Crusted metallic catalyst, method for preparation thereof, and a hydrocarbon production process

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

 

The technical field

The present invention relates to Korotkova metal catalyst and precursor korechkovogo metal catalyst and method of production thereof. In addition, the invention relates to the use of this korechkovogo metal catalyst, in particular in the method of producing hydrocarbons from synthesis gas.

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 from group VIII 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.

There is ongoing interest in the search for catalysts for use in the Fischer-Tropsch synthesis, which could provide increased activity and Ulu the high selectivity in the conversion of carbon monoxide into valuable hydrocarbons, especially in the hydrocarbons containing five or more carbon atoms (hereinafter "hydrocarbons C5+) and which 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 Korotkevich catalysts. These catalysts contain a catalytically active metal, located exclusively in the thin outer layer of the catalyst particles. Compared to traditional catalysts in which the catalytically active metal is uniformly distributed on the catalyst particles, Korotkova catalysts have a small diffusion length, i.e., they have low diffusion resistance and therefore have a relatively high selectivity for the formation of hydrocarbons C5+, and inhibited the formation of methane.

In addition to the processes of Fischer-Tropsch synthesis, Korotkova catalysts can be used in other processes of chemical transformations, in particular, where they play the role of diffusion limitations.

To ensure a high response speed or performance of the reactor, it is desirable that in the outer layer of the particles korechkovogo catalyst contained a large number of catalytically active metal. According to the U.S. patent 5545674 and references cited therein refer to the Cam, this can be achieved by re-impregnation solution containing the catalytically active metal particles of the medium, using the method of spraying or immersion, with intermediate stages of drying and calcination. This multi-stage method is not only cumbersome and time-consuming, in addition, when using method (re) impregnation of some part of the catalytically active metal can penetrate into the deeper layers of the catalyst particles, which is undesirable, since in this case korochkoy catalyst acquires the properties of a catalyst which contains a catalytically active metal is uniformly dispersed on the catalyst particles.

The present invention presents a way in which korochkoy metal catalyst containing a large number of catalytically active metal in the outer layer of the catalyst particles can be obtained in a simple way. Moreover, the inner layers of catalyst particles, i.e. where the catalytically active metal is practically absent, and which will be denoted by the term "core", can be made of a material that is different from the carrier that caused the catalytically active metal. This allows a qualified technician to modify the bulk properties of the catalysis of the Torah without a significant change in its chemical properties. Such volumetric properties can be density, thermal conductivity and strength. You can even obtain hollow particles of the catalyst, i.e. the catalyst particles in which the core is a partially or fully empty space.

Disclosure of the invention

The present invention provides a method of obtaining korechkovogo metal catalyst or precursor korechkovogo metal catalyst, which comprises steps:

1) applying the suspension containing the diluent, the catalytically active metal or its previous connection and optional refractory oxide (hereinafter "the first refractory oxide) of an element having atomic number of at least 20, or the predecessor of the first refractory oxide on the surface of the carrier particles with the nucleus with the formation of the wet coating and

2) removing at least part of the diluent from the wet coating, in which the suspension comprises at least 5 wt.% the catalytically active metal or its previous connection, based on the weight of the metal relative to the mass of the residue on ignition, which can be formed from the slurry in the drying and calcination.

The present invention also provides korochkoy metal catalyst or a precursor korechkovogo IU alicebraga catalyst, which can be obtained according to the method of this invention, and for use korechkovogo metal catalyst in the method of chemical conversion.

In addition, the present invention provides a method of producing hydrocarbons, and this method includes contacting a mixture of carbon monoxide and hydrogen with Korotkova metal catalyst according to the invention, in which the catalytically active metal contains a metal of group VIII, which is (at least partially) in the form of metal.

The media engine, which is used in stage 1) of the method of this invention includes preferably a material with a relatively low surface area, because the smaller the area of the inner surface, the less likely it is that the actual media engine will show catalytic activity. Preferably the carrier core has a surface area according to BET less than 20 m2/g, especially less than 10 m2/, Implies that the quoted here surface area by BET measurement-based surface area by BET according to the standard ASTM D3663-92.

Typically, the media engine includes an inorganic material such as a refractory oxide (hereinafter "the second refractory oxide), ceramic material, metal or carbon. Coming up is their second refractory oxides for use as the carrier core is silicon dioxide, aluminum oxide, zirconium dioxide, magnesium oxide and titanium dioxide and mixtures thereof. Preferred are silicon dioxide and aluminum oxide.

Use media engine, which 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 a Fischer-Tropsch synthesis. Suitable metals are aluminum, iron, copper, titanium and mixtures containing one or more of such metals, such as steel and brass. Due to the relatively low density aluminum and mixtures containing aluminum, are preferred, for example, mixtures which contain at least 95 wt.% aluminum. Such mixtures usually contain not more than 99.9 wt.% aluminum. A mixture containing aluminum, may include from 0.01 to 5 wt.% impurities or additives selected from, for example, magnesium, silicon and copper.

The carrier core may be partially or completely made out of carbon or organic material such as polymer, or other materials such as resin. Examples of suitable'or is hanicheskih materials are polystyrene, polyolefins, 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 very low density. In fact identify, remove kernels can be considered as his replacement on an empty space, and therefore the formed hollow (partly) on the catalyst particles can be incorporated into the classification of "korochkoy catalyst".

The surface of the carrier core may be pre-processed in order to obtain improved adhesion of the coating to the media engine, especially after the stage of calcination, which are described in the following. The surface of the carrier core can be modified, for example, by removing impurities or surface covering layer. So, the media engine may be washed with water or dilute acid, such as aqueous phosphoric acid, or it can be processed by Sol refractory oxide, such as silicasol or Sol of aluminum oxide or ceramic pigment, such as ceramic zirconocene pigment. The second refractory oxide can be pre-treated by calcination, for example, as a result of heating during avicennae temperature, preferably at a temperature between 450 and 650°Usually the duration of the 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.

As the continuous phase of the suspension includes a diluent, and the solid is dispersed in the diluent.

A trained professional can recognize that the media engine will have a larger size than the particles that make up the dispersed solid. The latter particles may be a fine powder, while the particles of the carrier core may be larger material.

Appropriate is the mean volume diameter of the particles of the dispersed phase from 0.0001 to 0.15 mm, preferably from 0.0002 to 0.1 mm, in particular from 0.0005 to 0.05 mm, an Average volume particle diameter specified in this patent application, invariably represents the average volume particle diameter, which is determined using the instrument MASTERSIZER MICRO PLUS (trade mark of the company Malvern Instruments Ltd., The UK employs a calculation method designated as "STHD", which provides the company Malvern Instruments Ltd., the investigated material is diluted with water to achieve the desired optical density and then after 30 seconds the Kund is determined by the average volume particle diameter).

The particle size of the carrier core is usually from 0,105 to 9.51 mm, more typically from 0,210 up to 5.66 mm, which is determined using standard sieves (U.S. ASTME11-61).

The shape of the particles korechkovogo metal catalyst, which will be obtained mainly determined by the shape of the carrier particles with the nucleus. Can be used in any form that is suitable for use in the chemical process, which can be used korochkoy metal catalyst. Suitable forms are, for example, spheres, cylinders and rings. In addition, it is acceptable when appropriate particles are pieces of material without a well-defined form.

The diluent may be an organic diluent such as a lower alcohol, a lower ketone, lower ester or ether, for example, ethanol, acetone, methyl ethyl ketone, ethyl acetate, diethyl ether or tetrahydrofuran. In this 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 solvent and water, preferably containing at least 50 wt.% water and less than 50 wt.% organic diluent, based on the total weight of the diluent. Most from the window to use water as the sole diluent.

The solids content in the suspension can vary dramatically. It is preferable that the solid content is in the range from 0.5 to 90 wt.%, more preferably from 1 to 80 wt.%, relative to the weight of the suspension.

Dispersed solid material may include, for example, a catalytically active metal or its compound, the precursor, and the first refractory oxide or its precursor may be missing; korochkoy metal catalyst or its precursor, which receive according to the invention, can finally contain the carrier core coated with a layer of catalytically active metal or its compounds predecessor.

However, it is preferable that korochkoy metal catalyst or its precursor, which receive according to the invention contain the carrier core coated with a layer that includes a first refractory oxide, which is a carrier for the catalytically active metal or its compounds predecessor. This can be achieved through use as dispersed solids of the first refractory oxide, which is a carrier for the catalytically active metal or its compounds predecessor. In this variant embodiment of the dispersed solid is preferably the tsya caused by the catalyst or its predecessor, which can be obtained by spray drying, optionally followed by calcination, as described in document WO-99/34917. This can also be achieved through use as dispersed solids of the first refractory oxide or its precursor and the use of a catalytically active metal or its compounds predecessor as more dispersed solids and/or dissolved in the diluent. In the latter embodiment, the suspension preferably is a suspension that can be obtained, as described in document WO-99/34917, which is in document WO-99/34917 for use in the process of spray drying.

This suspension includes at least 5 wt.% the catalytically active metal or its compounds predecessor based on the weight of the metal relative to the weight of the residue after calcination, which may be caused by drying and calcination of the slurry. In this regard, it is assumed that the calcination is carried out in normal conditions, by heating in air at 800°C, for 2 h In a preferred variant embodiment of the suspension contains not more than 90 wt.%, in particular in the range from 10 to 60 wt.% the catalytically active metal or its predecessor on the same database.

The suspension can be what must be separately obtained from stage (1). For example, you can get the suspension and then apply it on the surface of the carrier particles with the core by spraying or immersion of the particles in suspension or otherwise. In alternative embodiments, the suspension is get together with the stage (1), for example, by wetting the particles of the carrier with a core of a diluent, followed by contacting the moistened particles of solid in powder form. In the above-mentioned contacting the solid is in the form of a powder dispersed in a diluent, and thus formed suspension with simultaneous formation of the wet coating. This contacting may be accomplished by spraying or propilivanija powder on the moistened particles, or by obvalivanie or rolling the moistened particles in a solid.

When the suspension get separately from stage (1), the components of this suspension can be crushed together, usually within a period of 5 to 120 minutes, preferably from 15 to 90 minutes. This grinding process is conveniently carried out at normal pressure, and may use any available industrial equipment for grinding.

Preferably, the suspension is administered one or more agents that improve the properties and/or patitiri agents and consumable materials. Such additives and their note is out known from the prior art, see, for example, document WO-99/34917.

A suitable method and apparatus for spraying a suspension of particles of the media engine is known from the publication Arntz and other "Preparation of catalysts IV, B. Delmon and others (ed), Elsevier, 1987, p.137.

It is not necessary that the carrier particles with the nucleus were completely covered with a damp floor. Is acceptable when covered at least 80% of the total available surface, more preferably, when covered with at least 90% of the surface. Preferably the particles of the carrier core is coated completely.

The thickness of the wet coating is not the subject of the invention. Thus, the thickness of the wet coating can be selected in a wide range. Conveniently, when the thickness of the wet coating is such that, after drying and calcination in accordance with the standard conditions defined above, the thickness of the remaining coating meets certain criteria. The first criterion might be: the greatest thickness of the remaining coating is less than 0.2 mm; this means that the remaining coating no areas thicker than 0.2 mm, In particular, the maximum coating thickness is in the range from 0.002 to 0.15 mm, more specifically, in particular, in the range of 0.005 to 0.1 mm, the Second independent criterion might be: the average thickness of the remaining coating is in the range from 0.001 to 0.15 mm, prefer the LNO in the range of from 0.002 to 0.1 mm, in particular in the range of 0.005 to 0.08 mm of the Specified average thickness is defined here as the quotient of the total amount of remaining coverage (i.e., after drying and calcination in accordance with the specified standard conditions) and the surface area of the particles with the nucleus. Suppose that the average thickness, thus defined, is associated with a relatively large number of particles, e.g. particles present in the layer load displacement of about 1 m3.

In stage 2) of the wet coating is removed at least part of the diluent, resulting in the formation of particles of the carrier with a core, covered in dried coating. Convenient to the diluent was removed to such an extent that the coating has become stronger, in order to facilitate the subsequent manipulation of the particles. Preferably the diluent is removed almost completely, for example, at least 80%, in particular, removes at least 90% of a diluent. This removal can be done viparita diluent. Evaporation can be performed at elevated temperatures, e.g. above 30°C, preferably up to 400°S, more preferably up to 300°C. the Period of evaporation is usually up to 5 h, more preferably from 15 minutes to 3 hours

Preferably, the carrier particles with a core, covered in dried coating, came on stage PR is califonia, for example, after stage 2). The procedure of annealing increases the hardness and strength of the coating, and also improves the adhesion of the coating to the carrier particles with the nucleus. The 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 calcination is usually from 5 minutes to several hours, preferably from 15 min to 4 h Stage calcination convenient to carry in oxygen-containing atmosphere, preferably air. You can recognize that desire, stage 2) and the calcination can be combined.

According to the invention receive korochkoy a catalyst which contains a catalytically active metal or the preceding compound of a catalytically active metal. Usually, this metal is a metal of group VIII, as the catalyst metal of group VIII can be used in many chemical reactions, such as Fischer-Tropsch synthesis 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 relatively high the output 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.

Typically, the atomic ratio of the metal of group VIII to the additional metal, if present in the catalyst is at least 5:1 and typically does not exceed 200:1.

Additional metal may be introduced in the same manner and together with the metal of group VIII. The catalytically active metal and, optionally, additional metal may be introduced in connection predecessor. Such compounds are precursors include salts, such as nitrates, carbonates or acetates, hydroxides and oxides, and metals. You can also use complex compounds. Metal joining and/or its precursor can be soluble (or insoluble) in the diluent, or they can be partially soluble in the diluent. Usually at the stage of calcination will be the transformation of compounds, the precursors of the metal into the corresponding metal oxide.

First tohop the avco oxide includes an oxide of the element, having an atomic number of at least 20. Examples of suitable refractory oxides include silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide or mixed oxides containing aluminum oxide, titanium dioxide or zirconium dioxide, such as aluminosilicate, or physical mixtures such as a mixture of titanium dioxide and silicon dioxide. Preferably, the first refractory oxide comprises titanium dioxide, zirconium dioxide or mixtures thereof, in particular refractory oxide contains titanium dioxide.

In accordance with the preferred embodiment of the first 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, another 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.

Most preferably the first refractory oxide comprises 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.

You can admit that the particles of the first refractory oxide may not have VC is emy size and shape. Then you can use the procedure molding. Specialists are well known molding techniques, which include methods of spray drying and grinding.

Usually the first refractory oxide is a material with a large area of the inner surface. For example, the surface area is at least 25 m2/g, and more specifically, at least 35 m2/, Convenient to the surface area was less than 400 m2/g, particularly not more than 200 m2/, Preferably, the amount of surface area is in the range from 40 m2/g to 100 m2/year

The predecessor of the first refractory oxide is a compound that forms a first refractory oxide at the stage of calcination, which was previously described. The predecessor of the first refractory oxide can be dissolved in the diluent, which is used in the method of this invention. The predecessor of the first refractory oxide 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 acetylacetonates, allylacetate and chelates with lactic acid; an alcoholate, such as utility, aminoacylase and isopropylate; the alkyl compounds, such as ethyl and isooctyl connection. Alternatively, the precursor medium is an inorganic compound such as a hydroxide, or an inorganic salt such as a halide.

As an example, suitable compounds precursors of titanium dioxide are tetraethylsilane, isostearamide, and aktiengellschaft, and triethanolaminato. Very convenient connection, especially for use in combination with water, is the ammonium salt of lactic acid, chelated titanate. Such compounds are sold under the trademark Tyzor from Dupont company.

It is not excluded that korochkoy metal catalyst includes additional components, in addition to those mentioned above.

Let us return now to the possible application of korechkovogo metal catalyst or its precursor obtained according to the invention, as described above. Korochkoy metal catalyst can be used in the method of producing hydrocarbons from carbon monoxide and hydrogen. Usually when you use in this process the metal is present in Korotkova metal catalyst is a metal of group VIII, and usually, at least part of the metal of group VIII is present in the metallic state.

Therefore is usually the benefits of the s ' to activate the metal of group VIII in the catalyst before use, by recovery in the presence of hydrogen at elevated temperature. 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 may vary 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 may be preferable 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 part the social 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.) Typically in this method, the 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 product of C5+, i.e., the selectivity for the formation of hydrocarbons C5+.

However, in variant embodiments of this invention, in which the metal of group VIII is cobalt, and the additional metal is manganese and/or vanadium, which are present in the atomic ratio of cobalt/manganese + vanadium), equal to at least 12:1, the selectivity of the catalyst product of C5+ is very high, even when using a synthesis gas having a high molar ratio of hydrogen to carbon monoxide. In this variant embodiment can be used molar ratio of hydrogen to carbon monoxide in the range from 1.5 to 2.5.

About the lending rate of the gas (in subsequent OPG) can vary within wide limits, and usually in the range from 400 to 20000 standards. l/(l.h), preferably from 500 to 10000 norms. l/(l.h).

The term OPG well known in the prior art, it refers to the flow of the gas for 1 h, i.e. to 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 exposed for 1 h with 1 l of catalyst particles, i.e. excluding the empty space between particles. In the case of a fixed catalyst layer is usually OPG refers to 1 liter of the catalyst layer, that is, including the empty space between particles. In this case, the volumetric gas flow rate 1600 norms. l/(l.h) on the catalyst particles corresponding to approximately 1000 norms. l/(l.h) on the catalyst layer.

A method of producing hydrocarbons can be accomplished using a variety of reactor types and modes of reaction, for example, a mode with a fixed layer, the mode with the suspended phase or fluidized bed. It is preferable mode with a fixed layer. It should be recognized that the size and shape of the particles korechkovogo catalyst can vary depending on the mode of action for which they are intended. The selection of the most appropriate size and shape of the particles for a given mode of action refers to the competence of the specialist in this field of technology.

In addition, it is possible to recognize that a specialist in this is th technical field can select the most suitable conditions for a particular configuration of the reactor, mode of action and operational schemes. For example, the preferred volumetric gas flow rate may depend on the type of reaction that will be used. So, if it is desirable to perform the process of synthesis of hydrocarbons in the mode of the fixed layer, preferably the volumetric gas flow rate is chosen in the range from 500 to 2500 norms. l/(l.h). If it is desirable to perform the process of synthesis of hydrocarbons in suspended mode phase, preferably the volumetric gas flow rate is chosen in the range from 1500 to 7500 standards. l/(l.h).

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

Example 1

Predecessor korechkovogo metal catalyst was prepared as follows.

The paste is prepared by co-mixing and kneading available industrial 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 and water. This paste contains of 20.1 wt.% cobalt and 1.6 wt.% manganese, based on the weight of elemental cobalt and manganese, is related to the mass balance during annealing, which is formed by drying and calcination paste in air at 800°C, within 2 hours the Paste is dried and pulverized to obtain fine powder.

G is analy silica calcined in air at 550° With over 2 hours Sieved fraction from 0,841 to 1.19 mm (standard U.S. sieve, ASTM E11-61) moisten with water in a quantity sufficient only to fill the pores with water.

Moistened granules of silicon dioxide at the same time turn over and spray for 5 min with water and fine powder to granules of silicon dioxide formed coating. Coated granules of silicon dioxide is separated from the rest of the powder by sieving, dried at 120°C for 2 h and then calcined in air at 500°C for 2 hours Sieved fraction is coated and calcined granules of silicon dioxide (1,00-1,19 mm, standard U.S. sieve, ASTM E11-61) is separated and used for subsequent tests. The average thickness of the coating after annealing is 80 microns

Example 2

Predecessor korechkovogo metal catalyst was prepared as follows.

Aluminum particles (typical size of 0.1-4 mm) was washed with aqueous phosphoric acid (25 wt.%) and cover them available industrial pigment ceramic 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 carbonate (firm MEL Chemicals, sold under the brand name of WASTE 20) is applied by spraying on the aluminum frequent the hospitals. This suspension contains 67 wt.% cobalt based on the weight of cobalt metal, is related to the mass balance during annealing, which may be caused by drying and calcination of the slurry in air at 800°With over 2 hours Covered by spraying the particles are 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 3

Predecessor korechkovogo 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 (e.g., Dupont company, sold under the trademark Tyzor LA), available industrial pigment ceramic zirconium dioxide (obtained from the company ZYP Coatings, type ZO) and water. This suspension contains 16 wt.% cobalt and 1.0 wt.% manganese, based on the weight of elemental cobalt and manganese, referred to the weight of the residue after calcination, which may be caused by drying and calcination of the slurry in air at 800°C, within 2 hours the Average diameter of the solid is astiz, present in the suspension is less of 0.28 μm.

Aluminum shavings (typical dimensions: 4 mm, 1 mm, 0.1 mm) was washed with aqueous phosphoric acid (25 wt.%) and heated in air at 600°C for 4 h, 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 34 μm.

Example 4

Predecessor korechkovogo metal catalyst obtained in examples 1 and 2 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 particles of the catalyst precursor 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 precursor restore in place for 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 about 100%. 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 in soo is wearing H 2/SD=1,1:1 and a pressure of 32 bar (abs.). Values OPG and the reaction temperature, expressed as a weighted average temperature of the layer shown in table 1. After working for 40 h determine the performance, expressed in grams of hydrocarbon product per 1 l of catalyst particles (including the voids between particles), for 1 h; the selectivity for methane, expressed in wt.% of the total hydrocarbon product selectivity to hydrocarbons containing 5 or more carbon atoms (selectivity of C5+), expressed as weight % of the total hydrocarbon product, and the selectivity for carbon dioxide, expressed in wt.% of the total hydrocarbon product. These results are also shown in the table.

Table
Example123
Temperature,°230213237
OSPG, norms l/(l h)1188795800
Productivity, g/l/h1389286
The selectivity for methane, wt.%5,86,2the 5.7
The selectivity of C5+, wt.%86,58488
The selectivity for CO2,wt.% 1,52,01,8

1. The method of obtaining korechkovogo metal catalyst containing a catalytically active metal, characterized in that it comprises the following stages:

1) applying the suspension containing the diluent, the catalytically active metal selected from the group of cobalt and ruthenium, and not necessarily the first refractory oxide of an element having atomic number of at least 20 on the surface of the particles of the carrier core with the formation of the wet coating and

2) removing at least part of the diluent from the wet coating, in which the suspension comprises at least 5 wt.% the catalytically active metal, based on the weight of the metal relative to the mass of the residue on ignition, which can be formed from the slurry in the drying and calcination.

2. The method according to claim 1, characterized in that the diluent is water.

3. The method according to claim 1 or 2, characterized in that the solids content in the suspension is in the range from 0.5 to 90 wt.%, preferably from 1 to 80 wt.%, relative to the weight of the suspension.

4. The method according to claims 1 and 2, characterized in that the suspension contains not more than 90 wt.%, in particular from 10 to 60 wt.% the catalytically active metal per weight of metal relative to the mass of the residue on ignition, which can affect Atisa of the suspension in the drying and calcination.

5. The method according to claims 1 and 2, characterized in that the suspension contains the first refractory oxide in the form of dispersed solids and a catalytically active metal in the form of additional dispersed solids and/or dissolved in the diluent.

6. Korochkoy metal catalyst, which can be obtained in the manner specified in any one of claims 1 to 5.

7. Korochkoy metal catalyst according to claim 6, wherein the media engine includes a second refractory oxide, which is preferably selected from silicon dioxide, aluminum oxide, zirconium dioxide, magnesium oxide and titanium dioxide and mixtures thereof, or a metal, which is preferably selected from aluminium, iron, copper, titanium and mixtures containing one or more of these metals.

8. Korochkoy metal catalyst according to claim 6 or 7, characterized in that the first refractory oxide comprises titanium dioxide, zirconium dioxide or mixtures thereof, in particular the first refractory oxide comprises titanium dioxide.

9. Korochkoy metal catalyst according to any one of p-7, characterized in that the catalytically active metal is a metal of group VIII, preferably cobalt, more preferably cobalt, which is located at least partially in the form of metal.

10. A method of producing hydrocarbons, trichosis fact, the mixture of carbon monoxide and hydrogen in contact with Korotkova metal catalyst according to claim 9.



 

Same patents:

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

FIELD: chemical industry; conversion of synthesis gas into alcohols and hydrocarbons.

SUBSTANCE: proposed catalyst contains the following constituents, mass-%: active component in terms of CO; promoter-fluorine, 0.1-1.0; the remainder being carrier-aluminum oxide.

EFFECT: enhanced conversion of CO.

1 dwg, 2 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.

3 cl, 1 tbl, 15 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing mainly C5+-hydrocarbons. Method involves contacting carbon monoxide with hydrogen at temperature 180-270°C and under increased pressure in the presence of catalytic composition comprising as measure for the total mass of catalytic composition from 5 to 30 wt.-% of cobalt, from 0.01 to 5 wt.-% of manganese and at least from 0.01 to 0.9 wt.-% of rhenium and/or ruthenium on a carried made of titanium dioxide. Invention provides reducing amount of carbon dioxide evolved in the process of hydrocarbons synthesis by Fisher-Tropsh to the level 2% vol./vol., not above, but preferably to 1% vol./vol., not above, and without reducing C5+-selectivity.

EFFECT: improved preparing method.

7 cl, 2 tbl, 4 ex

FIELD: cobalt-based catalysts used in Fisher-Tropsh reaction in reactors with gas-liquid-solid agent fluidized bed.

SUBSTANCE: diameter of particles of cobalt-based catalyst applied to carrier is measured by means of Coulter LS230 in interval of from 70 to 250 mcm, area of surface exceeds 175 m2/g and volume of pores exceeds 0.35 cm3/g as measured by BET method. Specification contains also description of Fisher-Tropsh method in reactor with gas-liquid-solid agent fluidized bed. This method includes chemical interaction of CO with H2 for obtaining C5+ hydrocarbons in presence of said catalyst.

EFFECT: enhanced activity of catalyst; facilitated procedure.

8 cl, 3 dwg, 10 tbl, 6 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 ex

FIELD: petrochemical processes catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.

EFFECT: increased selectivity and productivity.

2 cl, 3 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.

EFFECT: increased heat conductivity and selectivity.

2 cl, 2 tbl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with catalysts showing high catalytic stability in production of chloroform from carbon tetrachloride via catalytic dehydrochlorination reaction. Catalyst containing γ-alumina-supported platinum is characterized by that platinum in the form of particles 1 to 12 nm in size is distributed throughout the bulk of microspheric γ-alumina particles having median diameter 30 to 70 μm and pore volume 0.3 -0.6 cm3/g. Preparation of catalyst involves impregnation step accomplished via spraying γ-alumina with aqueous platinum compound solution used in amount equal to or less than alumina pore volume followed by platinum compound reduction step, wherein this compound is deposited onto γ-alumina with aqueous solution of formic acid or alkali metal formate.

EFFECT: achieved retention of high catalyst activity and selectivity over a long time period without being preliminarily activated.

9 cl, 2 tbl, 4 cl

FIELD: synthesis gas generation catalysts.

SUBSTANCE: invention provides catalyst for steam generation of synthesis gas containing 2.2-8.2% nickel oxide and 3.0-6.5% magnesium oxide deposited on heat-resistant porous metallic carrier having specific surface area 0.10-0.15 m2/g, summary pore volume 0.09-0.12 cm3/g, predominant pore radius 2-20 μm, and porosity 40-60%. Synthesis gas is obtained by steam-mediated conversion of hydrocarbons at 450-850°C.

EFFECT: increased heat conductivity of catalyst and catalytic activity.

11 cl, 1 tbl, 8 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: immobilized ionic liquid is prepared by anion-assisted immobilization of ionic liquid, for which purpose a carrier is treated with anion source, for instance with inorganic halide to produce ionic liquid or applying it onto carrier. Alternatively, ionic liquid may be immobilized because of cation covalently linked to carrier, e.g. through silyl groups, or incorporated into carrier via synthesis of carrier in presence of acceptable base. Immobilized ionic liquid are meant for use as catalysts, e.g. in Friedel-Krafts reaction.

EFFECT: optimized preparation procedures.

18 cl, 10 ex

FIELD: precious metal technology.

SUBSTANCE: invention relates to a method for preparation of novel platinum-containing materials, which find always increasing demand in national economy, in particular in heterogeneous catalysis. According to invention, platinum is sublimated on high-temperature glass cloth with preliminarily deposited calcium oxide layer. Thus prepared material is a composite constituted by high-temperature glass cloth with deposited calcium oxide layer bearing (Ca,Si)O2 rods on its surface, said rods having oxidized platinum on their ends and metal particles 3-20 nm in size in underlayer.

EFFECT: enabled preparation of novel platinum-containing material with platinum in finely dispersed state.

7 cl, 1 dwg, 1 tbl, 6 ex

FIELD: production of catalytic neutralizers.

SUBSTANCE: high-efficiency catalytic neutralizer has internal and external layers on inert carrier which contain noble metals of platinum group deposited on materials of base and oxygen-accumulating components. Inner layer of proposed catalytic neutralizer contains platinum deposited on first base and first oxygen-accumulating component and its external layer contains platinum and rhodium deposited on second base only; this second layer contains additionally second oxygen-accumulating component. Production of catalytic neutralizer includes application of coat on carrier made from composition containing powder-like materials including first material of base and first oxygen-accumulating component followed by drying, calcining, immersing the carrier with coat in solution of platinum precursor; coat is calcined and external layer is applied over previous layer. Specification describes two more versions of production of catalytic neutralizer.

EFFECT: enhanced ability of catalytic neutralizer for reduction of catalytic activity after aging due to discontinuation of delivery of fuel.

24 cl, 1 dwg, 11 tbl, 5 ex, 3 ex

FIELD: production of catalytic elements for decontamination of gas emissions.

SUBSTANCE: proposed method includes forming catalytically active layer on metal carrier by plasma spraying of powder composition at linear velocity of 100-150 m/min, forming cellular structure in form of longitudinal passages due to corrugation of metal carrier with catalytically active layer applied to it. The catalytically inactive powder composition is used as initial material for plasma spraying at the following ratio of components, mass-%: aluminum, 3.5; chromium oxide, 2-5; tungsten oxide, 0.8-1.2; cerium, lanthanum and neodymium oxides, 1.8-2.2 in sum; the remainder being aluminum hydroxide.

EFFECT: enhanced strength of adhesion with substrate at high mechanical strength and catalytic activity.

5 cl, 3 tbl

FIELD: catalysts of selective hydrogenation of alkynes of C4 fractions.

SUBSTANCE: proposed catalyst contains 1-30 mass-% of copper used as first active component, 0.001-5 mass-% of palladium used as second active component, at least 0.001-6 mass-% of one metal selected from Al, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as co-catalyst; the remainder being one carrier selected from aluminum oxide, silicon dioxide and titanium oxide. Method of production of catalyst includes impregnation of carrier calcined preliminarily with solutions of active components depending on their content in catalyst. Alkynes are removed from C4 fractions enriched with alkynes by means of selective hydrogenation with the use of said catalyst.

EFFECT: enhanced selectivity and stability of catalyst.

31 cl, 2 tbl, 13 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 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

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

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