Process for production of hydrocarbons from carbon monoxide and hydrogen

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: process is effected in reactor containing compacted bed of supported catalyst including group VIII metal, in particular cobalt, said metal being partially present in its metallic form. Supported catalyst has, on its outside surface, catalytically active metal. Compacted bed is characterized by having hollow volume more than 50 vol % and specific surface area more than 10 cm2/cm3, which is calculated as total outside surface of particles divided by bed volume.

EFFECT: improved economical efficiency of process.

8 cl, 3 tbl, 7 ex

 

The technical field to which the invention relates.

The present invention relates to a method for producing hydrocarbons from carbon and hydrogen in the presence of a catalyst, carried out in a reactor which contains a compacted layer of deposited catalyst.

Prior art

Catalytic preparation of hydrocarbons from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen, is well known in the art and it is usually called the Fischer-Tropsch synthesis.

Catalysts that are suitable for use in the Fischer-Tropsch synthesis usually contain a catalytically active metal of the FRAGILE group of the Periodic table of the elements (Handbook of chemistry and physics, e edition, CRC Press, 1987-1988), deposited on a refractory oxide such as alumina, titanium dioxide, zirconium dioxide, silicon dioxide, or a mixture of such oxides. In particular, the well-known catalytically active metals such catalysts are iron, Nickel, cobalt and ruthenium. You can refer to the patents EP-A-398420, EP-A-178008, EP-A-167215, EP-A-168894, EP-A-363537, EP-A-498976 and EP-A-71770.

In the Fischer-Tropsch synthesis, as in many other chemical reactions caused catalyst, reagent, and diluent, if present, in contact with each other usually form a three-phase system containing gas, the liquid and the solid substance. This three-phase system can operate, for example, in the reactor with a thickened layer of the catalyst or reactor by sparging suspension. A reactor with a thickened layer may contain a compacted layer of solid, relatively large catalyst particles through which the flow of gas or liquid. The reactor bubbling suspensions may contain a continuous phase liquid from a solid, relatively small catalyst particles suspended in the liquid, and gaseous reactants passing through the fluid layer in the form of bubbles. Typically, the catalytically active metal is uniformly dispersed on all catalyst particles.

There is ongoing interest in the search for catalysts and catalytic systems for use in the Fischer-Tropsch synthesis, which could provide increased activity and improved selectivity in the conversion of carbon monoxide into valuable hydrocarbons, particularly hydrocarbons containing five or more carbon atoms (hereinafter "hydrocarbons C5+"), and are formed of a minimum number of methane, which is usually a hydrocarbon having a lower value.

In U.S. patent 5545674 discusses the application in Fischer-Tropsch synthesis catalysts, which have a small diffusion length, i.e. they have a low diffusion resistance. T is such catalysts can be in the form of fine powder for use in a reactor by sparging suspension, or they can be in the form of so-called "Korotkevich catalysts". These crackovia catalysts include relatively large particles, which contain the catalytically active metal, located exclusively in the thin outer layer of the particles, instead of the uniform distribution of the metal on all particles. Crackovia catalysts are of interest mainly for use in the reactor with a thickened layer. Compared with conventional catalysts, the catalysts with small diffusion length have a relatively high selectivity for the formation of hydrocarbons C5+, and these catalysts suppressed the formation of methane. As indicated above, the catalysts which have the form of a relatively fine powder, can be conveniently used in a reactor by sparging suspension. However, there are technological problems with Korotkevich catalysts in the reactor with a thickened layer. Indeed, taking into account the fact that in Korotkevich catalysts, the catalytically active metal is present only in the outer layer of the catalyst particles in the reactor, there is relatively small amount of catalytically active metal. This leads to the fact that the reactor has a relatively low productivity per volume of reactor, provided the immutability of the article the selected process parameters. This situation cannot be satisfactorily improved by the use of traditional forms of catalyst such as beads or spheres, extrudates, pillows or the like, for Example, if you resort to increasing the number present catalytically active metal by reducing the particle size of the catalyst, there may be problems associated with a large pressure drop in the catalyst bed.

In General, these problems occur in any process of chemical transformation, in which there is a flow of gas or liquid and which play the role of diffusion limitations associated with the solid catalyst. Thus, a more General consideration is desirable to find a solution to the problem of using korechkovogo catalyst in the reactor with a thickened layer in economically attractive operation mode.

Disclosure of the invention

As a solution to this problem in the present invention developed a method of producing hydrocarbons from a mixture of monograde and hydrogen in the presence of a catalyst in a reactor containing a compacted layer of deposited catalyst, which caused the catalyst has an outer surface containing a catalytically active metal. When a compacted layer has a volume of voids greater than 50 vol.% and the specific surface area of more than 10 cm2/cm 3which is calculated as the ratio of the total external surface area of the particles to the volume of the layer.

In the operation of the method of chemical transformations, which includes the flow of gas or liquid, a compacted layer, which is defined in accordance with this invention provides the advantages of low pressure drop in the compressed layer and high performance of the reactor. In accordance with the preferred embodiment of the invention this can be achieved through the use of compacted layer of catalyst particles, which are relatively thin and have an elongated shape, in particular particles, which are somewhat curved, such as shavings and pieces of twisted wire or a twisted ribbon. Preferably this invention is carried out in novotrubnom reactor with a fixed catalyst bed.

It should be borne in mind that a compacted layer of deposited catalyst includes a catalytically active metal is a metal of group VIII and who is present (at least partially) in the form of metal. Suitable compacted layer, which can be used in the present invention is a deposited catalyst in the form of a solid layer of relatively large particles or in the form of fixed structures (or organized packaging), such as p is Bolotnaya mesh, corrugated sheet material, which may be present (or absent) perforated holes, woven or non-woven structure, honeycomb and foam. For total consideration of columns with packing, especially organized packs, made reference to the Reference chemical engineer, Perry, 1984, 50 ppm edition, S. from 18-19 to 18-41. This reactor is particularly suitable for reactions carried out in the drop-down flow of gas/liquid.

In addition, in preferred embodiments, the embodiments that are shown below in the claims, this invention provides a compacted layer of catalyst particles, the actual catalyst particles, as well as a compacted layer, which includes a fixed structure or organised packages containing catalyst, for example in the form of a coating, and the fixed patterns or your own organized packing.

The specialist in this field of technology can immediately recognize that this invention eliminates the disadvantages of the method of operation in the column with the bubbling of the suspension. Namely, when working in a column with the bubbling of the suspension device is required to achieve and maintain uniform distribution of catalyst throughout the volume of the liquid, and there is a need for separation of reaction products from relatively small particles of powdered catalyst.

Suitably the volume of voids in the layer of catalyst is not more than 95 vol.%, preferably not more than 90 vol.%. Convenient to the volume of voids was at least 55 vol.%, preferably at least 60 vol.%, in particular at least 65%.

Preferably, the specific surface area of the compacted layer was at least 15 cm2/cm3more preferably, at least 20 cm2/cm3in particular at least 25 cm2/cm3calculated as the total area of the outer surface relative to the volume of the layer. Suitable specific surface area of the catalyst layer is not more than 500 cm2/cm3in particular not more than 300 cm2/cm3when the same calculation. The specific surface area of the compacted layer refers to external, i.e. the macroscopic surface area of individual particles present in the compacted layer, as opposed to their internal, that is, the microscopic surface area.

Caused the catalyst may contain particles and/or fixed structures, and/or organized packing. Usually patterns or packaging may contain inert frame (for example, available industrial mesh, corrugated sheet or woven (non-woven) structure), covered with a layer of catalyst. These particles can contain inert frame or they exist in the form of uniform particles, i.e. nasni surface layer, and the frame include a catalytically active metal.

The shape of the particles and / or the packaging is not the subject of the invention, since (during the unloading of the reactor or placing in the reactor) particles or packing form a compacted layer in accordance with this invention. A trained professional can recognize that in thus formed a compact layer voids uniformly distributed throughout the layer, i.e. there are no large empty spaces, and areas that do not contain voids. For example, particles that do not have a free flowing, not so easily loaded into the reactor, resulting in a compact layer can be large voids. In addition, less preferred are particles that can easily stick together, as they may lead to the formation of areas in which there are no voids, which leads to an increase of the differential pressure tight layer.

As noted above, in a preferred variant embodiment of a compacted layer includes particles that are relatively thin and have an elongated shape. In particular, they can be bent to some extent, because it leads to an increase in the content of voids in the compacted layer. Too a large degree of bending is less preferred and less predpochtite the flaxes branched particles. Indeed, too great a degree of bending and branching leads to the loss of free fluidity of the particles.

Convenient to have a relatively thin and elongated particles has the length that is the greatest particle size of at least 1 mm, in particular at least 2 mm. Convenient to have a relatively thin and elongated particles had a length of not more than 50 mm, in particular not more than 25 mm, a Relatively thin and elongated particles can be bent and/or curved, for example, in two or more specific locations, in more than one direction. If the particles are curved and/or twisted, it is assumed that their length is equal to the length of the same particles after straightening. A relatively thin and elongated particles may have a cross-section of any shape. Typical shapes are rectangular, oval and round.

Criterion forms a relatively thin and elongated particle is defined here as the ratio of their length to the partial volume and surface area. Usually the value of the criterion of the form equal to at least 10, and typically not more than 1000, more preferably this amount is in the range from 20 to 500. Regardless of this criterion and regardless of the degree of bending, the size of a relatively thin and elongated particles correspond to the boundaries of the dimensions of the hypothetical cylinder whose length is the length you mentioned the e particles, and in which the ratio of length to diameter round cross-section is usually at least 2, preferably at least 3, and usually does not exceed 100. More preferably, this criterion is in the range from 4 to 50.

Specifications particles, which are listed in the two preceding paragraphs applies, when all particles have the same size and shape. Often relatively thin and elongated particles have the same size and shape; in this case, it is preferable that at least 80%, in particular at least 90%, even more preferably, all of the individual particles corresponded to the above specifications.

The catalytically active metal may be evenly distributed over the catalyst particles. In this case, it is assumed that the contents of the cavities and the value of specific surface area of the compacted layer, which is defined above, the particle size of the catalyst are such that the catalyst had the characteristics of a small length of diffusion (i.e. small diffusion resistance). However, preferably the catalyst particles are particles korechkovogo catalyst, which include a core and an outer layer covering the core, and this outer layer contains a metal. A trained professional can recognize that the core is predpochtitel is but inert or potentially inactive, compared with the catalytic activity of the outer layer. Regardless, evenly if divided catalytically active metal on all catalyst particles or catalyst particles are particles korechkovogo type, preferably, the catalytically active metal was supported on a carrier.

Typically, the carrier is a material with a large area of the inner surface. For example, the area of the inner surface is at least 20 m2/g, especially at least 25 m2/g, and more specifically, at least 35 m2/, Convenient to the area of the inner surface was not more than 400 m2/g, particularly not more than 200 m2/, Preferably, the size of the inner surface is in the range from 40 m2/g to 100 m2/, Listed here the value of area of the inner surface defined as the surface area by BET method, which is measured in accordance with ASTM D3663-92.

The media can represent, for example, carbon media, but preferably it is a refractory oxide. Examples of suitable refractory oxides include silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide or mixed oxides containing silicon dioxide, aluminum oxide, titanium dioxide or dioxi is zirconium, such as aluminosilicate, or physical mixtures such as a mixture of titanium dioxide and silicon dioxide. Preferably, the refractory oxide comprises titanium dioxide, zirconium dioxide or mixtures thereof, in particular refractory oxide is titanium dioxide or zirconium dioxide.

In accordance with the preferred embodiment of the refractory oxide comprising titanium dioxide, zirconium dioxide or mixtures thereof, may optionally contain up to 50 wt.% another refractory oxide, typically silicon dioxide or aluminum oxide, calculated on the total weight of the refractory oxide. More preferably, the additional refractory oxide, if present, is contained in an amount up to 20 wt.%, even more preferably up to 10 wt.%, in the calculation on the same database.

The most preferred refractory oxide is titanium dioxide, in particular titanium dioxide, which is obtained in the absence of sulfur-containing compounds. An example of such a method of obtaining includes the hydrolysis of titanium tetrachloride in a flame.

In accordance with this invention, the catalyst particles comprise a catalytically active metal. Usually metal, as indicated earlier, is a metal of group VIII, as the catalyst metal of group VIII can be used in many chemical reactions, such as synthesis of f the Fischer-Tropsch or hydrogenation.

For use in the Fischer-Tropsch synthesis is preferred that the metal of group VIII selected from iron, Nickel, cobalt and ruthenium. More preferably, the metal of group VIII choose cobalt or ruthenium as catalysts based on cobalt catalysts based on ruthenium give a relatively high yield of hydrocarbons C5+. It is most preferable as the metal of group VIII choose cobalt. May be additional metal in order to increase the catalyst activity or selectivity for the conversion of synthesis gas into hydrocarbons. Suitable additional metals can be selected from manganese, vanadium, zirconium and rhenium. Preferred additional metal is manganese or vanadium, especially manganese.

If the catalytically active metal supported on a carrier, the amount of metal, in particular metal of group VIII present in the medium may vary within wide limits. When using the catalyst in the Fischer-Tropsch synthesis a typical amount of metal is in the range from 1 to 50 wt.%, based on the weight of the metal relative to the weight of catalyst particles, if the metal is distributed evenly, or about the weight of the outer layer of the particle, if the catalyst particles are particles korechkovogo produce the RA. In accordance with the above definition assumes that the outer layer is a layer at the periphery of the particle, which contains 90% of the catalytically active metal. Preferred intervals range from 3 to 40 wt.%, in particular from 5 to 30 wt.%, in the calculation on the same database.

Usually the metal of group VIII and an additional metal, if present in the catalyst are in the catalyst particles in the same places. The atomic ratio of the metal of group VIII to the additional metal is typically at least 5:1 and typically does not exceed 200:1.

If you are using korochkoy catalyst, the core preferably includes a material with a low area of the inner surface, since the smaller the area of the inner surface, the less chance that the very core of the particles will exhibit catalytic activity. Accordingly, if the catalytically active metal supported on a carrier, the value of the inner surface of the carrier is preferably greater than the area of the inner surface of the nucleus. Typically, the core can have a value of the inner surface of less than 20 m2/g, especially less than 10 m2/g and, in particular, less than 2 m2/year

Typically, the engine includes an inorganic material such as a refractory oxide, ceramic material, metal or coal is od. Suitable refractory oxides for use as cores are silicon dioxide, aluminum oxide, titanium dioxide, magnesium oxide and zirconium dioxide and mixtures thereof. The preferred refractory oxides for use as cores are silicon dioxide and aluminum oxide.

The use of kernel-based metal (i.e., the core is a metallic nature) can be advantageous because it provides korochkoy catalyst, which is durable and has a relatively high thermal conductivity. The relatively high thermal conductivity is advantageous when korochkoy the catalyst used in the process in which the reaction mixture must be removed (or in the mixture it is necessary to bring) a significant amount of heat, such as Fischer-Tropsch synthesis. Suitable metals are aluminum, iron, copper, titanium and mixtures containing one or more of such metals, such as steel and brass. Aluminum and mixtures containing aluminum, are preferred, for example mixtures which contain at least 80 wt.% aluminum, in particular at least 90 wt.% aluminum. Latest mixes usually contain not more than 99.9 wt.% aluminum, or even not more than 99.99 wt.% aluminum. A mixture containing aluminum, may include from 0.01 to 5 wt.% impurities or additives selected from, for example, the magician is Oia, silicon, copper, manganese, zinc, chromium and titanium.

The core may be partially or completely made out of carbon or organic material such as a polymer or other material such as resin. Examples of suitable organic materials are polystyrene, polyolefin, cellulose, hydrocarbon resin and epoxy resin. Carbon organic material can be removed at a later stage, for example, during the stage of calcination, as described in the following and in this case are hollow catalyst particles or catalyst particles in which the core has a low density (for example, the core having a foam structure). In fact identify, remove kernels can be considered as his replacement on an empty space, while the formed hollow (partly) particles of catalyst particles remain korechkovogo catalyst.

The surface of the core may be pre-processed in order to obtain improved adhesion of the outer layer to the core, especially after the stage of calcination, which are described in the following. The surface of the kernel can be modified, for example, by removing impurities or surface covering layer. Thus, the kernel can be washed with water or dilute acid, such as aqueous phosphoric acid; or it can be processed by Sol refractory oxide, the mayor as silicasol or Sol of aluminum oxide, or coating pigment such as zirconium oxide. If the core comprises a refractory oxide, it can be pre-treated by calcination, for example, by heating at an elevated temperature between 400 and 700°C, preferably between 450 and 650°C. Typically, the duration of calcination is from 5 minutes to several hours, preferably from 15 minutes to 4 o'clock This calcining is conveniently carried out in oxygen-containing atmosphere, preferably air. It is not excluded that korochkoy metal catalyst includes additional components, in addition to those mentioned above.

A trained professional can recognize that the prior art suitable methods of deposition of the catalytically active metal on the carrier. For example, applied catalysts can be obtained using methods known from WO-99/34917, EP-A-455307, EP-A-510771 and EP-A-510772. These links are associated with media from titanium dioxide, aluminum oxide, silicon dioxide and zirconium dioxide, respectively.

The catalytically active metal and more metal, if used, can be introduced to the media in the same way and together. Such additional compounds include salts such as nitrates, carbonates, and acetates, chelates, such as acetylacetonates and allylacetate, hydroxides and oxides and its own is significant metals. Usually at the stage of calcination will be turning more compounds into the corresponding metal oxide.

Applied catalysts can be obtained in the form of a powder after spray drying, or in the form of extrudates, which can be milled to obtain a powder. Thus obtained powder can be mixed with a diluent to prepare a suspension.

In a preferred variant embodiment, the suspension is obtained by mixing the catalytically active metal, optionally with additional metal carrier with the diluent.

Possibly, but not necessarily in order of suspension was attended by an additional connection, because after the stage of calcination, which are described in the following, it increases the strength of the applied catalyst and/or adhesion of the outer layer on the core, if it is used.

Additional connection may be a connection, which forms a refractory oxide at a stage of annealing. Additional connection may be soluble (or insoluble) in the diluent. Additional connection may be an organic salt or a complex compound, especially one that contains up to 20 carbon atoms. Examples of such salts and complex compounds are salts, such as acetates, propionate, citrates, chelates, such as acetylate the courses, allylacetate and chelates with lactic acid; an alcoholate, such as utility, aminoacylase and isopropylate; and alkyl compounds, such as ethyl and isooctyl connection. Alternatively, the additional compound is an inorganic compound such as a hydroxide or an inorganic salt such as a halide. The pigments of refractory oxides often include additional connection - refractory oxides.

As an example, such suitable compounds of titanium dioxide are tetraethylsilane, isostearamide, and aktiengellschaft, and triethanolaminato. Very convenient connection, especially for use in combination with water as a diluent, is the ammonium salt of lactic acid, chelated titanate.

The diluent for the preparation of suspensions may be an organic diluent such as a lower alcohol, a lower ketone, lower complex or a simple ester, for example ethanol, acetone, methyl ethyl ketone, ethyl acetate, diethyl ether or tetrahydrofuran. In this patent application, when the term "lower" used in conjunction with an organic compound, this term means that the organic compound has no more than 6 carbon atoms, particularly 4 carbon atoms. More suitable are aqueous diluents, such as a mixture of organic the CSOs diluent and water, preferably containing at least 50 wt.% water and less than 50 wt.% organic diluent, based on the total weight of the diluent. It is most convenient to use water as the sole diluent.

This suspension can be used for the coating of core particles by spraying to get korochkoy catalyst. A suitable method and apparatus for spraying a suspension of particles of the nucleus is known from the publication Arntz and other "Preparation of catalysts IV, .Delmon and others (ed), Elsevier, 1987, p.137. It is also possible wetting of the particles of a core with a diluent, followed by contacting the moistened particles of powder by spray or propilivanija powder on the moistened particles, or by obvalivanie moistened particles in the powder.

Alternative suspension can be subjected to extrusion forming catalyst particles, which do not have nuclei, i.e. which contain catalytically active metal, almost evenly distributed on the particles. Such extruded particles with a uniform distribution can also be obtained directly, using the methods of WO-99/34917, EP-A-455307, EP-A-510771 and EP-A-510772.

In alternative embodiments korochkoy the catalyst may be prepared by impregnation of a surface, for example, using the method of spraying or immersion, which the op is Sana'a in U.S. patent 5545674 and EPA-178008 and EPA-174696. When using surface impregnation is necessary that the core and the carrier of the outer layer constituted of the same material.

Preferably, the catalyst particles were directed at a stage of annealing. This stage of annealing increases the hardness and strength of the coating and improves the adhesion of the coating to the core. Stage of annealing includes heating at an elevated temperature, preferably at a temperature between 400 and 750°C, more preferably between 450 and 650°C. the Duration of the stage of calcination is usually from 5 minutes to several hours, preferably from 15 minutes to 4 hours Convenient to carry out stage of annealing in oxygen-containing atmosphere, preferably air. The typical thickness of the outer layer on the particles korechkovogo catalyst, after the stage of calcination is in the range of from 0.001 to 0.15 mm, preferably in the range from 0.002 to 0.1 mm, in particular in the range of 0.005 to 0.08 mm, the thickness of the outer layer on the particles korechkovogo catalyst is defined here in different ways for different types of particles korechkovogo catalyst. The thickness of the outer layer of the coated particles korechkovogo catalyst is defined as the ratio of the volume of the coating, which contains a catalytically active metal, and the outer surface of the particle core. The thickness of the outer layer on the particles is rockowego of the catalyst-impregnated surface is defined as the thickness (d) of the layer on the periphery of the particles, which includes 90% of the catalytically active metal, and this layer is chosen so that at any point on the inner side of the layer of the shortest distance to the periphery of the particles is the same and equal to d.

The thickness of the outer layer, which is specified in the previous paragraph applies in the case when all particles have the same thickness of the outer layer. Often the thickness of the outer layer is not the same for all particles, and in this case, it is preferable that at least 80%, in particular at least 90%, more specifically, all individual particles satisfy these requirements.

A suitable interval of catalytically active volume of compacted layer (i.e. the total amount of particles that contain a catalytically active metal, usually after stage annealing) is the interval from 5 to 50 vol.%, preferably from 10 to 40 vol.%, relative to the volume of the compacted layer. In this context, it is assumed that a catalytically active amount korechkovogo of the catalyst-impregnated surface represents the volume of the layer on the periphery of the particles, having a thickness d. A catalytically active amount of coated particles korechkovogo catalyst represents the volume of the coating. When the catalytically active metal is evenly distributed over all particles of a catalytically active amount represents the t of a total volume of particles.

Fixed packaging or organized packing, which can be used in the present invention, are well known in the literature and are often commercially available. These patterns or packaging is usually made of metal or metal alloys, or have the form of a ceramic foam/ceramic honeycombs. These patterns or packaging can be covered with a layer, which comprises a catalytically active metal or its previous connection, as described above. Preferred materials for structures or packages are the same as described above korechkovogo catalyst.

The claimed method of producing hydrocarbons is carried out in a reactor which consists of a tank that includes a communication input of raw materials, disposal of the product and the internal device, through which the compacted layer is maintained in a given position, and the reactor includes a comfortable incoming and outgoing lines for the secondary chemical agents and device for heating and/or cooling of the reactor and its contents. Typically, the reactor is designed so that it can withstand the internal pressure. The capacity can be filled with catalyst particles in the filling particles in the reactor. In the reactor can be a lot of tanks, so that the reactor can be located is ogeno many of compacted layers, for example 12500 or even up to 40,000 or more. The reactor can be Novotrubny reactor.

Optionally, the stage of calcination can be carried out inside the reactor.

A compacted layer may have the following dimensions. Usually the height of the compacted layer is in the range from 1 to 20 m Dimensions perpendicular to the height usually are in the range from 1 cm to 10 m, the ratio of the latest dimensions to the length of the catalyst particles typically lies in the range from 5 to 1000, preferably from 7 to 500.

The metal present in the catalyst is a metal of group VIII, and usually, at least part of the metal of group VIII is present in the metallic state.

This is why it is best to activate the metal of group VIII to use by recovery in the presence of hydrogen at elevated temperature. If the restoration can be carried out inside the reactor. Typically, the recovery involves the treatment of the catalyst at a temperature in the range from 100 to 450°at high pressure, typically from 1 to 200 bar (abs.), often in the course of from 1 to 200 hours During recovery can be used pure hydrogen, but usually prefer to use a mixture of hydrogen and inert gas, such as nitrogen. The relative amount of hydrogen present in the mixture can change is taken between 0.1 and 100 vol.%.

In accordance with the preferred embodiment of the recovery of the catalyst is heated to the desired temperature and pressure in a gaseous nitrogen atmosphere. Subsequently the catalyst is in contact with a gas mixture containing only a small amount of gaseous hydrogen, and the remainder represents nitrogen. In the process of restoring the relative amount of hydrogen in the gaseous mixture gradually rises to 50% or even up to 100%vol.

It is possible to activate the metal of group VIII of the catalyst in place, i.e. inside the reactor for the production of hydrocarbons from synthesis gas. In the document WO-97/17137 describes the process of activating the catalyst in place, which includes the contacting of the catalyst in the presence of a hydrocarbon liquid with a hydrogen-containing gas at a partial pressure of hydrogen of at least 15 bar (abs.), preferably at least 20 bar (abs.), more preferably at least 30 bar (abs.). Usually in this process, the partial pressure of hydrogen is not more than 200 bar (abs.).

Typically, the method of producing hydrocarbons from synthesis gas is carried out at a temperature in the range from 125 to 350°C, preferably from 175 to 275°C. Typically, the pressure is in the range from 5 to 150 bar (abs.), preferably from 5 to 80 bar (abs.), in particular from 5 to 50 bar (abs.). Usually in this SPO is both hydrogen and carbon monoxide (synthesis gas) are in a molar ratio in the range from 0.7 to 2.5. If you have a low ratio of hydrogen to carbon monoxide usually increases the selectivity of the catalyst C5+, i.e., the selectivity for the formation of hydrocarbons C5+.

Volumetric gas flow rate (in subsequent OPG) can vary within wide ranges and is typically in the range from 400 to 20000 standards. l/l/h, more typically, from 500 to 10000 norms. l/l/H. the Term OPG well known in the prior art, it refers to the speed of gas per hour, i.e. the volume of synthesis gas in normal litres (i.e. at standard temperature 0°C and a standard pressure of 1 bar, 100000 PA), which is in contact for 1 hour with 1 liter of catalyst particles, i.e. excluding the empty space between particles. Preferably the volumetric gas flow rate is chosen in the range from 500 to 5000 norms. l/l/h

Now the invention will be explained in more detail using the following examples.

Example 1

Korochkoy metal catalyst was prepared as follows. Preparing a suspension by the joint mixing and grinding industrial available powder of titanium dioxide (for example, P25, the Company Degussa, surface area 50 m2/g according to ASTM D 3663-92), industrial available jointly precipitated hydroxide of cobalt/manganese, industrial available ammonium salt of lactic acid titanate (for example, Dupont and sold under the trademark yzor LA), industrial available pigment ceramic zirconium dioxide (obtained from the company ZYP Coatings, type ZO) and water. This suspension contains 16 wt.% cobalt and 1 wt.% manganese, based on the weight of elemental cobalt and manganese, referred to the weight of the residue after calcination, which is formed by drying and calcination of the slurry in air at 800°within 2 hours

Aluminum shavings (typical dimensions: 6 mm, 1 mm, 0.1 mm, criterion form of approximately 120, bending to a curvature with a radius of 2 cm and deformation up to 90 degrees) washed with aqueous phosphoric acid (25 wt.%) and with water and dried. The suspension is applied by spraying on the treated aluminum shavings. Covered by spraying chips dried at 120°C for 2 h and then calcined in air at 500°C for 2 hours, the Average thickness of the coating after annealing is 30 μm.

Example 2

Korochkoy metal catalyst was prepared as follows. Straight pieces of aluminum wire (length 4 mm, the diameter of 0.26 mm) was washed with aqueous phosphoric acid (25 wt.%) and with water and dried. Suspension of Example 1 is applied by spraying on the treated aluminum wire. Covered by spraying pieces of wire dried at 120°C for 2 h and then calcined in air at 500°C for 2 hours, the Average thickness of the coating after use the air traffic management is 30 μm.

Example 3

Straight pieces of aluminum wire (length 4 mm, diameter 0.5 mm, with notches depth of 0.2 mm with an interval of 1 mm) was washed with aqueous phosphoric acid (25 wt.%) and with water and dried.

Example 4

Uncoated aluminum chips and pieces of wire from Examples 1, 2 and 3 and korochkoy metal catalyst of Examples 1 and 2 are loaded into a tubular reactor having a diameter of 2.54 cm (1 inch). Table 1 shows the values of the volume of voids (in vol %) specific surface area (cm/cm3the surface area of the particles relative to the volume of the layer), and a catalytically active volume (% vol.) compacted layer obtained in this way. In this table. 1 also shows the values of the differential pressure on the layer height (bar/m), measured at a flow rate of gaseous nitrogen 32.5 standards. l/h in model experiments, using uncoated particles.

Example 5

Korochkoy metal catalyst was prepared as follows.

Aluminum shavings (typical dimensions: 4 mm, 1 mm, 0.1 mm) was washed with aqueous phosphoric acid (25 wt.%) and cover available industrial pigment zirconium dioxide (obtained from the company ZYP Coatings, type ZO). Then aqueous suspension containing finely dispersed industrial available cobalt hydroxide and industrial available ammonium zirconium the th carbonate (firm MEL Chemicals, sold under the brand name of WASTE 20), is applied by spraying on the aluminum shavings. This suspension contains 67 wt.% cobalt based on the weight of cobalt metal, referred to the weight of the residue after calcination, which is formed by drying and calcination of the slurry in air at 800°With over 2 hours Covered by spraying chips dried at 120°C for 2 h and then calcined in air at 500°C for 2 hours, the Average thickness of the coating after annealing is 20 μm.

Example 6

Korochkoy metal catalyst obtained in example 5 is converted into an active catalyst for the Fischer-Tropsch through recovery and then use in the Fischer-Tropsch synthesis as follows.

The flow-through microreactor containing catalyst particles in the form of a fixed layer, is heated to a temperature of 280°and filled with nitrogen to a pressure of 1 bar (abs.) in continuous current of gas. The catalyst is restored at the place within 24 h the mixture gas of nitrogen and hydrogen. In the process of restoring the relative amount of hydrogen in the mixture is gradually increased from 0% to 100 vol.%. The water concentration in the exhaust gas is maintained at a level below 3000 ppm (by volume).

After repair carry out the preparation of hydrocarbons from a mixture of hydrogen and carbon monoxide at a ratio of N /, Equal to 1.1:1, and a pressure of 32 bar (abs.); value OPG equal 795 standards. l/l/H. the reaction Temperature, expressed as a weighted average temperature of the layer 213°C. After working for 40 h determine the performance, expressed in grams of hydrocarbon product per 1 liter of the catalyst particles (including the voids between particles), for 1 hour; the selectivity for methane, expressed in wt.% of the total hydrocarbon product; the selectivity to hydrocarbons containing 5 or more carbon atoms (selectivity of C5+), expressed as wt.% of the total hydrocarbon product; and the selectivity for carbon dioxide, expressed in wt.% of the total hydrocarbon product; all these values are given in table 2.

Table 2
Productivity, g/l/h92
The selectivity for methane, wt.%6,2
The selectivity of C5+, wt.%84
The selectivity for CO2, wt.%2,0

Example 7

Aluminum studs, received a wound from the melt (length 5 mm, diameter 0.5 mm, the firm Transmet Corp., Columbus, PCs Ohio, USA), first washed with toluene and acetone. Then the stud is washed with aqueous acid and demineralized water and dried.

Preparing the mixture of 1827,2 g of titanium dioxide (for example, P25, Degussa) with 896,7 joint With sediment/Mn (atomic ratio Mn/SD=6%) and water. The mixture is milled for 33 minutes.

From the above mixture to prepare a slurry with water and to this suspension is added a reagent Tyzor LA.HNO3to reduce the pH to approximately 7.

Korochkoy metal catalyst obtained by coating a dispersion of the above suspension on the said studs. Covered studs dried at 120°and calcined at 500°C.

Korochkoy metal catalyst is converted into an active catalyst for the Fischer-Tropsch through recovery, as described in example 6.

After recovery, then the catalyst used in the Fischer-Tropsch synthesis as follows. The preparation of hydrocarbons from a mixture of hydrogen and carbon monoxide is carried out at a ratio of N2/, Is approximately equal to 1.3, and a pressure of 32 bar (abs.); value OPG equal 1579 standards. l/l/H. the reaction Temperature, expressed as a weighted average temperature of the layer is equal to 227°C. After working for 109 h determine the capacity, selectivity of C5+ selectivity for methane and carbon dioxide, which is defined in the example; all these values are given in the following table:

Table 3
Productivity, g/l/h 198
The selectivity for methane, wt.%5,1
The selectivity of C5+, wt.%90
The selectivity for CO2, wt.%1,9

1. A method of producing hydrocarbons from a mixture of carbon monoxide and hydrogen in the presence of a catalyst, carried out in a reactor containing a compacted layer of deposited catalyst which comprises a metal of group VIII, in particular, cobalt, and the metal of group VIII is present at least partly in the metallic state, wherein the deposited catalyst has an outer surface containing a catalytically active metal, a compacted layer has a volume of voids greater than 50 vol.% and a specific surface area greater than 10 cm2/cm3which is calculated as the ratio of the total external surface area of the particles to the volume of the layer.

2. The method according to claim 1, characterized in that the volume of voids in the catalyst bed is at least 60 vol.%, in particular, at least 65%.

3. The method according to claim 1 or 2, characterized in that the specific surface area of the compacted layer is at least 20 cm2/cm3in particular, at least 25 cm2/cm3, which is calculated as the total surface area within the volume of the layer.

4. With whom persons according to claim 1 or 2, characterized in that a compacted layer contains particles that have a length of at least 1 mm, in particular at least 2 mm, and the criterion of the form equal to at least 10, in particular in the range from 20 to 500, and the criterion of the form is defined as the ratio of their length to the partial volume and surface area.

5. The method according to claim 1 or 2, characterized in that the compacted layer contains particles having a length of at least 1 mm, in particular at least 2 mm, and which correspond to the boundaries of the dimensions of the hypothetical cylinder whose length is the length of the particles, and the ratio of the length to the diameter of the circular cross-section is usually at least 2, preferably at least 3, more preferably in the range from 4 to 50.

6. The method according to claim 1 or 2, characterized in that the total amount of deposited catalyst which contains a catalytically active metal, is in the range from 5 to 50 vol.%, in particular, from 10 to 40 vol.% from the volume of the layer.

7. The method according to claim 1 or 2, characterized in that the catalyst having the external surface of the particles containing a metal of group VIII, is applied on the second carrier, which is a refractory oxide selected from the group consisting of silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide or mixed oxides containing silicon dioxide, ACS is on aluminum, titanium dioxide or zirconium dioxide, such as aluminosilicate, or physical mixtures such as a mixture of titanium dioxide and silicon dioxide, and the second carrier preferably has the form of particles, extrudates or foam.

8. The method according to claim 1 or 2, characterized in that the deposited catalyst consists of particles korechkovogo catalyst, which include relatively inert core and an outer layer covering the core, and the outer layer contains a metal, and preferably the core is based on a metal selected from aluminum, iron, copper, titanium and mixtures containing one or more of these metals, or the catalyst is in the form of a fixed structure or organized packing, preferably made of metal, and the metal has a convenient form of wire mesh, woven or non-woven structures, honeycomb or foam.

The priority of claims 1 to 8 - in 25.07.2000.



 

Same patents:

FIELD: chemical industry; methods of production of polyethylene in the tubular reactors with curing chambers or without them.

SUBSTANCE: the invention is pertaining to the method of production of polyethylene in the tubular reactors with the curing chambers or without them. The method provides, that the chain-radical initiator with cold ethylene or without it is fed into the flowing liquid medium containing ethylene with a comonomer. Conduct swirling of two being mixed streams at an angle or by means of the provided swirling component - in the cross section of the stream. In the zone of the area of introduction of the chain-radical initiator there is a narrowing of the cross-section, in which through a eccentrically located optimized outlet hole of the finger-shaped feeding component in the swirled stream introduce the chain-radical initiator.

EFFECT: the invention ensures a reliable introduction of the initiator in the tubular reactors with curing chambers or without them.

20 cl, 9 dwg

FIELD: catalyst preparation.

SUBSTANCE: invention relates to supported catalysts and provides a method for preparing catalyst-containing solid product comprising step, wherein ceramic carrier is applied onto metallic surface, and depositing catalytically active material onto ceramic carrier, which was preliminarily coated with supporting porous metallic material, ceramic carrier being applied onto and/or into supporting porous metallic material. Invention also describes device used in preparation of catalyst-containing solid product for applying supporting porous material onto inside or outside metallic surfaces of the hollow body.

EFFECT: increased stability of catalyst.

7 cl, 2 dwg

FIELD: catalyst regeneration processes.

SUBSTANCE: process comprises introducing catalyst into dense fluidized bed maintained in reactor at catalyst density 300 to 900 kg/m3, passing mixture of exhausted and regenerated catalysts from dense fluidized bed to fast fluidized bed formed in regenerator reactor, making the mixture contact oxidizing gas in fast, more rarefied fluidized bed at catalyst density 50 to 400 kg/m3, and obtaining regenerated catalyst from more rarefied fluidized bed. A portion of regenerated catalyst is discharged from regenerator while the rest of regenerated catalyst is recycled into dense fluidized bed. Regenerator and a method for updating it are also claimed.

EFFECT: enhanced process efficiency.

6 cl, 5 dwg

FIELD: chemical industry; pharmaceutical industry; other industries; methods of production of especially pure salts of lithium.

SUBSTANCE: the invention is pertaining to the method of production of especially pure salts of lithium and may be used in chemical, pharmaceutical and other industries. The method provides for bicarbonization of a water solution of a lithium carbonate by carbonic gas at stirring action, filtration of the solution of lithium bicarbonate, its purification on ion-exchange resin, debicarbonization, separation of the lithium carbonate, its flush by hot water and drying. The lithium carbonate is subjected to mechanoactivation; bicarbonization is conducted at the temperature of 0-18°C. The processes of bicarbonization and cleanouts by a sorbent are conducted at the similar temperature, and the processes of bicarbonization and debicarbonization are conducted in the vortex dispersible layer. For production of the high purity lithium fluoride the purified lithium carbonate is subjected to the repeated bicarbonization in the vortex dispersible layer, to filtration and to the subsequent interaction with the fluoridizer. The device consists of aggregates of bicarbonization of the lithium carbonate and debicarbonization of the lithium bicarbonate solution. Both aggregates contain the body with the disposed on it driver of the fan with the air intake, the vortex chamber, the reservoir with the branch-pipe dipped in the working solution. In the aggregate of the lithium carbonate bicarbonization the air intake of the fan, the vortex chamber and the reservoir space above the working solution are combined in the airproof closed gaseous loop with the mounted in it branch-pipe for feeding in it of carbon dioxide and with the carbon dioxide pressure indicator. The vortex chamber is equipped with the feeder with an inlet opening for feeding of the mechanoactivated technical lithium carbonate, which is arranged in the vortex chamber cover and adjacent to the blades of the vortex chamber from its internal side. In the aggregate for debicarbonization on the air intake inlet the air cleaning filter is installed. The aggregate body is supplied with the branch-pipe of the spent gases withdrawal from the space of the reservoir with the working solution connected through a carbon dioxide recuperator with a branch-pipe for inlet of carbon dioxide into the aggregate for the lithium carbonate bicarbonization. In both aggregates the branch-pipe dipped into the reservoir with the working solution is made out in the form of a regulated according to the depth of dipping intake pipe coupled by a pipeline through the circulation pump with the branch-pipe mounted on the cover of the vortex chamber above the hole of the ring type groove between the top cover and the blades of the vortex chamber from its internal side. The driver of the fan is made with an adjustable number of turns of the electromotor. The aggregates are equipped with the aids of adjustment and control. The offered invention allows to increase productivity of the chemical process, ensures optimal modes of operation of reactor equipment of the device, improves quality of the products, reduces charges of maintenance.

EFFECT: the invention ensures an increased productivity of the chemical process, optimal modes of operation of the device reactor aggregates, improved quality of the products, reduction of maintenance charges.

5 cl, 3 dwg, 2 ex

FIELD: petrochemical industry; devices and methods for realization of the catalytic cracking processes in the fluidized layers.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the reaction chamber for catalytic cracking process in the fluidized layer and the method of realization of the catalytic cracking in the fluidized layer. The reaction chamber contains in its upper part a means for separation of the catalytic agent particles from the product of the diluted phase delivered through a vertical pipe of the reaction chamber. The means of the separation are connected by the fluid medium to the pressure branch pipe of the vertical pipe of the reaction chamber and also are connected by the fluid medium to the devices for withdrawal from the chamber of the purified product delivered through a vertical pipe of the reaction chamber and are connected by the fluid medium to the devices for withdrawal of the separated catalytic agent into the lower part of the chamber. The reaction chamber in its lower part contains the devices for withdrawal of the catalytic agent from it. Between a side wall of the reaction chamber and a means for separation of the catalytic agent there is a protective jacket placed so, that it forms an external space between the reaction chamber wall and the protective jacket and the internal space inside the protection jacket. The internal space is freely communicating with the lower part of the reaction chamber, and the external space and the internal space communicate to each other through a hole. The reaction chamber has the gears feeding into the chamber external space a gas with a small amount of materials, which may form a carbon deposit. The invention also offers two versions of the method of realization of the catalytic cracking in a fluidized layer with utilization of the indicated reaction chamber.

EFFECT: the presented reaction chamber ensures an effective separation of the catalytic agent particles from the product of the diluted phase and feeding into the chamber external space a gas with a small amount of materials, which may form a carbon deposit.

8 cl, 1 dwg

FIELD: equipment for realization of the adsorption processes in the gas(vapor)-an adsorbent system.

SUBSTANCE: the invention is pertaining to the equipment for realization of the adsorption processes in the gas(vapor)-an adsorbent system. The continuously working adsorber includes: a cylindrical body, the upper part of which is made in the form of the conical-cylindrical chamber, in which there is a bin made in the form of an overturned cone with its vertex downwards and with a perforated lateral surface; the mesh-type plates with the weighted fluidized adsorbent beds and the overflow devices. At that in the bin installed in the conical-cylindrical chamber additionally there is a funnel mounted with a backlash in respect to the lateral surfaces of the chamber. The funnel consists of cylindrical surfaces having a bigger diameter and a smaller diameter, between which there is a perforated conical surface. At that the funnel is fastened at least, by three restraining components coupling the conical surfaces of the bin and the funnel, and, at least, by three restraining components coupling the conical surfaces of the bin and the cylindrical surface of the funnel small diameter. The invention ensures an increased degree of efficiency of purification of a gas stream from a target component and a dust due to an increased surface of contact of an adsorbent with the target component.

EFFECT: the invention ensures an increased degree of efficiency of purification of a gas stream from a target component and a dust due to an increased contact surface of the adsorbent with the target component.

4 cl, 1 dwg

FIELD: chemical industry; reactor having a circulating fluidized layer and a system of selective catalytic reduction.

SUBSTANCE: the offered invention is pertaining to the field of chemical industry. A combination of a device consisting of a reactor or a combustion chamber with a circulating fluidized layer and a selective catalytic reduction system contains the reactor chamber with a circulating fluidized layer, the primary solid particles separator, a means for return of the solid particles trapped by the primary solid particles separator to the reactor chamber, at least one surface of heat transfer of a vapor overheater or an intermediate vapor overheater, a system of the selective catalytic reduction, a dry scrubber located below on the production chain in respect to the system of the selective catalytic reduction and a means for introduction of ammonia in the flow of a smoke gas-solid particles. According to one of the offered versions the given device contains a multicyclone dust separator and a means for return of the solid particles trapped by the multicyclone dust separator to the reactor chamber. The given engineering solution ensures low outbursts of nitrogen oxides at the minimum operational cost.

EFFECT: the invention ensures low outbursts of nitrogen oxides at the minimum operational cost.

11 cl, 3 dwg, 2 tbl

FIELD: heat treatment of fluid products.

SUBSTANCE: the offered group of inventions is pertaining to the field of heat treatment of fluid products. The treatment is carried out by a means of heat produced at fluid friction which is created by a mechanical forced circulation of the fluid product in the heat treatment device which, at least, has one mechanical heater conducting a mechanical work on the treated product. At that the device consumed mechanical power within the range of the operational temperatures meets the following requirement: where W - is a mechanical power consumed by the heat treatment device ( expressed in W), W* - is a total power of heat losses (in W); T - is a rate of heating required in compliance with the production process (°\s); C - is the product heat capacity (Joule/ (kg·degree)), m - a mass of the product subjected to the heat treatment (kg); an index i is used to number the endothermic processes;qi - a-specific heat of formation of the resultant component in the i-th process (Joule/kg), MI - is a required speed of its formation at the temperature of realization of endothermic process (kg/s). The given engineering solution ensures composition of the product, its physical and chemical properties, a high speed of the process without deterioration of the product quality.

EFFECT: the invention ensures composition of the product, its physical and chemical properties, a high speed of the process without deterioration of the product quality.

15 cl, 2 dwg, 3 ex

FIELD: chemical engineering; production of reactors for catalytic synthesis.

SUBSTANCE: the invention is pertaining to the field of chemical engineering, predominantly to reactors of catalytic synthesis. The horizontal multi-shelved catalytic reactor consists of a load-bearing plate, a high-pressure cylindrical body with a cover, which may be transported along the axis of the catalytic unit. The reactor has the typical component and the design of components of the catalytic unit, which consists of the sealed cylindrical catalytic containers, the load-bearing support frame and the module-type heat-exchange devices. The load-bearing support frame represents a crosswise section beam cantileverly fixed on the load-bearing support plate. The vertical plane of symmetry of the frame coincides with the longitudinal axis of the high-pressure body, and on the shelves there are catalytic containers installed in two parallel rows. The frame is cantileverly fixed to the load-bearing plate, through which all inlets and outlets are carried out. The plate is upright mounted on the horizontal foundation and the high-pressure body is joined with it. In the module heat-exchange devices there are tracts for passage of the reactionary gases and the heat-transfer medium. The invention ensures improved conditions of the reactor operation, reduction of its overall dimensions and the mass, simplification of the process of manufacture.

EFFECT: the invention ensures improved conditions of the reactor operation, reduction of its overall dimensions and the mass, simplification of the process of manufacture.

2 cl, 6 dwg

FIELD: chemical industry; equipment for synthesis of hydrocarbons.

SUBSTANCE: the invention is pertaining to chemical industry, in particular, to the horizontal reactor for synthesis of hydrocarbons according to Fisher-Tropsh method. The offered reactor consists of the single-type design coaxial horizontal reactive sections. Each section is mounted on a wheeled trolley with adjustable supports and incorporates a casing, a fixed in it through adapters catalytic box with a built-in heat exchanger, through which the heat transfer medium is compulsorily pumped over. The catalytic box is made in the form of a package assembly of the same type catalytic modules is sectional with usage of the fastening strainers and tightening gaskets. The catalytic module is assembled with usage of welding from longitudinal or transversal in respect to the longitudinal axis sections, the square-type flat soldered on corrugations or ribs double walled panels with the general depth of 5-15 mm, at the thickness of walls of 1 - 2 mm, at the height of corrugations or ribs of 3-9 mm at their depth of 0.3-2.0 mm with the shanks welded to them. The catalytic area is formed due to selection of the depth of the shanks greater, than the depth of the panels, owing to what at their assembly in compliance with shanks by means of welding between the panels are left the vertical slits of 5...20 mm width where fragments-granules of the catalytic agent are placed. The given engineering solution ensures conditions close to isothermal requirements of the synthesis through the whole volume of the reaction zone, ease of assembly and maintenance of the reactor in all climatic zones, and also in provision of its reliability, transportability and repairability.

EFFECT: the invention ensures conditions close to isothermal requirements of the synthesis through the whole volume of the reaction zone, ease of assembly and maintenance of the reactor in all climatic zones, its reliability, transportability and repairability.

3 cl, 6 dwg

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.

EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.

5 cl, 7 tbl, 7 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.

EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.

17 cl, 3 tbl, 25 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.

EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.

13 cl, 1 tbl, 24 ex

FIELD: physical or chemical processes and apparatus.

SUBSTANCE: method comprises saturating the initial gas mixture that is comprises agents to be oxidized with vapors of hydrogen peroxide. The photocatalyst is made of pure titanium dioxide that contains one or several transition metals.

EFFECT: expanded functional capabilities and enhanced efficiency.

7 cl, 2 dwg, 1 tbl, 11 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

The invention relates to methods of producing catalysts based on titanium dioxide, which can be used in various fields, for example, catalytic air purification from CO or photocatalytic air purification and water from organic compounds and some inorganic compounds
The invention relates to electrochemical deposition of catalytically active layers containing metal oxides, and can be used in heterogeneous catalysis reactions

The invention relates to a catalyst for the receipt of vinyl acetate in the fluidized bed

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

Up!