METHODS FOR PREPARATION AND FORMATION OF ACTIVE METAL SUPPORTED CATALYZERS AND PRECURSORS

专利摘要:
Methods of Preparation and Formation of Active Metal Supported Catalysts and Precursors The invention relates to a method of preparing a supported catalyst, the method of which comprises: (i) producing a porous catalyst support consisting of a base having a porous internal structure containing one or more pores, whose porous internal structure contains a precipitator; (ii) contacting the catalyst support with a colloidal solution or suspension consisting of a catalytically active metal such that, upon contact with the precipitator, particles containing the catalytically active metal are precipitated into the internal pore structure of the base of the catalyst. catalyst support. The invention also relates to supported catalysts made according to the above method, and to the use of catalysts in catalyzed chemical reactions, for example in the fischer-tropsch hydrocarbon synthesis.
公开号:BR112014009541B1
申请号:R112014009541-8
申请日:2012-10-22
公开日:2019-08-06
发明作者:Richard Hyman
申请人:Igtl Technology Ltd；
IPC主号:

专利说明:

“METHODS OF PREPARATION AND FORMATION OF ACTIVE METAL SUPPORTED CATALYSTS AND PRECURSORS”
FIELD OF THE INVENTION [0001] The current invention relates to methods of preparing and forming active metal supported catalysts and precursors, and especially (but not exclusively) to catalysts useful for carbon oxide hydrogenation processes. In particular, the invention relates to methods of preparing catalysts that contain functionalized porous support bases, as found, for example, in zeolites containing particles having catalytically encapsulated active metal, nano particles or agglomerates that can be partially or totally reduced. The aspects of the invention are related to methods of using the catalysts thus prepared, with specific application to the synthesis and / or conversion of various classes of hydrocarbons.
BACKGROUND OF THE INVENTION [0002] Heterogeneous catalysts are used in a large number of chemical and petrochemical processes. In many cases, the viability of the process depends on the successful combination of the activity of the catalyst and its selectivity and stability. A catalyst that has a high activity but has poor selectivity for the desired products may not be useful for implementing a chemical reaction on a commercial scale. In addition, a catalyst having good activity and good selectivity for the desired product, but showing poor stability, may not be suitable for industrial application. An optimal balance must be obtained between activity, selectivity and stability in order to consider the practical application of a catalyst.
[0003] The practical application of catalysts is also limited by the economy and scale of production of its preparation methods. Many catalysts are described in the scientific literature that show acceptable performance in terms of activity, selectivity and stability, but their methods of preparation are often impractical outside a chemical laboratory or simply not.
2/47 are economically viable in an industrial application.
[0004] Small particles of metal or metal oxide having diameters in the nanoscale range are often referred to as agglomerates. There is an important motivation for researching the catalytic properties of metal or metal oxide agglomerates because they are very different from the properties presented by larger particles. Often, unexpected catalytic effects are attributed to the action of clusters.
[0005] There is an advantage in supporting agglomerates containing catalytically active metal over zeolitic materials. Zeolitic materials are exclusive supports for metal agglomerates because the steric restrictions imposed by their cages and pores limit the size of the agglomerates that can be formed within them. The restrictions imposed by the openings (often called windows) between the cages and the pores limit the size of what can enter and exit the pores and cages. Thus, agglomerates can be formed from small precursors (for example, metal salts) in the cages and be retained therein.
[0006] Cages made of zeolitic materials are small enough to exert solvent-like effects on the agglomerates formed within them and therefore the cages may induce different catalytic properties in the agglomerates they contain. The confinement of agglomerates in cages of zeolitic material prevents interactions and aggregation of the agglomerates and therefore increases the stability of the agglomerate.
[0007] Catalysts supported on metal and metal oxide agglomerates can be prepared in many ways. US patent number 4,552,855 describes a method of preparation that is made to produce zero-valence metal agglomerates supported on zeolites. Metal deposition is done by vaporizing the metal in a high vacuum.
[0008] Alternative methods of producing supported metal agglomerate catalysts involve impregnating the support with carbonyl-metallic complex precursors. An example of such a method of preparation is described in the US
3/47
4,192,777.
[0009] US 5,194,244 describes compositions containing a zeolite and an alkali metal compound where the sum of the amount of alkali metal in the compound with any metal exchange cation in the zeolite is in excess of that required to produce a cation exchange zeolite totally metallic. As soon as the compounds are placed inside the zeolite, it is calcined to produce an elevated temperature to form a basic material that can be used as a basic catalyst or as an adsorbent. Haber et al, in Pure and Applied Chemistry, vol 67, Nos 8/9, pp 1257 - 1306, discusses precipitation by deposition as a method for the formation of supported catalysts (section 2.1, 2.2), in which an active metal is deposited on a vehicle in a precipitation solution, through the slow addition or in situ formation of a precipitation agent. It is noted that for a porous support, deposition occurs preferably on the external parts.
[0010] US 4,113,658 describes a deposition precipitation process for the preparation of materials containing finely divided particles of metallic materials deposited substantially homogeneously on a nucleation surface such as silica. This is done by preparing a suspension of the nucleation surface, and crystallizing the metallic compound on the surface at the nucleation sites of a solution containing the metallic compound.
[0011] EP 2,314,557 describes a catalyst for the production of minor olefins from the synthesis gas, using a catalyst in which iron has been deposited on a support that is chemically inert to iron, such as alumina.
[0012] Promoters are chemical species added to solid catalysts or in processes involving catalysts to improve their performance in a chemical reaction. By itself, a promoter has little or no catalytic effect. Some promoters interact with active components of catalysts and thus alter their chemical effect on the catalyzed substance. The interaction may cause changes in the electronic or crystal structures of the active solid component. Commonly used promoters are metal ions embedded in
4/47 metal or metal oxide catalysts, reducing and oxidizing gases or liquids, and acids and bases added during the reaction or in the catalysts before they are used.
[0013] Potassium is a well-known promoter of group VIII metal catalysts, commonly used in high temperature iron-based Fischer-Tropsch (HTFT) catalysts. Potassium, however, facilitates the sintering of group VIII metals and metal oxides. For example, US 6,653,357 describes the effect of potassium migration on the Fischer-Tropsch process. The deactivation due to the migration of the promoter is of particular relevance if the promoter is a poison for a secondary catalytic function in bifunctional catalysts, for example, in a hydrocarbon synthesis process using a hydrocarbon synthesis catalyst and an acid catalyst, as described , for example, in US 7,459,485. A high potassium load can also cause loss of activity due to the blockage of the pores of the support, and in some applications, it has been shown that the promotional effects deteriorate when the potassium loads exceed 2% by weight.
[0014] Another problem associated with the preparation of supported metal catalysts is the tendency for metals to aggregate or be sintered during use, or during any high temperature pretreatment that may be required for activation. Such aggregation or sintering reduces the effective catalyst surface area available for the catalyzed reaction, which reduces the activity of the catalyst.
[0015] It is desirable to produce a metal or metal oxide catalyst that has long-term stability, and to develop a method for the preparation of such a catalyst, which avoids problems such as sintering and also the migration of components of the active catalyst during synthesis or use that could lead to the deactivation of the catalyst.
SUMMARY OF THE INVENTION [0016] In accordance with a first aspect of the current invention, a method of preparing a supported catalyst is presented, the method of which consists of the
5/47 steps of:
(i) the production of a porous catalytic support consisting of a base having an internal pore structure, the internal pore structure of which contains a precipitator;
(ii) the contact of the catalytic support with a colloidal solution or suspension containing a catalytically active metal, such that when in contact with the precipitator, the particles containing the catalytically active metal are precipitated within the internal pore structure of the base of the catalytic support.
[0017] According to a second aspect of the current invention, a supported catalyst produced by the above method is presented.
[0018] According to a third aspect of the current invention, the use of the supported catalyst in a catalyzed process, such as a Fischer-Tropsch synthesis process, is presented.
DETAILED DESCRIPTION [0019] The internal pore structure of the base of the catalytic support can be loaded with the precipitator, during the synthesis of the catalytic support, for example, by incorporating a precipitator into the synthesis mixture of the catalytic support or gel. Alternatively, the precipitator can be loaded by means of further treatment of the catalytic support, for example, through a method of impregnation, using a solution containing the precipitator, as by impregnating incipient moisture. The result is a catalyst support in which the precipitator is placed within the internal pore structure of the base.
[0020] When the catalytic support comes into contact with a colloidal solution or suspension containing a catalytically active metal, the colloidal solution or suspension penetrates the internal pore structure of the catalyst support base, and when in contact with the precipitator, precipitation or formation of insoluble particles, whose particles contain the catalytically active metal. Such particles containing the catalytically active metal are referred to herein as agglomerates. Typically, such clusters have effective diameters of less than
6/47
5.0 nm, more preferably, less than 2.0 nm, for example, less than 1.3 nm. Typically, the maximum dimension or effective diameter of the agglomerate is defined by the internal pore structure of the catalytic support base. The catalytically active metal can be dissolved in a solution or it can be a constituent of a suspended colloid, or both.
[0021] The agglomerates formed in this way containing the catalytically active metal can be catalytically active on their own, or can be treated to form an active catalyst, for example, through chemical reduction, heat treatment or by adding additional components such as co - catalysts or catalyst promoters.
[0022] The pores of the catalytic support are advantageously made up of one or more regions or chambers where the diameter of the pores is changed from a smaller diameter to a larger diameter. Such regions or chambers are often referred to as cages. Preferably, these cages are accessible only from the outer surface of the catalytic support through pores of smaller diameter, such sections of smaller diameter, often referred to as windows. In such embodiments, the formation of the catalytically active metal agglomerates takes place advantageously inside the cages, in such a way that the agglomerates have larger effective diameters than the windows. This helps to prevent agglomerates from migrating out of cages during use or activation, which improves their retention within the pores of the porous catalytic support, and helps to reduce or prevent sintering. Desirably, sintering is avoided because the agglomeration of agglomerates into agglomerates or larger particles reduces the total surface area of the catalytically active metal available for the reactants, which reduces catalytic activity and therefore leads to catalyst deactivation.
[0023] The catalytic support can be crystalline or amorphous, with preference for crystalline supports due to its well-defined pore structure and generally greater stability. The catalytic support is preferably an inorganic support, and more preferably, an oxide support. Examples of oxide supports include silica, alumina, zirconia, titania, ceria, lanthanum oxide, and mixed oxides from
Ί / Α7 same, such as alumina-silica. Other examples of catalytic supports include those having extended phosphate structures, for example, aluminum-phosphates, gallium-phosphates, silico-aluminum-phosphates and silico-gallium-phosphates.
[0024] The catalytic support, preferably, is an oxide material having a zeotype structure, exemplified by zeolites. Many zeotype structures are known, and are described in the Atlas of Zeolite Structures published and maintained by the International Zeolite Association. The preferred structures are those having a porous network with two dimensions and three dimensions, with intersections in the cages having a larger diameter than that of the pores. Examples of zeotype structures having such a two-dimensional and three-dimensional pore configuration include CHA, FAU, BEA, MFI, MEL and MWW. Three-dimensional pore structures are more preferred, as this favors better diffusion of reagents and products when catalysts are used to catalyze chemical reactions.
[0025] For oxide materials, pore windows are often defined by the number of so-called T atoms that form the circumference of the opening of the pores or pores / cage. A T atom is an atom other than oxygen in the basic structure of the oxide support. For example, in an aluminum-silicate material, T atoms are aluminum and silicon, and in an aluminum-phosphate T atoms are aluminum and phosphorus. Preferably, in at least one dimension of the internal pore structure the pore windows are formed by a ring with at least ten T atoms, more preferably at least twelve T atoms. Preferred structures are FAU, BEA, MFI and MWW .
[0026] The catalyst supports that are constituted by a zeolite structure produce a high surface area for supports of agglomerates containing catalytically active metal and allow an organized dispersion of agglomerates of the same size and distribution throughout the entire pore structure of the support of the catalyst.
[0027] The structure of the catalyst support can be made of structures with loads. For example, the zeolytic structures of aluminum-silicate and silico-aluminum phosphate have a negative charge, which requires balance with an extra-structure cation. O
8/47 use of catalytic supports a negatively charged structure can be advantageous because the charge balance cation can be chosen to be one more component of the final active catalyst, for example, a co-catalyst or a catalyst promoter, which interacts with, or can form part of, the agglomerates that constitute the catalytically active metal.
[0028] Where the catalytic support contains a negatively charged structure, for example, aluminum-silicate materials, especially aluminum-silicate zeolites, the support structure advantageously has an intermediate or low relationship between silicon and aluminum. In this context, an intermediate or low molar ratio between silicon and aluminum means a ratio of less than 10 (i.e., a SiO2: Al2O3 ratio less than 20). Preferably, the silicon: aluminum molar ratio is in the range of approximately 2 to 5 (i.e., a SiC ^ AhCh ratio in the range of 4 to 10). In a specific embodiment of the invention, the Si: Al ratio is approximately 2.4 (i.e. a SiC ^ A ^ Os ratio of approximately 4.8). In alternative embodiments of the invention, the silicon: aluminum ratio in the zeolite is less than 2 (ie a SiO2: Al2O3 ratio less than 4), and in one embodiment the silicon: aluminum in the zeolite ratio is approximately 1.0 (ie, a SiC ^ A ^ Os ratio of approximately 2), such as zeolite X.
[0029] By providing a catalytic support with a low or intermediate silica content, the basic structure of the zeolite has an improved capacity for ion exchange with charge-balance cations. When the load balancing cations can act as co-catalysts or catalyst promoters, then an increased charge can be obtained from such co-catalysts or promoters.
[0030] The basic structures are microporous structures that contain a number of cages connected by windows. Preferably, the cages of the basic zeolite structure have the largest dimension that is larger than the diameter of a window that provides access to the cage.
[0031] The largest dimension of the cage of the basic zeolitic structure may be greater than 5 angstroms (0.5 nanometers). Preferably, the largest cage size of the basic zeolitic structure is greater than 10 angstroms (1 nanometer), and more than
9/47 preference, is approximately 13 angstroms (1.3 nanometers). In a preferred embodiment of the invention, the catalyst support is, or consists of a Faujasite zeolite, which may be a Y zeolite or X zeolite. In the Faujasite structure (FAU) the cages are accessible only through the windows whose maximum dimensions are smaller than the maximum dimensions of the cages. Another example of a desirable structure is the MWW structure, as found, for example, in the MCM-22 zeolite.
[0032] Preferably, the catalytic support has pores that contain cages and windows, for example, in zeotype or zeolitic structures, where agglomerates containing a catalytically active metal are formed in the cages up to a kinetic diameter that is greater than the diameter of the windows that provide access to the cage. By preparing agglomerates with maximum dimensions greater than the dimensions of the windows, the aggregation or sintering of the metal oxide agglomerates is reduced or avoided even if the catalyst is subjected to high reaction temperatures.
[0033] The diameter of the window that provides access to the cage, is typically greater than 2 angstroms (0.2 nanometers). Preferably, the largest window size of the basic zeolite structure is greater than 4 angstroms (0.4 nanometers), and most preferably, it is approximately 7.4 angstroms (0.74 nanometers). Preferably, agglomerates containing the catalytically active metal have a kinetic diameter that is greater than 2 angstroms (0.2 nanometers), preferably greater than 4 angstroms (0.4 nanometers), and more preferably, greater than than 7.4 angstroms (0.74 nanometers).
[0034] For catalytic applications where suspended or fluidized bed processes are used, the catalytic support should preferably be chosen from those with good resistance to friction. Zeolites, especially aluminum-silicate zeolites like zeolite Y, are beneficial in this regard.
[0035] The supported catalyst produced according to the method currently claimed can be used to catalyze chemical reactions. Having a high dispersion of agglomerates throughout the internal pore structure of the basic structure
10/47 of catalyst support, the surface area of the catalytically active metal exposed to the reagents is high, which benefits the number of uses of the catalyst and the conversion of the reagent. In addition, the encapsulation of the catalytically active metal agglomerates within the pores, prevents the migration of the agglomerates and sintering, which results in the formation of larger agglomerates with a smaller total surface area. This, in turn, reduces the deactivation of the catalyst and improves the life span of the catalyst. Encapsulation and reduced sintering are improved where the pore structure contains cages with increased diameter, as described above, such pore structures being exemplified by the zeotype structures. The preferred structures contain a two-dimensional or three-dimensional pore network intersecting the cages of increased diameter compared to the cage windows. A structure with porous intersection is advantageous, because an improved dispersion of the catalytically active metal in the colloidal solution or suspension is obtained through a more efficient diffusion through the pores. In addition, less blockage of the porous network will occur if there is any blockage of pores by the agglomerates during the synthesis of the supported catalyst, or if any sintering occurs during use.
[0036] The catalytically active metal is added to the catalytic support as a colloidal solution or suspension, which is diffused into the internal pore structure of the basic structure of the catalytic support. When a colloidal suspension containing the catalytically active metal in the suspended phase is used, the effective diameter of the suspended / colloidal phase particles must be sufficiently low to allow entry through the pore or window openings and into the porous internal structure. However, as the particles contained within a colloidal suspension will diffuse more slowly through a restricted network of pores, and would have a greater potential to cause the blocking of the porous structure compared to a completely dissolved catalytically active metal, a solution of the catalytically active metal.
[0037] Other components of the catalyst can also be added to the internal pore structure of the basic catalyst support structure so
11/47 similar, i.e., through a colloidal solution or suspension. They can be incorporated separately into the catalytically active metal or as part of the same colloidal solution or suspension.
[0038] Where the basic support structure of the catalyst is anionic in nature, for example in alumino-silicates and zeolites and alumino-silicate, the exchange of ions can be done to replace the charge balance cations, for example, cations at least one group I or group II metal. Such a process is often called ion exchange, and preferably, ion exchange constitutes supplying the replacement cation by exposing the basic zeolitic structure to a saline solution containing the replacement cation. The saline solution may be aqueous. Alternatively or additionally, the solvent may consist of an organic solvent, such as an alcohol. The cation is preferably a promoter or co-catalyst for the catalytically active metal, and in a preferred embodiment, it is chosen from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium. Preferably, the cation is supplied in the form of a saline solution, such as a carbonate, and more preferably, a bicarbonate solution. The use of carbonates and bicarbonates specifically has been found to cause less disruption to the basic catalyst support structure. In the case of aluminum silicas and aluminum silicate zeolites, for example, the use of carbonate and bicarbonate tends to reduce the de-illumination of the basic structure, which in turn would result in rupture in the basic structure, and the formation of extra-structure particles. alumina base that can block pores, and reduce the capacity of agglomerates that contain catalytically active metal. As a result of the disruption of the basic structure, the ability to reduce sintering is also negatively affected.
[0039] According to an embodiment of the current invention, the catalytic support consists of a basic anionic zeolitic structure, for example, an aluminosilicate zeolite. The method may consist of the performance of an ion exchange using known techniques to charge the basic structure with a cation, for example, a cation of a group I or group II metal. This exchange of
12/47 ions can be made more than once if necessary to ensure that the basic support structure has a complete exchange as possible with the cation. When the cation is a promoter or co-catalyst, this acts to increase the promoter charge, which can benefit the activity of the catalyst. In addition, by reducing or eliminating any protons such as the counterbalance cation in the basic structure, less neutralization of a basic precipitate occurs.
[0040] In another embodiment, a first exchange of ions is made in the support of the basic zeolitic structure to load the basic zeolitic structure with cations of one or more metals of group I or group II; and then a second ion exchange is performed. The second exchange of ions may increase the load of the cation promoter in the basic structure. The cation charged in the second ion exchange is preferably the same as the one charged in the first ion exchange, but may be a different cation. In a preferred embodiment of the invention, the method consists of performing the first, second and third ion exchanges on the basic zeolitic structure to increase the load of the preferred cations on the basic structure.
[0041] The ion exchange may consist of heating the ion exchange solution. The ion exchange may also consist of drying and calcining the ion exchange zeolite before adding or impregnating the catalytically active metal.
[0042] When the catalyst support contains a basic anionic structure, for example, in aluminosilicates and aluminosilicate zeolites, the extension of the exchange of ions by one or more charge equilibration cations of the basic structure, preferably is greater than 2% by weight. Preferably, the proportion of the balance cations of each gas in the basic structure is greater than 5% by weight, and more preferably, the proportion of charge balance cations in the basic structure is greater than 10% by weight. In a specific embodiment of the invention, the proportion of load balancing cations in the basic structure is greater than 12% by weight.
[0043] Incipient moisture impregnation is a way of incorporating catalytically active metals and promoters or co-catalyst metals into
13/47 of the internal pore structure of the basic catalyst support structure. The incipient moisture impregnation consists of the addition of a volume of solution containing dissolved compounds (for example, salts) of one or more metals that is equal to a calculated volume of pores of the internal pore structure of the catalyst support. The incipient moisture impregnation method may consist of heating a solution to improve the dissolution of metallic compounds (for example, salts) in the solution. Examples of metal-containing salts that are suitable are nitrates, sulfates, carbonates, citrates, halides, alkoxides, phenoxides, acetates, benzoates, oxalates, acetyl acetonates and carboxylates. Preferred anions of salts are those that have an effective diameter small enough to allow entry into the internal pore structure of the basic structure of the catalytic support. Preferred anions have at least an acidic character when the salt is dissolved in an aqueous solution which can then react effectively with a basic precipitant, such as an alkali metal carbonate or bicarbonate, to form an agglomerate containing the catalytically active metal. Nitrate is an especially preferred anion.
[0044] The method, typically consists of a single treatment of the catalytic support with a solution containing a catalytically active metal. Additional treatment can be done with the same or different metals, if necessary, although this is preferably done after washing the impregnated material initially, and adding more precipitant when necessary.
[0045] The technique can be considered as a deposition-precipitation method involving the precipitation of catalytically active species in a colloidal solution or suspension on a solid support in which the precipitant (which is within the internal pore structure of the catalytic support) is in the phase solid at the point of contact with the impregnation solution, or liquid. In a preferred embodiment, precipitation occurs through an acid / base reaction.
[0046] The identity of the solvent or liquid phase of the colloidal solution or suspension is not particularly limited. Its purpose is to facilitate the diffusion of the catalytically active metal through the internal pore structure of the catalytic support, and is
14/47 chosen according to its ability to ensure the dissolution of a compound containing the catalytically active metal, or to stabilize a colloid containing catalytically active metal, in such a way that colloidal particles with appropriate size are obtained. The solution or colloid may contain additional components, for example, one or more additional catalytically active metals, components of any co-catalyst or components of any promoters. Mixtures of liquids that act as the solvent or liquid phase can be used. Water is a convenient solvent, especially if the pH control of a solution containing the catalytically active metal is required to ensure efficient precipitation of agglomerates within the pores of the catalytic support. However, the use of other solvents / liquids and mixtures is not ruled out. For example, organic liquids, such as alcohols, ketones, aldehydes, esters and ethers of carboxylic acids, can be used individually or in combination with another liquid.
[0047] The precipitant within the internal pore structure of the basic catalyst support structure causes the catalytically active metal to precipitate from the colloid or suspension solution to form agglomerates containing the catalytically active metal. For example, the precipitant is not part of the basic support structure of the catalyst, nor is it merely a charge-balance cation of a negatively charged basic structure. Typically, the precipitant is a compound that can be incorporated into the internal porous structure of the basic catalyst support structure, for example, being included as a non-reactive component of a synthesis gel, or through being impregnated in the internal porous structure by techniques post-synthesis such as incipient moisture impregnation. The precipitant can be, can be constituted, or can be converted into another component of the final active catalyst, for example, it can function as a promoter or co-catalyst, optionally after further treatment, such as heat treatment or chemical reduction.
[0048] The precipitant is preferably included in the internal pore structure of the catalyst support with a load of 2% by weight or more, based on the weight to be
15/47 dry of the catalyst support, optionally with the exchanged ion. Most preferably, the charge is 5% by weight or greater, and even more preferably, 10% by weight or greater. The more precipitant that can be included in the supporting internal pore structure, the greater the potential catalytically active metal charge that can be achieved.
[0049] Before contact with a colloidal solution or suspension containing the catalytically active metal, the catalyst support with the precipitant is in dry form. Therefore, when the precipitant has been added to the catalyst support by a solution based impregnation method, then the solvent is removed before contact with the catalytically active metal occurs. This ensures that the internal pore structure of the catalytic support is free of any liquid phase that may prevent the penetration of the solution containing the catalytically active metal or the colloidal suspension into the internal pore structure, and helps to improve efficiency and quantity precipitation of agglomerates containing the catalytically active metal.
[0050] The precipitant can work through acid-base precipitation. In one example, the precipitant may be basic, such as a carbonate or alkali metal bicarbonate salt. When the colloidal solution or suspension containing the catalytically active metal (and optionally, additional components, such as another catalytically active metal, promoter and co-catalyst) comes in contact with the basic precipitant, insoluble agglomerates containing the catalytically active metal form, for example example, through precipitation of insoluble hydroxide or oxide species. Such precipitated agglomerates can be converted to metal agglomerates by a reduction process before being used as a catalyst, for example, by heating in a reducing atmosphere containing hydrogen gas.
[0051] When the precipitant causes the formation of agglomerates through acid-base precipitation, the pH of the impregnation solution containing the catalytically active metal can be controlled or adjusted in advance to optimize the duration and efficiency of precipitation within the internal pore structure . The pH
16/47 can be adjusted by known means, for example, by adding a hydroxide, carbonate or bicarbonate salt, to increase the pH of the colloidal solution or suspension containing the catalytically active metal, or by adding an acid suitable for reduce the pH. Merely as illustrative examples for an aqueous solution or colloidal suspension, a hydroxide solution such as sodium, potassium, or preferably ammonium hydroxide, could be used to increase the pH, while nitric or carbonic acid could be used to reduce the pH. In embodiments, the colloidal solution or suspension, before adding to the catalyst support, has a pH in the range of about 1 to 2, for example, a pH in the range of 1.1 to 1.7. Typically, after contact with the catalyst support containing the precipitant, the pH of the solution or liquid phase of a colloidal suspension will preferably increase to a value of 4 or more, more preferably 5 or more, for example, 6 or more. An additional means of controlling the pH of the resulting colloidal impregnation solution or suspension is to control the amount of basic precipitant added to the catalyst support, in such a way that a higher charge, as a result, will have a stronger effect to increase the pH resulting from the impregnation solution.
[0052] Another advantage of the precipitant having a basic character, and the pH of the resulting solution being 4 or more, is that it can reduce or neutralize any harmful effects of any acidity associated with the colloidal solution or suspension containing the catalytically active metal on the catalyst support. For example, in the case of aluminum-silicate zeolites, exposure of such zeolites to acidic solutions can be detrimental to crystallinity, resulting in the loss of the basic structure. A breakage can be caused by gutting some of the components of the basic structure, for example, aluminum can be gutted from the basic structure to form extra-basic alumina particles within the pore structure. This not only disrupts the pore structure, which can reduce inhibition of sintering, but can also potentially result in pore blockage, which also reduces the volume of the internal pore structure that is available to form the catalytically containing metal clusters.
17/47 active. Therefore, such a disruption has negative consequences to prevent sintering, migration and / or aggregation of active catalyst products, which in turn negatively impacts the surface area and the performance of the catalyst, including its activity, selectivity, and / or stability.
[0053] The use of a basic precipitant, itself also alleviates these effects, allowing the possibility of solutions of metallic salts with a greater acidity to be used in impregnation with catalytically active metal and other components. This has the added benefit that solutions with a higher concentration of metallic salts and / or colloidal suspensions can be used than previously considered, if desired, which improves the load of the respective metals on the catalyst support. When the catalyst support is of an anionic nature, ensuring that the anion sites are neutralized as much as possible with charge balance cations, such alkaline metal cations also help to alleviate any acidity effect of any impregnation solution or liquid, and also reduces the potential loss of precipitant activity through neutralization.
[0054] Therefore, in the method according to the present invention, although there is still a certain amount of disruption of the basic structure of the catalytic support during the preparation of the catalyst, the invention produces a better retention of the basic structure. This is especially advantageous in catalyst supports having basic porous crystalline structures, such as zeolites.
[0055] Optionally, any precipitant that may be present on the external surface of catalyst support particles is removed prior to contact with the colloidal solution or suspension containing the catalytically active metal, while preventing the removal of the precipitant from inside the porous structure for example, avoiding repeated washing. The removal of the external precipitant can help to reduce the tendency of metallic agglomerates to form on the external surface of the catalyst support particles during impregnation, facilitating the precipitation of agglomerates containing the catalytically active metal within the internal pore structure. However, a small
18/47 amount of basic precipitant on the surface can help to alleviate any potential damage from the acid impregnation solution on the outer surface of the basic catalyst support structure.
[0056] In the case of a catalyst support having a negatively charged basic structure, for example, an aluminum silicate zeolite, which is subjected to ion exchange treatment, the catalyst support can be washed after the ion exchange while the zeolite support is in a partially dry, damp or paste-like condition.
[0057] To illustrate the principles set out above, an example of the preparation of an iron catalyst promoted by supported potassium will now be described. To prepare such a catalyst, a zeolite having a basic anionic structure can be used to support the catalyst, such as an aluminosilicate zeolite, which is often supplied or prepared with sodium as the charge equilibrium cation. The anionic catalyst support can be completely exchanged with potassium through one or more impregnations with an aqueous solution of potassium salt, in such a way that the basic structure is fully balanced in potassium loading and an excess of potassium salt remains within the internal porous structure. A convenient source of potassium salt in such circumstances is potassium carbonate and / or potassium bicarbonate, because these salts are basic in character and tend not to cause significant damage or disruption of the basic structure of the catalytic support. Excess potassium carbonate or bicarbonate can then act as a precipitant. The potassium-loaded material can be gently washed or rinsed to remove traces on the surface of the potassium carbonate / bicarbonate precipitant from the external surfaces of the catalyst support, but not so much that the precipitate within the internal porous structure is significantly removed . A solution of a salt containing iron, for example, an aqueous solution of iron (III) nitrate, can then be added to the resulting potassium modified zeolite, which results in the precipitation of iron-containing agglomerates within the internal pore structure of the zeolite.
19/47 [0058] In some aspects and embodiments of the invention, the method may consist of the formation of a cation-free metal oxide agglomerate. A cation-free metal oxide agglomerate is an oxide material that lacks cations, where the potentially excess negative charge that results from the lack of cations is compensated by an increase in the oxidation state of other cations in the agglomerate having the ability to adopt multiple oxidation states, for example, transition metal or lanthanide ions. Alternatively, as described in greater detail below, the excess negative charge can be counterbalanced by a different cation, for example, a charge-balancing cation of the basic structure or a cation associated with the precipitant.
[0059] The agglomerate can be of crystalline structure. In one embodiment, the agglomerate containing the catalytically active metal is a perovisque structure of the general formula ABO3 or a spiral structure of the general formula AB2O4. The perovisque structure is a crystalline phase adopted by the compound CaTiO3, although Ca and Ti can be replaced by other elements, while maintaining the same type of structure. A spiral structure is based on the structure of MgAI ₂ O ₄ , where 0 Mg and 0 Al, likewise, can be replaced by other elements maintaining the same structure. Examples of catalysts that have a perovisky structure include those described in WO 2007/076257, which are useful for Fischer Tropsch reactions, and include catalysts containing the elements K, Fe, Cu and La. Examples of catalysts having a spiral structure, which are active in relation to Fischer Tropsch reactions, include those described in US 4,537,867, containing iron and cobalt as metals A and B respectively, of the formula Fe _x Co _y O ₄ (x + y = 3), which can also be promoted by alkali metal. According to the current invention, such perovisque or spiral structure metals can be made by adding a solution containing the catalytically active metal and any promoter and co-promoter (for example, an aqueous solution containing dissolved salts of Fe, Mn and / or Co, or an aqueous solution containing salts of Fe, Cu and La), and impregnating the support containing a K salt
20/47 as a precipitant, for example, in the form of a basic potassium salt, such as potassium carbonate or bicarbonate, in an aluminum-silicate zeolite with total potassium exchange, optionally washing or rinsing with water, followed by drying the impregnated material to remove any water, and the calcination of the dry material at a high temperature, for example, a temperature in the range of 500 ° C to 630 ° C in an oxygen-containing atmosphere, which can result in the formation of perovisque or spiral material crystalline in the internal pore structure of the basic catalyst support structure. Spiral perovisque materials can be made with a lack of cations or cation deficiencies. Because of the small size of the clusters, and because the clusters are formed from soluble precursors, then the temperatures required to produce any of these crystalline phases are typically lower than in the methods of producing bulky crystalline structure, which often use materials of insoluble oxide separated as the starting materials.
[0060] Different types and structures of metal oxide agglomerates can be produced using the method of the current invention. The overall resulting structure will depend not only on the identity of the metals themselves, but also on their relative proportions and their positive charges. Therefore, an appropriate selection of metals and their relative amounts can be used to target the structure of the resulting metal oxide agglomerate.
[0061] It is hypothesized that a cluster containing metal lacking cations (sometimes referred to as cation deficient or deficient metal) will have an electrostatic interaction with cations associated with a negatively charged basic structure, and that this electrostatic interaction can help to alleviate or prevent the migration of the load balancing cations in the agglomerates, and additionally alleviate or prevent sintering or aggregation of the agglomerates, especially in window '7Cage structures, such as those presented by zeotype structures, such as in zeolites. Migration and / or sintering and aggregation are generally detrimental to the performance of the catalyst. Avoiding the migration of the catalyst cation compensation charge, and when the cation charge of
21/47 compensation acts as a promoter or as a co-catalyst, agglomerates containing the catalytically active metal can be formed with higher charges of co-catalyst / promoter, which increases any promotion or cocatalyst effect. This is different from the prior art, which teaches that an overload of the promoter is detrimental to the performance of the active metal particle, where the excess promoter migrates from the catalyst support resulting in loss of activity, and which can also affect other components that may be present in combination with the supported catalyst, for example, a second catalyst in a dual-function catalyst or bifunctional catalyst system.
[0062] After being contacted with the colloidal solution or suspension containing the catalytically active metal, the catalytic support can be dried, for example, in air in a conventional drying oven. Alternatively, drying can be carried out by microwave. In other embodiments, drying may be carried out by freeze drying in an oxidizing or neutral atmosphere. Any of these drying methods can be performed under vacuum. [0063] After the formation of the catalytically active metal agglomerates, the resulting material can be calcined in a neutral or oxidizing atmosphere, and may also consist of purging gaseous oxides. Before calcination or other subsequent treatment such as drying or reduction, the catalytic support can be washed to remove excess liquid from the external surface of the catalytic support. An intense washing at this stage is advantageous, because the catalyst or precipitated catalytically active metal is retained within the internal porous structure of the basic catalyst support structure, and therefore will not be removed in large quantities by washing, allowing any impurities or material not to be removed. reacted are removed without any significant detrimental effect on the load of agglomerates containing the precipitated catalytically active metal.
[0064] Previous methods for preparing agglomerates containing encapsulated catalytically active metal tend not to be easy to perform on a large scale. The current method provides an economical method for the large-scale commercial manufacture of oxide catalyst particles
22/47 metallic and metal encapsulated supported, thermally stable.
[0065] Supported catalysts made according to the process of the current invention can find utility in catalyzing chemical reactions.
[0066] For example, catalysts can be used to catalyze steam reforming or water-gas exchange reactions. In the steam reform, water is contacted with a hydrocarbon material or other organic product to produce singas. The water-gas exchange reaction converts carbon monoxide into carbon dioxide and hydrogen in the presence of water. Metal oxide agglomerates, such as spiral or perovisque structures can be used as catalysts for such reactions, without the need for prior reduction of catalysts to form metal agglomerates.
[0067] The Fischer Tropsch (FT) process is another example of a reaction that can be catalyzed by catalysts made according to the method of the current invention. The FT process can be used to convert singas (a mixture of carbon monoxide, hydrogen and typically also carbon dioxide) into liquid hydrocarbons. Singas can be produced through processes such as partial oxidation or steam reforming of raw materials, such as mass, natural gas, charcoal or solid organic or tailings containing carbon and or scrap. The FT process products can be adapted by changing the reaction conditions of the catalyst components, for example, to modify the paraffin / olefin ratio of hydrocarbons, and to increase or reduce the extent of oxygenated products, such as alcohols, ketones and aldehydes, which could be produced. In FT reactions, agglomerates containing catalytically active metal will typically be reduced chemically before use, for example, by high temperature treatment with hydrogen gas.
[0068] Generally, there are two types of Fischer Tropsch process, namely a high temperature process (HTFT) and a low temperature process (LTFT). Catalytically active metals, often used in FT catalysts, include those chosen from the group consisting of nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, rhenium, molybdenum, chromium, tungsten,
23/47 vanadium, rhodium, manganese and combinations thereof. This group of metals is referred to herein as group A. The catalytically active metal or at least one of the catalytically active metals is preferably chosen from iron and cobalt.
[0069] FT catalysts may also consist of an alkali metal or alkaline earth metals, preferably from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium. Alkali metal and alkaline earth metal promoters can be used as the only type of promoter, or in combination with other promoters. A preferred promoter in this category is potassium.
[0070] Examples of other promoters that can be used in a Fischer Tropsch catalyst include metals chosen from the group consisting of yttrium, lanthanum, cerium, any other lanthanide metal, and combinations thereof. This group of metals is referred to herein as group B. Such promoters can be used as the only type of promoter or in combination with other promoters. A preferred promoter in this group is chosen from one or more of the lanthanum and cerium.
[0071] Other examples of promoters that can be used include metals chosen from the group consisting of copper, zinc, gallium, zirconium, palladium and combinations thereof. This group of metals is referred to herein as group C. Such promoters can be used as the only type of promoter or in combination with other promoters. A preferred promoter in this group is copper.
[0072] Fischer Tropsch gas phase processes are typically classified as high temperature (HTFT) and low temperature (LTFT) processes. HTFT processes are typically catalyzed using an iron-containing catalyst, operating at temperatures in the range of 300 to 400 ° C, and pressures in the range of 10 to 25 bara (1.0 to 2.5 MPa). LTFT processes are typically catalyzed using catalysts containing cobalt, and can operate at temperatures in the range 150 - 240 ° C, and pressures from 10 - 25 bar (1.0 to 2.5 MPa). LTFT gas phase processes typically favor the formation of longer chain hydrocarbons. However, catalysts prepared according to the method of the current invention can be stable at higher temperatures.
24/47 high, and therefore the method provides flexibility in the range of processing conditions that can be tolerated by the resulting catalysts, which allows the temperature in the reaction zone of the catalyzed reactions to be controlled.
[0073] One or more catalytically active metals may be the only metal in the agglomerates formed by the method of the current invention. Alternatively, the agglomerates may consist of one or more metals from catalysts, cocatalysts and promoters. For a catalyst supported for an FT process, the catalytically active metal can be chosen, preferably, from group A or a combination thereof. Preferably, at least one of the catalyst metals is iron for an HTFT process, and at least one is cobalt for an LTFT process. Preferably, in addition, one or more of the metals chosen from alkaline or alkaline earth metals, group B metals and group C metals are preferably present. Preferably, at least one alkali metal is present, and preferably it is potassium.
[0074] In one embodiment, the method of the invention consists of:
the production of a catalytic support consisting of a basic structure of zeolite, the basic structure of zeolite containing charge-equilibrating cations of at least one group I or group II metal or combinations thereof;
the production of a metal salt solution consisting of: a metal salt chosen from group A above and combinations thereof; a second salt of a metal chosen from group B above and combinations thereof; and a third salt of a metal C chosen from group C above and combinations thereof; the impregnation of the basic structure of zeolite with the metal salt solution through an incipient moisture impregnation method; and calcination of the impregnated zeolite basic structure support to form the mixed metal oxide agglomerates in the zeolite basic structure support, the mixed metal oxide agglomerates having the formula A _x ByC _z O _n , where x, y, and z are respectively the relative proportions of metals A, B, and C, in the oxide,
25/47 where x + y + z is an integer, and where n is the relative proportion of oxygen that makes the charge of an oxide neutral.
[0075] In this realization, the formed agglomerate consists of a catalytically active metal of group A, and other metals of groups B and C, in addition to the metal of group I or II, in the form of oxide. The zeolite, in this embodiment, is preferably an aluminum-silicate zeolite.
[0076] The agglomerates thus formed may or may contain charge-impregnated metal hydroxides or oxides. Therefore, the method can consist of reducing and / or carburizing the agglomerates to activate the catalyst before the reaction starts, through the formation of metal or carbide species.
[0077] Under reaction conditions, agglomerates containing the catalytically active metal may have multiple oxidation states, depending on the conditions and the amount of oxygen in the reactants and products in the reaction. For example, in FT reactions, the presence of carbon monoxide and carbon dioxide provides a source of oxygen for the reaction, which can end up in products in the form of oxygenated compounds, such as alcohols, ketones, aldehydes and carboxylic acids. They can also produce an oxygen source that can cause oxidation or partial oxidation of the catalyst components. Therefore, during a reaction, such as an FT reaction, the agglomerates may be oxidized or partially oxidized, partially or totally reduced to the metallic state, and / or in a carbide or partial carbide phase.
[0078] The supported catalyst prepared according to the process of the current invention can be combined with other catalysts, for example, to form bi-functional or multifunctional catalysts.
[0079] For example, optionally the supported catalyst produced by the method of the current invention can be combined with an acid catalyst in a single reaction zone. Using the supported catalyst in combination with an acid catalyst, the products formed on the supported catalyst are
26/47 additionally purified in products with higher commercial value. For example, by adding an acid catalyst to an FT catalyst, the extent of olefin oligomerization can be increased, which can increase yields of useful liquid hydrocarbons having hydrocarbon chain lengths in a range suitable for use as diesel fuels.
[0080] An advantage of the method of the current invention is that, by reducing the migration of catalyst components, for example, catalytically active metals, promoters, co-catalysts and charge-balance cations, the migration of such cations is then inhibited out of the internal porous structure of the catalytic support, which prevents them from coming into contact with other components, for example, an additional acid catalyst, which reduces or eliminates deactivation through neutralization or other processes. Therefore, even when supported catalysts are used, for example, those consisting of zeolites with large amounts of alkaline or alkaline earth cations, deactivation of an acid catalyst component of a bifunctional catalyst is reduced or even eliminated through migration. of these cations.
[0081] In one embodiment, such a bifunctional catalyst is for use in carbon oxide hydrogenation processes, and consists of a supported FT catalyst prepared according to the method described above, and an acid catalyst. The acid catalyst may be a solid chosen from the group consisting of acid zeolite, silica-alumina, sulturated oxide, acid resins, solid phosphoric acid, acid clays, or a combination thereof. An example of such an acid catalyst is H-ZSM-5 zeolite.
[0082] The acid component may have activity in relation to reactions, such as cracking of hydrocarbons, oligomerization, cyclization and isomerization, and dehydration of oxygenates.
[0083] The supported catalyst may be or may contain a basic structure of zeolite as a catalytic support, which in turn may consist of at least one group I or group II metal charge neutralization cation, for example, potassium, as described above, and agglomerates consisting of a
27/47 catalytically active metal, such as iron.
[0084] In such an embodiment, a functional component of a bifunctional catalyst (the FT synthesis component) can be promoted by a basic cation, while avoiding any negative effects of such a basic cation on a functional component separate from the bifunctional catalyst (the acid component).
[0085] Therefore, a catalyst prepared according to the method of the current invention, can be used in a bifunctional catalyst, for example, one that is effective in hydrocarbon production reactions (for example, FT processes)) using the supported catalyst containing catalytically active metal agglomerates in combination with an acid catalyst, for example, which can isomerize hydrocarbons to produce hydrocarbons with a high octane number in the boiling range of gasoline.
[0086] A bifunctional catalyst can consist of different catalytic components linked in one body, for example, in particles, pellets, extrudates or granules. Alternatively, the bifunctional catalyst may consist of separate, unattached bodies of different catalytic components that are physically mixed, for example, essentially randomly distributed or layered within a catalytic bed.
[0087] The supported catalysts formed by the process of the current invention can be used in hydrogenation reactions of carbon monoxide / carbon dioxide.
[0088] For example, a gaseous raw material consisting of hydrogen and at least carbon monoxide and carbon dioxide can be fed into a reaction chamber containing the supported catalyst, such that in the presence of the supported catalyst (optionally after having been chemically reduced before the reaction), the carbon monoxide and / or carbon dioxide are hydrogenated to produce hydrocarbon products that can be removed from the reactor.
[0089] Hydrocarbon products may consist of saturated, unsaturated, oxygenated, non-oxygenated, aromatic, linear, branched or cyclic hydrocarbons. In one embodiment the hydrocarbon products
Preferred 28/47 are oxygenated hydrocarbons, among which alcohols are most desirable. In another embodiment, branched and / or linear non-oxygenated hydrocarbons in the C4 - C9 range, such as the C6 - C9 range, are the preferred hydrocarbon products. In yet another embodiment, linear non-oxygenated hydrocarbons in the C10 - C23 range, such as the C16 - C20 range, are the preferred hydrocarbon products. Selectivity for the desired products can be controlled by various means, for example, by controlling the reaction temperature and pressure, the relative concentrations or partial pressures of the reagents and the catalyst components, and by adding or recycling various components to the reactor. The processes of hydrogenation of carbon monoxide and carbon dioxide are well known in the art. In one embodiment, a second set of hydrocarbon products can be produced by reacting all or a portion of the reactor products with a different catalyst, or with a component of a bifunctional catalyst, for example, through a reaction of reform to produce higher octane gasoline components. The second set of hydrocarbon products may be C4 ⁺ hydrocarbons, saturated or unsaturated in gasoline, kerosene, diesel or in the boiling point range of lubricants, or combinations thereof.
[0090] The reform of the first set of hydrocarbon products, or a portion thereof, may consist of any process that converts low octane hydrocarbon products into products with higher octane rates, including, but not limited to oligomerization , isomerization, aromatization, hydrocracking, alkylation reactions, or combinations thereof.
Brief description of the drawings [0091] Various embodiments of the invention will now be described, by way of examples only, with reference to the drawings in which:
Figure 1A is a schematic representation of the structure of zeolite Y;
Figure 1B is a schematic representation of the MC-22 zeolite structure;
Figure 2 is a schematic representation of a catalyst according to
29/47 with one embodiment of the invention;
Figure 3 is a block diagram showing schematically a general method of preparing a catalyst according to an embodiment of the invention;
Figure 4 is a schematic representation of a bifunctional catalyst granule according to an embodiment of the invention;
Figure 5 is a schematic representation of a reaction scheme in which the catalysts according to the embodiments of the invention can be used;
Figure 6 is a schematic representation of an experimental set used in testing the catalysts of the invention;
Figure 7 is a graph showing the conversion and selectivity of a catalyst according to an embodiment of the invention, tested in a CO hydrogenation application; and
Figure 8 is a graph showing the conversion and selectivity of a catalyst according to an alternative embodiment of the invention, tested in a CO hydrogenation application.
Detailed description of the realizations of the invention [0092] The current invention can be illustrated by the production of a catalyst for use in the production or preparation of hydrocarbons, and will be described with reference to the non-limiting examples in applications related to the hydrogen monoxide hydrogenation reactions and carbon dioxide to form useful hydrocarbons. The invention has a broader application and the principles of the invention will be demonstrated by reference to the related theory and the application of the theory by the inventors.
[0093] The basic zeolitic support structures can be used as the catalyst support for catalysts with active metal agglomerates. Figure 1A shows a schematic representation of a basic structure unit of the zeolite Y, generally indicated as 10. The zeolite Y adopts the faujasite zeolitic structure (FAU) according to the nomenclature of the International Zeolite Association Structure commission. Zeolite X is another example of a zeolitic structure of
30/47 faujasita, different in its chemical composition from zeolite Y, especially its lower molar ratio between silicon and aluminum.
[0094] Faejasite structure zeolites are suitable supports for the catalytic compositions described here, because they have voids or cages 12 in the crystalline structure of a zeolitic material with dimensions on the order of some angstroms up to one or two nanometers. These empty spaces or cages are accessed through the openings or windows 14, which typically have maximum dimensions smaller than the maximum dimensions of the empty space that they involve. The empty spaces can be referred to as nano-cages or super-cages, depending on their position on the truss and their dimensions. In the case of a faujasite zeolitic structure corresponding to the zeolite Y shown in figure 1A, the empty space of the super-cage has a maximum dimension of 1.3 nanometers. The openings offer access to the empty space of the super-cage have a maximum dimension of 0.74 nanometers and are formed by rings with twelve members. The empty space of the super-cage in a faujasite zeolitic structure is also surrounded by ten smaller sodalite cages, which are connected through hexagonal prisms.
[0095] A zeolite with faujasite structure is suitable for the production of catalytic compositions according to the method of the current invention because they can be formed in the agglomerated empty spaces with maximum dimensions greater than the dimensions of the zeolite openings. In this way, the aggregation or sintering of the agglomerates containing the catalytically active metal is reduced because the agglomerates are encapsulated in the support super-cages and thus avoid contact with neighboring agglomerates.
[0096] Figure 1B shows a structural unit of an MCM-22 zeolite (Mobil composition of material number 22), generally indicated as 20, which adopts the basic MWW structure according to the International Zeolite Association Structure. The MCM-22 zeolite has 22 super-cages as defined by its crystalline structure and which has an empty space with a maximum dimension of 1.82 nanometers and a minimum width of 0.71 nanometers. The empty space of the super
31/47 MCM-22 zeolite cage is accessed through openings 24 whose maximum dimensions are smaller than the dimensions of the empty space of the super cage. As with faujasite zeolites, it is possible to form metal oxide clusters in the empty spaces of the MCM-22 zeolite to alleviate or prevent the aggregation or sintering of metal oxide clusters.
[0097] Figure 2 schematically shows a structural unit of a catalyst according to an embodiment of the invention, generally indicated as 30. The catalytic unit shown in figure 2 is supported on a basic structure 32 of the zeolite Y that has been subjected to the exchange of ions with the 34 cations of Group I or Group II, which in this case are potassium cations. Potassium cations are cations of the basic extra-structure and are connected in the exchange positions (negative charges) of the zeolite Y lattice. The potassium cations are placed on and are connected in the basic structure that surrounds the empty spaces of the zeolite cages Y. Potassium ions and other group I and II ions are known to have a promoting effect on catalytic function in hydrocarbon production processes such as Fischer-Tropsch processes, and especially, potassium reduces methane selectivity , increases the probability of chain growth and the olefinic character of the products in a Fischer-Tropsch process. The inventor recognized that it is desirable for promotion cations to be placed in the basic structure to provide an excess beyond the ion exchange capacity, and therefore are fully exchanged at ion exchange sites. Excess potassium that does not function as a charge balance cation is present as a separate or compound salt within the internal porous structure. In this embodiment, the total potassium load in the zeolite Y is greater than 14% by weight, and preferably, it is greater than 15% by weight, and even more preferably, it is greater than 20% by weight. If the precipitant used is potassium carbonate or potassium bicarbonate, then the charge of such potassium carbonate or bicarbonate in the exchanged potassium zeolite is preferably 5% by weight or greater, more preferably 10% by weight or greater, based on the dry weight of the zeolite catalytic support with exchanged ions.
32/47 [0098] In the empty spaces of the zeolite Y cages, agglomerates of active metal oxide 36 (ie, active in the catalysis reactions for which the catalyst is intended) are formed by the impregnation of a solution of metallic salt for inside the empty space. The metal salt precipitates in the empty space, and after calcination, it forms a metallic oxide. Metal oxide is formed to have a kinetic diameter that is larger than the maximum dimension of the openings that provide access to the zeolite Y cages. This reduces the probability of movement of the agglomerates and therefore reduces the aggregation or sintering of neighboring agglomerates.
[0099] Specific combinations of metals can form a cluster of mixed metal oxide that are deficient in cations. In one embodiment, these mixed metal oxide agglomerates have a perovisque or spiral structure. Without being limited by theory, it is believed that the formation of such a metal oxide agglomerate that is deficient or has no cations, can improve stability against migration and sintering. A metal oxide agglomerate without cations is one that has cation voids in the structure or lattice. A cation-deficient cluster can be combined with, or accept charge-balance cations, such as potassium promoter ions, (which are associated with the basic structure of zeolite).
[00100] Without wishing to be limited by theory, the inventors believe that this combination causes an electrostatic interaction between the cations of the basic extrastructure (in this case, potassium promoter charge balance cations) and the cation-free metal oxide agglomerate. This interaction can further help to reduce the migration of cations from the promoter. In catalysts prepared by previously known methods, migration of the atoms of the Group I and Group II promoter is a common cause of the deactivation of the catalyst promoted by alkali. By restricting or preventing migration, deactivation is reduced and the stability of the catalyst is increased. In addition, the proportion of promoter cations that can be included in the catalyst can be increased. In the past it has been seen that there is an upper limit on the amount of
33/47 promoter cations that can be incorporated in the active metal catalyst, due to the effects observed on the catalyst stability and deactivation when the promoter cation is migrated. In a different way, the hypothesis is formulated that in the preparation method of the current invention, the combination of a high cation promoter load and cation-free agglomerates can result in a stable basic structure and restricted cation migration.
[00101] The preferred support structures are those zeolites with intermediate or relatively low silica content, because these will tend to have a greater number of negatively charged places in the basic structure where cation promoters can be incorporated, and can therefore allow a higher degree of load of cation promoters.
[00102] A mixed metal oxide agglomerate can have the formula A _x ByC _z O _n , where x, y, and z are respectively proportions of metals A, B, and C, in the oxide. The sum of x, y, z is an integer, and n is the relative proportion of oxygen that makes the oxide charge neutral.
[00103] Metal A is a catalytically active metal, chosen from the group consisting of nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, manganese and combinations thereof. Iron is used in many applications, including Fischer-Tropsch processes, and in a preferred embodiment, metal A is iron or cobalt.
[00104] Metal B is chosen from the group consisting of yttrium, lanthanum, cerium, or any lanthanide metal, and combinations thereof. It is believed that the presence of a metal B (again without being limited by theory) lends a cation-free character to the agglomerate, which can improve the stability not only of the agglomerate but also of the basic structure. In addition, metal B can also lend improved hydrogen absorption characteristics to the supported catalyst.
[00105] Metal C is chosen from the group consisting of copper, zinc, gallium, zirconium, palladium and combinations thereof. Without being limited by theory, it is believed that the presence of metal C, especially Cu, has a positive effect of
34/47 promotion on metal A, in addition to reducing the temperature of reduction of mixed metal oxide clusters to form metal clusters. In a preferred embodiment, metal C is copper.
[00106] Figure 3 is a schematic block diagram representing a general method of preparing a catalyst according to the embodiments of the invention, generally indicated as 40. The following steps are taken to prepare a catalyst according to the invention current.
[00107] For an aluminum-silicate zeolite catalyst, the support material is typically supplied prepared with sodium charge balance cations; ie, the negative charge equilibrium cations and the basic support structure are sodium (Na ⁺ ). The positions of the load balancing cations in the basic zeolite structures are well defined, and the number of cations that can be exchanged depends on the relationship between silica and alumina of the support material. It is advantageous, but it is not essential that support materials with low silica to alumina ratios are used, as they offer a greater capacity for exchange cations. In preferred embodiments, zeolite Y or zeolite X are the support materials used.
[00108] If it is desired to replace the charge-balanced sodium ions with a different cation, an ion exchange 41 of the zeotype 51 support material can be used. This is the process in which the cations present in a zeotype material are exchanged for other cations. This process can be carried out by various methods known in the art. The most common is ion exchange in solution, where a diluted solution 52 of one or more salts, including the cations to be exchanged, is stirred, and the support material is added to the solution. During ion exchange, cations in solution progressively replace cations ionically bonded to the basic support structure, and the resulting solution 53 from the ion exchange process is discarded.
[00109] The solution can be heated to increase the speed at which the exchange takes place. To obtain the desired ion exchange levels in the current invention, it may be necessary to carry out more than one ion exchange process,
35/47 because the complete exchange may not be obtained in one step.
[00110] The ion exchange capacity of a specific zeotype material can be calculated if the relationship between silica and alumina is known, and it is possible to determine the content of a metal in a zeotype material and to compare the content of a material in a zeotype material with the calculated exchange capacity. This indicates whether a complete exchange was obtained, or whether more or less metal was retained than the maximum exchange capacity in the zeotype material.
[00111] In the example embodiments of the invention, the ion exchange was carried out using the Na-Y zeolite and potassium carbonate or bicarbonate as the source of charge balance, as well as the precipitant as the support material. After each ion exchange step, the resulting material was washed with water. The final step of ion exchange can result in the material containing the excess of potassium carbonate or bicarbonate in the pore structure of the zeolite that functions as a precipitant. In this case, a final washing step can be performed which aims to partially remove the solution of carbonate or potassium bicarbonate salt that remains on the outer surface of the material, but not the excess salt solution on the inner part of the support pores . Alternatively, after the final ion exchange step, the ion exchange zeolite material can be washed thoroughly after the ion exchange is completed, and subsequently dried, before the resulting material is subsequently treated with the excess solution. of potassium carbonate or bicarbonate, for example, by impregnating incipient moisture using a solution of potassium carbonate or bicarbonate, to add charge to the zeolite with the precipitate of potassium carbonate or bicarbonate. At this point, a mild wash / rinse can be performed to remove excess potassium carbonate or bicarbonate from the outer surface, to prevent precipitation of catalytically active metal agglomerates on the outer surface. Alternatively, such washing can be avoided, which can help to protect the outer surface of the catalytic support from damage by means of an acidic solution containing the catalytically active metal. It is advantageous to use an incipient moisture impregnation
36/47 final precipitant, because the use of a precipitant solution with known concentration, and with the knowledge of the pore volume of the catalyst support, a known amount of precipitant can be added within the internal pores of the support, which can help control the final charge of agglomerates containing the catalytically active metal.
[00112] After the washing step, the resulting material is dried to remove excess moisture. Drying can be performed by any of the conventional drying methods known in the art, for example, the material can be dried in a furnace at 100 to 120 ° C overnight.
[00113] After the material has been dried, a colloidal solution or suspension containing catalytically active metal A can be prepared, using, for example, an incipient moisture impregnation method. The incipient moisture impregnation technique involves the production of a colloidal solution or suspension containing the catalytically active metal, for example, in the form of one or more dissolved salts, which must be incorporated into the catalyst support material. The volume of liquid (colloidal solution or suspension) to be mixed with the support is close to or slightly greater than the pore volume of the support used, so that substantially all of the liquid enters the pores of the support. The amount of salt used to produce the colloidal solution or suspension will determine the final metal charge of the catalyst. Typically, the catalytically active metal (and any other metal, such as promoters or co-catalysts) are impregnated on the support using an aqueous solution. Example embodiments of the invention use double deionized water as the solvent for salts, such as iron, cerium and copper salts, in the incipient wet impregnation method. However, the invention applies to the use of other metallic salts and solvents.
[00114] During the incipient moisture impregnation 42a, the solution containing the catalytically active metal 54, may be an acidic solution, for example, it may contain a nitrate salt that is acidic. The solution penetrates the pores of the support, where a precipitant such as a Group I or Group II metal carbonate or bicarbonate salt is present. At this time, the pH of the solution increases due to the presence
37/47 of the basic precipitant, to the point where the catalytically active metal precipitate 42b precipitates, for example, in the form of an oxide or hydroxide. This increase in pH causes the effective and uniform precipitation of the precursor salts that contain the catalytically active metal within the pores and cages of the support to form agglomerates containing the catalytically active metal. The method, therefore, is a method of precipitation by deposition by means of incipient wet impregnation. The resulting material can be washed at this stage to remove excess potassium nitrate ions from the base structure and the outer surface.
[00115] Before impregnation, the pH of the solution containing the catalytically active metal can be adjusted to make it more basic, even just below the pH of the precipitation point, to maximize the extent of precipitation within the pores internal and also to reduce the negative effects of acidity, which can attack the basic structure of the zeolite. PH control can also help to improve the extent of precipitation by the precipitant.
[00116] After impregnation step 43, the material is dried. The suspension can be dried in a furnace or it can be dried by another conventional method. Water 55 is removed from the material.
[00117] When the material has been dried, the material is calcined 44. This calcination step is a heat treatment in air 56 that removes the anions from the salt used in the impregnation treatment and produces the metal oxides that act as an active catalytic species. For example, nitrate salts are decomposed to form metal oxides and volatile nitrogen compounds 57. Metal oxides formed during calcination are located predominantly in the cages of the zeolitic material, where the nitrogen compounds, if not removed from the material during washing, leave the support like a gas. In previous methods, where the catalytically active metal was added to a catalytic support (for example, a zeolite) as a charge-balance cation, the calcination procedure can partially affect the basic structure of the crystalline zeotype by partially transforming it into a material amorphous. Excessive aggregation of the oxide agglomerates can also produce damage
38/47 structural in the basic zeotype structure of the material. However, in the current realization, it is believed that due to the precipitant, a stabilizing effect is produced, so that the metal oxides are not aggregated during calcination (or during its subsequent use). In this way, damage to the basic structure of the zeotype can be limited, and the active metal oxide agglomerates are conserved, and a stabilized mixed oxide agglomerate precursor catalyst is produced 58.
[00118] The catalyst can be used in fixed bed reactors, fluidized bed reactors or suspended reactors. To be used in fixed bed reactors, it is beneficial to combine the catalyst with a binder or binders, and to form particles or granules of adequate size to prevent excessive pressure drop through the reactor, to improve structural integrity and resistance to catalyst friction. Suitable binders include kaolin clay, titanium dioxide, calcium oxide, barium oxide, silica, alumina, mixtures thereof and other binders known in the art. Catalysts prepared according to the current invention tend to have a high resistance to friction, even without the binder, which is advantageous in fixed bed, fluidized bed and suspension processes.
[00119] The catalyst can be used in hydrocarbon production processes, such as the Fischer-Tropsch process, in carbon dioxide absorption processes, to reduce carbon dioxide emissions and produce valuable hydrocarbons, and other conversion processes hydrocarbons, such as the dehydrogenation of ethyl benzene or the hydroisomerization of hydrocarbons. Catalysts made according to the current invention can also be used in conversions that do not involve the synthesis or conversion of hydrocarbons, for example, the production of ammonia from nitrogen and hydrogen, or the synthesis of methanol from singles.
[00120] The principles of the invention cause them to produce bifunctional catalysts, based on one or more embodiments of the invention. Figure 4 shows a bifunctional catalyst, usually indicated as 60, prepared by
39/47 combination of a primary metal oxide catalyst 30 according to an embodiment of the invention, with a solid acid catalyst 62 (which is the H-ZMS5 zeolite in this embodiment). The bifunctional catalyst 60 is combined with a peptizable alumina binder to form a granule 64. Other solid acid catalysts can be used for the production of bifunctional catalysts.
[00121] The bifunctional catalyst of this realization can be used, for example, in a hydrocarbon production process that uses a raw material rich in carbon dioxide. The function of the solid acid catalyst is the reforming of the primary products produced in the primary metal oxide agglomerate catalyst, in products with higher octane rates, through reactions typically produced on solid acid catalysts. Such reactions include isomerization, aromatization, oligomerization and hydro-cracking reactions. The bifunctional catalyst produces a product in the refined gasoline range, from a hydrocarbon production process with improved commercial value.
[00122] A specific feature of the bifunctional catalyst in figure 4 is that deactivation by poisoning the solid acid catalyst due to migration of the Group I or Group II cations from the primary catalyst is significantly reduced compared to other catalysts known in the art . This is despite the high cation content of Group I or Group II bonded in the basic structure of the primary catalyst. This reduced poisoning is attributed to the characteristics of the primary catalyst of the invention. The catalyst in figure 4, therefore, is a bifunctional catalyst with a high content of Group I and Group II promotion cations, which has a low level of poisoning due to the migration of Group I or Group II cations into the acid catalyst HZSM-5, thus allowing its reform function to be maintained for longer periods in operation.
[00123] Figure 5 represents a basic hydrocarbon production process 70 that is carried out in a fluidized bed reactor 72, which is a typical application for the catalysis of the invention. The reactor consists of cooling and heating elements 74. Cooling is done by circulating water through
40/47 inside the reactor, and heating is done by circulating water vapor through a heating coil placed inside the reactor.
[00124] The reactor supply stream is a stream of synthesis gas that is introduced through an inlet 76 at the bottom of the reaction vessel 78. The pressure at the bottom of the reactor is sufficient to overcome the pressure drop of the media support. reaction and fluidize the catalyst bed.
[00125] The synthesis gas is transformed into hydrocarbon products when it flows through the fluidized bed 80. The hydrocarbon products are extracted through an outlet connection 82 at the top of the reaction vessel. The fluidized bed contains a catalyst according to an embodiment of the current invention plus other materials that help to maintain the catalytic bed in the fluidized state and maintain a uniform temperature throughout the entire catalytic bed.
Examples [00126] The following is a detailed description of the example embodiments of the invention. The examples were tested in an experimental set shown schematically in figure 6. Experimental set 90 includes a reactor 92 with a volume of 840 ml determined gravimetrically by filling with water.
[00127] During the experiments, the feed flow was normally kept constant at 1,000 standard cubic cm per minute (sccm), which was sometimes changed to 200 sccm or 100 sccm during the tests. With 5 g of catalyst and a feed rate of 1,000 sccm, the modified residence time becomes 0.3 g sec per standard cubic cm (gs / sccm). The hourly space velocity of the gas is 7,800 per hr (11 ^-1 ).
[00128] The catalyst basket 94 (7 cm diameter) consists of two circular grids with an opening of 3 mm each, retaining a sintered stainless steel filter of 15 microns (or opening of 15 microns) installed. The catalyst (5 g), placed between the upper and lower sieve / felt closing devices, has an average particle diameter of 35 microns after sieving to remove the smaller fraction of 25 microns. The catalyst fills the
41/47 sieve openings, uniformly covering the basket floor area to a depth of 2 mm.
[00129] Before the start of the reaction the catalysts were reduced in situ in hydrogen at 723 K for 18h. A small part of the reactor effluent passes through a needle valve 96 to stop the sampling valve GC-FID 98 (equipped with a non-polar capillary column CP-Sil 5B) from where it returns to a separation stage 99 to condense the water and the C5 ⁺ hydrocarbons before the micro-GC-TCD takes a sample for analysis of the permanent gases: Air, CO, CH ₄₎ CO2 in a CO _X column with H2 carrier gas and a molecular sieve column for separation H2, CH ₄ , CO with Ar carrier gas.
Example 1 - Catalyst A [00130] The following steps have been taken to prepare catalyst A (Fe / Ce / Cu / KY).
[00131] The zeolite Y was prepared in the form of Na ⁺ cation exchange. However, an ion exchange was made with K ⁺ because K ⁺ is a better promoter than Na ⁺ for an HTFT catalyst based on Fe.
[00132] The exchange of NaY ions was done by adding 12 g of NaY to 600 ml of a 0.5M K2CO3 solution in doubly deionized water. The amount of K2CO3 in the solution represents an excess of six times K ⁺ in relation to the amount of charge of zeolite cation exchange sites. The resulting suspension was stirred and heated at 80 ⁰ C with cooling by refluxing for at least 4h. Subsequently, the zeolite resulting from ion exchange was filtered and washed with doubly deionized water.
[00133] This procedure was repeated three times to obtain a complete ion exchange and to provide excess cations in addition to the ion exchange capacity of the basic structure, and was dried before use.
[00134] The resulting KY zeolite was impregnated with an appropriate amount of Fe (NO ₃ ) 2, Ce (NC> 3) 2 and Cu (NO3) 2 · solution [00135] The volume of solution used was equal to the volume of pores of the added zeolite. These nitrate salts are highly soluble and allow the
42/47 metal impregnation is done simultaneously.
[00136] The resulting suspension was dried at 120 ° C and calcined in air at 550 ° C for 18h.
[00137] The general composition of the transition metal ions impregnated with the catalyst then reflects the following atomic proportions: Fe: Ce: Cu = 86: 9.5: 4.5. A zeolite Y with a Si / AI ratio of 2.9 contains 14.4% by weight theoretical K when fully exchanged.
[00138] 5 g of the resulting catalyst was added inside the reactor. Before the reaction, the catalyst was reduced in situ in hydrogen at 723 K for 18h.
[00139] The feed stream of the reactor consists of 159 ml / min of CO, 100 ml / min of Air, 635 ml / min of H2 and 106 ml / min of CO2, which are mixed before entering the reactor. The H2 / (2CO + 3 CO2) ratio is the same. The reaction temperature is 603 K and the hourly space velocity of the gas (GHSV) is 7800 h ' ¹ . The pressure in the reactor was 20 bar.
[00140] CO2 hydrogenation is a two-step process, first the catalyst shows high activity for the water-gas reverse exchange reaction, converting CO2 to CO followed by the conversion of CO to hydrocarbons, [00141] The test results are represented graphically in figure 7 and summarized in table A.
[00142] It can be seen that the conversion of CO in the constant state is 74% and there is no deactivation of the catalyst, as can be seen in figure 7. It can also be observed that in the transitional period there is a tendency to reduce the activity of water-gas exchange reaction, as evidenced by the reduced selectivity of carbon dioxide, and a tendency to increase in the selectivity of C5 ⁺ hydrocarbons and in the conversion of carbon monoxide. The selectivity of methane has a very stable profile.
[00143] The high value of the chain growth probability obtained in this example, which is not observed in conventional HTFT catalysts, is very significant. Typical values of chain growth probability (whose maximum theoretical value is 1) of a catalyst based on Fischer-Tropsch iron
43/47 high commercial temperatures are around 0.70 in the reaction conditions of this test. However, the catalyst in this example has a chain growth probability of 0.81 in the tests performed described in this example, and has high conversions of carbon monoxide (74%), low selectivity of methane (8.4%) and high condensate fraction (59.2%) in the steady state.
[00144] The good performance observed is stable over time and no deactivation effects were noted during the tests. This performance stability makes this invention very suitable for the commercial realization of a hydrocarbon formation process using catalysts made according to the method described in the current invention.
Table A
Cat A GHSV (hf ¹ ) 7800 H ₂ / (3CO ₂ + 2CO) 1 Temperature (K) 603 Pressure Bar 20 Conversion from CO 74 Selectivity (% mo C) CO ₂ 18.5 C1 8.4 C2-C4 24.9 C5 + 39.7 Oxygenates 8.7 Condensate fraction (%) 59.2 (C5 ⁺ + oxygen) / HC Increased probability jail 0.81 Olefinity ol./(ol. + Para.) 83.9
[00145] Catalyst A has also been tested for hydrogenation of carbon dioxide. The results of the catalyst A test on carbon dioxide hydrogenation are summarized in table B.
[00146] The feed stream of the reactor consists of 100 ml / min of air, 675 ml / min of H ₂ and 225 ml / min of CO ₂ which are mixed before entering the reactor. The H ₂ / (2CO + 3CO2) ratio is equal to one. The reaction temperature is 603 K and the hourly gas space velocity (GHSV) is 7800 h ' ¹ . The pressure in the reactor is 20 bar.
[00147] The fraction of condensate obtained is 45.6% of products. The probability of
44/47 chain growth is around 0.7. The selectivity of methane is 9.3 and the selectivity for C5 ⁺ hydrocarbons is 21.8.
[00148] For comparison purposes, another catalyst, catalyst B, was prepared following the same procedure for preparing catalyst A, except that no copper salt was added in the incipient moisture impregnation step. The test results of catalyst B on hydrogenation of carbon dioxide are summarized in Table B.
[00149] CO2 conversion and CO selectivity are similar for both catalysts A and B.
[00150] Catalyst A produces a little more oxygen and the selectivity of methane is less than with 0 catalyst Β. The probability of chain growth is higher with catalyst A, as well as C5 ⁺ selectivity. The fraction of condensate obtained with catalyst A is 45.6 while that obtained with catalyst B is 33.7.
[00151] This comparison exemplifies that the addition of a metal chosen from group C, in this case 0 copper, to form a supported mixed oxide agglomerate catalyst has additional benefits over the supported mixed oxide agglomerate catalyst that does not contain any metals group C.
Table B
Cat A Cat B GHSV (hr ' ¹ ) 7880 7880 H ₂ / (3CO ₂ + 2CO) 1 1 Temperature (K) 603 603 Pressure Bar 20 20 CO ₂ conversion 22.1 22.2 Selectivity (% rnols C)C1 9.3 12.5 C2-C4 25.7 29.3 C5 + 21.8 16.8 Oxygen 7.6 4.5 Condensate fraction (%) (C5 + oxygen) / HC 45.6 33.7 Chain growth probability 0.71 0.65
45/47
Olefinity ol./(ol. + Para.) 79.8 77.4
Example 2 - Catalyst E [00152] As described above, the catalysts of the present invention are also suitable components for the preparation of bifunctional catalysts. In this example, catalyst E was prepared by combining 5 g of catalyst A with 5 g of ZSM-5 zeolite extrudates (80% of H-ZSM-5 zeolite, 20% of alumina binder) that were placed on top of the catalyst A in the catalyst sixth of the STIRR reactor. This arrangement is equivalent to a bifunctional catalyst containing catalyst A and zeolite H-ZSM-5.
[00153] Catalyst E was tested in hydrogenation of carbon monoxide at different heavy hourly spatial speeds. The test results are shown in figure 8 and table C summarizes the test results at the highest heavy hourly space speed used.
[00154] In figure 8, catalyst E shows a conversion of carbon monoxide of 74.3% in constant state with an hourly gaseous spatial velocity of 7800 h ' ¹ with a fraction of condensate in the products of 43.4% and a C5 * selectivity of 35.9%. The selectivity of methane is 19.3%.
Table C
CatE GHSV (hr ' ¹ ) 7800 H ₂ / (3CO ₂ + 2CO) 1 Temperature (K) 603 Pressure Bar 20 CO ₂ conversion 74.3 Selectivity (% rnols C)CO2 18 C1 19.3 C2-C4 27.3 C5 + 35.9 Oxygen 0.3 Condensate fraction (%) (C5 + oxygen) / HC 43.4
[00155] Table D is a comparison of the test results on the carbon dioxide hydrogenation of catalyst A and catalyst E under the same test conditions. The main differences are in the C5 ⁺ selectivity, 21.8% for catalyst A
46/47 and 30.0% for catalyst E, and in selectivity for oxygenates, which is 7.6% for catalyst A and 0.9% for catalyst E. The condensate fraction of catalyst E is 49.3 %, while for catalyst A it is 45.6%.
[00156] By comparing the test results it can be concluded that catalyst E produces more liquid hydrocarbon product and less oxygenated than catalyst A.
[00157] The performance stability of catalyst E can be seen in figure 8, which shows no sign of a drop in conversion. Typically the acidic function of the bifunctional catalyst is poisoned by the basic cations that migrate from the main catalyst to the acidic sites of the solid acid catalyst. The constant selectivity for aromatics after 340 hours in operation is evidenced by the fact that the acid function remains unaffected due to the absence of migration of the cations of group I or group II of the primary catalyst. The changes to 268 hours in operation in figure 8 are due to GHSV at this point having been changed from 7800 to 1560.
Table D
Cat A Cat B GHSV (hr ' ¹ ) 7800 7800 H ₂ / (3CO ₂ + 2CO) 1 1 Temperature (K) 603 603 Pressure Bar 20 20 CO ₂ conversion 22.1 24.2 Selectivity (% mo C) CO 35.5 37.1 C1 9.3 12.0 C2-C4 25.7 20.5 C5 + 21.8 30.0 Oxygen 7.6 0.9 Condensate fraction (%) (C5 + oxygen) / HC 45.6 49.3
[00158] Table E shows the effect of the potassium precipitant on the internal porous structure of the basic catalyst support structure. Catalyst A was analyzed at 19% K and catalyst A 2880 was analyzed at 13% K.
Table E
Cat A Cat A2880
47/47
GHSV (hr ' ¹ ) 7800 7800 H ₂ / (3CO ₂ + 2CO) 1 1 Temperature (K) 603 603 Pressure Bar 20 20 CO ₂ conversion 22.1 6.7 Selectivity (% mo C) C1 9.3 26.4 C2-C4 25.7 12.2 C5 + 21.8 1.5 Oxygen 7.6 0.0 Condensate fraction (%) (C5 + oxygen) / HC 45.6 3.8 Chain probability 0.71 0.48 Olefinity ol./(ol. + Para.) 79.8 11.4
[00159] Various modifications may be made within the scope of the invention, as is the intention here, and the embodiments of the invention may include combinations of characteristics different from those expressly claimed here.

权利要求:
Claims (15)
[1]
1. Method for the preparation of a supported catalyst, whose method is characterized by the fact that it comprises the steps of:
(i) providing a porous catalyst support comprising a basic structure having an internal pore structure comprising one or more pores and the internal pore structure of which comprises a basic precipitant;
(ii) contacting the catalyst support in dry form with a colloidal solution or suspension comprising a catalytically active metal, such that when in contact with the precipitant, particles comprising the catalytically active metal are precipitated within the internal pore structure of the main catalyst support structure.
[2]
2. Method according to claim 1, characterized by the fact that the internal porous structure has one or more regions (cages) that are accessible through sections with a smaller pore diameter (windows), in which optionally the particles comprising metal catalytically active has a larger effective diameter than windows and where optionally the pore diameter or window diameter is greater than 0.2 nm.
[3]
Method according to any of claims 1 to 2, characterized by the fact that the catalyst support has a zeotype structure, optionally adopting the FAU, BEA or MWW structure, according to the International Zeolite Association database of structures of zeolite.
[4]
4. Method according to claim 3, characterized by the fact that the catalyst support is an aluminum-silicate zeolite, optionally having a molar ratio between silicon and aluminum less than 10, for example, in the range of 2 to 5 .
[5]
Method according to any of claims 1 to 4, characterized in that the catalyst support comprises a basic structure with a negative charge, balanced by one or more charges of equilibrium cations.
[6]
6. Method according to claim 5, characterized by the fact
2/3 that the charge-balance cations are chosen from alkali metal or alkaline earth metal cations, preferably potassium, in which the charge-balance cation of the basic structure can optionally act as a promoter or cocatalyst .
[7]
7. Method according to claim 6, characterized by the fact that:
a) the precipitant comprises the same cation as the charge equilibration cation, and the total cation content in the supported catalyst is greater than the total ion exchange capacity of the catalyst support; and / or
b) the catalytically active metal is chosen from one or more elements of the group consisting of nickel, cobalt, iron, ruthenium, osmium, platinum, iridium, rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, manganese; and / or
c) the supported catalyst comprises Fe, Cu, K.
[8]
8. Method according to claim 7, characterized in that it additionally comprises:
a) contacting the catalyst support with a colloidal solution or suspension comprising one or more metals chosen from the group consisting of yttrium, lanthanum, cerium, and any other lanthanide metal, whose metals also form part of the particles containing catalytically active metal; and / or
b) contacting the catalyst support with one or more elements chosen from the group consisting of copper, zinc, gallium, zirconium, palladium, whose elements also form part of the particles containing catalytically active metal.
[9]
Method according to any of claims 1 to 8, characterized in that it comprises the additional step (s) of:
a) calcination of the resulting material comprising a catalyst support with particles containing catalytically active metal in air, optionally after drying the resulting material; and / or
b) chemical reduction of particles containing catalytically active metal, for example, at high temperature and in the presence of gas
3/3 hydrogen.
[10]
Method according to any of claims 1 to 9, characterized in that the precipitant is first charged into the porous internal structure of the basic catalyst support structure.
[11]
Method according to any of claims 1 to 10, characterized in that the precipitant is a carbonate or bicarbonate, for example, potassium carbonate or bicarbonate.
[12]
Method according to any of claims 1 to 11, characterized in that the catalyst support is contacted with a colloidal solution or suspension comprising the catalytically active metal, using incipient moisture impregnation.
[13]
Method according to any of claims 1 to 12, characterized in that the supported catalyst is a FischerTropsch catalyst.
[14]
14. Supported catalyst, characterized in that it is produced by a method as defined in any of claims 1 to 13.
[15]
15. Use of the supported catalyst as defined in claim 14, characterized in that it is like a catalyst in a catalyzed chemical process, such as a Fischer-Tropsch process.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-05-28| B09A| Decision: intention to grant|

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2019-08-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/10/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/10/2012, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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GB201118228A|GB201118228D0|2011-10-21|2011-10-21|Methods of preparation and forming supported active metal catalysts and precursors|

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GB1118228.4|2011-10-21|

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GBPCT/GB2012/000803|2012-10-19|

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GB2012000803|2012-10-19|

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PCT/EP2012/070897|WO2013057319A2|2011-10-21|2012-10-22|Methods of preparation and forming supported active metal catalysts and precursors|

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