Modified catalyst support and catalyst supported thereon

Abstract

1. A reforming catalyst support in the form of titania particles modified with refractory oxides of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium and neodymium, the particles having a volume median diameter in the range of 100 to 1000 μm, wherein the total refractory oxide content of the reforming catalyst support is in the range of 0.1 to 15 wt. %, and the reforming catalyst support has a volume median diameter of 0.2 to 0.6 cm. 3 A modified catalyst support is described, having a pore volume in the range of 1 / g and an average pore diameter in the range of 30-60 nm. The modified catalyst support can be used to prepare cobalt Fischer-Tropsch catalysts suitable for use in fixed-bed processes.

Description

[Technical Field]

[0001] The present invention relates to a modified catalyst support material, and to a cobalt-containing Fischer-Tropsch catalyst precursor and a catalyst supported thereon. [Background technology]

[0002] Fischer-Tropsch catalysts with a nominal diameter of less than approximately 1 mm offer the potential for high reaction rates and improved selectivity for C5+ hydrocarbons. Such catalysts are typically used in suspensions, such as in slurry bubble reactors, because their use in fixed-bed reactors on a commercial scale is usually impractical due to unacceptably high pressure drops. International Publication 2012 / 146903(A1) discloses a Fischer-Tropsch process using a fixed-bed catalyst with small particle size, where the catalyst is arranged in multiple catalyst vessels placed within an externally cooled reaction tube. The catalyst particles may have a diameter of approximately 100 μm to approximately 1 mm.

[0003] Titania microspheres can have a regular shape, are essentially non-toxic, can increase the median pore diameter, and promote the growth of long hydrocarbon chains on well-dispersed small cobalt crystallites, thus providing an ideal support for fixed-bed cobalt Fischer-Tropsch catalysts.

[0004] However, the strength of titania microspheres may be lower than that of other supports, and if calcined at high temperatures to increase their strength, the pore volume rapidly collapses and anatase is converted to rutile. These changes are undesirable because they affect the support's ability to maintain cobalt crystallites in the pores, and consequently affect the activity and selectivity of the catalyst. Furthermore, titania microspheres are typically prepared from titania particles produced by flame hydrolysis of titanium tetrachloride. This results in microspheres with a high chloride content, which poses a risk of stress corrosion cracking in austenitic stainless steel, which is typically used in catalyst manufacturing equipment.

[0005] Surprisingly, it was found that modifying titania microspheres with certain refractory metal oxides at low concentrations improved their strength while retaining the pore structure necessary to produce an effective Fischer-Tropsch catalyst. Even more surprisingly, these modified supports were found to offer improved catalytic activity compared to unmodified titania supports. Furthermore, a significant reduction in the chloride content of the modified supports was also observed. [Overview of the project]

[0006] Accordingly, the present invention relates to a modified catalyst support in the form of titania particles having a volume median diameter in the range of 100 to 1000 μm, modified with a refractory oxide of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium, wherein the total refractory oxide content of the modified catalyst support is in the range of 0.1 to 15% by weight, and the modified catalyst support is 0.2 to 0.6 cm 3 The present invention provides a modified catalyst support having a pore volume in the range of / g and an average pore diameter in the range of 30 to 60 nm.

[0007] The present invention further provides a catalyst precursor comprising cobalt oxide crystallites arranged within the pores of a modified catalyst support.

[0008] The present invention further provides a catalyst comprising cobalt metal crystallites disposed within the pores of a modified catalyst support.

[0009] The present invention further provides a method for preparing a modified catalyst support, comprising the steps of: impregnating titania particles having a volume median diameter in the range of 100 to 1000 μm with a solution of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium; and drying and calcining the impregnated titania support to form a refractory metal oxide modified titania support containing 0.1 to 15% by weight of a refractory oxide.

[0010] The present invention further provides a method for preparing a catalyst precursor, comprising the steps of impregnating a modified titania support with a cobalt compound, and drying and calcining the impregnated modified titania support to form cobalt oxide crystallites in the pores of the modified titania support.

[0011] The present invention further provides catalyst precursors or catalyst combinations that are placed in catalyst carriers suitable for use in the reaction tubes of reactors or in the channels of microchannel reactors.

[0012] The present invention further provides the use of catalyst precursors, catalysts, or combinations within a reactor in a process for producing hydrocarbons from synthesis gas containing hydrogen and carbon monoxide.

[0013] The modified catalyst support, catalyst precursor, catalyst, and combinations are all particularly suitable for use in the Fischer-Tropsch process for synthesizing hydrocarbons from synthesis gas containing hydrogen and carbon monoxide.

[0014] "Titania" refers to titanium dioxide, or TiO2.

[0015] The volume median diameter D[v,0.5] of the modified titania carrier is in the range of 100 to 1000 μm, preferably 300 to 900 μm, more preferably 350 to 650 μm, and most preferably 400 to 500 μm. The term volume median diameter D[v,0.5] is sometimes referred to as D50 or D0.5 and is defined by Dr. Alan Rawle in the paper "Basic Principles of Particle Size Analysis," available from Malvern Instruments Ltd (Malvern, UK) (www.malvern.co.uk), and is calculated from particle size analysis, which can be conveniently achieved by laser diffraction using, for example, the Malvern Mastersizer®. The particle size is appropriately determined according to ASTM D4464.

[0016] The titania particles used to prepare the modified catalyst support can be commercially available or can be conveniently prepared from commercially available titania powder. Since commercially available titania powder typically has a very small particle size, typically less than about 5 micrometers, the titania support used to prepare the modified catalyst support can contain aggregates of such titania powder. The aggregates can be formed by any suitable shaping technique that produces spheres, such as spray drying, granulation, spray granulation, drip casting, or extrusion / spheronization.

[0017] Since the modified titania catalyst support is prepared from unmodified titania particles by impregnation, the particle size of the modified titania catalyst support is the same as the particle size of the unmodified titania particles.

[0018] The titania particles are preferably spherical so that they flow easily during operation and are consistently packed within the catalyst bed, providing an acceptable pressure drop across the reactor in which the titania particles are placed. The term "spherical" used to describe the support includes shapes having a sphericity (ψ) of at least about 0.90, preferably at least about 0.95, and approximately spherical aggregates of titania powder. The spherical titania particles and the resulting modified catalyst support can be referred to as "microspheres".

[0019] Titania can exist in the rutile or anatase crystalline form. The modified titania catalyst support is preferably anatase-rich support in which anatase-type titania is present in an amount greater than 50% by weight of the support. More preferably, the modified titania catalyst support has an anatase content of at least 70% by weight of the support, most preferably at least 80% by weight of the support, for example 80 - 90% by weight of the support. Anatase-type titania is more porous and softer than rutile-type, making it particularly suitable for use as a Fischer-Tropsch catalyst support. It has been found that by including a refractory oxide in the catalyst support, the conversion of anatase to rutile during the production of the support and the catalyst is advantageously suppressed, allowing the use of higher calcination temperatures.

[0020] The modified titania catalyst support preferably contains few elements that have been found to be toxic to the cobalt-catalyzed Fischer-Tropsch reaction, such as sulfur and alkali metals. Therefore, the sulfur content of the modified titania catalyst support is preferably less than 30 ppmw, and the alkali metal (e.g., Na or K) content is preferably less than 50 ppmw. Furthermore, to avoid corrosion of the catalyst manufacturing and processing equipment, the chloride content of the modified titania catalyst support is preferably less than 1500 ppmw, and particularly less than 650 ppmw.

[0021] The titania support is modified with one or more refractory oxides of metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium. These oxides are called refractory oxides because of their high melting points. Zirconia (ZrO2) is a refractory metal oxide characterized by its high melting point (2715°C). Similar materials include La2O3 (2315°C), CeO2 (2400°C), Y2O3 (2425°C), and Nd2O3 (2233°C). Therefore, the modified oxides for titania are one or more of ZrO2, La2O3, CeO2, Y2O3, and Nd2O3. CeO2 is less preferred because, although it increases the strength of the catalyst support, it may not provide the benefits of increased activity. ZrO2 is preferred for its balance of catalytic performance, availability, and ease of use. The refractory oxide content of the modified catalyst support is in the range of 0.1 to 15% by weight, preferably 1.0 to 10% by weight, and most preferably 1.5 to 8.5% by weight.

[0022] The pore volume of the modified catalyst support is 0.20 to 0.60 cm³. 3 / g, preferably 0.30-0.50 cm 3 / g, more preferably 0.35~0.45cm 3 The range is / g. The average pore diameter of the modified catalyst support is preferably in the range of 30-60 nm, more preferably in the range of 40-50 nm.

[0023] The BET surface area of ​​the modified catalyst support is 25-75 m². 2 / g, preferably 45-55mg 2It could be in the range of / g.

[0024] The BET surface area and nitrogen pore volume can be measured using nitrogen physicoadsorption techniques. The BET surface area can be determined in this way according to ASTM method D3663-03. The pore volume may also be determined using mercury porosimetry. In this invention, mercury porosimetry, also known as mercury intrusion porosimetry, can be more preferably used due to the relatively large pore diameter. Mercury intrusion porosimetry is a well-known technique that involves exposing a powder sample to mercury under pressure and measuring the change in volume. A particularly suitable method for establishing the pore volume in this way is ASTM method D4284-03.

[0025] The "average pore diameter" refers to the pore volume divided by the surface area (4V / A), which is four times the pore volume. This relationship is derived from the shape of a right cylindrical cylinder with diameter D and height h, in which case the surface area (A) is given by πDh and the volume (V) is given by πD 2 It is given by h / 4.

[0026] The pore volume and average pore diameter of modified titania carriers can be affected by calcination. Typically, calcination of porous materials reduces their pore volume. The effect of calcination on the average pore diameter is not very predictable, and small changes that appear to result from calcination may actually be experimental errors. Preferably, the pore volume of unmodified titania particles is 0.2–0.6 cm². 3 The range may be in the order of / g. Preferably, the average pore diameter of the unmodified titania particles may be in the range of 30 to 60 nm.

[0027] The modified catalyst support is prepared by impregnating a titania support with a refractory metal, drying the impregnated titania support, and calcining it to form a modified titania support. If necessary, the impregnation, drying, and / or calcination process can be repeated to obtain the desired amount of refractory metal oxide supported.

[0028] Refractory metals can be impregnated into titania particles by any known method. The refractory metal can be introduced by forming a solution of a suitable refractory metal compound and applying it to the surface of the titania particles in a suitable mixer. The refractory metal compound may be a suitable organometallic compound such as a metal salt, e.g., a metal nitrate or oxynitrate, or a metal acetate, or a metal acetylacetonate. Aqueous solutions are preferred because they are easier to use on a large scale. Water-soluble metal compounds, such as refractory metal salts, are preferred. Metal nitrates are particularly preferred because they are readily available, dissolve well in water, and decompose into oxides without leaving trace amounts of toxins that could degrade the performance of the Fischer-Tropsch catalyst. Impregnation can be conveniently carried out at temperatures in the range of 10 to 95°C. Impregnation can be carried out under reduced pressure, increased pressure, or ambient pressure. The concentration of the refractory metal in the solution should be as high as possible to reduce the amount of energy required to remove the solvent.

[0029] The volume of the refractory metal compound solution used is preferably close to or less than the total pore volume of the unmodified titania support. Such impregnation advantageously minimizes the amount of drying required. In a preferred method, the volume of the impregnation solution is made close to or less than the pore volume of the titania particles, and the concentration of the refractory metal in the solution is adjusted to control the amount of refractory metal oxide in the modified catalyst support.

[0030] The impregnated carrier is dried to remove the solvent, typically water, present in the refractory metal compound solution. The drying step is preferably carried out at a temperature in the range of 50 to 150°C, especially when the solvent is water. The drying step can be carried out at atmospheric pressure in air or an inert gas such as nitrogen, or under vacuum. The drying time may be in the range of 0.5 to 16 hours as needed, but is more preferably carried out at 80 to 120°C for 1 to 5 hours.

[0031] The dried modified support is typically a free-flowing powder containing one or more refractory metal compounds. To produce the modified catalyst support, the dried material is subjected to a heat treatment, which may be referred to as calcination, to convert one or more refractory metal compounds into oxide form. The heat treatment can be carried out conventionally by heating in air or under nitrogen or another suitable gas mixture for the dried material, or by heating under vacuum. The heat treatment can be carried out in a fixed-bed oven or a moving-bed oven, preferably a rotary calcination furnace or a fluidized-bed calcination furnace. The calcination temperature is desirably in the temperature range of 400 - 900 °C, preferably 450 - 850 °C, more preferably 450 - 750 °C. By using the highest possible calcination temperature, a beneficial increase in strength as large as possible can be obtained without degrading other properties of the modified support. The calcination time may range from 0.5 to 16 hours, but is preferably carried out for 1 to 4 hours at 400 - 900 °C, preferably 450 - 850 °C, more preferably 450 - 750 °C. Under fluidized-bed conditions, the hourly space velocity (GHSV) of the calcination gas is 1000 - 5000 hr -1 , preferably 2000 - 4000 hr -1 and can be.

[0032] Without being bound by theory, it has been observed that the modification of titania particles with refractory metal compounds in combination with high-temperature calcination improves the properties of the support and, as a result, a catalyst precursor and a catalyst are obtained. Without modification, it is impossible to heat the titania particles to the high temperatures necessary to achieve improved strength without reducing the porosity and anatase content of the support.

[0033] The catalyst precursor contains cobalt oxide crystallites in the pores of a modified titania catalyst support. The cobalt in the precursor may exist as one or more cobalt oxides, but preferably, the cobalt oxide crystallites consist essentially of Co3O4. The average grain size of the cobalt oxide crystallites may be in the range of 6 to 18 nanometers (nm), preferably 7 to 16 nm, and more preferably 8 to 12 nm. The average grain size can be determined by X-ray diffraction (XRD). A particularly preferred method is to use a Bruker D8 Advance XRD instrument with a Lynxeye PSD detector at a CuKα wavelength of 1.5406 Å. This detection system is useful because its operating settings can be adjusted to suppress fluorescence produced by the presence of cobalt. Rietveld analysis and line expansion (Scherrer) are common methods for determining crystallite size. Either method can be used, but Rietveld analysis is preferred.

[0034] The catalyst precursor may have a ratio of average cobalt oxide crystallite size to average pore diameter in the range of 0.1:1 to 0.6:1, preferably 0.2:1 to 0.4:1. This ratio is surprising because it is generally believed that the pore diameter of the support controls the metal oxide crystallite size, and consequently, pores with larger average diameters result in larger cobalt oxide crystallites. Surprisingly, the applicant discovered that small cobalt oxide crystallites are formed within the relatively large pores of the modified titania support. The applicant found that a combination of the physical properties of the modified titania support, the cobalt source, and the preparation conditions yields a Fischer-Tropsch catalyst with improved performance compared to an unmodified titania-supported catalyst.

[0035] The cobalt content of the catalyst precursor can range from 5 to 25% by weight, preferably 8 to 16% by weight, expressed as Co on a lossless basis. Despite the relatively low cobalt content, the resulting catalyst exhibits surprisingly high activity per gram in the Fischer-Tropsch reaction. In the active catalyst, the proportion of cobalt in the active catalyst increases as at least a portion of the cobalt oxide in the catalyst precursor is reduced to its elemental form and oxygen atoms in the cobalt oxide are removed. Particularly effective catalysts contain 8 to 12% by weight of cobalt with a reduction degree of 70 mol% or more of cobalt oxide.

[0036] The catalyst precursor has the same particle size characteristics as the modified titania support. Therefore, when used in a commercial-scale fixed-bed reactor, particularly as a fixed bed within a catalyst carrier in a multi-tube Fischer-Tropsch reaction vessel, the catalyst precursor provides a highly active catalyst with an acceptable pressure drop.

[0037] The catalyst precursor may optionally further contain one or more additives that may exist as oxides to improve catalytic performance in the Fischer-Tropsch process. Preferred additives are selected from oxides of one or more additive metals selected from nickel (Ni), zinc (Zn), thorium (Th), magnesium (Mg), manganese (Mn), or silicon (Si). Alternatively, or in addition, the catalyst precursor may optionally contain one or more promoters that may exist in oxide or elemental form to improve catalyst activation or reduction. Preferred promoter metals include one or more of rhodium (Rh), iridium (Ir), ruthenium (Ru), rhenium (Re), platinum (Pt), and palladium (Pd). Additives and / or promoters can be incorporated into the catalyst precursor on the modified catalyst support before or after cobalt impregnation by using suitable compounds such as acids like perrhenic acid, metal salts such as metal nitrates and oxynitrates or metal acetates, or suitable organometallic compounds such as metal alkoxides or metal acetylacetonates. The amount of added metal can vary between 1 and 15% by weight in total, preferably between 1 and 10% by weight, in the catalyst precursor. The amount of promoter metal can vary between 0.01 and 1.00% by weight in total, preferably between 0.01 and 0.50% by weight, in the catalyst precursor.

[0038] The catalyst precursor is prepared by impregnating a modified titania support with a cobalt compound. This can be conveniently carried out by forming a solution of the cobalt compound and applying it to the modified catalyst support. The cobalt compound may be any suitable soluble cobalt compound, such as a cobalt salt or a cobalt complex, but cobalt nitrate is particularly preferred because it does not introduce a catalyst poison and is relatively easy to handle compared to other compounds. The cobalt compound is preferably cobalt(II) nitrate hexahydrate, which can be dissolved in its water of hydration by heating, for example, to above 50°C, to form a concentrated solution of molten cobalt nitrate. Alternatively, cobalt nitrate can be dissolved in water or another solvent to form a more dilute solution. Water is a preferred solvent.

[0039] The impregnated modified titania support is dried and calcined to form cobalt oxide crystallites within the pores of the modified titania support. If necessary, the impregnation, drying, and / or calcination process can be repeated to obtain the desired catalyst precursor.

[0040] Impregnation can be carried out by adding a cobalt compound solution to the modified titania carrier in a suitable mixer, such as a Prosher mixer. The volume of the cobalt compound solution used is preferably approximated by the total pore volume of the modified titania carrier. Such impregnation, which may be called “dry impregnation” or “initial wet impregnation,” favorably improves the deposition of the cobalt compound in the pores of the modified carrier and minimizes the amount of drying required. If desired, suitable additives and / or promoter compounds may be added to the cobalt compound solution in suitable amounts. Alternatively, these may be combined with catalyst precursors before or after drying and / or before final calcination.

[0041] The impregnated modified support is dried to remove the solvent present in the cobalt compound solution, typically water, preferably leaving the cobalt compound in the pores of the support. The drying process is preferably carried out at a temperature in the range of 50 to 150°C. The drying process can be carried out at atmospheric pressure in air or an inert gas such as nitrogen, or under vacuum. The drying time may be in the range of 0.5 to 16 hours as needed, but is more preferably carried out at 80 to 120°C for 1 to 5 hours.

[0042] The dried impregnated modified carrier is a fluid powder containing one or more cobalt compounds, preferably partially hydrated cobalt nitrate such as Co(NO3)2·xH2O(x<6). To produce a catalyst precursor, the dried material can be subjected to heat treatment (sometimes called calcination) to convert the cobalt compounds into cobalt oxide crystallites. The heat treatment can be carried out conventionally in air, or by heating the dried material under nitrogen or another non-reducing gas mixture, or by heating under vacuum. The heat treatment can be carried out in a static or moving bed oven, or preferably in a fluidized bed reactor. Surprisingly, the fluidized bed reactor has been found to produce catalyst precursors having small average cobalt oxide crystallite sizes, for example, in the range of 6–12 nm, particularly 8–10 nm. The calcination temperature may be in the range of 220–320°C, preferably 240–300°C, to minimize sintering of cobalt oxide crystallites and maintain the cobalt surface area. The firing time may range from 0.5 to 16 hours as needed, but is preferably carried out at 240 to 300°C for 1 to 4 hours. Under fluidized bed conditions, the space velocity per hour (GHSV) of the firing gas is 1000 to 5000 hr at ambient temperature and pressure (NTP). -1 Preferably 2000-4000 hours -1 It is possible.

[0043] If desired, the firing process may be followed by a polishing process in which the fired material is heated in a diluted hydrogen stream under conditions that do not cause reduction of cobalt oxide to its elemental form. The polishing process can be advantageously used to reduce the residual nitrate content of the fired material. The hydrogen stream may consist of, for example, an inert gas such as nitrogen, with, for example, 0.1 to 10 volume percent of hydrogen, preferably 1 to 5 volume percent of hydrogen. The pressure may be 1 to 10 bar absolute, preferably 1 to 3 bar absolute. The maximum temperature of the polishing process may be in the range of 100 to 225°C, preferably 140 to 200°C. The polishing process can be suitably carried out for 0.5 to 16 hours as needed, but is preferably carried out for 1 to 3 hours at 140 to 200°C. The gas-per-hour space velocity (GHSV) of the hydrogen / inert gas stream in the polishing process is 50 to 2000 hr. -1 This may be done, but preferably at room temperature and pressure (NTP) for 50 to 1000 hours. -1 , comfortable 100~500hr -1 Under these conditions, the reduction of cobalt oxide essentially does not occur. The polishing step reduces the residual nitrate in the catalyst precursor to less than 0.1% by weight, so that the subsequent reduction can be carried out without the need for special steps to control the ammonia formed during the reduction. This is particularly useful when the catalyst precursor is reduced in situ, i.e., in the reactor used in the Fischer-Tropsch process.

[0044] The catalyst precursor is introduced into a reactor used in the Fischer-Tropsch reaction and activated to form a catalyst by reducing at least a portion of the cobalt oxide to its elemental form in situ. Such activation can be carried out using any suitable reducing agent, but preferably using a reducing gas stream. The reducing gas stream can be selected from a hydrogen gas stream or a synthesis gas stream containing hydrogen and carbon monoxide. Thus, the reducing gas stream may consist of 1 to 100 volume percent hydrogen in an inert gas such as nitrogen. Alternatively, a synthesis gas containing hydrogen and carbon monoxide, and optionally other components, may be used. The synthesis gas is preferably a Fischer-Tropsch synthesis gas essentially consisting of hydrogen and carbon monoxide, with a hydrogen:carbon monoxide molar ratio in the range of 1.6 to 2.2. Alternatively, the reducing gas may include a mixture of these gases. The gas-per-time space velocity (GHSV) of the reducing gas passing through the catalyst precursor is 4000 to 10000 hhr at room temperature and atmospheric pressure (NTP). -1 This is possible. The space velocity per second of the reducing gas may be altered during reduction to control the exposure of cobalt oxide and reduced cobalt to water vapor formed as a byproduct during reduction. The maximum temperature used in the reduction step may be in the range of 250 to 400°C, but is preferably in the range of 250 to 300°C to minimize sintering of the reduced cobalt crystallites. Reduction can be carried out at ambient pressure or rising pressure, i.e., the pressure of the reducing gas may be an absolute pressure of 1 to 50 bar.

[0045] Alternatively, the catalyst precursor may be pre-reduced ex-situ in a reduction vessel to provide the catalyst. Pre-reduction can be carried out using any suitable reducing agent, but is preferably carried out using a hydrogen gas stream operating in a loop that removes by-product water from the recirculated reducing gas stream. The hydrogen stream may consist of 10–100 volume% hydrogen in an inert gas such as nitrogen. The concentration of hydrogen in the reducing gas stream may change during reduction. The gas-per-hour space velocity (GHSV) of the hydrogen / inert gas stream is 4000–10000 hr at room temperature and atmospheric pressure (NTP). -1This is possible. The space velocity per second of the reducing gas stream may be altered during reduction to control the exposure of cobalt oxide and reduced cobalt to water vapor. The maximum temperature used in the reduction stage may be in the range of 250 to 400°C, but is preferably in the range of 250 to 300°C to minimize sintering of the reduced cobalt crystallites. Reduction can be carried out at ambient pressure or rising pressure, i.e., the pressure of the reducing gas may be an absolute pressure of 1 to 50, preferably 1 to 20, more preferably 1 to 10 bar.

[0046] Reduced catalysts can be difficult to handle because they may spontaneously react with oxygen, which can lead to undesirable self-heating and loss of activity. As a result, reduced catalysts can be protected by encapsulating them with a suitable barrier coating. In the case of Fischer-Tropsch catalysts, this is preferably a hydrocarbon wax, such as a wax produced by Fischer-Tropsch synthesis. The encapsulating wax can be introduced into the Fischer-Tropsch reactor, for example, by heating the catalyst under a hydrogen gas stream or a synthesis gas stream, and then removed from the catalyst. Alternatively, the reduced catalyst can be passivated by exposure to dilute oxygen in a carrier gas such as nitrogen, so that a protective layer of cobalt oxide forms around each cobalt oxide crystallite.

[0047] Regardless of the route chosen to convert the oxidation catalyst precursor into the active FT catalyst, cobalt catalysts prepared from refractory metal-modified titania supports exhibit a larger metal surface area per gram of reduced metal. For example, when the catalyst precursor is reduced with hydrogen at 250°C, it is preferably 5 m², as measured by hydrogen chemisorption. 2 It may have a cobalt surface area of ​​1 / g or more.

[0048] Catalysts obtained from catalyst precursors are particularly effective for the Fischer-Tropsch synthesis of hydrocarbons. The Fischer-Tropsch synthesis of hydrocarbons using cobalt catalysts is well-established. The Fischer-Tropsch synthesis converts a mixture of carbon monoxide and hydrogen into hydrocarbons, preferably hydrocarbons with a carbon chain length of 5 or more. The mixture of carbon monoxide and hydrogen is typically a synthesis gas with a hydrogen:carbon monoxide ratio in the range of 1.6 to 2.2:1. The reaction can be carried out in a continuous or batch process using one or more reactors, such as a fixed-bed reactor, slurry-phase reactor, bubble column reactor, loop reactor, or fluidized-bed reactor. This process can operate at pressures in the range of 0.1 to 10 MPa and temperatures in the range of 150 to 350°C. The gas-per-hour space velocity (GHSV) for continuous operation is 1,000 to 25,000 hr. -1 This may be within the range. The catalyst of the present invention is particularly suitable as a fixed-bed catalyst, that is, a catalyst bed fixed in a reaction vessel through which the reactant synthesis gas passes.

[0049] The physical properties of the catalyst precursor mean that it is suitable for use in microchannel reactors, i.e., Fischer-Tropsch reactors having multiple catalyst-containing channels with widths or heights ranging from 2 to 10 mm through which synthesis gas passes.

[0050] The physical properties of the catalyst precursor mean that it is particularly suitable for use as a catalyst carrier placed in the reaction tubes within a Fischer-Tropsch reaction vessel, such as a downflow multitubular Fischer-Tropsch reaction vessel.

[0051] The catalyst or catalyst precursor has been found to be particularly effective when used in combination with a catalyst carrier suitable for use in a tubular reactor. Any suitable catalyst carrier may be used. "Catalyst carrier" means a catalyst container, for example, in the form of a cup or can, configured to allow gas and / or liquid to enter and exit the carrier and flow through a bed of catalyst or catalyst precursor arranged within the carrier. The flow of gas and / or liquid within the catalyst carrier may be radial and / or axial. Preferably, the catalyst or catalyst precursor is arranged as an annular catalyst bed in the center of the catalyst carrier. The flow through the catalyst bed within the carrier is preferably radial. The catalyst bed may be surrounded by a heat transfer zone at its periphery and spaced apart from the heat transfer zone. The catalyst bed and heat exchange zone may be in fluid communication with each other. In one configuration, the catalyst carrier is described in International Publication No. 2011 / 048361, the contents of which are incorporated herein by reference. The catalyst carrier described in International Publication No. 2011 / 048361 is an annular container for holding a catalyst in use, the container having a perforated inner wall defining a tube, a perforated outer wall, a top surface for closing the annular container, and a bottom surface for pouring into the annular container; a surface for closing the bottom of the tube formed by the inner wall of the annular container; a skirt extending upward from the perforated outer wall of the annular container to a position below the seal, from a position at or near the bottom of the container; and a seal located at or near the top surface, extending from the container by a distance beyond the outer surface of the skirt. In a preferred configuration, the catalyst carrier is disclosed in International Publication No. 2016 / 050520, the contents of which are incorporated herein by reference. Therefore, a catalyst carrier is a container suitable for holding a catalyst precursor or catalyst in a predetermined position, and the container may comprise: a container having a bottom surface that closes the container and a top surface; a carrier outer wall extending from the bottom surface to the top surface of the container; and a seal extending a distance from the container beyond the carrier outer wall, the carrier outer wall having an opening located below the seal.In a preferred configuration, the catalyst carrier may include an annular vessel suitable for holding a catalyst precursor or catalyst in a predetermined position, the vessel having a perforated inner vessel wall defining an inner channel, a perforated outer vessel wall, a top surface closing the annular vessel, a bottom surface closing the annular vessel, and a surface closing the bottom of the inner channel formed by the inner vessel wall of the annular vessel. The catalyst carrier is generally sized such that its dimensions are smaller than the internal dimensions of the reaction tube in which it is placed when in use. The seal is sized to interact with the inner wall of the reaction tube when the catalyst carrier of the present invention is in a predetermined position within the reaction tube.

[0052] When used in a vertical reactor with a downflow, the reactants flow downward through the reaction tube and therefore first come into contact with the top surface of the catalyst carrier. The seal prevents the reactants from passing around the sides of the carrier, so its top surface directs them into an inner channel defined by the inner vessel wall. The reactants then enter the annular vessel through the perforated inner vessel wall and then pass radially through the catalyst bed toward the perforated outer vessel wall. During passage from the inner to the outer vessel wall, the reactants come into contact with the catalyst, and the Fischer-Tropsch reaction takes place. The unconverted reactants and reaction products then flow out of the vessel through the perforated outer vessel wall. The carrier outer wall then directs the reactants and products upward between the inner surface of the carrier outer wall and the perforated outer vessel wall of the annular vessel until they reach an opening in the carrier outer wall. They are then directed through the opening located in the carrier outer wall and flow downward between the outer surface of the carrier outer wall and the inner surface of the reaction tube, where heat transfer occurs. If the reactor is operated in a way that reverses the flow, the pathways of the reactants and products will also be reversed.

[0053] The catalyst precursor can be loaded into a catalyst carrier, and the resulting combination can be loaded into the reaction tube of a Fischer-Tropsch reaction vessel to reduce and activate the catalyst in situ as described above. Alternatively, the combination may be subjected to ex-situ reduction in a reduction vessel, or the combination may be sealed or passivated. The resulting combination can be safely loaded into the reaction tube of a Fischer-Tropsch reaction vessel and activated in situ more quickly and easily than when using an oxidation catalyst precursor. [Examples]

[0054] The present invention will now be further described with reference to the following examples.

[0055] In the example, the following measurements were performed.

[0056] Particle size: Particle size was determined according to ASTM D4464 by laser light scattering using a Malvern Mastersizer 3000 laser diffraction particle size analyzer, using the optical properties of TiO2 (anatase) from the Malvern MS3000 optical properties database in the instrument software (refractive index 2.51, absorptive 0.01). Wet dispersion measurements were performed in deionized water using 0% and 85% sonication and a stirring rate of 50% with a Hydro MV sample dispersion unit. Sufficient sample was added to the unit until the laser beam was blocked by 0.1–20%. Five measurements were taken for each aliquot of the sample, with a measurement time of 5 seconds. Dry dispersion measurements were performed at a 20% supply rate in an Aero dry dispersion unit equipped with a microvolume tray and standard venturi, using dispersion air pressures of 0.5 bar and 3.0 bar with site-compressed air. One measurement was taken per aliquot of the sample, and the entire aliquot was measured in each measurement. If the laser beam is blocked by 0.1-10%, the measurement time is 15 seconds. To calculate the results, the Malvern software uses Mie theory to convert the obtained diffraction pattern into a particle size distribution.

[0057] Pore ​​volume. Mercury intrusion / extrusion data were measured using a Micromeritics AutoPore 9520 mercury porosimetry, according to ASTM method D4284-03; Test method for determining the pore volume distribution of catalysts by mercury intrusion porosimetry. Intrusion curves were measured over a pressure range of 0.5 to 60,000 psia, followed by extrusion to atmospheric pressure. An equilibrium time of 15 seconds was used for each data point in both the intrusion and extrusion curves, with a mercury contact angle of 140° and a mercury surface tension of 485 dynes / cm. Before analysis, samples were dried overnight in an oven at 115°C. The effects of temperature and pressure present during porosimetry measurements were accounted for by performing blank correction with an empty hardness test tube, and then subtracted from the experimental data.

[0058] Surface area was measured using a Micromeritics 2420 ASAP physicoadsorption analyzer, applying the BET method according to ASTM Method D 3663-03; standard test for surface area. Nitrogen was used as the adsorbate, and measurements were performed at liquid nitrogen temperature (77K). The cross-sectional area of ​​the nitrogen molecule was assumed to be 16.2 Å. Before analysis, the sample was degassed by purging with dry nitrogen gas at 140°C for at least 1 hour. Five relative pressure / volume data pairs were acquired over the relative pressure range including 0.05–0.20 P / Po. The equilibration time at each point was 10 seconds. Surface area is reported based on the weight of the degassed sample.

[0059] Average pore diameter. The average pore diameter was calculated from measured pore volume and surface area. The average pore diameter is obtained by dividing the calculated surface area by four times the corrected pore volume (4V / A). This relationship is derived from the shape of a right cylindrical cylinder with diameter D and height h, in which case the surface area (A) is given by πDh and the volume (V) is given by πD 2 It is given by h / 4.

[0060] Median pore diameter. The median pore diameter was derived from the measured pore volume. "Median pore diameter" refers to the pore diameter at the midpoint of the cumulative mercury intrusion curve, corrected for void packing between particles.

[0061] Chloride and sulfur content. Chloride and sulfur content was measured by combustion ion chromatography (CIC). The test sample was heated in a furnace in the presence of flowing, moisture-containing air. Halides and / or sulfur compounds present in the sample were combusted and released into the airflow. The air exiting the furnace was cooled to produce a liquid condensate. The resulting liquid was diluted to a set volume, and aliquots were injected into an ion chromatography (IC) column to separate the anions of interest. The eluate from the IC column was passed through a conductivity detector to generate a series of peaks corresponding to the anions present in the sample. Calibration of the detector using standard anion solutions facilitated the calculation of the chloride and / or sulfur content of the sample.

[0062] Cobalt content. Determined by ICPAES (Inductively Coupled Plasma Atomic Emission Spectroscopy) or ICPMS (Inductively Coupled Plasma Mass Spectrometry) of the calcined catalyst precursor, and expressed as a weight percentage of cobalt on a lossless basis.

[0063] Cobalt oxide crystallite size. Cobalt oxide crystallite size was determined by XRD using a Bruker D8 Advance X-ray diffractometer. Powdered catalyst precursor samples were pressed into a sample holder and loaded into the instrument. Parallel beam (Gobel mirror) optical instrument. Software: Bruker EVA for phase identification; Topas for patterning. The diffractometer conditions were as follows:

[0064] [Table 1]

[0065] The cobalt oxide crystallite size was determined using Rietveld analysis (Bruker Topas v4.2). Rietveld analysis of powder XRD data begins with a diffraction pattern calculated based on symmetry information and approximate structure. Then, Rietveld analysis uses least-squares minimization to compare all observation points with the calculated plot, refining the calculated structure and minimizing the differences.

[0066] Cobalt surface area. The surface area of ​​cobalt metal was measured using a Micromeritics 2480 HTP 6 Station Chemisorption Analyser. The sample was reduced with 100 vol% hydrogen at 250°C for 120 minutes at a hydrogen flow rate of 200 SCCM. After the reduction step was complete, the sample was purged with helium for 15 minutes and then cooled to the analytical temperature of 35°C under vacuum. After reaching a vacuum of less than 10 μmHg, evacuation was continued for 45 minutes. Then, 100 vol% hydrogen was added to the sample over a pressure range of 100–760 mmHg. At each pressure, the chemisorbed hydrogen was equilibrated, and the hydrogen uptake volume was measured and automatically recorded. Pressure / uptake pairs were plotted to obtain isotherms showing a clearly defined plateau region. Data points were selected within this region to achieve a nearest linear fit, which was then extrapolated back to zero pressure. Using the intercept value, the cobalt surface area was calculated using a stoichiometry of 1.0 for H2 / Co, and the cobalt surface area was reported based on the mass of the reduced catalyst.

[0067] Example 1: Zirconia-modified titania carrier a) Effects of increased ZrO2 content A series of zirconia-modified TiO2 microsphere carriers were prepared by initial wetting impregnation using an aqueous solution of ZrO(NO3)2·2H2O (calculated Zr content 34.133 wt / wt%). In all cases, the pore volume of water was 0.41 cm³. 3 300g of TiO2 microspheres ( / g) were weighed and loaded into a preheated Z-blade mixer (50°C), where they were left to warm for approximately 15 minutes. The mass of zirconium(IV) oxynitrate dihydrate (ZrO(NO3)2·2H2O) required to achieve the target ZrO2 load (listed in the table below) was weighed into a beaker containing 100mL of desalinated water. This was then placed on a hot plate stirrer and heated to 50°C. Once the temperature was reached, 120cm of desalinated water was added. 3The volume was adjusted and reheated to 50°C. The solution was then slowly added to the TiO2 microspheres being mixed in a Z-blade mixer. The addition of the solution took approximately 90 seconds. After adding the solution, the sample was mixed for a further 60 seconds. The sample was then removed from the Z-blade mixer and placed in an alumina sagar. The sagar was placed in a furnace preheated to 110°C and held for 3 hours. After that, the furnace temperature was increased to 500°C at a rate of 2°C / min and held for 2 hours.

[0068] [Table 2]

[0069] The ZrO(NO3)2·2H2O and TiO2 microspheres were obtained commercially.

[0070] The TiO2 microspheres, in their original condition, possessed the following typical characteristics:

[0071] [Table 3]

[0072] For comparison, samples of unmodified titania microspheres were also calcined at 500°C.

[0073] The particle strength measured by air jet abrasion tests was found to increase with increasing ZrO2 load, while the residual chloride content decreased. The results are shown below.

[0074] [Table 4]

[0075] Despite the significant increase in strength due to the ZrO2 loading, there was no loss of surface area and virtually no loss of porosity as a result of the zirconia modification.

[0076] b) Effect of firing temperature The experiment was repeated at firing temperatures of 400, 600, 700, 800, and 900°C. The results are as follows:

[0077] [Table 5]

[0078] The residual chloride content decreases as the calcination temperature increases, and these results demonstrate a decrease in surface area and porosity in the absence of refractory oxides, as well as the conversion of anatase to rutile.

[0079] [Table 6]

[0080] [Table 7]

[0081] [Table 8]

[0082] Surprisingly, even as the calcination temperature increased, the pore volume and BET surface area and pore volume of the modified carrier remained relatively unchanged up to the maximum calcination temperature in the range of 750–800°C. This observation was valid for the range of zirconia content investigated. For each of the ZrO2 modified carriers, the anatase content determined by XRD remained stable at 80–90 wt / wt% up to a calcination temperature of approximately 750°C. It is clear that the addition of low concentrations of ZrO2 alters the reaction of titania to calcination, requiring higher temperatures to initiate the loss of BET surface area and pore volume. In parallel, zirconia modification of titania resulted in the anatase-to-rutile transition and rutile crystallite growth at higher temperatures than in the case of unmodified TiO2. Similar to TiO2, calcining of modified TiO2 at higher temperatures resulted in a decrease in chloride content in all cases.

[0083] Example 2: La2O3, CeO2, Y2O3 and Nd2O3 modified titania carrier Using the method of Example 1, a series of modified TiO2 microsphere carriers were prepared using the same titania microsphere carrier, with a refractory metal oxide loading of 3.5 wt / wt% and a firing temperature of 750°C. In all cases, the pore volume of water was 0.42 cm³. 3 300g of TiO2 microspheres (1 / g) were weighed and loaded into a Z-blade mixer preheated to 50°C, where they were left to warm for approximately 15 minutes. As shown in the table below, the required mass of modified metal nitrate crystals was weighed into a beaker containing 100mL of demineralized water. This was then placed on a hot plate stirrer and heated to 50°C. Once the temperature was reached, 129cm³ of demineralized water was added. 3 The volume was adjusted to the specified amount. The excess water added in each catalyst preparation is detailed in the table below. The solution was then slowly added to the TiO2 microspheres being mixed in a Z-blade mixer. The addition of the solution took approximately 40 seconds. After adding the solution, the sample was mixed for a further 30 seconds. After this, the sample was removed from the Z-blade mixer and placed in an alumina sagar. The sagar was placed in a furnace preheated to 110°C and held for 3 hours. After this, the furnace temperature was increased to 750°C at a rate of 2°C / min and held for 2 hours.

[0084] [Table 9]

[0085] The characteristics of these modified supports are shown below:

[0086] [Table 10]

[0087] The physical properties of the modified support are remarkably similar. The anatase / rutile ratio of the parent material is maintained, as are the crystallite sizes of anatase and rutile. There is a dramatic increase in strength for all modified oxides, and air-jet abrasion decreases from 68 wt / wt% in the raw state to 14-19 wt / wt% (a 3-4x reduction). The median mercury pore diameter shows a slight increase as a result of the modification process.

[0088] Example 3: Preparation of catalyst precursor The support of Example 2 was converted to un-enhanced (Co) and enhanced (Co / Pt and Co / Ru) oxide Fischer-Tropsch catalyst precursors. In each case, the support was impregnated with the metal solution required by the desired catalyst formulation, dried, and calcined. The metal salts used were cobalt(II) nitrate hexahydrate, tetraammineplatinum(II) nitrate, and ruthenium(III) nitrosylnitrate. The only crystalline form of cobalt oxide identified by XRD in the oxide FT catalyst precursor was Co3O4.

[0089] a) Zirconia-modified TiO2 microsphere carrier Catalyst A: 11 wt / wt% Co on titania / zirconia microspheres 250.00 g of zirconia-modified titania microspheres (3.5 wt / wt% ZrO2, calcined at 750°C) were placed in the preheated mixing chamber of a Z-blade mixer. The circulating water bath was set to 90°C. 163.4 g of cobalt nitrate hexahydrate crystals and 14.3 g of demineralized water were placed in a stainless steel beaker and heated to 75°C on a hot plate. The temperature of the titania before adding the solution was 63°C, and the temperature of the mixer wall was 68°C. The solution was poured into the mixed spheres over 43 seconds. After adding the solution, mixing was continued for 1 minute. 413.0 g of the impregnated material was removed and placed in three stainless steel trays. This material was then dried at 110°C for 3 hours. The temperature was increased at a rate of 2°C / min to the calcination temperature of 250°C and held for 2 hours.

[0090] Catalyst B: 11 wt / wt% Co and 0.022 wt / wt% Pt on titania / zirconia microspheres 250.03 g of the same zirconia-modified titania spheres were placed in the preheated mixing chamber of a Z-blade mixer. The circulating water bath was set to 90°C. 163.6 g of cobalt nitrate hexahydrate crystals, 2.0 g of tetraammineplatinum(II) nitrate solution (3.367 wt / wt% Pt), and 13.2 g of demineralized water were placed in a stainless steel beaker and heated to 75°C on a hot plate. The temperature of the titania before adding the solution was 65°C, and the temperature of the mixer wall was 69°C. The solution was poured over the mixed titania microspheres over 43 seconds. After adding the solution, mixing was continued for 1 minute. 413.1 g of the impregnated material was removed and placed in three stainless steel trays. This material was then dried at 110°C for 3 hours. The temperature was increased at a rate of 2°C / min to a firing temperature of 250°C and held for 2 hours.

[0091] Catalyst C: 11 wt / wt% Co and 0.11 wt / wt% Ru on titania / zirconia microspheres 250.3 g of the same zirconia-modified titania spheres were placed in the preheated mixing chamber of a Z-blade mixer. The circulating water bath was set to 90°C. 163.8 g of cobalt nitrate hexahydrate crystals, 2.3 g of ruthenium(III) nitrosylnitrate solution (13.88 wt / wt% Ru), and 12.8 g of demineralized water were placed in a stainless steel beaker and heated to 75°C on a hot plate. The temperature of the titania microspheres before adding the solution was 64°C, and the temperature of the mixer wall was 66°C. The solution was poured over the mixed titania microspheres over 40 seconds. After adding the solution, mixing was continued for 1 minute. 412.3 g of the impregnated material was removed and placed in three stainless steel trays. This material was then dried at 110°C for 3 hours. The temperature was increased at a rate of 2°C / min to a firing temperature of 250°C and held for 2 hours.

[0092] For comparison, a similar catalyst was prepared using the same method and apparatus as described in Example 1, using unmodified TiO2 microspheres in their raw state. Comparative catalyst D: 11 wt / wt% Co on titania microspheres. Comparative catalyst E: 11 wt / wt% Co and 0.022 wt / wt% Pt on titania microspheres. Comparative catalyst F: 11 wt / wt% Co and 0.11 wt / wt% Ru on titania microspheres.

[0093] [Table 11]

[0094] Air jet wear of the FT catalyst oxide precursor is lower than that of the precursor support because its density increases due to the impregnation of the catalyst metal onto the support. Catalysts A, B, and C, prepared on the modified support, exhibit slightly lower wear than catalysts D, E, and F, prepared on unmodified TiO2. Furthermore, the support modification process reduced the chloride content of the catalyst oxide.

[0095] b) Refurbished oxide-modified TiO2 microsphere carriers A method for preparing catalyst precursors for TiO2 supports modified with La2O3, CeO2, Y2O3, and Nd2O3.

[0096] For each example, 50 g of the modified TiO2 microsphere carrier from Example 2 was weighed into a plastic bag. Cobalt nitrate hexahydrate, demineralized water, and any necessary promoter (if present) were weighed and placed in a glass beaker (see the table below for weights). The beaker was then heated and stirred on a hot plate / magnetic stirrer until the contents were completely dissolved. The solution was then added to the carrier in three aliquots. Between each addition, the bag was sealed and the contents were shaken or kneaded from the outside of the bag to obtain a fluid powder. The mixed intermediate was then placed on a stainless steel tray and dried in an oven preheated to 110°C for 3 hours. The oven temperature was then increased at a rate of 2°C / min to a firing temperature of 250°C and held for 2 hours.

[0097] [Table 12]

[0098] The following oxide FT catalyst precursors were prepared using this method.

[0099] [Table 13]

[0100] [Table 14]

[0101] Example 4: Catalyst Test The experiment was conducted using 0.5 g of catalyst precursor diluted with 2.00 g of SiC in a 4 mm inner diameter experimental reaction tube. In situ reduction was performed in pure hydrogen at 300°C (gradient 1°C / min) for 7 hours at a flow rate of 60 mL / min. The temperature was then reduced to 150°C, the gas was switched to synthesis gas (H2:CO=2:1), and the reactor was pressurized to 20 barg at a flow rate of 110 mL / min. After 6 hours, the temperature was increased to 210°C (1°C / min) and left overnight for approximately 16 hours. The flow rate was then reduced first to 50 mL / min, and then to the flow rate required to achieve 50% synthesis gas conversion, with data collection continuing throughout the experiment (approximately 160 hours unless otherwise specified). The inflow gas was measured into the reactor using a mass flow controller. Gases, liquids, and solid hydrocarbon products, as well as the aqueous phase, were analyzed by gas chromatography to achieve mass balance for calculating CO conversion and selectivity. Alpha is calculated from the slope of the plot of log(Wn / n) as a function of n, where the gradient is log(α), where Wn is the weight fraction of a hydrocarbon with n carbon atoms and α is the chain growth probability. This equation is the Anderson-Schultz-Flory distribution, Wn = nα n-1 (1-α) 2 It was derived from C. Typically, 20 ~C 40 This was the range of carbon atoms used in the calculation of alpha. The performance data for the zirconia modified catalyst is shown in the table below.

[0102] [Table 15]

[0103] On unmodified TiO2 supports, enhancement with platinum and ruthenium shows the expected relative increase in activity compared to unenhanced cobalt, along with a slight increase in methane selectivity. Surprisingly, the TiO2 / ZrO2-supported catalysts are far more active than comparable TiO2-supported catalysts. For unenhanced cobalt, the relative increase in activity is 1.00 to 1.57 (57%). For the catalyst variants enhanced with platinum and ruthenium, the relative increases in activity are 34% and 16%, respectively.

[0104] The performance data for other refractory oxide reforming catalysts is shown in the table below.

[0105] [Table 16]

[0106] With the exception of the Co / TiO2 / CeO2 catalyst, all catalysts prepared from the modified TiO2 support clearly showed improved activity compared to their unmodified TiO2-supported counterparts. The most active catalysts were catalyst H (Co / Pt / TiO2 / La2O3), catalyst B (Co / Pt / TiO2 / ZrO2), and catalyst Q (Co / Pt / TiO2 / Nd2O3). The relative activities of these catalysts were 1.92, 1.95, and 1.97, respectively, meaning they were approximately twice as active as the unmodified, unenhanced catalyst D in these tests.

[0107] In summary, modifying TiO2 microspheres with a refractory metal, followed by drying and high-temperature calcination, yields a catalyst support that is stronger than the original microspheres and has a lower chloride content, while retaining the microstructural characteristics necessary for producing active and selective Fischer-Tropsch catalysts. Cobalt-based Fischer-Tropsch catalysts prepared on TiO2 microsphere supports modified with refractory metal oxides as described above are generally significantly more active than equivalent catalysts prepared on unmodified TiO2 microspheres. Furthermore, the disclosure of the present invention may include the following embodiments. (Aspect 1) A modified catalyst support in the form of titania particles having a volume median diameter in the range of 100 to 1000 μm, modified with a refractory oxide of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium, wherein the total refractory oxide content of the modified catalyst support is in the range of 0.1 to 15% by weight, and the modified catalyst support is 0.2 to 0.6 cm 3 A modified catalyst support having a pore volume in the range of / g and an average pore diameter in the range of 30-60 nm. (Aspect 2) The modified catalyst support according to Embodiment 1, wherein the volume median diameter D[v,0.5] is in the range of 300 to 900 μm, preferably 350 to 650 μm, and more preferably 400 to 500 μm. (Aspect 3) The modified catalyst support according to Embodiment 1 or Embodiment 2, wherein the titania particles are spherical, having a sphericity (ψ) of at least about 0.90, preferably at least about 0.95. (Aspect 4) The modified catalyst support according to any one of embodiments 1 to 3, wherein the modified titania catalyst support has an anatase content of at least 70% by weight, preferably at least 80% by weight, of the support. (Appendix 5) A modified catalyst carrier according to any one of embodiments 1 to 4, having a chloride content of less than 1500 ppmw, preferably less than 650 ppmw. (Aspect 6) The aforementioned refractory oxide is zirconia, ZrO 2 A modified catalyst support according to any one of embodiments 1 to 5, comprising the above. (Aspect 7) The modified catalyst support according to any one of embodiments 1 to 6, wherein the refractory oxide content of the modified catalyst support is in the range of 1.0 to 10% by weight, preferably 1.5 to 8.5% by weight. (Pattern 8) The pore volume is 0.30 to 0.50 cm³. 3 / g, preferably 0.35-0.45cm 3 A modified catalyst carrier according to any one of embodiments 1 to 7, wherein the range is in the range of / g. (Aspect 9) The modified catalyst support according to any one of embodiments 1 to 8, wherein the average pore diameter is in the range of 40 to 60 nm. (Aspect 10) 25~75m 2 / g, preferably 45-55mg 2 A modified catalyst support according to any one of embodiments 1 to 9, having a BET surface area in the range of / g. (Aspect 11) A catalyst precursor comprising cobalt oxide crystallites disposed within the pores of a modified catalyst support according to any one of embodiments 1 to 10. (Aspect 12) The catalyst precursor according to embodiment 11, wherein the cobalt oxide crystallites have an average particle size in the range of 6 to 18 nanometers (nm), preferably 7 to 16 nm, and more preferably 8 to 12 nm. (Aspect 13) The catalyst precursor according to embodiment 11 or embodiment 12, wherein the ratio of the average cobalt oxide crystallite size to the average pore diameter is in the range of 0.1:1 to 0.6:1, preferably 0.2:1 to 0.4:1. (Aspect 14) A catalyst precursor according to any one of embodiments 11 to 13, having a cobalt content in the range of 5 to 25% by weight, preferably 8 to 16% by weight, expressed as Co on a lossless basis. (Aspect 15) A catalyst precursor according to any one of embodiments 11 to 14, comprising a total of 1 to 15% by weight of one or more additives selected from oxides of one or more additive metals selected from nickel (Ni), zinc (Zn), thorium (Th), magnesium (Mg), manganese (Mn), or silicon (Si). (Aspect 16) A catalyst precursor according to any one of embodiments 11 to 15, comprising a total of 0.01 to 1.00% by weight of one or more promoter metals selected from rhodium (Rh), iridium (Ir), ruthenium (Ru), rhenium (Re), platinum (Pt), and palladium (Pd). (Aspect 17) A catalyst comprising cobalt metal crystallites disposed within the pores of a modified catalyst support according to any one of embodiments 1 to 10. (Aspect 18) A method for preparing the modified catalyst support described in any one of embodiments 1 to 10, wherein the volume median diameter is in the range of 100 to 1000 μm and the support is 0.2 to 0.6 cm. 3 A method comprising the steps of: impregnating titania particles having a pore volume in the range of / g and an average pore diameter in the range of 30 to 60 nm with a solution of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium; and drying and calcining the impregnated titania carrier to form a refractory metal oxide modified titania carrier containing 0.1 to 15% by weight of refractory oxides. (Aspect 19) The method according to embodiment 18, wherein the firing step is carried out in a moving bed reactor at a temperature in the range of 400 to 900°C, preferably 450 to 850°C, and more preferably 450 to 750°C. (Aspect 20) A method for preparing a catalyst precursor according to any one of embodiments 11 to 16, comprising the steps of impregnating the modified titania support with a cobalt compound, and drying and calcining the impregnated modified titania support to form cobalt oxide crystallites in the pores of the modified titania support. (Aspect 21) A catalyst precursor according to any one of embodiments 11 to 16, or a combination of catalysts according to embodiment 17, placed in a catalyst carrier suitable for use in the reaction tube of a reactor. (Aspect 22) A combination of a catalyst precursor according to any one of embodiments 11 to 16, or a catalyst according to embodiment 17, placed within the channel of a microchannel reactor. (Aspect 23) Use of a catalyst precursor according to any one of embodiments 11 to 16, a catalyst according to embodiment 17, or a combination according to embodiments 21 and 22 in a reactor for a process of producing hydrocarbons from synthesis gas containing hydrogen and carbon monoxide.

Claims

1. A modified catalyst support for the cobalt-based Fischer-Tropsch reaction, in the form of titania particles having a volume median diameter in the range of 100 to 1000 μm, modified with a refractory oxide of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium, wherein the total refractory oxide content of the modified catalyst support is in the range of 1.5 to 8.5% by weight, and the modified catalyst support is 0.2 to 0.6 cm ３ It has a pore volume in the range of / g and an average pore diameter in the range of 30 to 60 nm. A modified catalyst support for a cobalt-based Fischer-Tropsch reaction, wherein the modified catalyst support has an anatase content greater than 50% by weight of the support.

2. The cobalt-based Fischer-Tropsch reaction modifying catalyst support according to claim 1, wherein the volume median diameter D [v, 0.5] is in the range of 300 to 900 μm.

3. The cobalt-based Fischer-Tropsch reaction modifying catalyst support according to claim 1 or claim 2, wherein the titania particles are spherical with a sphericity (ψ) of at least about 0.

90.

4. The modified catalyst support for a cobalt-based Fischer-Tropsch reaction according to any one of claims 1 to 3, wherein the modified catalyst support has an anatase content of at least 70% by weight of the support.

5. A cobalt-based Fischer-Tropsch reaction reforming catalyst carrier according to any one of claims 1 to 4, having a chloride content of less than 1500 ppmw.

6. The aforementioned refractory oxide is zirconia, ZrO ２ A cobalt-based Fischer-Tropsch reaction reforming catalyst support comprising the above, according to any one of claims 1 to 5.

7. The pore volume is 0.30 to 0.50 cm³. ３ A cobalt-based Fischer-Tropsch reaction reforming catalyst support according to any one of claims 1 to 6, wherein the amount is in the range of / g.

8. The cobalt-based Fischer-Tropsch reaction modified catalyst support according to any one of claims 1 to 7, wherein the average pore diameter is in the range of 40 to 60 nm.

9. 25-75m ２ A cobalt-based Fischer-Tropsch reaction reforming catalyst support according to any one of claims 1 to 8, having a BET surface area in the range of / g.

10. A catalyst precursor for a Fischer-Tropsch reaction, comprising cobalt oxide crystallites disposed within the pores of a cobalt-based Fischer-Tropsch reaction reforming catalyst support according to any one of claims 1 to 9.

11. The Fischer-Tropsch reaction catalyst precursor according to claim 10, wherein the cobalt oxide crystallites have an average particle size in the range of 6 to 18 nanometers (nm).

12. The Fischer-Tropsch reaction catalyst precursor according to claim 10 or claim 11, wherein the ratio of the average grain size to the average pore diameter of the cobalt oxide crystallites is in the range of 0.1:1 to 0.6:

1.

13. A catalyst precursor for the Fischer-Tropsch reaction according to any one of claims 10 to 12, having a cobalt content in the range of 5 to 25% by weight, expressed as Co on a lossless basis.

14. A catalyst precursor for the Fischer-Tropsch reaction according to any one of claims 10 to 13, comprising a total of 1 to 15% by weight of one or more additives selected from oxides of one or more additive metals selected from nickel (Ni), zinc (Zn), thorium (Th), magnesium (Mg), manganese (Mn), or silicon (Si).

15. A catalyst precursor for the Fischer-Tropsch reaction according to any one of claims 10 to 14, comprising a total of 0.01 to 1.00% by weight of one or more promoter metals selected from rhodium (Rh), iridium (Ir), ruthenium (Ru), rhenium (Re), platinum (Pt), and palladium (Pd).

16. A cobalt-based Fischer-Tropsch reaction catalyst comprising cobalt metal crystallites disposed within the pores of a reforming catalyst support according to any one of claims 1 to 9.

17. A method for preparing the modified catalyst support according to any one of claims 1 to 9, wherein the volume median diameter is in the range of 100 to 1000 μm and the support is 0.2 to 0.6 cm. ３ A method comprising the steps of: impregnating titania particles having a pore volume in the range of / g and an average pore diameter in the range of 30 to 60 nm with a solution of one or more metals selected from the group consisting of zirconium, lanthanum, cerium, yttrium, and neodymium; and drying and calcining the impregnated titania particles to form a refractory metal oxide modified titania carrier containing 1.5 to 8.5% by weight of a refractory oxide.

18. The method according to claim 17, wherein the step of forming the refractory metal oxide modified titania carrier is carried out in a moving bed reactor at a temperature in the range of 400 to 900°C.

19. A method for preparing a Fischer-Tropsch reaction catalyst precursor according to any one of claims 10 to 15, comprising the steps of impregnating the modified catalyst support with a cobalt compound and drying and calcining the impregnated modified catalyst support to form cobalt oxide crystallites in the pores of the modified catalyst support.

20. A combination of a catalyst carrier suitable for use in the reaction tube of a reactor, and a catalyst precursor for the Fischer-Tropsch reaction according to any one of claims 10 to 15 or a cobalt-based catalyst for the Fischer-Tropsch reaction according to claim 16, disposed within the catalyst carrier.

21. A combination of a channel of a microchannel reactor and a Fischer-Tropsch reaction catalyst precursor according to any one of claims 10 to 15 or a cobalt-based Fischer-Tropsch reaction catalyst according to claim 16, disposed within the channel of the microchannel reactor.

22. Use of a Fischer-Tropsch catalyst precursor according to any one of claims 10 to 15, a cobalt-based Fischer-Tropsch catalyst according to claim 16, or a combination according to claim 20 or 21 in a reactor for a process of producing hydrocarbons from synthesis gas containing hydrogen and carbon monoxide.

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