Fischer-tropsch process catalyst (variations) and a method for preparation thereof

FIELD: organic synthesis catalysts.

SUBSTANCE: invention provides fischer-tropsch process catalyst comprising at least one metal suitably absorbing carbon monoxide and at least one promoter, said metal and said promoter being dispersed on a substrate to form catalytic particle having BET surface area between 100 and 250 m2/g so that size of metal oxide crystallites ranges from 40 to 200 while said metal and said promoter are different compound and said particle has predominantly smooth and uniform morphology of surface. substrate is characterized by particle size between 60 and 150 μm, surface area 90 to 210 m2/g, pore volume 0.35 to 0.50 mL/g, and pore diameter 8 to 20 nm. Described are also catalyst and a method of preparing catalyst including cobalt dispersed onto substrate to form catalyst particle.

EFFECT: increased surface of catalyst, improved uniformity in distribution of metal, and reduced size of metal crystallites.

33 cl, 9 dwg, 1 tbl, 10 ex

 

The technical field

The present invention relates to a catalyst for use in the Fischer-Tropsch process and to a method of preparation of the catalyst. The catalyst of the present invention has more sellersville surface, a more uniform distribution of the metal and the smaller size of the crystallites of the metal than the catalysts of the Fischer-Tropsch process, known previously.

Background of invention

Around 1923, the process of the Fischer-Tropsch (f-T), which includes the transmission of a continuous stream of syngas (synthetic gas or gaseous mixture of hydrogen and carbon monoxide) over a metal catalyst deposited on a substrate, is used for the conversion of synthetic gas into more valuable industrial products, such as gasoline, diesel fuel, linear alcohols and α-olefins. The catalysts used in these processes are usually in the form of granules or powder, having active areas of metal on the surface of essentially chemically inert material media. When the components of the synthetic gas in contact with the active site of the catalyst, carbon monoxide torn and hydrogensource, producing a mixture of hydrocarbon products. In commercial operations it is desirable that the gas was passed over the catalyst, in the main, with a constant and high speed. But due to the fact that the asset is the first section of the catalyst may be busy at the moment only one molecule, the most effective catalysts contain a large number of active sites and have a high rate of conversion (or conversion).

Like all catalysts, the catalyst Fischer-Tropsch not subject to constant change during the reaction. However, over time the efficiency of the catalyst may decrease due to contamination of the active sites, for example by deposition of carbon or other contaminants present in the original mixture of synthetic gas, or due to coking, or by deposition of waxy hydrocarbon on the catalyst surface, thus making it necessary that the catalytic layer was purified or regenerated. In addition, the efficiency of the catalyst can be permanently reduced if the catalyst particles are sintered (fused together) or crumble during packing of the catalyst in the catalytic layer, due to the fact that impeded the passage of the gas and decreases the number of available active sites. Since most industrial operations using continuous streams of synthetic gas can be that clear or, in other circumstances, to regenerate or replace the catalyst layer is a very expensive and inefficient. Thus, most preferably, the catalysts of the Fischer-Tropsch process can be used for long what about the period of time between stages of regeneration of the catalyst and that they do not require frequent replacement of the catalytic layer in the normal industrial process.

It is known that in the technical field composition and physical characteristics of the catalyst particles Fischer-Tropsch affect catalytic activity. Typically, the catalysts of the Fischer-Tropsch include one or more metals selected from group VIII of the periodic table of elements (iron, cobalt, Nickel, ruthenium, rhenium, palladium, osmium, iridium, platinum), a promoter and a carrier or substrate. The metal of group VIII is administered to create an effective conversion of synthetic gas and it is chosen on the basis of the original product and the desired mixture of products. (For more specific discussion of the Fischer-Tropsch process see, for example, "Practical and theoretical aspects of the catalytic process of the Fischer-Tropsch" ("Practical and Theoretical Aspects of The Catalytic Fischer-Tropsch Process), Applied Catalysis A: General 138 (1996) 319-344, author ..Dry; publication here by reference). Usually the catalysts of the Fischer-Tropsch process using a cobalt because of its commercial availability, efficiency in the conversion of synthetic gas into hydrocarbons with longer chains, ease of process control, low activity in the reactions of conversion of water vapor and its relatively low cost compared with other metals of group VIII. To improve certain properties of the catalyst or to improve the catalytic selectivity add the promoters and is commonly for the catalysts based on cobalt are used as promoters ruthenium, copper and alkali metals. Media, such as silicon dioxide, aluminum dioxide or silicates, provide a means for increasing the surface area of the catalyst. For a more complete overview of the catalytic compositions of the Fischer-Tropsch see, for example, U.S. patent 5248701 issued Soled and co., and literary sources (which are introduced here by reference).

The physical characteristics of the catalyst Fischer-Tropsch process are also important. Because hydrogen and carbon monoxide must physically be in contact with the metal of group VIII to was the process of transformation, the catalyst particles with a uniform distribution of metal, a homogeneous packing of metal and sellersville surfaces have higher levels of activity in the industrial sludge layer of the reactor than particles with metal, localized on the surface.

Thus, it is desirable to have a catalyst for Fischer-Tropsch cobalt-based, which is characterized sellersville surface, smooth, homogeneous surface morphology and a uniform distribution of metal throughout the catalyst. As research has shown that the crystallite size of the metal can affect the hydrogenation reaction, it is desirable that the catalyst, preferably, had a smaller crystallite size than the existing kata is isatori Fischer-Tropsch process. In addition, the catalyst should be easy to manufacture on an industrial scale.

Brief description of the invention

The catalyst for the Fischer-Tropsch process of the present invention is a catalyst based on a transition metal having sellersville surface, smooth, homogeneous surface morphology essentially uniform distribution of cobalt on the substrate and the small size of the crystallites of the metal. In the first embodiment, the catalyst has a surface area from about 100 to about 250 m2/g; essentially, a smooth, homogeneous surface morphology; essentially uniform distribution of metal throughout the inert surface of the substrate and the crystallite size of the metal oxide from about 40 to about 200 Å. In the second embodiment, the catalyst Fischer-Tropsch process is a catalyst based on cobalt with the first promoter based on the noble metal and the second promoter based on a metal, disposed on a substrate of alumina, and the catalyst contains from about 5 to about 60 wt.% cobalt; from about 0.0001 to about 1 wt.% the first promoter and from about 0.01 to about 5 wt.% the second promoter.

The catalysts of the present invention on the basis of metal with Celerity surface is prepared in conditions of sour solution at pH higher than about 7.0 and taking as initial sour integrated connection is the transition metal. The resulting product is a catalyst with uniform distribution of metal catalyst particles with a smooth and uniform surface morphology and slow growth of crystallites during heating.

Brief description of drawings

Figa represents a secondary electron image of scanning electron micrograph, at a magnification of 1600 X (measured when the image is projected in the stencil paper size of 8.5"×11"), a variant of the catalyst of the present invention, consisting of promoted platinum cobalt covering the aluminum oxide, and the catalyst prepared as described in Example 2.

Figv is the electronic image with the inverse scattering scanning electron micrograph, at a magnification of 1600 X (measured when the image is projected in the stencil paper size of 8.5"×11"), the same catalyst particles, which is shown in Figa.

Figa represents a secondary electron image of scanning electron micrograph, at a magnification 1640 X (measured when the image is projected in the stencil paper size of 8.5"×11"), the catalyst prepared using the method of nitrate impregnation, the catalyst consists of promoted platinum cobalt covering the oxide of al is MINIA and cooked, as described in Example 6.

Figv is the electronic image with the inverse scattering scanning electron photomicrograph, at magnification 1640 X (measured when the image is projected in the stencil paper size of 8.5"×11"), the same catalyst particles, which is shown in Figa.

Figure 3 represents the electronic image with the inverse scattering scanning electron photomicrograph, at magnification 17000 X (measured when the image is projected in the stencil paper size of 8.5"×11"), the internal cross-section of the same catalyst particles, which is shown in Figa.

Figure 4 represents the electronic image with the inverse scattering scanning electron micrograph, magnification 5000 X (measured when the image is projected in the stencil paper size of 8.5"×11"), the internal cross-section of the same catalyst particles, which is shown in Figa.

Figure 5 is a graph showing the effect of temperature of calcination on the area of the BET surface of the cobalt catalyst of the present invention prepared without promoter.

6 is a graph showing the effect of temperature of calcination on the average size of crystallites of cobalt catalyst of the present invention prepared without promoter; and

Fig.7 is gr the FIC, showing thermal stability promoted platinum cobalt catalyst covering the aluminum oxide, prepared as described in Example 1.

A detailed description of the preferred options

The catalyst of the present invention is intended for use in the process of Fischer-Tropsch (f-T). The composition of the catalyst is similar to f-T catalysts of the prior art and comprises cobalt and a carrier or substrate. However, due to the method by which the finished catalyst, the physical characteristics of the catalyst of the present invention include more sellersville surface more smooth, more uniform surface morphology, a more uniform distribution of active sites and a smaller crystallite size than the catalysts of the prior art. (For more specific discussion of catalysts based on cobalt-look "Design, synthesis and use of a catalyst based on cobalt, obtained by Fischer-Tropsch synthesis" ("Design, Synthesis and use of cobalt-based Fischer-Tropsch synthesis catalyst"). Applied Catalysis A: General 161 (1997) 59-78, author .Iglesia; publication here by reference.)

the Fischer-Tropsch process is a catalyzed process-surface polymerization, which converts synthesis gas (a mixture of gaseous hydrogen and carbon monoxide) in ug is avodarte with a wide range of lengths of chains and functionality. It is recognized that the initial stage of the process is the adsorption of carbon monoxide on the catalyst surface. Hydrogenation of adsorbed carbon monoxide produces monomers CHχthat remain on the catalyst surface. The growth of hydrocarbon chains is due to the joining surface of methylene links to adsorbed alkyl groups. The chain dropped and released from the catalytic surface due to the hydrogenation of adsorbed alkyl groups with the formation of n-paraffins or by cleavage β-hydrogen and alkyl groups with the formation of linear α-olefins. (For more specific discussion of the Fischer-Tropsch process, see "Practical and theoretical aspects of the catalytic process of the Fischer-Tropsch ("Practical and Theoretical Aspects of The Catalytic Fischer-Tropsch Process), Applied Catalysis A: General 138 (1996) 319-344, author ..Dry, and Fischer-Tropsch Synthesis: a modern mechanism and future needs" ("the Fisher-Tropsch Synthesis"), Preprint, ACS Fuel Division, 45(1), (2000) 129-133 SA 132; 239079; publications listed here by reference).

Typically, the catalysts used in the Fischer-Tropsch process, include at least one metal, which is an effective absorber of carbon monoxide and which is effective for hydrogenation reactions. The metals that are most often used in f-T kata is satarah, are Nickel, cobalt and iron. Research has also been undertaken with ruthenium, osmium, platinum, palladium, iridium, rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, copper and zinc (see, for example, U.S. patent 4801573 issued by Eri and co., and references, which are given here by reference). Catalysts based on cobalt are preferred for the production of a spectrum of hydrocarbons while minimizing the production of carbon dioxide. Catalysts based on Nickel tend to the production of large quantities of methane, catalysts based on iron produce a range of hydrocarbons, but also produce sufficiently large quantities of carbon dioxide; and catalysts based on ruthenium generate predominantly methane or high-melting wax, depending on the reaction conditions. The catalysts of the present invention is made on the basis of cobalt, the catalyst contains from about 5 to about 60 wt.% cobalt relative to the total weight of the catalyst including cobalt. In a more preferred embodiment, the catalyst includes from about 10 to about 40 wt.% cobalt and in the most preferred embodiment, the amount of cobalt is from about 10 to about 30 wt.%.

The catalysts of the Fischer-Tropsch usually also include at least one promoter, which is added to the Ucrania selective properties of the catalyst or to modify the activity and/or selectivity of the catalyst. In the present invention, in the preferred embodiment, the catalyst includes two promoter - first promoter of the noble metal and the second promoter metal, because the combination of the promoters believed to be the most effective for producing the desired hydrocarbon mixtures, starting with natural gas. However, it is not required to add a promoter to prepare a catalyst having sellersville surface, smooth, homogeneous surface morphology, uniform distribution of active sites and small crystallite size. For catalysts based on cobalt prior art offers a variety of promoters such as boron, cerium, chromium, copper, iridium, iron, lanthanum, magnesium, molybdenum, palladium, platinum, rhenium, rhodium, ruthenium, strontium, tungsten, vanadium, zinc, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, magnesium oxide, titanium oxide, zirconium oxide, and other rare earth metals such as scandium, yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. In the most preferred embodiment of the present invention the promoter of the noble metal is chosen preferably from the group consisting of palladium, platinum, ruthenium, rhenium, rhodium, iridium, and combinations thereof, and vtoro the promoter chosen from the group consisting of potassium, boron, cesium, lanthanum, cerium, strontium, scandium, yttrium, prasetiya, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, palladium, platinum, ruthenium, rhenium, rhodium, iridium, and combinations thereof. Other metals can be used as substitutes or for the first or second promoter, if so desirable to the consumer to modify the properties of the catalyst or to modify the activity and/or selectivity of the catalyst. Promoters usually give in smaller concentrations than the cobalt, and in the present invention the promoter of the noble metal comprises from about 0.0001 to about 1 wt.% and, more preferably includes from about 0.001 to about 0.05 wt.% the total weight of the catalyst, and the second promoter comprises, preferably, from about 0.01 to about 5 wt.% and, more preferably includes from about 0.1 to about 1 wt.% the total weight of the catalyst.

The metal and the promoter catalyst Fischer-Tropsch usually dispersed on a carrier or substrate or mixed with a carrier or substrate. The substrate provides a means for increasing the surface area of the catalyst. Recommended carriers include alumina, γ-aluminum oxide monohydrate, aluminum, aluminum trihydrate, aluminum silicate, magnesium silicate, silicon dioxide, silicate, silicalite, y-zeolite, organic, titanium, thorium, zirconium, niobium, hydrotalcite, diatomaceous earth, attapulgite clay, zinc oxide, other clays, other zeolites, and combinations thereof. The catalyst of the present invention is prepared with a substrate of high-purity aluminum oxide having a particle size of from about 60 to about 150 microns, a surface area of from about 90 to about 210 m2/g, pore volume from about 0.35 to about 0,50 ml/g and average pore diameter of from about 8 to about 20 nm.

The physical structure of the catalyst Fischer-Tropsch also affect the activity of the catalyst and, as is known in the art, the choice of an appropriate design of catalyst for a particular type of reactor can rezultirase in relatively high production rates and relatively low operating costs for a commercial manufacturer. The design of the catalyst involves selecting the correct type and shape of the catalyst for this situation, then determine its size, porosity, distribution of catalytic particles and other properties. Structural or mechanical properties of the catalyst, including the strength of the particles and abrasion resistance, depend on the chemical stability and microstructure of the substrate and from the presence of binding agents. The shape of the catalyst particles and size affect properties such as flow distribution and pressure drop.

Rolled atory Fischer-Tropsch usually use either gas-phase reactor with fixed bed, either in the reactor with liquid-phase slurry layer. In the reactor with a fixed bed catalyst is Packed in tubes or distribute along the tray and leave, mainly in stationary position while the reacting substances is passed over the catalyst layer. Because the catalyst particles are usually tightly Packed (and link) in multiple layers, and due to the fact that the replacement catalytic layer requires much time and is expensive, the catalyst preferably made so as to achieve maximum catalytic strength and porosity and to maximize the service life of the catalyst. In addition, due to the fact that the reacting substances pass over the catalyst layer in the form of a continuous stream, it is advantageous that the catalyst particles were relatively large (in the range of from about 1 to about 10 mm)to the catalyst by design, was able to minimize the pressure drop and diffusion resistance and then to the active sites of the catalyst are readily accessible. For example, in U.S. patent 5545674 issued Behnnann and co., which is introduced here by reference, describe a cobalt catalyst on a substrate having a catalytically active film, where, basically, the entire active cobalt are precipitated on the surface of particles of the substrate, while iskluchau the camping presence of cobalt on the inner surface of particles, thus providing easy access to the active sites for reactant synthetic gas and minimizing the diffusion of the reacting substances.

In the present invention the catalyst is intended for use in the reactor with liquid-phase slurry layer. In the reactor with the slurry layer of the catalyst suspended in the reaction solvent and continuously stirred when reacting substances fed into the reactor. Catalysts for use in reactors with sludge layer is preferably made so as to ensure maximum activity, selectivity and resistance to friction and to the metal distribution and the morphology of the surface had a significant influence on the performance of the catalyst. Because the catalyst particles in the reactor with the slurry layer is usually thin-dispersed powder particles, the catalyst activity can be increased by deposition of metal on the large surface area of the substrate by the inclusion of particles into the inner surface of the substrate, thereby increasing accessibility to the active sites for the reacting substances. In addition, due to the fact that the intensity of circulation per plot (the rate at which a molecule of starting material is converted to product and is released from the active site) is constant the La of the metal, the increase in the number of active sites on the catalyst surface leads to higher initial conversion material and, consequently, to a higher output of product per unit of time. The catalyst particles, designed for a reactor with the slurry layer, are typically small (in the range of from about 20 to about 200 microns in diameter) and ideally have sellersville surface, smooth, homogeneous surface morphology and a uniform distribution of metal particles. (For a discussion of the design of catalysts and catalytic reactors, see Bartholomew and co. "Design of a catalytic reactor" ("Catalytic Reactor Design") Chemical Engineering, 1994, p.70-75, publication, introduced here by reference).

The degree of dispersion of the metal in the catalyst Fischer-Tropsch process is influenced by several factors, including the surface area of the substrate, the crystallite size of the original metal or a metal oxide, a metal interconnection substrate and the ability to provide a homogeneous mixture of the metal with the substrate. When the surface area of the substrate increases, a higher concentration of metal can be dispersed on the surface as a monolayer. For example, if cobalt is dispersed on a substrate with a surface area BET surface of 50 m2/g, approximately 67% of the surface is covered completely dispersed Monos the OEM of cobalt with 5%cobalt loading. However, if the area BET surface of the substrate is 200 m2/g with 5%cobalt loading, only about 17% of the surface is covered with a cobalt monolayer and approximately 67%of the surface coverage is not achieved until such time as cobalt load will not be about 20%. In a preferred embodiment of the present invention the area of the BET surface of the substrate is from about 90 to about 210 m2/g (square BET surface" refers to the surface area of the particles, as it is defined by using the equation of Brunauer, Emmett, Teller for monomolecular adsorption). For more detailed information on BET equation and its application, see the Introduction to colloid chemistry and surface chemistry (Introduction to Colloid and Surface Chemistry) 2eedition, D.J.Shaw published Butterwoth (publishers) Inc., 1978).

The crystallite size of the metal is inversely proportional to the dispersion of the metal, i.e. when the crystallite size decreases, the variance increases. However, there is a practical lower limit to the size of the crystallite, because if too small of a size of crystallite sintering occurs during operation, disrupting the use of the catalyst. For f-T catalyst cobalt-based studies have shown that when the size of the crystallites of cobalt, less than about 50 Å in diameter, the crystallites fast is deactivated in the presence of water, which is usually present in the Fischer-Tropsch process (see Iglesia, p.64). In a preferred embodiment of the invention, the crystalline size of cobalt oxide, as determined based on the extension lines diffractogram of x-rays by using methodology known in this field, is greater than about 40 Å in diameter and preferably is less than about 200 Å. More preferably, the crystallite size is from about 50 to about 150 Å and, most preferably, the crystallite size is from about 50 to about 120 Å.

The interaction of the metal/substrate also affects the dispersion of metal, because if there is a strong affinity between the metal and the substrate, it appears that the metal will be less likely to be moved along the surface of the substrate, and thus, the metal remains dispersed. The interaction of the metal/substrate depends on the initial connection to metal (predecessor)used for the deposition of metal on the surface of the substrate, and the method of preparation of the catalyst, especially temperature, is used to restore the original connections for metal. For f-T catalysts cobalt-based studies have shown that the optimal dispersion of cobalt is achieved when the source connection for cobalt can be recovered in the odd slow taking place at relatively low temperatures of recovery and it is desirable to maintain the temperature recovery, less than about 530°in order to minimize the degree of sintering (see Iglesia, p.64). In a preferred embodiment of the present invention, the source connection for cobalt choose to restore the original connection was carried out by slowly increasing the temperature, and the temperature recovery is in the range between from about 250 to about 500°and the temperature increases at a rate from about 0.1 to about 10°C/min and the recovery time ranges from between about 5 to about 40 hours, and more preferably from about 10 to about 30 hours.

The dispersion of metal and other physical characteristics of the catalyst Fischer-Tropsch process are equally important for the efficiency of the catalyst as the catalyst composition, and directly depend on the method used to prepare the catalyst. The catalysts of the Fischer-Tropsch cobalt-based well-known technology can be prepared using the method of impregnation, the method of acid-base deposition or a method of compounding. The method includes impregnating or spraying, or immersion of the carrier or substrate in an aqueous solution of cobalt salts. For the button to cover the substrate a desired amount of cobalt, usually you need to substrate was dipped many times, which makes the cooking time consuming and expensive. It is also hard to control where the cobalt was deposited on the surface as the concentration of metal meets. Most often in the process of impregnation using a solution of nitrate of cobalt, but the substrate is covered by nitrate solution should be dried and carcinomatosa (burn) after each impregnation by spraying or immersion, increasing the time of preparation of the catalyst, energy consumption and cost of preparation. The use of a solution of nitrate of cobalt also produces by-products, nitrogen oxides (NOx), which are harmful to the environment. Alternatively, in the process of impregnation is possible to use a solution of cobalt acetate. While this version eliminated the formation of nitrogen oxides, the process is time-consuming and expensive because it requires a large number of stages of impregnation. The method of acid-base precipitation usually includes the provision of a basic agent solution deposition and mixing it with an acidic solution of starting compound to cobalt metal, usually in the form of salts of cobalt, and the substrate material, thereby causing the original connection for metal cobalt deposited with the substrate material. Used the usual agents of deposition include ammonium carbonate or ammonium hydroxide, and the cobalt nitrate is often used as a starting compound for the metal cobalt. The catalyst prepared with the help of this acid-base plating process, works well and for a very long time, but by-products on the basis of ammonium, such as ammonium nitrate formed during the preparation stage, represent a danger to health personnel. Alternatively, instead of the compounds based on ammonium can be used as agents of deposition of sodium carbonate or sodium bicarbonate. However, this substitution increases the risk of contamination of the catalyst with excess sodium, which can have harmful effects on catalytic activity and selectivity. Respectively, must be added the multi-stage washing process for removing sodium, increasing the time and cost of preparation. Compounding involves mixing a water-soluble salt of cobalt from the substrate over an extended period of time and then heat-drying the product. The main disadvantage of the method of compounding is the difficulty in achieving uniformity of metal with a mixture of substrate material. Metal cobalt has to a certain extent, the tendency to coagglomeration. In addition, the temperature required for drying to the of talization on the substrate, can cause sintering or decomposition of the substrate.

In the present invention, although the catalyst composition similar to the composition of the catalysts of the Fischer-Tropsch prior art, the process by which to prepare the catalyst, gives a catalyst with unique physical characteristics, including more than sellersville surface more smooth, more uniform surface morphology, a more uniform distribution of active sites and a smaller crystallite size than the f-T catalysts of the prior art. Being well presented, the process of preparing the preferred option of the catalyst of the present invention enables direct processing of the substrate of the catalyst in an aqueous solution of cobalt salts (reference compound to cobalt)having a pH value greater than the point of zero charge of the substrate, and then drying/calcining the coated substrate by known methods of drying and subsequent reduction of the initial compounds for metal slowly at relatively low temperatures and then stabilization of the catalyst by known methods.

More specifically, for the preparation of the catalysts of the present invention with Celerity the surface of the cobalt-based prepared catalyst slurry of the substrate by introducing the substrate into the water when is remesiana and at the same time maintaining the reaction temperature in the range from about 35 to about 210° With and, more preferably, from about 65 to about 120°C, at a pressure of from about 500 to about 2000 mm Hg and, more preferably, from about 700 to about 900 mm Hg as soon As the temperature of the sludge substrate becomes stable, while continuing mixing an aqueous solution of cobalt salts are added to the reaction vessel or by injection of saline solution into the reservoir, or by adding a salt solution in a volumetric portions in the process. The dose may vary depending on the volume of prepared products, the frequency of addition and evaporation of the reaction solvent. It is desirable that the temperature of the slurry and the amount of prepared products remained largely constant in the preparation of the substrate is coated. The volume can be adjusted either by adding salt solution, or by adding water, and the rate of addition can be changed if necessary to maintain the reaction temperature. After the cobalt salt solution is added to the slurry of the substrate, the temperature of the slurry is maintained within the range from about 65 to about 120°and the amount of support, mainly constant by adding water until such time as the reaction of the coating will not be basically completed. The liquid is then decanted from the coated substrate and the substrate is washed with water to remove the AC is wow any loose material. The washed substrate is then dried and calicivirus using spray dryers, ovens, vacuum dryers, dryers fluidized bed, belt dryers and similar means for drying, which are known in this field. Preferably the drying temperature maintained within the range from about 90 to about 375°and, more preferably, from about 120 to about 260°and the air flow rate is more than about 1000 liter/hour/liter of catalyst.

In a preferred embodiment, the substrate is aluminum oxide, high cleaning having a particle size of from about 60 to about 150 microns in diameter, the surface area of from about 90 to about 210 m2/g, pore volume from about 0.35 to about 0,50 ml/g and average pore diameter of from about 8 to about 20 nm. One of these substrates is Puralox®SCCa 5/150, manufactured by CONDEA Vista company, Houston, TX 77224-9029. Other substrates can replace aluminum oxide, but the backing substitute must have, basically, the same characteristics of particle size, surface area, pore volume and pore size.

An aqueous solution of cobalt salts is a combination of a specific salt of cobalt - source connection for cobalt and water. In a preferred embodiment, the salt of the cobalt complex compound of the carbonate hexamine cobalt (II). The solution hexamine cobalt dobavlaut sludge substrate, consisting of aluminum oxide, by pumping so fast that the time decay ranged from about 2 to about 12 hours and preferably from about 4 to about 8 hours, at the same time maintaining the temperature of the slurry in the range of from about 65 to about 120°until then, until the reaction is complete. For hexamine cobalt source compound decomposition or the completion of the reaction is determined by the color change of the reaction solution from red to pale orange or mainly to colorless and the color depends on the amount of residual amine ion cobalt, temperature, and time decay. A substrate of aluminum oxide coated hexaamminecobalt, then subjected to oven drying at a temperature of about 93°air flow corresponding to about 17 SCFH (standard cubic foot per hour) (0,48 m3/hour)for about 20 hours.

You can use other cobalt salts for the catalyst, provided that the salt is a complex compound of cobalt (II), which has a pH value greater than the point of zero charge of the substrate in the aquatic environment. The point of zero charge (PZC) corresponds to this value of pH at which the surface of the oxide particles of metal suspended in the aqueous medium, is effective neutral. When the particles of metal oxide are in the water, each of the th particle appears the resulting surface charge due to the fact, the particles adsorb protons, creating a positively charged surface) or hydroxide ions (creating a negatively charged surface) of the surrounding water. PZC is the intermediate value of pH at which the proton adsorption of ions is balanced mainly by the adsorption of hydroxide ions. You can use various methods known in this field to determine the PZC for any particular substrate. For example, in a preferred embodiment, the cobalt salt may be any complex compound of cobalt (II)with ligands of the coordination sphere, such as water, chlorine ion, ammonia, pyridine, triphenylphosphine, 1,2-diaminoethane, Diethylenetriamine, Triethylenetetramine, acetate, oxalate, 2,4-pentandiol, ethylendiamin tetraoxane acid, and combinations thereof, and preferably, the ligands of the coordination spheres represent water molecules or ligands that are coordinated to the metal through the nitrogen atom, and combinations thereof. Since the cobalt-ligand coordination sphere can be cationic, outside the scope of such a complex may include one or more anions to balance the charge. You can use any anionic group, which will not contaminate the substrate or to adversely affect the recovery of cobalt, such as hydroxide, nitrate, carbonate,bicarbonate, chloride, sulfate, bisulfate and combinations thereof. The cobalt salt is dissolved in water before you enter into a slurry of the substrate, and the concentration of the cobalt salt solution can be changed if desired. Various techniques of regulation, which are known in this field can be used to determine when the solution has not left the original salt complex, such as fixing a noticeable discoloration of the reaction solution, titration, chromatography, or other methods of control that are known to specialists in this field.

If in the composition include one or more promoters, the promoters can be added either to the solution of cobalt salts before the introduction of saline into the sludge substrate or promoters can be impregnate on a substrate, coated with cobalt. When the promoter is added to the salt solution, the salt solution/promoter is introduced into the slurry of the substrate in the same manner as described for the cobalt salt solution without promoters. In a preferred embodiment, the oxide of rhenium (VII) and nitrosylated ruthenium added to a solution of carbonate hexamine cobalt and then fed to a slurry of the substrate with a complex compound of cobalt. The substrate coated with alumina was washed with water and then dried at about 93°air flow corresponding to about 17 SCFH (0,48 m3/hour).

3/hour)until drying.

The dried coated substrate recover by slowly heating the substrate from ambient temperature to a temperature of from about 300 to about 500°at a speed of from about 0.1 to about 10°/mi is within the period of time from about 5 to about 40 hours and, more preferably, from about 10 to about 30 hours. Figures 5 and 6 show the effect of temperature calcination of cobalt catalyst of the present invention prepared without promoter. As shown in Figure 5, when the temperature of calcination increases, the area BET surface decreases. At the same time, as shown in Fig.6, when the temperature of calcination increases the average crystallite size also increases. Due to the fact that the dispersion of the metal increases in the catalyst particles, when increasing the surface area and decreases when the size of the crystallites, for the process of preparation of the catalyst based on cobalt is preferred relatively low temperature calcination. In a preferred embodiment, the dried substrate of alumina treated with the reference compound carbonate hexamine cobalt and containing promoters in the form of an oxide of rhenium (VII) and nitrosylated ruthenium, restore, using a tubular reactor with a fixed bed at a temperature of approximately 350°C, under pressure of 350 psig (2413 kPa), besides having a constant volumetric rate of more than about 10,000 liters per hour. Recovery begins when the ambient temperature and the temperature rises gradually at a rate of about 1°/min up to 350°and then the temperature is adopted at 350° C for from about 12 to about 16 hours.

Thus, the cobalt catalyst of the present invention are made by direct processing of the substrate of the catalyst source compound to cobalt, having a pH value greater than the point of zero charge podoski, then drying/calcining the coated substrate using known methods of drying and recovery of the parent compound for metal slowly at relatively low temperatures. The resulting catalyst has a largely uniform distribution of cobalt in the catalyst particle has a small size of the crystallites of cobalt and has a smoother, more uniform surface morphology than f-T catalysts of similar composition produced by the methods of the prior art. The cobalt crystallites of small size have a tendency to spontaneous combustion, therefore, the catalyst particles preferably stabilized using known methods, such as coating of the catalyst particles with oil before subjecting them to weathering.

The following examples illustrate and explain the present invention but they should not be construed as limiting the present invention in any respect. Examples 1-4 describe ways to prepare the catalysts of this izobreteny is, cooked without promoter (Example 1), with the promoter of platinum (Example 2), with the promoter of ruthenium (Example 3) and promoter of the ruthenium/rhenium (Example 4). Examples 5-10 describe the preparation of catalysts with similar compositions as catalysts of examples 1-4, except that the catalysts of examples 5-10 are prepared by using the methods of impregnation of the prior art. If the reaction needs deionized water, water can be diiodotyrosine using commercially available ion-exchange cartridges. Other materials are commercially available from Aldrich Chemical Company, 1001 West Saint Paul Avenue, Milwaukee, Wis., 53233; CONDEA Vista Company, Houston, TX 77224-9029 and Noah Technologies, San Antonio, TX 78249. The reaction is carried out in a mixing tank stainless steel, which can be equipped with a steam heater, and/or propeller stirrers. Where indicated stage of drying, the catalyst is dried in a convection oven manufactured Forma Scientific.

Example 1

In a preferred embodiment, the cobalt catalyst without promoter is prepared using the compound of carbonate hexaamminecobalt (II). In a mixing tank having a total volume of about 15 gallons (57 liters for 1 US gallon=3.8 liters and equipped with a steam heater with a closed coil and a propeller stirrer, enter about 6 gallons (23 liters) of deione the new water. The water is stirred with a speed of from about 500 to about 1000 rpm using a stirrer driven by air, and heated by steam up until the water temperature reaches a temperature from about 82 to about 85°C. the Rate of steam flow is measured by the pressure indicator longitudinal flow Brooks 3604&09 Hi Pressure Thru-Flow Indicator and at a temperature of about 168°C and a pressure of about 100 psig (689 kPa), the rate of steam flow varies from about 10 pounds per hour (4.5 kg h) to 13 pounds per hour (5,9 kg per hour). In the mixing tank add 3677,5 g substrate of alumina (CONDEA, Puralox®SCCa 5/150). The heated vapor regulate to maintain the temperature of a solution of aluminum oxide, or slurry, at a temperature of from about 82 to about 85°C. In a separate mixing vessel, prepare a solution of aminocarbonyl cobalt by the interaction of cobalt powder with an aqueous ammonia solution in the presence of carbon dioxide based 3.58 g With 100 ml of water. After stabilization of the temperature in the mixing tank solution aminocarbonyl cobalt pumped into the mixing tank at a rate of about 50 ml / min using a peristaltic pump (Model 7523-20, available from Cole-Parmer instrument Company, Vernon Hills, IL 60061-1844). The rate of introduction of the solution of aminocarbonyl cobalt can be adjusted to compensate for the loss of steam and ammonia from the slurry, at this price the firm is to maintain, basically, a constant volume of slurry is about 19 liters in a mixing tank. In General, the mixing tank is injected around 30,99 liters of solution aminocarbonyl cobalt during the period of time from about 10 to about 11 hours. After you have completed the solution aminocarboxylate, in the mixing tank impose additional ionized water to maintain the total volume of the slurry of about 19 liters. The temperature of the slurry is maintained within the temperature range from about 82 to about 85°until complete decomposition or within about 5-6 hours. For hexaamminecobalt source of complex decomposition is determined by the color change of the sludge from red or pink to pale orange. The sludge is then allow to cool in a mixing tank to the ambient temperature by stopping the flow of steam. Solid material in the sludge allow to settle and the liquid decanted from the solids. The solid material is then washed on the filter with a volume of deionized water equal to about 4 gallons (15 liters). The washed material is then distribute on the stainless steel container in a layer thickness of about 1 inch (2.5 cm). The material is then dried in a convection oven Forma Scientific, equipped with input for air, set to 480 litres per hour (siph), using temperature is adjusting the furnace 93° C. the Total drying time is about 20 hours. The catalyst-coated cobalt aluminium oxide then calicivirus in an electric furnace (Model 7075 available from The Electric electrotherapy exercising Company, Inc, Philadelphia, PA)set at a temperature of about 240°C, for 2 hours. Then perform the recovery of the catalyst particles by heating these particles from ambient temperature to a temperature of from about 300 to about 500°C at heating rate from about 0.1 to about 10°C/min over a period of time from about 5 to about 40 hours.

Example 2: the Cobalt catalyst with a promoter of platinum is prepared using the compound of carbonate hexaamminecobalt (II). About one liter of deionized water is introduced into the beaker of stainless steel, having a total capacity of about 4 liters and equipped with a propeller stirrer. The water stirred at the maximum setting, using a stirrer RZR 1 (Cafrano Ltd., Wharton, ON, Canada, NOH 2TO), and heated on a heating plate until, until the temperature reaches a value of from about 82 to about 85°C. In a glass add 174,15 g Puralox®SCCa 5/150 and temperature of the slurry is maintained within the range from about 82 to about 85°C. In a separate mixing vessel, prepare a solution of metal salts by combining approximately 958 ml of an aqueous solution of carbonate hexaamminecobalt (II), prepared by the CSO by the interaction of cobalt powder with an aqueous ammonia solution in the presence of carbon dioxide from the calculation of 5.2 g With 100 ml of water, and about 0,4096 ml of a solution of platinum chloride (Colonial Metals, Elkton, MD 21922). The solution of metal salts is then poured into a substrate of aluminum oxide. The temperature of the slurry is maintained within the range from about 77 to about 85°C for about 6 hours. The sludge is then allow to cool slowly to ambient temperature. The solid material in the slurry is filtered, washed with deionized water in a volume of 500 ml of the Washed material is then distribute on the stainless steel container in a layer thickness of from about 0.5 (1.7 cm) to about 1 inch (2.5 cm) and dried in a convection oven at a temperature of about 93°C. the Total drying time is about 16 hours. The catalyst-coated cobalt aluminium oxide then calicivirus in an electric furnace set at a temperature of about 240°C, within 2 hours.

Example 3: a Cobalt catalyst with a promoter of ruthenium prepared in a similar fashion as the catalyst promoter from the platinum of Example 2, except that 200 g of Puralox®SCCa 5/150 added to 2.4 liters of deionized water; solutions of metal salts are prepared by combining about 1730 ml of carbonate hexaamminecobalt (II), prepared from a rate of about 3.5 g With 100 ml of water, and about 37,08 g of the solution of nitrosylated ruthenium (Noah Technologies, 1,23% Ru, catalog number 90443); and the metal salt solution is added to the slurry in f is RME about 200 ml of aliquot spaced about 30 minutes until while the metal salt solution will not be spent. The solid material washed with water initially about one liter of deionized water on the filter, and then about two liters of deionized water on a filter press. The solid material calicivirus as in Example 2.

Example 4: a Cobalt catalyst with a promoter of ruthenium and rhenium is prepared from a cobalt/aluminum oxide catalyst, prepared as described in Example 1. In a separate vessel dissolve 3.25 g of rhenium oxide (Noah Technologies, 99.99% purity catalog number 12199) and $ 2.68 g nitrosylated ruthenium (Noah Technologies, 1,23% Ru, catalog number 90443) in about 60 ml of deionized water. Then 272,98 g of the material from the cobalt/alumina prepared in Example 1 are added to a solution, placed in a plastic bucket with a capacity of 1 gallon (3.8 l), for the initial impregnating wetting. The contents of the bucket vigorously stirred at predefined intervals of time within about one hour. The material is then filtered off, washed and dried in a convection oven set at a temperature of 93°C, air flow corresponding to about 2.5 SCFH (0,07 m3/h)during the night.

Example 5: Cobalt catalyst without promoter is prepared using the method of nitrate impregnation of the prior art. 3,68 M solution of nitrate of cobalt (II) prepare p is the dissolution of about 380 g of uranyl nitrate cobalt (II) (Shepherd Chemical Company, Norwood, Ohio, catalog number 1275, technical grade) in deionized water to obtain total volume of about 355 ml to About 125 ml of a solution of nitrate of cobalt (II) poured almost 250 g Puralox SCCa 5/150, which in 3.8-liter plastic vessel at ambient temperature. The vessel set the lid and mix by hand for about 1 minute or until until uniform wetting of the carrier of aluminum oxide. This material is dried at a temperature of about 80°C for about 10 hours air flow corresponding to about 1.7 SCFH (0.05 m3/hour), and then calicivirus at a temperature of about 240°C for about 4 hours air flow corresponding to approximately 10,2 SCFH (0,29 m3/hour). The second and third initial impregnating wetting accompanied by the same drying and calcination after each impregnation.

Example 6. Cobalt catalyst with a platinum promoter is prepared using the method of nitrate impregnation of the prior art. In a 1000 ml beaker quickly pour about 110 ml of molten crystals of nitrate of cobalt (Shepherd Chemical Company, Norwood, Ohio, catalog number 1275, technical grade) to about 300 g Puralox®SCCa 5/150 at ambient temperature. This material calicivirus at a temperature of about 340°10 hours who is ear thread appropriate about 10,2 SCFH (0,29 m3/hour). Calcined material then impregnorium 99 ml of molten crystals of nitrate of cobalt and calicivirus at a temperature of about 340°C for about 12 hours. Calcined material then impregnorium about 90 ml of molten crystals of nitrate of cobalt and calicivirus at a temperature of about 340°C for about 12 hours. In a separate vessel diluted around 1.30 g of the solution of amylnitrate platinum (Aldrich Chemicals, Milwaukee, WI53201, catalog number 27872-6) with deionized water to a volume of about 47 ml of a Diluted solution of platinum compounds add then to about 200 g of calcined material, and platinum impregnated material calicivirus at a temperature of about 340°C for about 12 hours.

Example 7: a cobalt catalyst with a promoter of ruthenium are using basically the same method described in Example 6, except that about 8.8 g of a solution nitrosylated ruthenium (NOAH Technologies, San Antonio, TX 78249, 99.9% purity catalog number 90443) take instead of 1.30 g of the solution of amylnitrate platinum.

Example 8: a cobalt catalyst with a promoter of ruthenium are using basically the same method described in Example 5, except that about 385 ml aqueous starting solution of compounds of cobalt/ruthenium prepared by dissolving about 36,15 g of uranyl nitrate of cobalt and 37,12 grams of nitrosylated ruthenium in deionized water. A solution of compounds of cobalt/ruthenium is taken instead of the solution of compound of Example cobalt 5.

Example 9: a Cobalt catalyst with a promoter from ruthenium/rhenium are using basically the same method described in Example 8, except that some of 3.42 g of the oxide of rhenium (VII) (NOAH Technologies, San Antonio, TX 78249, 99.99% purity catalog number 12199) is added to the original solution of compounds of cobalt/ruthenium.

Example 10: a Cobalt catalyst with a promoter from ruthenium/rhenium prepared using the method of acetate impregnation of known technology. In a 1000 ml beaker prepare a solution of metal compounds by dissolving about 204 g of crystals of cobalt acetate (Aldrich, mark A.C.S. Reagent, catalog number 40302-4) in deionized water to bring the final volume up to about 600 ml and then adding about 4.65 g of the solution of nitrosylated ruthenium (NOAH Technologies, San Antonio, TX 78249, 99.9% purity catalog number 90443) and 2.75 g of the oxide of rhenium (VII) (NOAH Technologies, San Antonio, TX 78249, 99.9% purity catalog number 12199). The volume of solution of metal compounds then bring to volume of about 630 ml by addition of deionized water. In some 3.8 l plastic bucket about 84 ml of a solution of metal compounds is added to about 153 g Puralox®SCCa 5/150. Processed material aluminum oxide is dried at a temperature of about 120°With air circulating ne and the air flow, appropriate about 5 SCFH (0,14 m3/hour). Then add about 80 ml of a solution of metal compounds to the treated material aluminum oxide, and the material is dried in a similar way as at the first dive. Then add about 75 ml of a solution of metal compounds to the treated material aluminum oxide. The material then calicivirus in chamber furnaces with air at about 240°C for about 4 hours air flow, corresponding to 10.2 SCFH (0,29 m3/hour). The process is then repeated twice with the material, which was pregnenolone using about 84 ml of a solution of metal compounds, then about 80 ml of a solution of metal compounds, then about 75 ml of a solution of metal compounds with drying between each application, as noted above, and with the stage of calcination after each of the third impregnation, so that the material was impregnable generally nine times, and was caliciviral three times. The decomposition of acetate is accompanied by a noticeable exothermic reaction at about 320°C.

Table 1 summarizes data on surface area, pore volume, pore size and size of the crystallites of cobalt for catalysts prepared according to examples 1-10. The catalysts of the present invention have more sellersville surface, a larger pore volume and a smaller crystallite size (which corresponds to b is a larger dispersion of cobalt), than the catalysts prepared by the method of impregnation.

Table 1
Cooking methodExample%PromotersSurface area

(m2/g)
Pore volume

(cm3/g)
The diameter of pores (Å)Co3About4< / br>
The average size
crystallites (MCS) (Å)
Raw Puralox SCCa 5/150UTS.UTS.160,00,5011output reached 125.5Not the treatment tip can.
The present invention120,9UTS.171,00,303666,564
Nitrate impregnation521,0 UTS.97,40,2756of 113.2231
The present invention219,80.017% of Pt212,60,302256,952
Nitrate impregnation624,10,031% Pt76,00,261985,5Not the treatment tip can.
The present invention320,50,11% EN1640,28055
Nitrate impregnation721,60,014% EN105,40,2742104,2248
Nitrate impregnation8of 21.20,12% EN980,274155
The present invention420,80,013% Ru/ 1,02% Re167,70,265163,286
Nitrate impregnation9of 21.90,015% Ru/ 1,05% Re104,00,2682103,2194
Acetate impregnation1022,70,02% Ru/ 0,95% Re115,20,275295,551

Figures 1A, 1B and 3 are scanning electron micrograph version of the catalyst of the present invention, prepared as described in example 2, which is a catalyst consisting of promoted platinum cobalt covering the aluminum oxide. As shown in Figures 1A and 1B, the catalyst has a relatively smooth surface morphology and, as shown in Figure 3, the catalyst has a largely uniform distribution of cobalt in the catalyst particle with a small cobalt crystallites. For comparison, Figures 2A and 2B and 4 are scanning electron micrographs of the catalyst prepared as described in Example 6, using the method of nitrate impregnation, the catalyst having the composition, in the main, identical cat is the lyst Figa. As shown in Figures 2A and 2B, the catalyst has a more rough surface morphology than the catalyst in Figures 1A and 1B, and as shown in figure 4, the catalyst has a more sporadic distribution of cobalt in the catalyst particle with the large size of the crystallites of cobalt than the catalyst 3. Fig.7 is a graph showing thermal stability of promoted platinum cobalt catalyst covering the aluminum oxide, prepared as described in Example 2.

The catalyst of the present invention is intended for use in the Fischer-Tropsch process and has a composition similar to the f-T catalyst of the prior art. However, the process by which the catalyst is prepared, produces a final product having a specific desired physical characteristics - more visarite surface more smooth, more uniform surface morphology, a more uniform distribution of active sites and a smaller crystallite size than the f-T catalysts of the prior art. It is clear that the composition of the catalyst and the specific process conditions can be modified without going beyond the scope of this invention.

1. The catalyst for use in the Fischer-Tropsch process, comprising at least one metal that t is aetsa effective adsorbent - carbon monoxide and at least one promoter, and the specified metal and the promoter dispersed on the substrate with the formation of the catalytic particles having a size BET surface of from 100 to 250 m2/g, while the specified metal and the promoter dispersed on the substrate so that the crystallite size of the metal oxide is from 40 to 200 Åwhile the metal and the promoter are different compounds, and said particle has a mostly smooth, homogeneous surface morphology, with this substrate has a particle size of from 60 to 150 microns, a surface area of from 90 to 210 m2/g, pore volume of 0.35 to 0.50 ml/g and a pore diameter of from 8 nm to 20 nm.

2. The catalyst according to claim 1, wherein said particle comprises from 5 to 60 wt.% cobalt and from 0.0001 to 1 wt.% the first promoter and from 0.01 to 5 wt.% the second promoter.

3. The catalyst according to claim 2, wherein said particle comprises from 10 to 30 wt.% cobalt and from 0.01 to 0.05 wt.% specified the first promoter and from 0.1 to 1 wt.% the specified second promoter.

4. The catalyst according to claim 1, characterized in that said metal is chosen from the group consisting of Nickel, cobalt, iron, ruthenium, osmium, platinum, palladium, iridium, rhenium, molybdenum, chromium, tungsten, vanadium, rhodium, copper, zinc and their combinations.

5. The catalyst according to claim 4, characterized in that asany metal is cobalt.

6. The catalyst according to claim 1, characterized in that the promoter is chosen from the group consisting of boron, cerium, chromium, copper, iridium, iron, lanthanum, magnesium, molybdenum, palladium, platinum, rhenium, rhodium, ruthenium, strontium, tungsten, vanadium, zinc, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, magnesium oxide, titanium oxide, zirconium oxide and other rare earth metals such as scandium, yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and combinations thereof.

7. The catalyst according to claim 2, wherein said first promoter is selected from the group consisting of palladium, platinum, ruthenium, rhenium, rhodium, iridium and combinations thereof; and the specified second promoter selected from the group consisting of potassium, boron, cesium, lanthanum, cerium, strontium, scandium, yttrium, prasetiya, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, palladium, platinum, ruthenium, rhenium, rhodium, iridium and combinations thereof.

8. The catalyst according to claim 1, characterized in that the specified substrate, vibrat from the group consisting of aluminum oxide, γ-aluminum oxide monohydrate aluminum, three-hydrate of aluminum, aluminum silicate, magnesium silicate, silicon dioxide, silicate, silicalite, y-zeolite, mordenite, titanium, thorium, zirconium, niobium, hydrotalcite, diatomaceous earth, attapulgite clay, zinc oxide, other clays, other zeolites and combinations thereof.

9. The catalyst according to claim 8, characterized in that the substrate is γaluminum oxide.

10. The catalyst for use in the Fischer-Tropsch process, comprising cobalt dispersed on a substrate with the formation of the catalyst particles, which is formed by carrying out the following stages:

a) introduction of a specified substrate in water when mixed with sludge formation and maintaining the temperature of the slurry in the range from 35 to 210°C;

b) adding an aqueous cobalt salt solution having a pH value greater than the point of zero charge specified substrate to the specified slurry with stirring while maintaining the specified temperature of the slurry in the range from 65 to 120°C;

c) mixing the specified slurry and maintaining the specified temperature of the slurry in the range from 65 to 120°up until the specified salt of cobalt, mostly, not completely reacts with the specified substrate;

d) separation of the specified slurry into a solid part and the liquid part;

e) washing the specified solid parts water;

f) drying and calcining the specified solids at a temperature of from 90 to 375°with the formation of catalyst particles;

g restore these catalyst particles by heating these particles from ambient temperature to a temperature of from 300 to 500° C at heating rate of 0.1 to 10°C/min over a period of time from 5 to 40 hours

11. The catalyst according to claim 10, characterized in that the above substrate is chosen from the group consisting of aluminum oxide, γ-aluminum oxide monohydrate aluminum, three-hydrate of aluminum, alumina-silicate, magnesium silicate, silicon dioxide, silicate, silicalite, y-zeolite, mordenite, titanium, thorium, zirconium, niobium, hydrotalcite, diatomaceous earth, attapulgite clay, zinc oxide, other clays, other zeolites and combinations thereof.

12. The catalyst according to claim 11, characterized in that the substrate is aluminum oxide.

13. The catalyst according to claim 11, characterized in that the substrate has a particle size of from 60 to 150 microns, a surface area of from 90 to 210 m2/g, pore volume of 0.35 to 0.50 ml/g and a pore diameter of from 8 to 20 nm.

14. The catalyst according to claim 10, characterized in that the cobalt salt solution comprises water and a compound of cobalt (II)with ligands of the coordination sphere selected from the group consisting of water, chlorine ions, ammonia, pyridine, triphenylphosphine, 1,2-diaminoethane, Diethylenetriamine, Triethylenetetramine, acetate, oxalate, 2,4-pentanedione, ethylendiamine tetraoxane acid and combinations thereof.

15. The catalyst 14, characterized in that the compound of cobalt (II) has the ligands coordinating the ion sphere, selected from the group consisting of molecules of water, ammonia, pyridine, diaminoethane, Diethylenetriamine, Triethylenetetramine and their combinations.

16. The catalyst according to item 15, wherein the specified complex compound of cobalt (II) carbonate is hexamine cobalt (II).

17. The catalyst according to claim 10, characterized in that the temperature of the slurry is maintained within the range from 65°to 120°at the stage a).

18. The catalyst according to claim 10, characterized in that the specified hard part is dried at a temperature of from 120°With up to 260°in stage f).

19. The catalyst according to claim 10, characterized in that the said particles is restored at stage g) by heating these particles from ambient temperature to 350°at a speed of 1.0°/min and then by keeping these particles at a temperature of 350°C for 12 to 16 hours.

20. The catalyst according to claim 10, characterized in that the particles are additionally stabilized to prevent pyrophoric reactions when these particles are in the air.

21. The catalyst according to claim 20, characterized in that the particles are stabilized by coating them with oil.

22. The catalyst according to claim 10, characterized in that it further comprises at least one promoter, which is injected with the indicated solution of cobalt salts.

23. The catalyst according to item 22, characterized in that FR is specified, the promoter is the salt of the metal, selected from the group consisting of an oxide of rhenium (VII), nitrosyl ruthenium nitrate, platinum chloride, amylnitrate platinum, amenhorrea platinum and combinations thereof.

24. The catalyst according to claim 10, characterized in that it further comprises at least one promoter, impressively on the specified catalytic particle after the specified particle dried in stage f), with the indicated promoter impregnorium on the specified particle by immersing the specified particles in an aqueous solution of the indicated promoter while maintaining stirring, and then the separation of these impregnated particles from the specified solution, and drying the above impregnated particles.

25. The method of preparation of the catalyst for use in the Fischer-Tropsch process, comprising cobalt dispersed on a substrate for forming catalyst particles, including:

a) introduction of a specified substrate in water, with stirring, with the formation of the slurry, and maintaining the temperature of the slurry in the range from 35 to 210°C;

b) adding an aqueous cobalt salt solution having a pH value greater than the point of zero charge specified substrate to the specified slurry with stirring while maintaining the specified temperature of the slurry in the range from 65 to 120°C;

c) mixing pointed to by the first slurry and maintaining the specified temperature of the slurry in the range from 65 to 120° With up until the specified salt of cobalt, mostly, not completely reacts with the specified substrate;

d) separation of the specified slurry into a solid part and the liquid part;

e) washing the specified solid parts water;

f) drying and calcining the specified solids at a temperature of from 90 to 375°with the formation of catalyst particles; and

g) the restoration of these catalyst particles by heating these particles from ambient temperature to a temperature of from 300 to 500°C at heating rate of 0.1 to 10°C/min over a period of time from 5 to 40 hours

26. The method according A.25, characterized in that the substrate is aluminum oxide.

27. The method according to p, characterized in that the compound of cobalt (II) carbonate is hexamine cobalt (II).

28. The method according to item 27, wherein the temperature of the slurry is maintained within the range from 65 to 120°at the stage a).

29. The method according to p. 25, wherein the specified hard part is dried at a temperature of from 120 to 260°in stage f).

30. The method according A.25, characterized in that the said particles is restored at stage g) by heating these particles from ambient temperature to 350°at a speed of 1.0°/min and then by keeping these particles when the temperature is e 350° C for 12 - 16 hours

31. The method according A.25, characterized in that the particles are additionally stabilized by coating them with oil.

32. The method according A.25, characterized in that it further comprises at least one promoter, and the specified promoter injected with the indicated solution of cobalt salts.

33. The method according to p, characterized in that the promoter is the salt of a metal selected from the group consisting of an oxide of rhenium (VII), nitrosyl ruthenium nitrate, platinum chloride, amylnitrate platinum, amenhorrea platinum and combinations thereof.



 

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3 cl, 9 ex, 9 dwg

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: alternate fuels.

SUBSTANCE: invention relates to production of synthetic gas via catalytic hydrocarbon conversion in presence of oxygen-containing gases and/or water steam as well as to catalysts suitable for this process. Invention provides catalyst, which is complex composite constituted by supported precious element, or supported mixed oxide, simple oxide, transition element, wherein support is a metallic carrier made from metallic chromium and/or chromium/aluminum alloy coated with chromium and aluminum oxides or coated with oxides of chromium, aluminum, or mixtures thereof. Catalyst preparation procedure and synthetic gas production process are also described.

EFFECT: increased conversion of hydrocarbons, selectivity regarding synthetic gas, and heat resistance of catalyst at lack of carbonization thereof.

4 cl, 3 tbl, 9 ex

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: preparation of middle-temperature carbon monoxide conversion catalysts, which can be used in industrial production of ammonia synthesis destined nitrogen-hydrogen mixture, comprises mechanical activation of iron-containing component with calcium and copper oxides, mixing with water to form plastic mass, extrusion forming, drying, and calcination, said iron-containing component being iron metal powder and said mechanical activation of components being accomplished by passing air enriched with oxygen to 30-100%. Under these circumstances, catalyst activity rises by 19.4-23.1%.

EFFECT: increased catalyst activity, eliminated formation of waste waters and emission of toxic nitrogen oxides, and reduced (by 30%) number of process stages.

1 tbl, 3 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to preparation of catalysts used in styrene oligomerization processes producing dimers useful in manufacture of synthetic rubbers, heat carriers, insulation oil, polystyrene solvents. Catalyst is prepared through interaction of palladium (II) compound and boron trichloride compound in styrene medium at 333-353 K, said palladium (II) compound being, in particular, palladium acetylacetonato-bis(triarylphosphine) tetrafluoroborate of general formula [(Acac)Pd(PR3)2]BF4, wherein Acac denotes acetylacetonate, PR3 tertiary phosphine, and R phenyl, o-tolyl, or p-tolyl, and atomic ratio B/Pd = 3:10.

EFFECT: increased process efficiency to 153000 mole styrene per 1 g-atom Pd with dimer formation selectivity to 91%.

3 tbl, 15 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides copper and silica-based catalyst containing 22.5-53.0% copper. Catalyst is prepared by reductive thermal decomposition of copper silicate in hydrogen flow at 380-450°C. catalyst is used in dihydroxyalkane production processes carried out at 180-200°C.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 1 tbl, 8 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides copper and silica-based catalyst containing 22.5-53.0% copper. Catalyst is prepared by reductive thermal decomposition of copper silicate in hydrogen flow at 380-450°C. catalyst is used in dihydroxyalkane production processes carried out at 180-200°C.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 1 tbl, 8 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to petrochemical processes, in particular production of ethylbenzene via alkylation of benzene with ethylene catalyzed by solid acid catalyst, and provides elevated-strength (cleavage strength above 2 kg/mm diameter) catalyst showing high characteristics regarding activity (theoretical yield of ethylbenzene 65.83-70.7%) and selectivity (yield of ethylbenzene based on converted benzene 68,18-71.4%). This is achieved by way of mixing Pentasil-type zeolite with binder, said zeolite having been preliminarily subjected to exchange of cations: consecutively ammonium and calcium or magnesium. As binder, pseudoboehemite-structure aluminum hydroxide, to which inorganic acid was add to pH 2-4, is utilized. Molding mass is characterized by calcination loss 35-45 wt %. Heat treatment is effected in one to three steps.

EFFECT: improved strength, activity and selectivity of catalyst.

2 tbl, 5 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides gasoline fraction reforming catalyst containing 0.1-0.5% platinum, 0.1-0.4% rhenium, halogen (chorine, 0.7-1.5%, or chorine and fluorine, 0.05-0.1%), and carrier: surface compound of dehydrated aluminum monosulfatozirconate of general formula Al2O3·[ZrO(SO4)]x with weight stoichiometric coefficient x = 0.45·10-2 - 9.7·10-2 and real density 3.3±0.01 g/cm3. Catalyst preparation process comprises preparation of carrier by mixing (i) aluminum hydroxide, from which iron and sodium impurities were washed out (to 0.02%) and which has pseudoboehemite structure, with (ii) aqueous solution of monosulfatozirconic acid HZrO(SO4)OH containing organic components (formic, acetic, oxalic, and citric acids) followed by drying, molding, and calcination. Carrier is treated in two steps: first at temperature no higher than and then at temperature not below 70°C.

EFFECT: enabled production of reforming gasolines with octane number not below 97 points (research method) with yield not less than 86% and increased activity and selectivity of catalyst.

4 cl, 2 tbl, 13 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: ammonia synthesis catalyst is based on ruthenium on carrier of inoxidizable pure polycrystalline graphite having specific BET surface above 10 m2/g, said graphite being characterized by diffraction pattern comprising only diffraction lines typical of crystalline graphite in absence of corresponding bands of amorphous carbon and which graphite being activated with at least one element selected from barium, cesium, and potassium and formed as pellets with minimal dimensions 2x2 mm (diameter x height). Catalyst is prepared by impregnating above-defined catalyst with aqueous potassium ruthenate solution, removing water, drying, reduction to ruthenium metal in hydrogen flow, cooling in nitrogen flow, water flushing-mediated removal of potassium, impregnation with aqueous solution of BaNO3 and/or CsOH, and/or KOH followed by removal of water and pelletizing of catalyst.

EFFECT: increased activity of catalyst even when charging ruthenium in amount considerably below known amounts and increased resistance of catalyst to methane formation.

12 cl, 1 tbl

FIELD: gas treatment processes and catalysts.

SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.

EFFECT: increased yield of elemental sulfur.

9 cl, 5 tbl, 9 ex

FIELD: gas treatment processes and catalysts.

SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.

EFFECT: increased yield of elemental sulfur.

9 cl, 5 tbl, 9 ex

FIELD: alternate fuels.

SUBSTANCE: invention relates to production of synthetic gas via catalytic hydrocarbon conversion in presence of oxygen-containing gases and/or water steam as well as to catalysts suitable for this process. Invention provides catalyst, which is complex composite constituted by supported precious element, or supported mixed oxide, simple oxide, transition element, wherein support is a metallic carrier made from metallic chromium and/or chromium/aluminum alloy coated with chromium and aluminum oxides or coated with oxides of chromium, aluminum, or mixtures thereof. Catalyst preparation procedure and synthetic gas production process are also described.

EFFECT: increased conversion of hydrocarbons, selectivity regarding synthetic gas, and heat resistance of catalyst at lack of carbonization thereof.

4 cl, 3 tbl, 9 ex

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