. In some embodiments further described herein, the manganese / cobalt weight ratio present in the synthesis catalyst is from 0.05 to 3.0 based on elemental composition. For example, in a particular embodiment, the weight ratio is 0.05 to 2.5, or 0.05 to 2.0, or 0.05 to 1.5, or 0.05 to 1.2, or 0.05 to 1, or 0.2 to 3.0, or 0.2 to 2.5, or 0.2 to 2.0, or 0.2 to 1.5, or 0.2 to 1.2, or 0.2 to 1, or 0.3 to 3.0, or 0.3 to 2.5, or 0.3 to 2.0, or 0.3 to 1.5, or 0.3 to 1.2, or 0.3 to 1, or 0.5 to 3.0, or 0.5 to 2.5, or 0.5 to 2.0, or 0.5 to 1.5, or 0.5 to 1.

[0035] Suitable synthesis catalysts can typically have diverse transition metal loadings. In some embodiments, as further described herein, the synthesis catalyst contains at least 0.5 wt% manganese based on elemental weight. In some embodiments, the synthesis catalyst contains up to 25 wt% manganese based on elemental weight. For example, the synthesis catalyst may contain 0.5 to 25 wt% manganese based on elemental weight, such as 0.5 to 25 wt%, or 0.5 to 20 wt%, or 0.5 to 15 wt%, or 0.5 to 12 wt%, or 1 to 12 wt%, or 1 to 12 wt%, or 1 to 11 wt%, or 1.5 to 11 wt%, or 1.5 to 10 wt%, or 2 to 10 wt%. Alternatively, the synthesis catalyst may contain at least 2.5 wt% manganese based on the element, for example 3 to 25 wt%, or 4 to 20 wt%, or 5 to 15 wt%, or 2.5 to 12 wt%, or 3 to 12 wt%, or 4 to 12 wt%, or 5 to 12 wt%, or 2.5 to 11 wt%, or 3 to 11 wt%, or 4 to 11 wt%, or 5 to 11 wt%, or 2.5 to 10 wt%, or 3 to 10 wt%, or 4 to 10 wt%, or 5 to 10 wt%.

[0036] In some embodiments as further described herein, the synthesis catalyst comprises at least 0.5 wt% cobalt based on elemental weight. In some embodiments, the synthesis catalyst comprises up to 35 wt% cobalt based on elemental weight. For example, in some embodiments, the synthesis catalyst comprises cobalt in amounts based on elemental weights of 0.5-35 wt%, such as 0.5-25 wt%, or 0.5-20 wt%, or 0.5-15 wt%, or 0.5-12 wt%, or 1-12 wt%, or 1-12 wt%, or 1-11 wt%, or 1.5-11 wt%, or 1.5-10 wt%, or 2-10 wt%, or 5-35 wt%, or 7-35 wt%, or 10-35 wt%, or 2-25 wt%, or 5-25 wt%, or 7-25 wt%, or 10-25 wt%. In certain specific embodiments, the synthesis catalyst contains 2-20% by weight, for example 5-20% by weight, or 7-20% by weight, or 10-20% by weight, or 2-15% by weight, or 5-15% by weight, or 7-15% by weight, based on the element.

[0037] In some embodiments as further described herein, the total amount of cobalt and manganese in the synthesis catalyst, based on the total weight of the synthesis catalyst and on an elemental basis, is no more than 40% by weight. For example, in certain embodiments, the total amount of cobalt and manganese in the synthesis catalyst is no more than 30% by weight, or no more than 25% by weight, or no more than 22% by weight, or no more than 20% by weight. In some embodiments, the total amount of cobalt and manganese in the synthesis catalyst is no more than 15% by weight. In some embodiments as further described herein, the total amount of cobalt and manganese in the synthesis catalyst, based on the total weight of the synthesis catalyst and on an elemental basis, is at least 2% by weight. For example, in certain embodiments, the total amount of cobalt and manganese in the synthesis catalyst is at least 5% by weight, or at least 8% by weight, or at least 10% by weight.

[0038] In a further aspect of this disclosure, a supported Co-Mn Fischer-Tropsch synthesis catalyst is provided, comprising cobalt oxide microcrystals with a particle size of less than 150 angstroms (15 nanometers), preferably less than 100 angstroms (10 nanometers), or less than 80 angstroms (8 nanometers), and comprising at least 0.5% by weight of manganese based on the total weight of the supported synthesis catalyst; wherein the manganese / cobalt weight ratio is 0.05 or greater based on the elemental weight, and the support material of the supported Co-Mn Fischer-Tropsch synthesis catalyst comprises a material selected from alumina, zirconium oxide, zinc oxide, cerium dioxide, silicon dioxide, and titanium dioxide. For example, in a particular embodiment, the support material of the synthesis catalyst comprises titanium dioxide, or titanium dioxide.

[0039] In a further aspect of this disclosure, a supported Co-Mn Fischer-Tropsch synthesis catalyst is provided, comprising at least 0.5% by weight of element-based manganese based on the total weight of the supported synthesis catalyst; and wherein the manganese / cobalt weight ratio is 0.05 or greater based on element-based weight, the support material of the supported Co-Mn Fischer-Tropsch synthesis catalyst comprises a material selected from titanium dioxide, zinc oxide, zirconium oxide, silicon dioxide, aluminum oxide and cerium dioxide, and wherein the catalyst comprises cobalt oxide microcrystals with a particle size of less than 150 angstroms (15 nanometers), preferably less than 100 angstroms (10 nanometers).

[0040] In some of the methods described herein, the Fischer-Tropsch synthesis reaction is carried out at an absolute pressure of 10 to 100 bar (1.0 to 10.0 MPa). In a preferred embodiment, the pressure of the Fischer-Tropsch reaction is 10 to 80 bar (1 to 8 MPa), for example 10 to 60 bar (1 to 6 MPa), for example 15 to 50 bar (1.5 to 5 MPa) or 20 to 45 bar (2 to 4.5 MPa).

[0041] The supported Co-Mn Fischer-Tropsch synthesis catalyst used according to this disclosure can be prepared by any suitable method capable of providing the desired manganese / cobalt weight ratio and the desired manganese concentration on the supported catalyst. Preferably, the supported Co-Mn Fischer-Tropsch synthesis catalyst used according to this disclosure is prepared by impregnating cobalt and manganese onto a support material.

[0042] Suitable impregnation methods include, for example, impregnating the carrier material with cobalt-containing and manganese-containing compounds that can be thermally decomposed into oxides. Impregnation of the carrier material with cobalt-containing and manganese-containing compounds can be achieved by any suitable method known to those skilled in the art, such as by vacuum impregnation, initial wet impregnation, or impregnation in an excess liquid.

[0043] The initial wet impregnation technique is so named because it requires pre-determining the volume of the impregnation solution to provide the minimum volume of solution needed to just wet the entire surface of the carrier, without excess liquid. Excess solution techniques, as the name suggests, require an excess of impregnation solution, which is then typically removed by evaporation.

[0044] The carrier material can be in the form of powder, granules, shaped particles such as pre-formed spheres or microspheres, or extrusions. The term "powder" or "granules" as used herein is understood to refer to free-flowing particles of the carrier material or particles of the carrier material that have been granulated and / or sieved into specific shapes (e.g., spherical) and size ranges. The term "extrusion" as used herein is intended to indicate a carrier material that has undergone an extrusion step and can therefore be shaped. In this disclosure, the powder or granules are in a form suitable for impregnation with solutions containing cobalt and manganese compounds and subsequently extruded or shaped into other shaped particles.

[0045] The support material is used to bind catalyst particles and may also affect catalytic activity. In some embodiments, as further described herein, the support material comprises one or more oxides selected from alumina, zirconium oxide, zinc oxide, cerium dioxide, silica, and titanium dioxide. In specific embodiments, the support material is one of alumina, zirconium oxide, zinc oxide, cerium dioxide, silica, and titanium dioxide. For example, in some embodiments, the catalyst comprises titanium dioxide (e.g., the support material is titanium dioxide).

[0046] It should be understood that the support material can be of any form, provided it is suitable for use as a support for a Fischer-Tropsch synthesis catalyst, and preferably wherein the support material has not been pre-impregnated with a metal source (i.e., other than cobalt and / or manganese) that may have an adverse effect on the performance of the active catalyst and may interfere with the benefits of the method disclosed herein. Therefore, although support materials pre-loaded with cobalt and / or manganese metals or their precursors may be used according to this disclosure, additional pretreatment of other metal sources is preferably avoided. Preferred support materials are substantially free of foreign components that may adversely affect the catalytic activity of the system. Therefore, preferred support materials are at least 95% w / w pure, more preferably at least 98% w / w pure, and most preferably at least 99% w / w pure. The amount of impurities is preferably less than 1% w / w, more preferably less than 0.50% w / w, and most preferably less than 0.25% w / w. The pore volume of the support is preferably greater than 0.150 mL / g, more preferably greater than 0.30 mL / g. The average pore radius of the carrier material (before impregnation) is 10 to 500 angstroms, preferably 15 to 100 angstroms, more preferably 20 to 80 angstroms, and most preferably 25 to 60 angstroms. The BET surface area is suitably 2 to 1000 m² / g, preferably 10 to 600 m² / g, more preferably 15 to 300 m² / g, and most preferably 30 to 150 m² / g.

[0047] BET surface area, pore volume, pore size distribution, and average pore radius can be determined by nitrogen adsorption isotherms at 77 K using a Micromeritics TRISTAR 3000 static volumetric adsorption analyzer. Applicable procedures are British Standard Methods BS4359: Part 1: 1984 'Recommendations for gas adsorption (BET) methods' and BS7591: Part 2: 1992 'Porosity and pore size distribution of materials' - Method of evaluation by gas adsorption. The obtained data can be simplified using the BET method (in the pressure range of 0.05–0.20 P / Po) and the Barrett, Joyner & Halenda (BJH) method (for pore sizes of 20–100 Å) to obtain surface area and pore size distribution separately.

[0048] Appropriate references for the above data simplification method are Brunauer, S, Emmett, PH, & Teller, E, J. Amer. Chem. Soc. 60, 309, (1938) and Barrett, EP, Joyner, LG & Halenda PP, J. Amer. Chem. Soc. 1951, 73373-380.

[0049] When in powder form, the median particle size (d50) is preferably less than 50 micrometers, more preferably less than 25 micrometers. When the carrier material is in particulate form, the median particle size (d50) is preferably 300 to 600 micrometers. The particle size (d50) can be suitably determined using a particle size analyzer (e.g., a Microtrac S3500 particle size analyzer).

[0050] It is known that using shaped particles, such as extrudates, in Fischer-Tropsch catalysis is advantageous, particularly in fixed-bed reactor systems. For example, it is known that for a given shape of catalyst particles, a reduction in particle size in a fixed bed results in a corresponding increase in the pressure drop across the bed. Therefore, relatively large shaped particles result in a smaller pressure drop across the catalyst bed in the reactor compared to corresponding powdered or granular supported catalysts. Shaped particles, such as extrudates, also typically exhibit greater strength and less wear, which is particularly valuable in fixed-bed arrangements where very high bulk crush strength is required.

[0051] The terms "impregnation" or "impregnating" as used herein refer to contacting a carrier material with one or more solutions of, for example, cobalt-containing and manganese-containing compounds prior to drying, to achieve precipitation of the cobalt-containing and manganese-containing compounds. Impregnation with one or more completely dissolved solutions of cobalt-containing and manganese-containing compounds ensures good dispersion of the cobalt-containing and manganese-containing compounds on the carrier material and is therefore preferred. This contrasts with the use of, for example, partially dissolved cobalt-containing and / or partially dissolved manganese-containing compounds in a "solid solution" or suspension, where the dispersion levels of the cobalt-containing and manganese-containing compounds on the surface and pores of the carrier material can fluctuate depending on the precipitation characteristics on the carrier material. Furthermore, the use of one or more completely dissolved solutions of cobalt-containing and manganese-containing compounds has less impact on the resulting morphology and packing crush strength of the extrudate formed subsequently compared to solid solutions. Nevertheless, the benefits of the methods disclosed herein can also be achieved in the case of using one or more solid solutions of partially undissolved cobalt-containing and / or manganese-containing compounds.

[0052] When the powder or particles of the carrier material are contacted with one or more solutions containing cobalt and manganese compounds, the amount of solution used preferably corresponds to a liquid amount suitable for achieving a mixture with a consistency suitable for further processing, such as extrusion molding. In this case, complete removal of the solvent from the impregnation solution can be carried out after the formed particles, such as extrudates, are formed.

[0053] Suitable cobalt-containing compounds are those that can thermally decompose into cobalt oxides upon calcination and are preferably completely soluble in the impregnation solution. Preferred cobalt-containing compounds are cobalt nitrates, acetates, or acetylacetonates, with cobalt nitrates, such as cobalt nitrate hexahydrate, being the most preferred. Halides are preferably avoided, as they have been found to be harmful.

[0054] Suitable manganese-containing compounds are those that can be thermally decomposed upon calcination and are preferably completely soluble in the impregnation solution. Preferred manganese-containing compounds are manganese nitrates, acetates, or acetylacetonates, with manganese acetates being the most preferred.

[0055] The solvent for one or more impregnation solutions can be an aqueous solvent or a non-aqueous organic solvent. Suitable non-aqueous organic solvents include, for example, alcohols (e.g., methanol, ethanol, and / or propanol), ketones (e.g., acetone), liquid alkanes, and ethers. Alternatively, aqueous organic solvents, such as aqueous alcohol solvents, can be used. Preferably, the solvent for the impregnation solution is an aqueous solvent.

[0056] In a preferred embodiment, the impregnation of the carrier material with cobalt-containing and manganese-containing compounds is carried out in a single step, without any intermediate drying or calcination steps to separate the loading of different components. As those skilled in the art will recognize, the cobalt-containing and manganese-containing compounds can be applied to the carrier material sequentially or simultaneously in separate impregnation solutions or suspensions, or preferably, an impregnation solution or suspension containing both cobalt-containing and manganese-containing compounds can be used.

[0057] There are no particular limitations on the concentration of cobalt-containing and manganese-containing compounds in the impregnation solution(s), although, as discussed above, it is preferable that the cobalt-containing and manganese-containing compounds are completely dissolved. When impregnating the powder or granules of the carrier material and immediately following the extrusion step, the amount of the impregnation solution(s) is preferably suitable for forming an extrudable paste.

[0058] In a preferred embodiment, the concentration of the impregnation solution is sufficient to provide a supported catalyst containing 5% to 35% by weight of cobalt, more preferably 7.5% to 25% by weight of cobalt, and even more preferably 10% to 20% by weight of cobalt, based on the total weight of the supported synthesis catalyst.

[0059] In another preferred embodiment, the concentration of the impregnation solution is sufficient to provide a supported catalyst containing, after drying and calcination, 0.5% to 15% manganese by element based on the total weight of the supported synthetic catalyst, preferably 3.0% to 10.5% manganese, for example 3.0% to 10% manganese, or even 4.0% to 8.0% manganese.

[0060] Suitable concentrations of cobalt-containing and / or manganese-containing compounds are, for example, 0.1 to 15 mol / L.

[0061] It should be recognized that, when the carrier material is in powder or granular form, once impregnated with cobalt-containing and manganese-containing compounds, the impregnated carrier material can be extruded or shaped into shaped particles at any suitable stage before or after drying and calcination.

[0062] After impregnation of the carrier material, the impregnation solution is typically dried to allow cobalt and manganese compounds to precipitate onto the carrier material, and preferably also to remove the binding solvent (e.g., water) of the impregnation solution. Therefore, drying does not, for example, lead to the complete decomposition of the cobalt compounds or otherwise cause a change in the oxidation state of the cobalt compounds. It will be appreciated that, in embodiments involving extrusion, complete drying and removal of the solvent (e.g., binding solvent) of the impregnation solution can be performed, for example, after extrusion to form shaped particles. Drying is suitably carried out at temperatures from 50°C to 150°C, preferably from 75°C to 125°C. Suitable drying times are, for example, from 5 minutes to 72 hours. Drying can suitably be carried out in a drying oven or box furnace, for example, under an inert gas flow at elevated temperatures.

[0063] In the case of impregnated molded particles such as extrudates, it will be appreciated that the carrier can come into contact with the impregnation solution by any suitable means, as mentioned above, including, for example, vacuum impregnation, initial wet impregnation, or impregnation in an excess liquid. In the case of impregnating powder or granules of carrier material, the powder or granules can be mixed with the impregnation solution by any suitable means known to a person skilled in the art, for example by adding the powder or granules to a container of the impregnation solution and stirring.

[0064] When the step of forming shaped particles, such as extrusion, immediately follows the impregnation of powder or granules, the mixture of powder or granules and impregnation solution may be further processed if it is not yet suitable for forming shaped particles (e.g., by extrusion). For example, the mixture may be ground to reduce the presence of larger particles that may not be easily extruded or otherwise formed into shaped particles, or whose presence would otherwise impair the physical properties of the resulting shaped particles, such as the extrudate. Grinding typically involves forming a paste suitable for forming (e.g., by extrusion). Any suitable grinding or kneading apparatus known to those skilled in the art can be used for grinding in this disclosure. For example, pestles and mortars may be suitably used in some applications, or a Simpson mill may be suitably used. Grinding is typically carried out for a period of 3 to 90 minutes, preferably 5 to 30 minutes. Grinding may suitably be carried out within a temperature range, including ambient temperature. A preferred temperature range for grinding is 15°C to 50°C. Grinding may suitably be carried out under ambient pressure. As mentioned above, it should be appreciated that complete removal of the binding solvent from the impregnation solution can be carried out, for example, after forming shaped particles by extrusion, to achieve complete precipitation.

[0065] In embodiments where the impregnated powder or granules are calcined to completely remove the solvent from the impregnation solution, the calcined powder or granules may be further processed to form a mixture suitable for, for example, extrusion molding into shaped particles. For example, an extrudable paste may be formed by combining the calcined powder or granules with a suitable solvent, such as the solvent used for impregnation, preferably an aqueous solvent, and grinding as described above.

[0066] The preparation of supported Co-Mn Fischer-Tropsch catalysts involves a calcination step. It will be understood that calcination is required to convert the cobalt-containing compound already impregnated on the support material into cobalt oxides. Therefore, calcination results in the thermal decomposition of the cobalt-containing compound, rather than simply removing the binding solvent of the impregnation solution, for example, under dry conditions.

[0067] Calcination can be carried out by any method known to those skilled in the art, such as in a fluidized bed or rotary kiln at a temperature of at least 250°C, preferably 275°C to 500°C. In some embodiments, calcination can be carried out as part of an integrated process in which the calcination and reduction activation of the synthesis catalyst are performed in the same reactor to produce a reduced Fischer-Tropsch synthesis catalyst. In a particularly preferred embodiment, the supported Co-Mn Fischer-Tropsch synthesis catalyst used in the methods of this disclosure is obtained or is available by a method comprising the following steps:

[0068] (a) Impregnating a carrier material with a cobalt-containing compound and a manganese-containing compound in a single impregnation step to form an impregnated carrier material; and

[0069] (b) Drying and calcining the impregnated support material to form a supported Co-Mn Fischer-Tropsch synthesis catalyst.

[0070] A particular advantage of this embodiment is the convenience of modifying and converting the support material into a supported Co-Mn Fischer-Tropsch synthesis catalyst using only a single impregnation step followed by drying and calcination steps. Therefore, in a preferred embodiment, the support material used in conjunction with the method of this disclosure is not pre-modified prior to impregnation in step (a) of the method, for example by the addition of accelerators, dispersants, strength enhancers, and / or binders or their precursors.

[0071] The supported Co-Mn Fischer-Tropsch synthesis catalyst used in the methods of this disclosure may additionally include one or more promoters, dispersants, or binders. Promoters may be added to facilitate the reduction of cobalt oxide to cobalt metal, preferably at lower temperatures. Preferably, the one or more promoters are selected from ruthenium, palladium, platinum, rhodium, rhenium, chromium, nickel, iron, molybdenum, tungsten, zirconium, gallium, thorium, lanthanum, cerium, copper, and mixtures thereof. Promoters are typically used at a cobalt / promoter atomic ratio of up to 250:1, more preferably up to 125:1, even more preferably up to 25:1, and most preferably 10:1. In a preferred embodiment, the one or more promoters are present in the resulting cobalt-containing Fischer-Tropsch synthesis catalyst in an amount of 0.1 wt% to 3 wt% based on the total weight of the supported synthesis catalyst. In other preferred embodiments, the cobalt-containing Fischer-Tropsch synthesis catalyst does not contain any promoters.

[0072] The addition of promoters, dispersants, strength enhancers, or binders can be integrated into several stages of the catalyst preparation process. Preferably, the promoter, dispersant, or binder, or its precursor, is introduced during the impregnation step, in which cobalt-containing and manganese-containing compounds are introduced. Supported Co-Mn Fischer-Tropsch synthesis catalysts can be readily converted into reduced supported Co-Mn Fischer-Tropsch synthesis catalysts by reduction activation using any known means known to those skilled in the art capable of converting cobalt oxide into active cobalt metal. Therefore, in one embodiment, the method of this disclosure further includes a prior step of reducing the Co-Mn Fischer-Tropsch synthesis catalyst by contacting it with a hydrogen-containing gaseous feed stream to form a reduced Co-Mn Fischer-Tropsch synthesis catalyst. The step of forming the reduced synthesis catalyst can be carried out batchwise or continuously in a fixed-bed, fluidized-bed, or slurry-phase reactor, or in situ in the same reactor as subsequently used for the Fischer-Tropsch synthesis reaction. Reduction is suitably carried out at temperatures from 150°C to 500°C, preferably from 200°C to 400°C, more preferably from 250°C to 350°C.

[0073] It will be recognized that the gaseous reactant mixture supplied to the Fischer-Tropsch reaction may also be suitable for reducing supported Co-Mn Fischer-Tropsch catalysts to form reduced supported Co-Mn Fischer-Tropsch catalysts in situ, without requiring any prior or separate reduction activation steps.

[0074] In the Fischer-Tropsch reaction disclosed herein, the volume ratio of hydrogen to gaseous carbon oxides in the gaseous reactant mixture (H2:CO) x The ratio of hydrogen to gaseous carbon oxides in the gaseous reactant mixture is at least 0.5:1, preferably at least 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 this disclosure, the volume ratio of hydrogen to gaseous carbon oxides in the gaseous reactant mixture (H2:CO) is... xThe optimal volume ratio of hydrogen to gaseous carbon oxides in the gaseous reactant mixture is at most 5:1, preferably at most 3:1, and most preferably at most 2.2:1. x Examples of these ranges include: 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, water, methane, and other saturated and / or unsaturated light hydrocarbons, each preferably present at a concentration of less than 30% by volume.

[0075] As discussed above, it has been surprisingly found that the Fischer-Tropsch synthesis methods of this disclosure provide Fischer-Tropsch catalysts exhibiting high selectivity for alcohols; it has also been surprisingly found that the Fischer-Tropsch synthesis methods of this disclosure provide Fischer-Tropsch catalysts exhibiting high selectivity for olefins. Furthermore, at least in some embodiments, excellent catalytic activity has been found.

[0076] Conventional Fischer-Tropsch temperatures can be used to prepare alcohols and liquid hydrocarbons according to this disclosure. For example, the contact temperature between a mixture of hydrogen and gaseous carbon oxides (e.g., in the form of a syngas mixture) and an olefin co-feed with a supported cobalt-manganese Fischer-Tropsch catalyst can suitably be between 100 and 400 °C, such as 100 to 350 °C, or 100 to 300 °C, or 100 to 250 °C, or 150 to 400 °C, or 150 to 350 °C, or 150 to 300 °C, or 150 to 250 °C. In some embodiments, the contact is carried out at a temperature not exceeding 350 °C, for example, not exceeding 325 °C, or not exceeding 300 °C, or not exceeding 280 °C, or not exceeding 260 °C. In some embodiments, the contact pressure (i.e., the temperature of the Fischer-Tropsch reaction) may suitably be between 10 and 100 barg (1 to 10 MPa), such as 15 to 75 barg (1.5 to 7.5 MPa), or 20 to 50 barg (2.0 to 5.0 MPa). For example, in some embodiments, the contact is carried out at a pressure not exceeding 7.5 MPa absolute.

[0077] In a particular embodiment, the temperature of the Fischer-Tropsch reaction is between 150 and 350°C, more preferably between 180 and 300°C, and most preferably between 200 and 260°C. In a preferred embodiment, the pressure of the Fischer-Tropsch reaction is between 10 and 100 bar (1 to 10 MPa), more preferably between 10 and 60 bar (1 to 6 MPa), and most preferably between 20 and 45 bar (2 to 4.5 MPa).

[0078] This disclosure provides a reaction between hydrogen and a mixture of gaseous carbon oxides. In some embodiments, as further described herein, the gaseous carbon oxide is carbon monoxide. Carbon monoxide that is substantially free of carbon dioxide can be provided, for example. However, in other embodiments, the gaseous carbon oxide is carbon dioxide, or a combination of carbon monoxide and carbon dioxide.

[0079] The inventors have unexpectedly discovered that adding an olefin co-feed to the Fischer-Tropsch reaction mixture can advantageously improve the method selectivity for alcohols. In addition to the direct and efficient conversion of the olefin feed (which is beneficial in itself), the increased alcohol recovery can exceed what would be expected from an olefin feed alone (even with controlled increases in the molecular weight of the alcohol product relative to the olefin reactants). This unexpected result enables the selective synthesis of alcohols in high yields by adjusting the olefin co-feed composition and feed rate.

[0080] I don't want to be bound by theory, but I currently believe that it includes C. n At least one product of an olefin co-feed (i.e., an unsaturated hydrocarbon having n carbon atoms) is formed by reacting with gaseous carbon oxides (e.g., carbon monoxide) and optionally hydrogen to form C n+1 Alcohols. For example, a co-feed containing propylene can produce a product stream containing butanol. Under this theory, those skilled in the art can advantageously select specific olefin co-feeds to produce a product stream with an increased amount of the desired alcohol product.

[0081] The olefin co-feed can be present in various weight proportions to achieve this result. In some embodiments, as further described herein, the olefin co-feed is present in an amount of 0.001 wt% to 30 wt% relative to the total amount of hydrogen, gaseous carbon oxides, and olefins, for example, 0.001 wt% to 20 wt%, or 0.001 wt% to 10 wt%, or 0.001 wt% to 15 wt%, or 0.001 wt% to 5 wt%. For example, in some embodiments, the olefin co-feed is present in an amount of 0.01 wt% to 30 wt% relative to the total amount of hydrogen, gaseous carbon oxides, and olefins, for example, 0.01 wt% to 15 wt%, 0.01 wt% to 10 wt%, or 0.01 wt% to 5 wt%. In a further embodiment, the olefin co-feed is present in an amount of 0.1 wt% to 20 wt%, for example, 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt%, or 0.1 wt% to 5 wt%, relative to the total amount of hydrogen, gaseous carbon oxides, and olefins. In a further embodiment, the olefin co-feed is present in an amount of 0.2 wt% to 20 wt%, for example, 0.2 wt% to 15 wt%, 0.2 wt% to 10 wt%, or 0.2 wt% to 5 wt%, relative to the total amount of hydrogen, gaseous carbon oxides, and olefins.

[0082] Depending on the availability of the feed stream and the desired product composition, the olefin co-feed can have a variety of compositions. In some embodiments further described herein, the olefin co-feed is at least 70 wt%, or at least 80 wt%, or at least 90 wt% C2-C 14 Alkenes or C2-C 10 Olefins. For example, in some embodiments, the olefin co-feed is at least 70 wt%, or at least 80 wt%, or at least 90 wt% of C2-C5 olefins. In specific embodiments, the olefin co-feed is at least 70 wt%, or at least 80 wt%, or at least 90 wt% of propylene and / or ethylene. For example, the olefin co-feed can be more than 95 wt% propylene. The olefins can be a pure feed stream or a mixture containing olefins within the desired carbon range.

[0083] Olefins of various chemical structures can be used to modulate reaction conditions to achieve increased yields of specific products. Therefore, in some embodiments as further described herein, the olefin co-feed comprises a straight-chain olefin (e.g., at least one straight-chain olefin). Examples of straight-chain olefins include straight-chain α-olefins (e.g., ethylene, propylene, 1-hexene, 1-heptene, 1-octene, and / or other suitable C2-C...). 14 (olefins) or inner straight-chain olefins (e.g., 3-hexene and other suitable C2-C) 14 Olefins). In some embodiments as further described herein, the olefin co-feed comprises a cyclic olefin (e.g., at least one cyclic olefin). Examples of suitable cyclic olefins include cyclohexene, cycloheptene, cyclooctene, bicyclic olefins, and other suitable cyclic C4-C... 14 Olefins. In some embodiments as further described herein, the olefin co-feed comprises branched olefins (e.g., at least one branched olefin). In a particular embodiment, the at least one branched olefin is a terminal olefin (e.g., an α-olefin), wherein the olefin is an internal olefin. For example, in some embodiments as further described herein, the at least one branched olefin has a structure (R... 1 (R) 2 C = CH2, where R 1 and R 2 It is an substituted alkyl group (i.e., R) 1 and R 2 Neither of them are H). R 1 and R 2 They can be straight-chain or branched alkanes. They can be substituted by one or more groups selected from hydroxyl, halogen, and amino groups.

[0084] The Fischer-Tropsch synthesis reaction can be carried out in any suitable type of reactor, such as a fixed-bed reactor, a slurry-bed reactor, or a CANs reactor.

[0085] In another aspect of this disclosure, a supported Co-Mn Fischer-Tropsch synthesis catalyst is provided, comprising at least 0.5% by weight of element-based manganese based on the total weight of the supported synthesis catalyst; and wherein the manganese / cobalt weight ratio is 0.05 or greater based on element-based weight, the support material of the supported Co-Mn Fischer-Tropsch synthesis catalyst comprises a material selected from titanium dioxide, zinc oxide, zirconium oxide, silicon dioxide and cerium dioxide, and wherein the supported Co-Mn Fischer-Tropsch synthesis catalyst is prepared by impregnation.

[0086] For the purposes of this disclosure, the particle size of Co3O4 crystallites is determined by X-ray diffraction.

[0087] It will be appreciated that the support materials and methods used to prepare the supported Co-Mn Fischer-Tropsch synthesis catalysts of the other aspects described above can be as defined above. For example, the synthesis catalyst is preferably obtained or can be obtained by a method comprising the following steps:

[0088] (a) Impregnating a carrier material with a cobalt-containing compound and a manganese-containing compound in a single impregnation step to form an impregnated carrier material; and

[0089] (b) Drying and calcining the impregnated support material to form a supported Co-Mn Fischer-Tropsch synthesis catalyst.

[0090] The supported Co-Mn Fischer-Tropsch synthesis catalysts described above in this disclosure can also be used to i) improve the selectivity of alcohol production in the Fischer-Tropsch process, and / or ii) improve the conversion rate in the Fischer-Tropsch process.

[0091] In another aspect of this disclosure, a method for controlling the crystallite size of cobalt oxide in the preparation of a supported cobalt-containing Fischer-Tropsch synthesis catalyst is provided, the method comprising the step of supplying acetic acid or a metal salt of acetic acid during impregnation of a support material with a cobalt-containing compound, wherein the metal is selected from ruthenium, palladium, platinum, rhodium, rhenium, manganese, chromium, nickel, iron, molybdenum, tungsten, zirconium, gallium, thorium, lanthanum, cerium, copper, and mixtures thereof; preferably wherein the metal is selected from manganese, ruthenium, rhenium, and platinum, and more preferably manganese.

[0092] The methods of this disclosure will now be further described with reference to the following exemplary embodiments, which are exemplary only. In the embodiments, CO conversion is defined as the number of moles of CO used / the number of moles of CO supplied x 100, while carbon selectivity is defined as the number of moles of CO attributed to a particular product / the number of moles of CO converted x 100. Unless otherwise stated, the temperatures mentioned in the embodiments are applied temperatures, not catalyst / bed temperatures. Unless otherwise stated, the pressures mentioned in the embodiments are absolute pressures. Example

[0093] The following examples illustrate specific implementations of the methods of this disclosure and their various uses. They are for illustrative purposes only and should not be considered as limiting the scope of this disclosure.

[0094] Example 1: Addition of propylene co-feed

[0095] Several catalysts with different compositions were prepared (see Table 1) in a 16-channel reactor by heating from 25°C to 150°C at a rate of 2°C / min, followed by heating from 150°C to 300°C at a rate of 1°C / min. Common feed, temperature, and pressure were maintained between the catalyst channels. C1-C8 catalysts were analyzed online. The catalysts were subjected to atmospheric pressure and 8000 hr... -1 Activated at 100% H2 at 300°C with a gas hourly space velocity (GHSV). This was achieved by [further action] at 30 barg and 3000 hr. -1 The Fischer-Tropsch reaction was carried out by contacting the respective catalysts with a 1.8H₂:CO mixture at a gas hourly space velocity (GHSV) under 20% N₂ gas atmosphere. To test the effect of olefin co-feeding, olefins were introduced instead of nitrogen co-feeding.

[0096] The reaction was carried out without an olefin co-feed (see “Baseline” below) and with a 0.5 wt% propylene co-feed. The results are summarized in Table 1 below:

[0097] Table 1

[0098]

[0099]

[0100] As shown in Table 1, the addition of olefin co-feeds, such as propylene co-feeds, resulted in an average increase of +4.2% in C1-C8 alcohol selectivity. As is known in the art, C1-C8 alcohol selectivity typically represents total alcohol selectivity. Therefore, it can be expected that olefin co-feeds also improve total alcohol selectivity. Further improvements are likely to be achieved through further optimization. The observed improvements appear to depend largely on the catalyst support material. This observation reinforces the theory that the addition of olefin co-feeds enhances Fischer-Tropsch reaction kinetics, rather than simply increasing the availability of unsaturated reactants. Importantly, the observed improvement in alcohol selectivity was achieved without compromising CH4 selectivity or C1-C8 selectivity. 5+ Selectivity, neither of these was significantly changed by the addition of propylene co-feed.

[0101] It can be suggested that the increased alcohol selectivity shown in Table 1 is at least partly a result of the conversion of olefins to the corresponding alcohols. However, even if 0.5 wt% propylene feed were completely converted to butanol, it would only yield approximately 0.9 wt% butanol, far less than the lowest observed increase in alcohol selectivity of +2.4 wt% observed in Table 1, and significantly lower than the average increase of +4.2 wt%. Therefore, we propose that the olefin co-feed and the Fischer-Tropsch reaction have an unexpected synergistic effect, favorably leading to increased alcohol production.

[0102] Various exemplary embodiments of this disclosure include, but are not limited to, the embodiments listed below, which can be combined in any number and any combination that are not technically or logically contradictory.

[0103] Implementation Scheme 1. A method for converting a mixture of hydrogen and gaseous carbon oxides into a product composition comprising an alcohol and a liquid hydrocarbon via a Fischer-Tropsch synthesis reaction, wherein the gaseous carbon oxides are carbon monoxide, carbon dioxide, or a combination thereof, the method comprising:

[0104] A mixture of hydrogen and gaseous carbon oxides (e.g., in the form of a syngas mixture) and an olefin co-feed are contacted with a supported cobalt-manganese Fischer-Tropsch synthesis catalyst to provide a product composition;

[0105] The olefin co-feed contains at least one C2-C 14 Olefins, present in an amount of 0.001% to 40% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins;

[0106] Based on elemental analysis, the manganese / cobalt weight ratio in the catalyst is at least 0.05; and

[0107] In the mixture of hydrogen and gaseous carbon oxides, the molar ratio of hydrogen to gaseous carbon oxides is at least 0.5.

[0108] 2. The method of embodiment 1, wherein, based on elemental composition, the manganese / cobalt weight ratio present in the synthesis catalyst is 0.05 to 3.0 (e.g., 0.1 to 2.5, or 1.5 to 2.0, or 0.2 to 1.5, or 0.2 to 1.2, or 0.2 to 1, or 0.3 to 3.0, or 0.3 to 2.5, or 0.3 to 2.0, or 0.3 to 1.5, or 0.3 to 1.2, or 0.5 to 3.0, or 0.5 to 2.5, or 0.5 to 2.0, or 0.5 to 1.5, or 0.5 to 1).

[0109] 3. The method of embodiment 1 or embodiment 2, wherein the synthesis catalyst comprises at least 0.5% by weight of manganese based on elemental composition.

[0110] 4. The method of embodiment 1 or embodiment 2, wherein the synthesis catalyst comprises up to 25% by weight, for example 2.5-25% by weight of manganese based on elemental weight.

[0111] 5. The method of any one of embodiments 1-4, wherein the synthesis catalyst comprises 2-35% by weight, for example 5-35% by weight, or 7-35% by weight, or 10-35% by weight, or 2-25% by weight, or 5-25% by weight, or 7-25% by weight, or 10-25% by weight, based on the elemental composition.

[0112] 6. The method of any one of embodiments 1-4, wherein the synthesis catalyst comprises 2-20% by weight, for example 5-20% by weight, or 7-20% by weight, or 10-20% by weight, or 2-15% by weight, or 5-15% by weight, or 7-15% by weight, based on the elemental composition.

[0113] 7. The method according to any one of embodiments 1-6, wherein, based on the total weight of the synthetic catalyst and based on elements, the total amount of cobalt and manganese in the synthetic catalyst is not greater than 40% by weight.

[0114] 8. The method of any one of embodiments 1-7, wherein the synthesis catalyst comprises Co3O4 microcrystals having a particle size of less than 150 angstroms.

[0115] 9. The method of any one of embodiments 1-8, wherein the catalyst comprises a support material, the support material comprising at least one oxide selected from alumina, zirconium oxide, zinc oxide, cerium dioxide, silicon dioxide and titanium dioxide.

[0116] 10. The method of any one of embodiments 1-8, wherein the carrier material comprises titanium dioxide (e.g., titanium dioxide).

[0117] 11. The method according to any one of embodiments 1-10, wherein the contact is performed at a pressure of 1.0 to 10.0 MPa absolute pressure.

[0118] 12. The method described in any one of embodiments 1-11, wherein the contact is performed at a pressure not exceeding 7.5 MPa absolute pressure.

[0119] 13. The method of any one of embodiments 1-12, wherein the contact is performed at a temperature not exceeding 350°C.

[0120] 14. The method of any one of embodiments 1-13, wherein the gaseous carbon oxide is carbon monoxide.

[0121] 15. The method of embodiment 14, wherein the gaseous carbon oxide is carbon dioxide or a mixture of carbon monoxide and carbon dioxide.

[0122] 16. The method of any one of embodiments 1-15, wherein the olefin co-feed is present in an amount of 0.001 wt% to 30 wt%, for example 0.001 wt% to 10 wt%, or 0.001 wt% to 5 wt%, relative to the total amount of hydrogen, gaseous carbon oxides and olefins.

[0123] 17. The method of any one of embodiments 1-15, wherein the olefin co-feed is present in an amount of 0.1 wt% to 20 wt%, for example 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt%, or 0.1 wt% to 5 wt%, relative to the total amount of hydrogen, gaseous carbon oxides and olefins.

[0124] 18. The method of any one of embodiments 1-15, wherein the olefin co-feed is present in an amount of 1% to 20% by weight, for example 1% to 15% by weight, 1% to 10% by weight, or 1% to 5% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins.

[0125] 19. The method of any one of embodiments 1-18, wherein the olefin co-feed comprises at least one straight-chain olefin.

[0126] 20. The method of any one of embodiments 1-19, wherein the olefin co-feed comprises at least one cyclic olefin.

[0127] 21. The method of any one of embodiments 1-20, wherein the olefin co-feed comprises at least one branched olefin.

[0128] 22. The method of embodiment 21, wherein the at least one branched olefin is a terminal olefin (e.g., an α-olefin), and wherein the olefin is an internal olefin.

[0129] 23. The method of embodiment 21 or embodiment 22, wherein the branched olefin has a structure (R 1 (R) 2 C = CH2, where R 1 and R 2 It is an alkyl group that is optionally substituted.

[0130] 24. The method according to any one of embodiments 1-23, wherein the olefin co-feed is at least 90% C2-C 14 Olefins.

[0131] 25. The method of any one of embodiments 1-23, wherein the olefin co-feed is at least 90% C2-C 10Olefins.

[0132] 26. The method of any one of embodiments 1-23, wherein the olefin co-feed is at least 90% C2-C5 olefin.

[0133] 27. The method of any one of embodiments 1-23, wherein the olefin co-feed is at least 90% propylene and / or ethylene.

[0134] 28. The method of any one of embodiments 1-27, wherein the product composition comprises at least 10% by weight of alcohol, for example at least 15% by weight of alcohol.

[0135] 29. The method of any one of embodiments 1-28, wherein the product composition comprises at least 20% by weight of alcohol, for example at least 25% by weight of alcohol.

[0136] 30. The method of any one of embodiments 1-29, wherein the alcohol comprises C1-C 24 alcohol.

[0137] 31. The method of any one of embodiments 1-30, wherein the alcohol comprises C1-C8 alcohols.

[0138] Various exemplary embodiments of this disclosure include, but are not limited to, the embodiments listed herein, which can be combined in any number and any combination that are not technically or logically contradictory.

[0139] The details shown herein are illustrative and are provided only to illustrate certain embodiments of this disclosure, and are intended to provide the most useful and readily understood description of the principles and concepts of various embodiments of this disclosure. In this regard, no attempt is made to show details related to the methods of this disclosure beyond the level of detail necessary for a basic understanding of the methods described herein; the descriptions, drawn in conjunction with examples, make it clear to those skilled in the art how the methods of this disclosure can be embodied in several forms in practice. Therefore, before describing the disclosed methods and apparatus, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and thus can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to constitute limitation unless specifically defined herein.

[0140] Unless otherwise specified herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar indicators used in the text describing the methods of this disclosure (especially in the text of the following embodiments and claims) shall be interpreted as covering both the singular and the plural.

[0141] Unless otherwise specified herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order of steps. The use of any and all instances or exemplary wording (such as “as”) provided herein is intended only to better illustrate the methods of this disclosure and not to limit the scope of this disclosure. None of the wording in the specification should be construed as indicating that any unclaimed element is essential to the practice of the methods of this disclosure.

[0142] Unless the context explicitly requires otherwise, throughout the specification and claims, the terms “comprise”, “comprising,” etc., should be interpreted in an inclusive sense rather than an exclusive or exhaustive sense; that is, in the sense of “including but not limited to.” The use of singular or plural terms also includes both singular and plural forms, respectively. Furthermore, when used in this application, the terms “this article,” “above,” and “below,” and similar terms, should refer to the entire application and not any particular part thereof.

[0143] As will be understood by those skilled in the art, the various embodiments disclosed herein may comprise, consist substantially of, or be composed of their specific specified elements, steps, ingredients, or components. The transitional terms “comprise” or “comprises” as used herein mean, but are not limited to, and allow the inclusion of unspecified elements, steps, ingredients, or components, even in substantial quantities. The transitional phrase “composes of” excludes any unspecified elements, steps, ingredients, or components. The transitional phrase “consistently composed of” limits the scope of the embodiments to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiments.

[0144] Unless otherwise stated, all percentages, ratios and proportions in this document are by weight.

[0145] Although the wide range of numerical values ​​and parameters described in this disclosure are approximate, the values ​​described in the specific embodiments are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation present in their respective experimental measurements.

[0146] The grouping of alternative elements or embodiments in this disclosure should not be construed as limiting. Each member of a group may be mentioned and claimed individually or in any combination with other members of that group or other elements found herein. It is anticipated that one or more members of a group may be added to or removed from the group for convenience and / or patentability reasons. When any such addition or removal occurs, this specification is deemed to contain the modified group and thus satisfy the written description of all Markush groups as used in the appended claims.

[0147] Various embodiments of this disclosure have been described herein, including the best mode known to the inventors for carrying out the methods described herein. Of course, variations on these described embodiments will be apparent to those skilled in the art upon reading the foregoing description. Such variations will be utilized as appropriate by those skilled in the art, and thus the methods of this disclosure may be implemented differently from the specific descriptions herein. Therefore, the scope of this disclosure includes all modifications and equivalents of the subject matter items listed in the appended claims as permitted by applicable law. Furthermore, unless otherwise specified herein or clearly contradicted by the context, this disclosure covers any combination of the foregoing elements under all possible variations.

[0148] The phrase “at least a part” as used in this article is used to indicate that at least a part of the quantity is required, and at most all possible quantities.

[0149] Finally, it should be understood that the various embodiments described herein are illustrative of the methods of this disclosure. Other modifications may be employed within the scope of this disclosure. Therefore, alternative configurations of the method may be utilized in accordance with the teachings of this document, rather than as examples or limitations. Thus, the methods of this disclosure are not limited to those precisely shown and described.

Claims

1. A method for converting a mixture of hydrogen and gaseous carbon oxides into a product composition comprising an alcohol and a liquid hydrocarbon via a Fischer-Tropsch synthesis reaction, wherein the gaseous carbon oxides are carbon monoxide, carbon dioxide, or a combination thereof, the method comprising: A mixture of hydrogen and gaseous carbon oxides and an olefin co-feed is contacted with a supported cobalt-manganese Fischer-Tropsch synthesis catalyst to provide a product composition; The olefin co-feed contains at least one C2-C 14 Olefins, and present in an amount of 0.1% to 20% by weight relative to the total amount of hydrogen, gaseous carbon oxides and olefins; The synthesis catalyst contains at least 0.5% by weight of manganese based on elemental calculations; The synthesis catalyst contains 2-35% by weight of cobalt based on elemental composition; Based on elemental analysis, the manganese / cobalt weight ratio in the catalyst is from 0.1 to 2.5; and In the mixture of hydrogen and gaseous carbon oxides, the molar ratio of hydrogen to gaseous carbon oxides is at least 0.

5.

2. The method of claim 1, wherein, based on elemental analysis, the manganese / cobalt weight ratio present in the synthesis catalyst is 0.2 to 1.

3. The method of claim 1, wherein the synthesis catalyst comprises 2.5-25% by weight of manganese based on elemental composition.

4. The method of claim 1, wherein the synthesis catalyst comprises 5-20% by weight of cobalt based on elemental composition.

5. The method of claim 1, wherein, based on the total weight of the synthetic catalyst and based on elements, the total amount of cobalt and manganese in the synthetic catalyst is not greater than 40% by weight.

6. The method of claim 1, wherein the catalyst comprises a support material, the support material comprising at least one oxide selected from alumina, zirconium oxide, zinc oxide, cerium dioxide, silicon dioxide and titanium dioxide.

7. The method of claim 1, wherein the contact is performed at a pressure of 1.0 to 10.0 MPa absolute pressure.

8. The method of claim 1, wherein the contact is performed at a temperature not exceeding 350°C.

9. The method of claim 1, wherein the gaseous carbon oxide is carbon monoxide.

10. The method of claim 1, wherein the gaseous carbon oxide is carbon dioxide or a mixture of carbon monoxide and carbon dioxide.

11. The method of claim 1, wherein the olefin co-feed comprises at least one straight-chain olefin.

12. The method of claim 1, wherein the olefin co-feed comprises at least one cyclic olefin or at least one branched olefin.

13. The method of claim 1, wherein the olefin co-feed is at least 90% by weight C2-C 14 Olefins.

14. The method of claim 1, wherein the olefin co-feed is at least 90% by weight of C2-C5 olefin.

15. The method of claim 1, wherein the product composition comprises at least 10% by weight of alcohol.

16. The method of claim 1, wherein the product composition comprises at least 20% by weight of alcohol.

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