A Fischer-Tropsch catalyst containing at least 40% by weight of cobalt, a Fischer-Tropsch method using the same, and a method for producing the same.

Abstract

The present invention provides a Fischer-Tropsch catalyst containing greater than about 40 wt.% cobalt and having a packed apparent bulk density greater than about 1.30 g / mL.

Description

[Technical Field]

[0001] The present invention relates to cobalt-containing Fischer-Tropsch catalysts, and more particularly to cobalt-containing Fischer-Tropsch catalysts for use in microchannel reactors. [Background technology]

[0002] The Fischer-Tropsch reaction is widely used to produce fuel from carbon monoxide and hydrogen, and can be represented by the following equation. (2n+1)H2+nCO→C n H 2n+2 +nH2O

[0003] This reaction is highly exothermic and is catalyzed under high temperature (typically at least 180°C, e.g., above 200°C) and high pressure (e.g., at least 1000 kPa) conditions, using a Fischer-Tropsch catalyst, usually a cobalt-based catalyst. [Overview of the project] [Problems that the invention aims to solve]

[0004] A product mixture is obtained, where n typically ranges from 1 to about 90. It is desirable to minimize the selectivity for light gases (e.g., methane), i.e., minimize the proportion of methane (n=1) in the product mixture, and maximize the selectivity for paraffins of C5 or greater (n≧5), typically to a level of about 80% or more, or about 85% or more. Preferably, at least about 40% w / w of the product mixture is n≧20. This is because shifting the selectivity from lighter products to heavier products increases economic value. Several factors affect this selectivity, including operating temperature, with lower operating temperatures resulting in lower selectivity for light hydrocarbons. The parameter used to compare selectivity is the Anderson-Schulz-Flory alpha value. A higher alpha value indicates lower selectivity for light hydrocarbons. At high alpha values, small changes in alpha have a significant economic effect on product yield. This is illustrated in Table 1. For example, and using the model of Vervloet et al. (Catal. Sci. Technol., 2012, 2, 1221-1233) as an indicator, a shift in operating temperature from 210°C to 200°C can increase alpha by 0.03. Therefore, it is preferable to carry out the reaction at a lower temperature, preferably without sacrificing productivity.

[0005] [Table 1]

[0006] The raw materials for hydrogen and carbon monoxide are generally synthesis gas. [Modes for carrying out the invention]

[0007] Unless otherwise specified in the context, any phrase containing the term “synthesis gas” shall be interpreted as meaning a gas primarily composed of hydrogen and carbon monoxide. Other components, such as carbon dioxide, nitrogen, argon, water, methane, tar, acidic gases, high molecular weight hydrocarbons, oils, volatile metals, char, phosphorus, halides, and ash, may optionally be present.

[0008] The use of the above terms to describe synthesis gas should not be taken as restrictive. Those skilled in the art will understand that each term is interpreted to mean a gas primarily comprising hydrogen and carbon monoxide.

[0009] The synthesis gas may be produced by, for example, vaporizing a carbonaceous material at a high temperature of at least about 600°C, at least about 700°C, or at least about 800°C. The carbonaceous material may optionally contain any carbon-containing material that can be vaporized for the production of synthesis gas. The carbonaceous materials described above may optionally include non-plant resources such as biomass (e.g., plant or animal materials, and biodegradable waste), food resources (e.g., corn and soybeans), and / or coal (e.g., low-grade coal, high-grade coal, and clean coal), oil (e.g., crude oil, heavy oil, tar sands oil, and shale oil), solid waste (e.g., urban solid waste, hazardous waste), waste-derived fuel (RDF), tires, petroleum coke, scrap, garbage, biogas, sewage sludge, animal waste, agricultural waste (e.g., corn leaves and stalks, switchgrass, mowed grass), building demolition materials, plastic materials (e.g., plastic waste), cotton ginning machine waste, and mixtures of two or more of these.

[0010] Alternatively, synthesis gas may be produced by other means, such as the reforming of natural gas or landfill gas, or the reforming of gas produced by anaerobic digestion processes. Furthermore, synthesis gas may be produced by CO2 reforming using electrolysis, such as in a hydrogen source (e.g., the so-called "electricity-to-fuel" process).

[0011] The synthesis gas produced as described above may optionally be treated in preparation for supplying the Fischer-Tropsch catalyst to adjust the molar ratio of H2 to CO by steam reforming (e.g., steam methane reforming (SMR) reaction in which methane is reacted with steam in the presence of an SMR catalyst), partial oxidation, autothermal reforming, carbon dioxide reforming, water-gas shift reaction, or a combination of two or more of these (also called fresh synthesis gas).

[0012] The term "water-gas shift reaction" or "WGS" is interpreted as a thermochemical method involving the conversion of carbon monoxide and water into hydrogen and carbon dioxide. The synthesis gas obtained after the WGS reaction may be interpreted as shifted (i.e., regulated) synthesis gas.

[0013] The molar ratio of H2 to CO in fresh synthesis gas is preferably within the range of approximately 1.6:1 to approximately 2.2:1, or approximately 1.8:1 to approximately 2.1:1, or approximately 1.95:1 to approximately 2.05:1.

[0014] The fresh synthesis gas may optionally be combined with a regenerated tail gas (e.g., regenerated Fischer-Tropsch tail gas) which itself contains H2 and CO, to form a reactant mixture. The tail gas may optionally contain H2 and CO in a molar ratio of H2 to CO in the range of about 0.5:1 to about 2:1, or about 0.6:1 to about 1.8:1, or about 0.7:1 to about 1.2:1.

[0015] The aforementioned reactant mixture may optionally contain H2 and CO in molar ratios within the range of approximately 1.4:1 to approximately 2.1:1, approximately 1.7:1 to approximately 2.0:1, or approximately 1.7:1 to approximately 1.9:1.

[0016] When the recycled tail gas is used, the volume ratio of fresh syngas to the recycled tail gas used to form the reactant mixture may optionally be in the range of about 1:1 to about 20:1, or about 1:1 to about 10:1, or about 1:1 to about 6:1, or about 1:1 to about 4:1, or about 3:2 to about 7:3, or about 2:1.

[0017] The consequence of the highly exothermic Fischer-Tropsch reaction is the need to remove the heat of reaction so that the industrial scale process can operate effectively. One approach to this problem is to limit the volumetric productivity so that the rate at which heat is removed can keep pace with the rate at which heat is generated. This is the principle behind the slurry bubble column reactors and conventional fixed bed reactors commonly used in the art. Alternatively, by using a reactor design that can remove the heat of reaction more efficiently, such as within a microchannel reactor, the volumetric productivity can be increased many times while still maintaining the local reaction temperature within a few degrees of the process target value. This enables smaller reactors to achieve economic goals at a sufficiently high production rate.

[0018] For low productivity reactors, one aspect of high volumetric productivity is a higher transient impurity load passing through a given catalyst volume. As an example, when the volumetric productivity is 10 times higher than that of a normal fixed bed reactor, the rate of impurity-related deactivation is generally also 10 times higher. This requires extremely strict tolerance for the acceptable concentration of ultra-trace amounts of catalyst poisons in the syngas feed.

[0019] One possible way to mitigate this problem is to increase the number of reaction sites per unit volume of the catalyst charge. Thus, at the same volumetric productivity and the same time-averaged impurity concentration, it takes longer before the charge becomes uneconomical to operate through poisoning. Such an approach has limited value in either of the two common reaction systems employed in Fischer-Tropsch synthesis, which are slurry bubble columns or conventional fixed beds. In slurry bubble columns, the volumetric productivity is constrained by the acceptable solids content in the slurry. Consequently, slurry bubble column reactors are essentially constrained in terms of those volumetric productivities, which are far lower than those employed in Fischer-Tropsch microchannel reactors. In conventional fixed bed reactors, adopting highly engineered catalyst shapes to prevent excessive mass transfer effects based on the conversion selectivity to shorter and less economically valuable hydrocarbons can make temperature control and process stability even more problematic due to the increased reaction site density. Thus, the present invention is particularly advantageous in microchannel reactors.

[0020] In view of the above, it is desirable to increase the number of reaction sites per unit volume of the catalyst charge. There are two means by which this can be achieved. a) Reduce the cobalt crystallite size. This can result in an increase in the metal surface area and, consequently, an increase in activity. However, this will compromise the low methane selectivity and the increase in catalyst deactivation. b) Increase the cobalt loading percentage. This can increase the cobalt metal surface area and density, but it results in the redundancy of the catalyst preparation procedure.

[0021] Catalysts of the prior art are improved in either one of a) or b) above.

[0022] French Patent Publication No. 2992236 describes a SiC-based catalyst support at least partially coated with TiO2. 5% to 40% by mass of cobalt is then deposited on the support and used in the Fischer-Tropsch reaction. Table 2 describes three catalysts containing 10% by mass of cobalt, and from the data in the table, it can be inferred that the packed apparent bulk density (PABD) of the cobalt in these catalysts is 0.078 to 0.084 g / mL.

[0023] Cao et al. (Catalysis Today, 2009, 140, 149-156) described the use of alumina-based cobalt-containing catalysts with diameters of 150 and 45 μm in a microchannel reactor. However, the cobalt loading of these catalysts was only 30% by weight.

[0024] International Publication No. 2016 / 011299, incorporated herein by reference, describes a composition comprising Co3O4 and a second oxide, wherein the average particle size of the Co3O4 in the composition is at least 8.8 nm, and the porosity of the composition is at least 0.35. The composition may optionally contain 30 to 60% by weight of cobalt. However, the packing apparent bulk density of the cobalt is kept relatively low, within an approximate range of 0.4 to 0.49 g / mL.

[0025] Therefore, in this technology, there is a need for a catalyst that simultaneously improves both a) and b), thereby increasing both the cobalt loading and the apparent bulk density of the catalyst. A catalyst is desired that has high activity and improved impurity stability, while maintaining product selectivity, and preferably can be obtained by a simple synthesis.

[0026] According to a first aspect of the present invention, a Fischer-Tropsch catalyst is provided that contains more than about 40% by weight of cobalt and has a packing apparent bulk density of more than about 1.30 g / mL.

[0027] The apparent bulk density of cobalt in the above catalyst may optionally be greater than about 0.60 g / mL. Accordingly, according to another aspect of the present invention, a Fischer-Tropsch catalyst is provided which contains more than about 40% by weight of cobalt and has an apparent bulk density of cobalt greater than about 0.60 g / mL.

[0028] The inventors have found that both the weight percentage of cobalt in the catalyst and the apparent bulk density of the catalyst can be increased, thus resulting in a greater apparent bulk density of cobalt. The catalyst of the present invention can achieve approximately twice the apparent bulk density of cobalt compared to prior art catalysts (such as those disclosed in International Publication No. 2016 / 011299). The inventors have found that this increase in the apparent bulk density of cobalt leads to improved toxicity stability, particularly against sulfur and nitrogen poisoning, and higher stability during the catalyst lifetime.

[0029] The catalyst described above may optionally contain more than approximately 45% by weight or more than approximately 50% by weight of cobalt.

[0030] The catalyst described above may optionally contain cobalt in an amount of approximately 60% by weight or less, or approximately 55% by weight or less.

[0031] The catalyst may optionally contain approximately 40% to 60% by weight of cobalt, or approximately 45% to 60% by weight of cobalt, or approximately 50% to 60% by weight of cobalt. The catalyst may optionally contain approximately 40% to 55% by weight of cobalt, or approximately 45% to 55% by weight of cobalt, or approximately 50% to 55% by weight of cobalt.

[0032] The apparent bulk density of the catalyst packing may be, arbitrarily, greater than approximately 1.35 g / mL, greater than approximately 1.40 g / mL, greater than approximately 1.45 g / mL, greater than approximately 1.50 g / mL, greater than approximately 1.55 g / mL, or greater than approximately 1.60 g / mL.

[0033] The apparent bulk density of the catalyst packing may be arbitrarily about 1.70 g / mL or less, or about 1.65 g / mL or less.

[0034] The apparent bulk density of the catalyst packing may be arbitrarily about 1.30 g / mL to about 1.70 g / mL, or about 1.35 g / mL to about 1.70 g / mL, or about 1.40 g / mL to about 1.70 g / mL, or about 1.45 g / mL to about 1.70 g / mL, or about 1.50 g / mL to about 1.70 g / mL, or about 1.50 g / mL to about 1.65 g / mL.

[0035] The apparent bulk density of the cobalt packing in the above catalyst may be, arbitrarily, greater than approximately 0.65 g / mL, greater than approximately 0.70 g / mL, greater than approximately 0.75 g / mL, or greater than approximately 0.80 g / mL.

[0036] The apparent bulk density of the cobalt packing in the above catalyst may be arbitrarily about 0.90 g / mL or less.

[0037] The apparent bulk density of the cobalt packing in the above catalyst may be arbitrarily about 0.60 g / mL to about 0.90 g / mL, or about 0.65 g / mL to about 0.90 g / mL, or about 0.70 g / mL to about 0.90 g / mL, or about 0.75 g / mL to about 0.90 g / mL, or about 0.80 g / mL to about 0.90 g / mL.

[0038] The cobalt particle diameter and / or average cobalt particle diameter of the catalyst described above may be, arbitrarily, about 5 nm to about 20 nm, or about 5 nm to about 15 nm, or about 6 nm to about 12 nm, or about 8 nm to about 10 nm. The cobalt particle diameter and / or average cobalt particle diameter of the catalyst described above may be, arbitrarily, less than about 20 nm, or less than about 19 nm, or less than about 18 nm, or less than about 17 nm, or less than about 16 nm, or less than about 15 nm, or less than about 14 nm, or less than about 13 nm, or less than about 12 nm, or less than about 11 nm. The inventors have found that by ensuring that the cobalt particles have an appropriate diameter, it is possible to maximize the utilization and efficiency of the cobalt-loaded catalyst. Previously, it was thought that increasing the cobalt load would lead to an increase in cobalt particle size (as shown in den Breejen et al., J. Am. Chem. Soc. 2009, 131, 20, 7197-7203), resulting in a decrease in catalytic efficiency.

[0039] The catalyst may optionally contain at least one precious metal. The precious metal may optionally be one or more of, for example, Pd, Pt, Rh, Ru, Re, Ir, Au, Ag, and Os. Preferably, the precious metal is one or more of ruthenium, rhenium, and / or platinum. More preferably, the precious metal is one or more of rhenium and / or platinum. The catalyst may optionally contain less than about 3% by weight of the precious metal (relative to the total weight of the catalyst), less than about 1% by weight, or less than about 0.5% by weight. The catalyst may optionally contain about 0.01% to about 3% by weight of the precious metal (relative to the total weight of the catalyst), less than 0.05% to about 1% by weight, or about 0.1% to about 0.5% by weight.

[0040] The catalyst may optionally contain one or more other metal-based components as promoters or modifiers. These metal-based components may optionally be further present in the catalyst as carbides, oxides, or elemental metals. Suitable metals for the one or more other metal-based components may optionally be one or more of, for example, Zr, Ti, V, Cr, Mn, Ni, Cu, Zn, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg, Tl, and 4f-block lanthanides. Suitable 4f-block lanthanides may optionally be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and / or Lu. The metals for the one or more other metal-based components may optionally be one or more of, for example, Zn, Cu, Mn, Mo, and W. The metals of one or more other metal-based components may optionally be, for example, one or more Re and Pt. The catalyst may optionally contain, in the total of the other metals, about 0.01 to about 10% (based on the total weight of all other metals as a percentage of the total weight of the catalyst), or in the total of the other metals, about 0.1 to about 5%, or in the total of the other metals, about 3%.

[0041] The catalyst may optionally contain a catalyst support. The support may optionally contain a refractory metal oxide, carbide, nitride, or a mixture of two or more thereof. The support may optionally contain alumina, zirconia, silica, titania, or a mixture of two or more thereof. Alternatively, the support may optionally be alumina-free. The surface of the support may optionally be modified by treatment with silica, titania, zirconia, magnesia, chromia, alumina, or a mixture of two or more thereof. The materials used for the support and the materials used to modify the support may optionally be different.

[0042] Preferably, the support contains silica. The surface of the silica may optionally be treated with a refractory solid oxide such as titania. The material used to modify the support may optionally be used to improve the stability of the supported catalyst (for example, by reducing deactivation). The modified support may optionally contain silica and titania. The material used to modify the support may optionally be used to improve the stability of the supported catalyst (for example, by reducing deactivation).

[0043] The catalyst support described above may optionally contain up to about 30% by weight, or about 1% to about 30% by weight, or about 2% to about 20% by weight, or about 3% to about 15% by weight, or about 4% to about 10% by weight, or about 5% to about 8% by weight, of an oxide used to modify the surface of the support (e.g., silica, titania, magnesia, chromia, alumina, or a mixture of two or more thereof).

[0044] The catalyst support may optionally be in the form of a structured shape, pellets, or powder. The catalyst support may optionally be in the form of granular solids.

[0045] The catalyst may optionally be derived from a catalyst precursor that has been activated to produce a Fischer-Tropsch catalyst by heating the catalyst precursor in, for example, hydrogen and / or hydrocarbon gas (e.g., methane), or in hydrogen or hydrocarbon gas diluted with another gas such as nitrogen and / or methane, for the conversion of at least some of the carbides or oxides into elemental metals. In the activated catalyst, cobalt may optionally be in the form of its carbides or oxides, at least partially.

[0046] The catalyst may optionally have any size and geometric configuration that fits inside the reactor. The catalyst may optionally be in the form of a granular solid (e.g., pellets, powders, and fibers) with a median particle size of about 1 to about 1000 μm, or about 10 to about 750 μm, or about 25 to about 500 μm. The median particle size may optionally be in the range of 50 to about 500 μm, or about 100 to about 500 μm, or about 125 to about 400 μm, or about 170 to about 300 μm. The catalyst may optionally be in the form of a fixed bed of granular solid.

[0047] The catalyst described above may optionally exhibit a CO hydrogenation rate of more than approximately 55 millimoles of CO per hour per gram of cobalt after operation at approximately 180°C for at least approximately 48 hours, with a feed flow of approximately 10 mol% inert tracer gas, an absolute pressure of approximately 354.6 kPa (3.5 atm), an H2 / CO ratio of approximately 10, and a flow rate such that the CO conversion rate is between approximately 18% and approximately 22%.

[0048] The catalyst described above may optionally exhibit a CO hydrogenation rate of more than approximately 60 millimoles of CO per gram of cobalt per hour, or more than approximately 65 millimoles of CO per gram of cobalt per hour, or more than approximately 70 millimoles of CO per gram of cobalt per hour, or more than approximately 75 millimoles of CO per gram of cobalt per hour, or more than approximately 80 millimoles of CO per gram of cobalt per hour, or more than approximately 85 millimoles of CO per gram of cobalt per hour, or more than approximately 90 millimoles of CO per gram of cobalt per hour, after operation at approximately 180°C for at least approximately 48 hours with a feed flow of approximately 10 mol% of inert tracer gas, an absolute pressure of approximately 354.6 kPa (3.5 atm), an H2 / CO ratio of approximately 10, and a flow rate such that the CO conversion rate is between approximately 18% and approximately 22%.

[0049] The catalyst described above may optionally exhibit a CO hydrogenation rate of more than approximately 1.20 millimoles of CO per mole of cobalt per second, or more than approximately 1.25 millimoles of CO per mole of cobalt per second, or more than approximately 1.30 millimoles of CO per mole of cobalt per second, or more than approximately 1.35 millimoles of CO per mole of cobalt per second, or more than approximately 1.40 millimoles of CO per mole of cobalt per second, or more than approximately 1.45 millimoles of CO per mole of cobalt per second, or more than approximately 1.50 millimoles of CO per mole of cobalt per second.

[0050] According to another aspect of the present invention, a method is provided for carrying out a Fischer-Tropsch reaction in a reactor, comprising the step of passing a gas mixture containing CO and H2 over a catalyst according to the first aspect of the present invention.

[0051] The reactor may optionally be, for example, a fixed-bed reactor, a continuous-stirred-tank reactor, a slurry bubble tower reactor, a circulating fluidized-bed reactor, or a microchannel reactor. Preferably, the reactor is a microchannel reactor. Microchannel reactors are disclosed in the applicant's title in International Publication No. 2016 / 201218, incorporated herein by reference, and similarly in LeViness et al. “Velocys Fischer-Tropsch Synthesis Technology - New Advances on State-of-the-Art”, Top Catal., 2014, 57, 518-525.

[0052] The inventors have found that the catalyst of the present invention is particularly effective in microchannel reactors. The capability of microchannel reactors lies in maintaining near isothermal conditions, which allow for the full utilization (capitalization) of their high reaction site density to obtain a product composition with reduced light hydrocarbon selectivity while maintaining high volume productivity.

[0053] Furthermore, microchannel reactors are designed to increase the Fischer-Tropsch reaction compared to conventional reactors such as fixed-bed reactors. The catalyst according to the present invention, with its increased weight percent of cobalt and increased packing apparent bulk density, is more favorably suited to this increased reaction than conventional catalysts.

[0054] A "microchannel" is a channel having at least one internal dimension (wall to wall, catalyst not measured) of 10 mm or less, preferably 2 mm or less, and greater than 1 μm (preferably greater than 10 μm), and in some embodiments 50 to 500 μm, wherein the microchannel has a length of at least 10 mm, preferably at least 200 mm, and preferably remains within these dimensions. In some embodiments, the length is in the range of 50 to 1000 mm, and in some embodiments, in the range of 100 to 600 mm. A microchannel is further defined by the presence of at least one inlet distinct from at least one outlet. A microchannel is not simply a channel passing through zeolite or mesoporous material. The length of the microchannel corresponds to the direction of flow through the microchannel. The height and width of the microchannel are substantially perpendicular to the direction of flow through the channel. In the case of a multilayer device where the microchannel has two main surfaces (e.g., a surface formed by laminated and bonded sheets), the height is the distance from main surface to main surface, and the width is perpendicular to the height. A microchannel may optionally be linear or substantially linear, i.e., capable of drawing an unobstructed linear line through the microchannel ("unobstructed" means before particle introduction). Typically, a device includes multiple microchannels sharing a common header and footer. A microchannel device may have multiple headers and footers, even if some devices have a single header and footer.

[0055] A microchannel reactor is characterized by the presence of at least one reaction channel having dimensions (wall to wall, catalyst not measured) of 10 mm or less, preferably 2 mm or less (about 1 mm or less in some embodiments) and greater than 100 nm (preferably greater than 1 μm), and in some embodiments 50 to 500 μm. A channel containing a catalyst is a reaction channel. More generally, a reaction channel is a channel in which a reaction takes place. Microchannel devices are similarly characterized, except that they do not require a catalyst-containing reaction channel. Both the height and width are substantially perpendicular to the direction of the flow of reactants through the reactor. The sides of the microchannel are defined by the reaction channel walls. These walls are preferably made of hard materials such as ceramics, iron-based alloys such as steel, or Ni, Co, or Fe-based superalloys such as Monel. The choice of material for the reaction channel walls may depend on the reaction intended in the reactor. The walls of the reaction chamber may optionally include stainless steel or Inconel®, which are durable and have good thermal conductivity. Typically, the walls of reaction channels are formed of a material that provides primary structural support for the microchannel device. The microchannel device can be manufactured by known methods, and optionally, by stacking shims, where shims designed for reaction channels are preferably sandwiched between shims designed for heat exchange. Some microchannel devices include at least 10 (or at least 100) layers stacked within the device, each of which contains at least 10 (or at least 100) channels. The device may optionally include other layers having fewer channels.

[0056] The heat exchange fluid may flow through heat transfer channels (preferably microchannels) adjacent to process channels (preferably reaction microchannels), and may be a gas or a liquid, and may optionally contain vapor, liquid metal, or any other known heat exchange fluid, and the system may be optimized to cause a phase transition within the heat exchanger. Multiple heat exchange layers may optionally be sandwiched between multiple reaction microchannels. For example, there are at least 10 heat exchangers sandwiched between at least 10 reaction microchannels, and preferably 10 heat exchange channel arrays (preferably microchannel arrays) sandwiched between at least 10 layers of reaction microchannels. Each of these layers may contain simple, linear channels, or the channels within the layer may have a more complex geometry.

[0057] The Fischer-Tropsch reaction is well known, and the reaction conditions may be any conditions known to those skilled in the art, for example, the conditions discussed in International Publication No. 2008 / 104793. For example, the Fischer-Tropsch reaction may be carried out optionally at a temperature of about 150 to about 300°C, or about 200 to about 260°C, at a pressure of about 100 to about 10000 kPa, or about 1500 to about 2500 kPa, with a molar ratio of H2 to CO of about 1.1 or about 1.2 to about 2.2, or about 1.5 to about 2.0, or about 1.8, and over a period of about 200 to about 5000 hours. -1 , or approximately 1000 to 2000 hours -1 The process may be carried out at a gas space velocity per hour. In a microchannel reactor, the above gas space velocity per hour can be arbitrarily set to approximately 5,000 to approximately 30,000 hours. -1 That's fine.

[0058] The contact time of the reactant with the catalyst may optionally range up to a maximum of about 3600 milliseconds, or up to a maximum of about 2000 milliseconds, or from about 10 to about 2600 milliseconds, or from about 10 milliseconds to about 2000 milliseconds, or from about 20 milliseconds to about 500 milliseconds, or from about 200 to about 450 milliseconds, or from about 240 to about 350 milliseconds.

[0059] The space velocity of the gas mixture flow in the microchannel reactor (or gas hourly space velocity (GHSV)) may optionally be at least about 1000 hr -1 (the defined number of liters of feed per hour per liter of the volume inside the process microchannel), or at least about 1800 hr -1 , or from about 1000 to about 1000000 hr -1 , or from about 5000 to about 20000 hr -1 and may be so.

[0060] The pressure inside the above process microchannel may optionally be within a range of up to about 10200 kPa, or from about 100 to about 10200 kPa, or from about 100 to about 7600 kPa, or from about 200 to about 4100 kPa, or from about 200 to about 1100 kPa, or from about 1000 to about 5100 kPa, or from about 2000 to about 3100 kPa.

[0061] During the Fischer-Tropsch reaction, the above catalyst gradually deteriorates due to impurities. Such impurities can cause either renewable or non-renewable deactivation. This deterioration of the catalyst requires gradually increasing the temperature to reduce its effectiveness, offset the loss of activity, and maintain an acceptable carbon monoxide conversion rate. This is described in Steynberg et al., “Fischer-Tropsch catalyst deactivation in commercial microchannel reactor operation”, Catalysis Today, 2018, 299, 10-13.

[0062] The above operating temperature continues to rise until the product composition becomes economically undesirable. In this regard, the catalytic activity can be partially recovered through regeneration, which reverses the activity loss due to a regenerative mechanism. Since the non-regenerative deactivation pathway does not reverse, the starting temperature after continuous regeneration becomes shorter than that of each of the previous cycles until the temperature operation window of the above cycle becomes impractical and catalyst replacement is required.

[0063] The above temperature upper limits are relatively fixed values. However, by using the catalyst of the present invention, the starting temperature can be substantially lowered, which allows for longer cycles between recovery from regenerative deactivation mechanisms and longer overall cycles between catalyst replacements resulting from non-regenerative deactivation mechanisms. As a non-limiting example, an initial operating temperature 10°C lower can extend the overall operating period to more than 300 days.

[0064] Therefore, the reaction temperature when using a fresh catalyst may optionally be less than about 210°C, preferably less than about 205°C. "Fresh catalyst" preferably means that the catalyst has not been used in a Fischer-Tropsch reaction in the past. The reaction temperature when using a fresh catalyst may also be referred to as the "start temperature." Therefore, the above start temperature may optionally be less than about 210°C, preferably less than about 205°C.

[0065] The conversion rate of CO from fresh synthesis gas may be, optionally, about 70% or more, or about 75% or more, or about 80% or more, or about 90% or more, or about 91% or more, or about 92% or more, or about 88% to about 95%, or about 90% to about 94%, or about 91% to about 93%. If tail gas regeneration is used, the one-pass conversion rate of CO for CO in the reactant mixture (i.e., fresh synthesis gas and regenerated tail gas) may be, optionally, in the range of about 50% to about 90%, or about 60% to about 85%.

[0066] The productivity of the C5+ liquid in the above method may optionally be at a volume CO consumption rate of approximately 50 mmol CO per mL of catalyst per hour, with at least approximately 0.5 g of liquid per gram of catalyst per hour. Alternatively, the productivity of the C5+ liquid in the above method may optionally be at a volume CO consumption rate of approximately 100 mmol CO per mL of catalyst per hour, with at least approximately 1.0 g of liquid per gram of catalyst per hour.

[0067] The reaction product before the separation step may optionally contain methane of about 15% or less. The above product may optionally contain methane of about 10% or less, or about 5% or less. The above product may optionally contain methane in amounts of about 0.01% to about 10%, or about 0.1% to about 5%.

[0068] The alpha of the wax product may optionally be greater than about 0.94, preferably greater than about 0.95. The wax product is preferably a C25-C90 wax product of the Fischer-Tropsch reaction. A larger alpha value is economically valuable. The inventors have found that lower reaction temperatures that can be used with the catalyst of the present invention provide advantageously good selectivity, product distribution, and therefore larger alpha values.

[0069] The catalyst deactivation rate may be any rate such that, in Fischer-Tropsch reactions lasting more than approximately 300 hours, or more than approximately 3000 hours, or more than approximately 12000 hours, or more than approximately 15000 hours, the catalyst can be used before any catalyst reactivation or regeneration is required.

[0070] The deactivation rate of the catalyst may be, at will, less than approximately 1.6% per day, less than approximately 1.4% per day, less than approximately 1.2% per day, less than approximately 1.0% per day, less than approximately 0.8% per day, less than approximately 0.6% per day, or less than approximately 0.4% per day.

[0071] According to another aspect of the present invention, a Fischer-Tropsch reaction system is provided, comprising a reactant stream containing CO and H2 and a reactor containing a catalyst according to the first aspect of the present invention.

[0072] According to another aspect of the present invention, a) Impregnating the carrier with a solution or suspension containing a cobalt compound to more than 100% of its pore volume, and b) Drying the solution or suspension under heat at a temperature lower than the reflux temperature. A method for preparing a Fischer-Tropsch catalyst is provided, which includes [the specified element].

[0073] Conventional cobalt-containing Fischer-Tropsch catalysts are typically prepared using an initial wet impregnation method, which does not require step b). However, obtaining a catalyst containing more than approximately 40% by weight of cobalt using the initial wet impregnation method requires more than eight or nine impregnation steps. While this number can be even greater on an industrial scale, high-load catalysts prepared using the initial wet impregnation method are not very feasible to scale up because this adds to the overhead costs of catalyst preparation.

[0074] Figure 1 illustrates the effect of increasing the degree of impregnation based on the number of synthesis steps required to reach a certain cobalt load. For example, to target a cobalt load of over 50% by weight, 15 synthesis steps are required to impregnate 90% of the pore volume (typical of the initial wet impregnation method). To reduce the number of pathways (and limit production costs), the amount of solution per pathway must be increased.

[0075] The inventors have surprisingly found that, compared to the use of the initial wet impregnation method, the use of over-wet impregnation (i.e., more than 100% of the pore volume of the support) enables the synthesis of high-load cobalt catalysts with fewer synthesis steps and lower production costs. Furthermore, they have found that the above over-wet impregnation method also significantly reduces the number of impregnations required to achieve catalysts with more than 50% by weight of cobalt. Moreover, these catalysts surprisingly maintain extremely high efficiency despite the high cobalt load and wet initial impregnation conditions.

[0076] Step a) may optionally include impregnating the carrier with a solution or suspension containing a cobalt compound to more than 105%, 110%, 115%, 120%, 125%, 130%, or 135% of its pore volume.

[0077] Suitable cobalt-containing compounds include cobalt benzoyl acetonate, cobalt carbonate, cobalt cyanide, cobalt hydroxide, cobalt oxalate, cobalt oxide, cobalt nitrate, cobalt acetate, cobalt acetylacetonate, and cobalt citrate. These cobalt compounds may be used individually or in combination. These cobalt compounds may optionally be in hydrate or anhydrous form. In some cases where the cobalt compound is insoluble in water, such as cobalt carbonate or cobalt hydroxide, a small amount of nitric acid or carboxylic acid may optionally be added to enable the compound to dissolve completely in an aqueous solution or suspension. Preferably, the cobalt-containing compound is cobalt nitrate hexahydrate.

[0078] Preferably, a cobalt-containing compound, such as cobalt nitrate, reacts with a complexing agent such as citric acid during sintering. The citric acid may optionally act as a complexing agent and / or fuel (i.e., a reducing agent for cobalt nitrate) in the sintering reaction.

[0079] Suitable complexing agents for use in the above method are polar organic compounds. Preferred complexing agents are urea, as well as carboxylic acids such as acetic acid, citric acid, glycolic acid, malic acid, propionic acid, succinic acid, lactic acid, and oxalic acid. Mixtures of complexing agents may also be used as optional. Preferably, the complexing agent is citric acid.

[0080] Step b) is carried out at a temperature lower than the reflux temperature of the solution or suspension. It is essential that reflux does not occur; otherwise, this may cause condensation that washes away the dry material and reduce the uniformity of the impregnated cobalt salt. The above temperature may optionally be in the range of about 80°C to about 100°C, or about 90°C to about 95°C. The time required for Step b) may optionally be about 1 minute to about 60 minutes, or about 5 minutes to about 50 minutes, or about 10 minutes to about 40 minutes, or about 15 minutes to 30 minutes, provided that the desired temperature is reached.

[0081] The inventors further found that it is important to ensure that the drying step is uniform and that there is no temperature gradient that could cause the dried catalyst to draw the impregnation liquid away from the undried catalyst.

[0082] Step b) may optionally be carried out until the catalyst is free to flow. For easier transfer, it is beneficial for the catalyst to be free to flow before sintering.

[0083] The carrier impregnated with the solution or suspension may optionally be sintered at a temperature preferably in the range of about 200°C to about 350°C, more preferably in the range of about 200°C to about 250°C. In other words, the above method may optionally further include step c) sintering the impregnated carrier. Sintering may optionally be carried out in a box oven, furnace or rotary sinterer. In one non-limiting example, sintering is carried out by heating at a temperature that rises at a ramp rate of 2°C / min to a final temperature of 250°C. The temperature is held at 250°C for about 3 hours. In another non-limiting example, sintering is carried out by heating at a temperature that rises at a ramp rate of 2°C / min to a temperature of 200°C, and then holding at 200°C for about 3 hours before raising the temperature again at a ramp rate of 1°C / min to a temperature of 250°C and holding at that temperature for a further 3 hours. Since sintering at high temperatures can have an effect that reduces catalyst stability, it is preferable that the final temperature does not exceed about 400°C.

[0084] Steps a), b), and c) if present may be repeated one or more times as desired. Steps a), b), and c) if present may be repeated 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times as desired. For each repeat, the solution or suspension used in the deposition step may be the same or different as desired. If the solution or suspension is the same in each repeat, the repetition of the step allows for a stepwise increase in the amount of catalyst metal on the support to a desired concentration. If the solution or suspension is different in each repeat, the repetition of the step allows for a different amount of catalyst metal to be increased to a desired concentration in a series of steps in which the scheme is performed.

[0085] According to another aspect of the present invention, a) Impregnating the carrier with a solution or suspension containing a cobalt compound to more than 100% of its pore volume, and b) A step of drying under heat at a temperature lower than the reflux temperature. A method for preparing a Fischer-Tropsch catalyst according to a first aspect of the present invention is provided, which includes [the specified element].

[0086] According to another aspect of the present invention, a) Impregnating the carrier with a solution or suspension containing a cobalt compound to more than 100% of its pore volume, and b) A step of drying under heat at a temperature lower than the reflux temperature. A Fischer-Tropsch catalyst prepared by a method including the following is provided.

[0087] To avoid misunderstanding, all characteristics related to catalysts can, where appropriate, be optionally applied to methods for carrying out Fischer-Tropsch reactions, to reaction systems, and to methods for preparing Fischer-Tropsch catalysts, and vice versa.

[0088] Preferred embodiments of the present invention are described below, by example, with reference only to Figures 1-3 of the accompanying drawings. [Brief explanation of the drawing]

[0089] [Figure 1] Figure 1 illustrates the effect of increasing the degree of impregnation based on the number of synthesis steps required to reach a certain cobalt load. [Figure 2] Figure 2 illustrates the time required for the two catalysts to lose their activity when exposed to the same load as the renewable toxin NH3. [Figure 3] Figure 3 illustrates the CO conversion rate compared to the H2S flow for three different catalysts.

[0090] Catalytic synthesis The synthesis of comparative catalyst 1 in Table 3 is summarized below. Catalysts 1 to 11 in Tables 3 and 4, which satisfy the scope of the present invention, were prepared using similar methods on both PD12058 and LC150 (which are different batches of silica), while varying the amounts of Co, Ti, and Re.

[0091] material Table 2 summarizes the materials used in the synthesis of the catalyst.

[0092] [Table 2]

[0093] Preparation of modified carriers 16 g of PD12058 was weighed out and dried in a fan oven at 100°C for 2 hours. 11.66 g of hot silica was immediately weighed into an alumina bowl, covered, and allowed to cool to room temperature. 2.5 g of citric acid was weighed out and mixed with 1.2 mL of deionized water at a temperature of up to 50°C until completely dissolved. Then, 11.54 g of TALH was weighed out and added to the cooled citric acid solution, and mixed until homogeneous. The above mixture was poured into a graduated cylinder, rinsed with 1 mL of deionized water in a beaker, and the volume was adjusted to 25.2 mL. The above solution was added to the cooled silica in four portions, stirring after each addition until the mixture was homogeneous and the liquid was absorbed. After the final addition, the impregnated silica was transferred to a weighed crucible and spread evenly to cover the surface of the crucible, so that the material did not exceed a depth of 10 mm. The crucible described above was transferred to a muffle furnace and dried / sintered using the following program: increased to 100°C at a rate of 2°C / min, held for 5 hours, then increased to 250°C at a rate of 2°C / min, held for 5 hours. After the material was sintered and cooled to below 50°C, the sample weight was obtained and the purity of the carrier was calculated by comparing it to the expected material weight.

[0094] Catalytic synthesis 9.1 g of the modified support material from the previous step was weighed out and placed in an alumina bowl. 12.47 g of cobalt nitrate hexahydrate was weighed out, 3.1 mL of deionized water was added, and the mixture was heated on a hot plate to 50°C and stirred until completely dissolved. 0.2698 g of perrhenium acid was weighed out and added to the cobalt nitrate solution while stirring. The above solution was poured into a measuring cylinder and the volume was adjusted to 11.5 mL with deionized water. After cooling to room temperature, the above solution was added to the modified support in four parts, and after each addition, the mixture was stirred until homogenized and the liquid was absorbed.

[0095] After the final addition, the impregnated carrier was transferred to a weighed crucible and spread uniformly so that the material covered the surface of the crucible to a depth of 10 mm. The crucible was then transferred to a muffle furnace and dried / sintered using the following program: sintered at 2°C / min up to 100°C, held for 5 hours, then at 2°C / min up to 200°C, held for 3 hours, then at 1°C / min up to 250°C, held for 3 hours. After sintering and cooling, the cobalt impregnation process described above was repeated by adding 1.79 g of citric acid to the cobalt nitrate solution before impregnation. The sintering program for this additional step was sintered at 2°C / min up to 100°C, held for 5 hours, then at 2°C / min up to 250°C, held for 3 hours.

[0096] The final step in the synthesis was the addition of platinum as an accelerator. 0.4518 g of tetramine platinum hydroxide was weighed out, rinsed into a graduated cylinder, and water was added to a solution up to 10.7 mL. Then, this solution was added in four portions to the dried and sintered material from the final step, stirring after each addition until the mixture was homogenized and the liquid was absorbed.

[0097] After the final addition, the impregnated carrier was transferred to a weighed crucible and spread uniformly to cover the surface of the crucible, with the material not exceeding a depth of 10 mm. The crucible was then transferred to a muffle furnace and dried / sintered using the following program: 100°C at 2°C / min, held for 5 hours, then 250°C at 2°C / min, held for 3 hours. After the final catalyst had cooled, it was weighed and transferred to labeled bottles.

[0098] Excessive Wetting and Impregnation For drying the over-wet impregnated catalyst, a rotary evaporator was adapted to a rotary drying unit. This allowed the impregnated catalyst to be dried under heat and mixed into a rotary paddle flask, roughly mimicking the operation of industrial paddle drying. To prevent reflux, the vacuum tube was held at the base of the neck inside the container, creating airflow into the open container and outside the vacuum tube along with any evaporated moisture. Mineral oil was used as the heating medium in a heating bath to allow a wider temperature range than that possible with water.

[0099] As an example, the catalyst according to the present invention (42.0% Co, 0.2% Re, 0.03% Pt on 10% TiO2 / AGC) was prepared by impregnating the support by excess liquid impregnation, then drying it in a simulated paddle drying apparatus to reduce the volume of the solution until the impregnated material could flow freely inside the paddle flask. Tests were conducted with 75 mL of support to provide sufficient material to allow proper mixing by the paddle. For drying, the oil bath was preheated to 60°C. For each step, the catalyst support was impregnated in the drying flask to minimize losses during transfer. The flask was then mounted in the setup and rotated at 20 rpm to initiate airflow, and the oil bath was heated to 90-95°C at approximately 1°C / min, and held at that temperature for 15-30 minutes, which usually takes 15-30 minutes, until the impregnated catalyst could flow freely. Subsequently, the dried impregnated catalyst was sintered in a muffle furnace using the heating procedure described above.

[0100] Measurement of apparent bulk density of packed areas The apparent bulk density (PABD) was measured in a 5 mL graduated cylinder. However, any graduated cylinder with an appropriate volume (e.g., 5 mL, 25 mL, 100 mL, or 250 mL) can be used without causing any significant difference in the results (i.e., a difference of 1% or less). The cylinder was filled with catalyst, hand-tapped to fix the solid, and then more material was added and tapped until the volume was close to 5 mL. The graduated cylinder was then loaded onto a Quantachrome Autotap DAT-4 apparatus and tapped 1500 times. After the volume of the fixed catalyst was measured, the catalyst mass was measured. The apparent bulk density was calculated by dividing the gram weight of the catalyst by the mL volume after 1500 taps. The apparent bulk density of cobalt was calculated by multiplying the apparent bulk density of the catalyst by the weight percentage of cobalt in the catalyst.

[0101] The method described above generally follows the procedure of ASTMD7481-09 (i.e., D7481, approved or reapproved in 2009): a standard method for measuring the loose bulk density and tap bulk density of powders using a graduated cylinder.

[0102] Preferably, the measured catalyst mass is the dry mass. Because the tapping method is time-consuming, the catalyst collects moisture from the atmosphere to varying degrees depending on the relative humidity, pre-exposure, and exposure time. If the "non-dry" mass is measured, the apparent bulk density of the cobalt packing may be overestimated. This is because the accumulated moisture increases the mass of the given volume of catalyst by the amount of water collected, resulting in an inflated apparent bulk density of the cobalt packing due to the relative moisture content. Therefore, to ensure accurate and consistent results, it is preferable to perform the measurement on a "dry" basis. The dry mass may optionally be measured using humidity equilibrium, which may include a heating step to remove absorbed moisture.

[0103] In a microchannel reactor, the apparent bulk density of the cobalt packing can optionally be measured by the steps of: densifying the input material inside the reactor's microchannel using an appropriate method (such as those disclosed in International Publication No. 2013 / 013077, incorporated herein by reference under the applicant's name); measuring the total mass of the input catalyst; and deriving the apparent bulk density of the cobalt packed into the reactor from which the catalyst was introduced.

[0104] Catalyst and fixed-bed reactor test results Table 3 shows nine catalysts synthesized according to the present invention, as well as comparative catalysts known in the art. The apparent packing bulk density was at least 1.32 g / mL, and the weight percentage of cobalt in the catalysts of the present invention varied from 43% to 53%.

[0105] For the fixed-bed reactor test, a 0.1285 mL volume of catalyst sample was diluted with 2.184 mL of SiC (1:18 volume ratio) and introduced into the reactor. H2 was added at atmospheric pressure for 15,000 hours. -1 The catalyst was activated by flowing GHSV at 400°C for 2 hours. After activation, the reactor was cooled to 165°C, and the gas flow was switched to synthesis gas (H2:CO2:1, 5% N2 diluent) before holding at this temperature for 2 hours. Subsequently, the pressure was increased to 2000 kPa (20 bar), and the reactor temperature was raised (ramp) to the target test temperature of 205°C. The above test was performed for 140 hours. Deactivation was measured at the time intervals of 0 to 24 hours and 116 to 140 hours, along with the conversion rate and selectivity recorded at 24 hours and 140 hours.

[0106] As can be seen from the fixed-bed reactor test results in Table 3, all catalysts according to the present invention exhibited significantly higher CO conversion rates than the comparative examples. The highest CO conversion rate was observed with catalyst #9, which contains 53% by weight of cobalt, has an apparent packing bulk density of 1.63 g / mL, and an apparent packing bulk density of cobalt of 0.86 g / mL. Furthermore, all catalysts according to the present invention exhibited lower deactivation rates than the comparative examples, allowing them to be used for longer periods in the Fischer-Tropsch reaction before regeneration is required.

[0107] Table 4 shows two catalysts synthesized according to the present invention, as well as several comparative catalysts. C2-C14 represents ActOCat 1200, which is a catalyst known in the art. The PABD of cobalt for the reference catalyst (#C2) is 0.426 g / ml, the PABD of cobalt for comparative catalysts #C3-C14 is 0.596 g / ml, and the PABD of cobalt for the catalysts according to the present invention (#10-11) is 0.784 g / ml.

[0108] The last column of Table 4 shows the cobalt time yield (CTY), which is the number of moles of CO converted per mole of cobalt in the sample per unit time, and is representative of the catalyst's efficiency.

[0109] Comparing C2 in Table 4 with C3-C14, as expected, increasing the PABD of the catalyst increases the PABD of cobalt, which is equivalent to the number of moles of CO converted per hour per 1 mL of catalyst (29 mmol CO ml). -1 h -1 From 37-44 millimoles COml -1 h -1 It can be seen that this increases the ) However, the catalyst efficiency (CTY ​​above) does not increase and remains at almost the same value (1.00~1.2 mmol COmolar Co -1 s -1 In contrast, 1.1 millimoles of CO and 1.1 moles of Co -1 s -1 ).

[0110] However, comparing #10-11 in Table 4 with C2-C14, it can be seen that increasing the PABD of the catalyst, thereby increasing the PABD of cobalt, increases both the number of moles of CO converted per hour per mL of catalyst and the catalyst efficiency. The above efficiency (CTY) is for 1.00-1.2 mmol CO and moles of Cobalt compared to the comparative catalyst. -1 s -1 Therefore, the catalyst according to the present invention contains approximately 1.5 millimoles of CO. -1 s -1 It increases to a certain extent. Therefore, the catalyst of the present invention not only increases the PABD of cobalt in the catalyst so that the number of moles of converted CO increases, but also achieves this in a much more efficient manner than conventional catalysts.

[0111] This is achieved by using the method for preparing Fischer-Tropsch catalysts according to the present invention. Catalysts #12-13 are prepared using AGC silica and an excess liquid impregnation method, where the support is impregnated to 130% of its pore volume. Therefore, the method for preparing Fischer-Tropsch catalysts according to the present invention results in a more efficient catalyst than conventional catalysts.

[0112] [Table 3]

[0113] [Table 4]

[0114] Toxic resistance Poisoning by reactive nitrogen compounds is rare because they are not "lethal," but rather cause deactivation of catalysts that eventually saturate at non-zero catalytic activity. The exact saturation activity depends on both the catalyst and the type of reactor used, but is usually in the range of 30% to 50% of the fresh catalytic activity.

[0115] Figure 2 compares the toxicity resistance of catalyst #9 with that of comparative example ActOCat 1200, a known catalyst in this technology containing 43% by weight of cobalt. Catalyst #9, containing 53% by weight of cobalt, shows approximately 184% higher PABD of cobalt in the reactor compared to the comparative example.

[0116] As can be seen in the figure, the ActOCat 1200 catalyst undergoes saturated deactivation after approximately 250 hours of exposure. In contrast, catalyst #9 does not reach saturated deactivation until approximately 640 hours of exposure, or about 2.5 times longer, at the same NH3 feed concentration. This explains the greatly improved toxicity resistance of the catalyst of the present invention compared to those of the prior art.

[0117] Figure 3 demonstrates the improved resistance of the catalyst of the present invention to sulfur poisoning. The average amount of sulfur exposed to the catalyst was approximately 2.9 x 10⁻⁶. -3 The molar ratio of S to Co is approximately the same as the expected exposure level of 5 ppbv over a 2-year lifespan.

[0118] As can be seen in the figure, in the same H2S flow, the rate at which the CO conversion rate of the high-cobalt catalyst of the present invention declines is significantly lower compared to the comparative ActOCat 1200 catalyst. Due to the high cobalt surface area per unit packing volume of catalyst in the reactor, the catalyst of the present invention can accommodate H2S better than the comparative catalyst.

[0119] Operating temperature Catalyst #9 in Table 3 was used in the Fischer-Tropsch reaction and compared with ActOCat 1200. Catalyst #9 contains 53 wt% cobalt, while ActOCat 1200 contains 43 wt% cobalt, resulting in a lower PABD of cobalt.

[0120] The reaction conditions were as follows: Feed H2:CO = 1.77, inertness 32%, contact time 290 milliseconds, inlet pressure 2.461 MPa (357 psig). Both C15 and C16 used ActOCat 1200, but with slightly different average reactor temperatures.

[0121] [Table 5]

[0122] As can be seen from Table 5, the comparative data above suggests that catalyst #9 can be used at a reactor temperature approximately 8-10°C lower while maintaining the same performance (i.e., the same activity) under the same operating conditions.

[0123] Furthermore, the low operating temperature used with catalyst #9 provides an improvement in the alpha number of approximately 0.07–0.10, as analyzed in the C25–C90 wax carbon number range. As mentioned above, this favorably increases the economic value of the products of the above reaction.

[0124] A further consequence of the lower operating temperature used with catalyst #9 compared to conventional catalysts is that the time before regeneration is required is longer, thus improving the economic value of the reaction method.

Claims

1. A Fischer-Tropsch catalyst containing more than 40% by weight of cobalt and having a packed apparent bulk density of more than 1.30 g / mL, The catalyst comprising a catalyst support is a Fischer-Tropsch catalyst.

2. The catalyst according to claim 1, wherein the apparent bulk density of the cobalt packed in the catalyst is greater than 0.60 g / mL.

3. The catalyst according to claim 1 or 2, wherein the catalyst contains more than 45% by weight of cobalt.

4. The catalyst according to any one of claims 1 to 3, wherein the apparent bulk density of the catalyst packing is greater than 1.35 g / mL.

5. The catalyst according to any one of claims 1 to 4, wherein the average cobalt particle size of the catalyst is 5 nm to 20 nm.

6. The catalyst according to any one of claims 1 to 5, wherein the catalyst contains less than 3% by weight of a noble metal selected from Pd, Pt, Rh, Ru, Re, Ir, Au, Ag, and Os.

7. The catalyst according to claim 6, wherein the precious metal comprises rhenium and / or platinum.

8. The catalyst according to claim 1, wherein the catalyst support contains silica.

9. The catalyst according to claim 1, wherein the catalyst support comprises an oxide, optionally a titania oxide.

10. The catalyst according to claim 9, wherein the catalyst support contains up to 30% by weight of an oxide used to modify the surface of the support.

11. The catalyst according to any one of claims 1 to 10, wherein the catalyst support is in the absence of alumina.

12. CO and H ２ A method for carrying out a Fischer-Tropsch reaction in a reactor, comprising the step of passing a gas mixture containing over a catalyst according to any one of claims 1 to 11.

13. C ５＋ The method according to claim 12, wherein the liquid productivity is at a volume CO consumption rate of 50 mmol CO per 1 mL of catalyst per hour, and at least 0.5 g of liquid per 1 g of catalyst per hour.

14. C ５＋ The method according to claim 12 or 13, wherein the liquid productivity is at a volume CO consumption rate of 100 mmol CO per 1 mL of catalyst per hour, and at least 1.0 g of liquid per 1 g of catalyst per hour.

15. The method according to any one of claims 12 to 14, wherein the reaction product prior to the separation step contains 15% or less methane.

16. The method according to any one of claims 12 to 15, wherein the reactor is a microchannel reactor.

17. The method according to any one of claims 12 to 16, wherein a fresh catalyst is used and the reaction temperature is less than 210°C.

18. The method according to any one of claims 12 to 17, wherein the alpha of the wax product is greater than 0.

94.

19. The method according to any one of claims 12 to 18, wherein the catalyst deactivation rate is less than 0.6% / day.

20. CO and H ２ Reactor stream including A reactor comprising the catalyst according to any one of claims 1 to 11, Fischer-Tropsch reaction system.

21. a) Impregnating the carrier with a solution or suspension containing a cobalt compound to more than 100% of its pore volume, and b) Drying the solution or suspension under heat at a temperature lower than the reflux temperature. A method for producing a Fischer-Tropsch catalyst according to any one of claims 1 to 11, comprising:

22. c) The method according to claim 21, further comprising the step of sintering the impregnated carrier.

23. The method according to claim 21 or 22, wherein step a) includes impregnating the carrier to more than 105% of its pore volume.

24. The method according to any one of claims 21 to 23, wherein step a), b), and c) if present are repeated once or two or more times.

Images