Method of catalytically active lamellar silicates production

FIELD: technological processes.

SUBSTANCE: subject of invention is method of catalytically active lamellar silicates production with single or multiple layers, in particular, clays with interlaminar struts from A1 and/or Ti, for purification of spent gases. At that at the stage of interlaminar struts formation, metal solution is added into lamellar silicate and the received mixture at the stage of drying/calcination is heated with formation of struts supporting intermediate layer out of metal atoms. After that catalytically active salt of transition metal is added in the dry form to the received dry substance. Finally the prepared dry mixture is heated up to the temperature of higher than 300°C, as a result catalytically active transition metal atoms are introduced into immediate layer, and at the same time dry mixture calcination takes place. As metal solution, solutions of aluminium, titanium, iron, copper and chrome are used. As catalytically active salt of metal, in particular, nitrate or sulphate of copper, titanium or lanthanum are used.

EFFECT: method allows to relatively quickly obtain catalytically active lamellar silicates without exhausts.

15 cl, 1 ex, 1 tbl, 1 dwg

 

The invention relates to a method for catalytically active layered silicate with one or more intermediate layers, in particular, clays with interlayer pillars of Al and/or Ti (Al, Ti-pillared clays).

Catalysts, in particular catalysts "Denox"used for removal of oxides of nitrogen (NOx) of the exhaust gas, are widely used in automobiles for processing exhaust gases. In the case of catalytic post-combustion catalysts consist of a carrier with an active coating and vibration-resistant, insulated bearings in the housing. As carriers are applied and sintered granulate of Al2O3monoliths. Active catalytic layer consists of small amounts of noble metals (Pt, Rh, Pd) and has a known sensitivity to lead.

Such automotive catalysts or catalysts triple or selective actions have proved positive and serve to the first stage to reduce the NO content with the formation of NH3. Then, in the second stage, after the secondary air is almost complete oxidation of CO and HC. It also burns NH3forming NO.

Such catalysts are used for a long time, however, from the point of view of ecology and medicine, they are not completely perfect. It was established only in recent studies, PR is maintained in respect of petrol and diesel engines for cars, and is reflected in the results of a study of automobile emissions in the current legislation. The reason is that over time these catalysts is detached active catalytic layer consisting, for example, of platinum, and its emission into the atmosphere of air. Consequently, the human body is the accumulation of platinum, about the possible negative consequences which there is not yet clarity. In any case, there is a need to create catalysts, not forming emissions.

Furthermore, only recently, according to which under the action of carbon monoxide in the platinum catalysts on the basis of the formation of toxic components. Such components can cause mutation of cells (see "Chemical and Engineering News", July 2002, p.8).

The prior art discussion of alternative catalytic projects, for example, on the basis of zeolites. These zeolites are processed transition metals. However, in this case marked the formation of harmful by-products, for example HCNO. In addition, these catalysts do not have the desired resistance to water, oxides of sulfur and heavy metals.

In the prior art, taken as a basis in the present invention, described getting a catalytically active layered silicates, the so-called clay with IU the layer supports (pillared clays), and typical of zeolite catalysts, and compensating the charge of the cations are replaced in the intermediate layers of the respective layered silicates larger inorganic cations gidroximetilland. This happens mostly in aqueous solution. Thereafter, the resulting material is dried and calicivirus (see R.Q.Long and R.T.Yang "promoting The role of rare earth oxides on Fe-exchanged TiO2-pillared clay for selective catalytic reduction on nitric oxide by ammonia" (Positive effect of rare earth oxides on clay with replaced with iron and the interlayer pillars of TiO2for selective catalytic reduction of nitric oxide by ammonia); Applied Catalysis B (Practical kataliz): best manufacturers in China, No. 27, 2000, p.87-95. From the point of view of implementation, the method is complicated.

In the source of information "Preparation of acidic forms of montmorillonite clay via solid-state ion-exchange reactions" (Getting the acidic forms of montmorillonite clay by ion-exchange solid-phase reactions), Msgorig and others (Catalysis Letters, No. 15, 1992, str-345) raised the question about the possibility of holding a solid-phase ion exchange in montmorillonite. To do this, at room temperature, pulverized nitrate suitable metal, along with a corresponding clay. For carrying out ion exchange proposed, in principle, two ways: ultrasonic treatment and heating. Judging by the results, when heated, ion exchange does not occur.

The basis of the invention is the technical problem to develop a method of obtaining a catalytically active layered silicates, with which it is possible to just get the main catalytic substance, almost forming emissions.

To solve this task, a subject of the invention is a method of obtaining a catalytically active layered silicates, in particular nanocomposite layered silicate with one or more intermediate layers, in particular clays with interlayer pillars of Al and/or Ti, in which the layered silicate is introduced a solution of metal, mainly poly solution of the metal, and then is dried mixture with the formation of the intermediate support layer supports of metal atoms, after which the thus prepared dry matter introduces a salt of the metal, in particular, transition metal, to obtain the dry mixture, and finally the dry mixture is preferably heated to a temperature of over 300°With the result that the metal atoms or transition metal embedded in the intermediate layer with a gas and simultaneously calcining the dry mixture.

As catalytically active layered silicates are used, as a rule, the so-called nanocomposite layered silicates, i.e. such layered silicates, in which there is described firmly asny ion exchange or the introduction of metal atoms or transition metal in the nanometer range. The same applies to the formation of poles of the atoms of the metal supporting the respective intermediate layer. We have in mind mainly the oxides or polyoxide metals, i.e. in principle metal compounds (oxygen content), providing support through education supports in the respective intermediate layer.

For the formation of the intermediate layer in the layered silicate is injected a solution of a suitable metal or poly solution of the metal ion complex solution of the metal, and then the mixture is dried with education supports (Pillars), which supports the respective intermediate layer, calicivirus and if necessary transferred in the form of ammonium. It is usually in an alkaline environment, and to prepare the solution of the metal used in most cases sodium lye.

When described wet chemical modification of layered silicate allocate contained in a solution of sodium hydroxide or aluminum, with ions or complex ions of the metal deposited in the intermediate layer or on the surface of layered silicates. After drying they form in the intermediate layer support nanometric range. In the intermediate layers or between the layers of the silicate is not only expanding, but is set in the specified position.

It was found that as the solution of the metal can be optimally use a solution of aluminum and/or titanium and/or iron. Along with this can also be applied to solutions of copper and/or chromium, or a mixture of polyoxides of these metals. In principle, this can be used, in particular, any transition metals in pure form or as mixtures. It is preferable to use the titanium chloride in combination with sodium hydroxide. The same applies to the combination of ferric chloride with sodium hydroxide. If the corresponding solutions of aluminum salts (in this case: salt aluminium chloride) mixed in water with sodium lye or sodium hydroxide (NaOH)is formed, for example, aluminum hydroxide (Al(OH)3). In the case of the solution shown generally poorly soluble aluminum hydroxide.

In any case described wet chemical modification of layered silicate leads to that present in solution, the metal atoms (for example, atoms of aluminum, iron, titanium and others) are deposited in the intermediate layer or layers of the layered silicate and after drying, form a support intermediate support layer of metal atoms. Thus, the gaps between the layers of the silicate is not only expanding, but also set a certain way.

In this regard, it should additionally be noted that, as a catalytically active layered silicate can also be used separately prepared mixture. For example, perhaps the subsequent preparation of a mixture of the Ling with the interlayer supports made of aluminium and titanium. Thus, in the obtained dry substance or mixture considered different catalytic action, on the one hand, for example, the supports of titanium atoms with copper coating and, on the other hand, supports made of aluminium atoms with copper coating. In the first case, i.e. when applied formed by titanium atoms bearing with copper coating, is achieved in a particularly effective catalytic activity in the low temperature range, while formed by the atoms of the aluminum support with a copper coating is particularly effective at high temperatures. Therefore, the mixture of layered silicates for the preparation of dry matter, past various processes of education supports, you can achieve optimal catalytic activity in a wide temperature range. Dry matter, cooked from both past different pre-processing of layered silicates, then subjected together with the metal salt or the transition metal, as described, the solid-phase/solid-phase reactions. If this case applies salt of copper, there is described a coating or injection of copper atoms in the intermediate layer.

These metal atoms or transition metal, which are, as a rule, the copper atoms, primarily responsible - together with the previously formed the supports of metal atoms for the catalytic action. is the result of applying the salt of the transition metal or its atoms are not only able to maintain low costs, associated with obtaining such catalytically active layered silicate, but also, particularly with respect to copper is not present (more) the danger that under the action of high temperatures in the catalyst, it will evaporate into the environment. This is an obvious contrast to previously used noble metals such as platinum.

Needless to say that the drying process may be preceded by various other stages of the method. For example, the invention provides that the mixture of the layered silicate and the first cationic complex solution polyperoxide after addition of the solution of the first metal was filtered, then was filtered and then slowly heated to, for example, to a temperature of 100°C, the reaction education gidratirovannykh of nanopar or supports of metal atoms occurs at room temperature.

On the contrary, the subsequent drying process is carried out under conditions of rapid or abrupt temperature increase from about 100°With (for example, 100°With about 10 or more minutes) to about 500° (or more), resulting in the corresponding intermediate layer are formed is described support from the metal atoms. Indeed in the intermediate layers is even more or less pronounced supports migration of metal atoms, and at the end when the loud notes uniform distribution in the intermediate layers digitalisierung, ie if necessary, freed from water and hydroxide (sodium) supports of metal atoms. There is a direct relationship between thermal digitalizacie and subsequent recombination of the supports of metal atoms. Such recombination is largely irreversible.

It was found that this modification of the layered silicate can maintain the necessary temperature resistance up to about 100°and can be used as a catalyst.

After the formation of the pillars of metal atoms in the intermediate layers of the layered silicate by an acid treatment is in the cationic state, and by alkaline treatment in anionic, then washed and dried.

However, in the intermediate layer formed by using the supports of metal atoms, it is necessary to introduce catalytically active cations for the most part in the form of ions of transition metals such as titanium, iron, cobalt, Nickel, copper, zinc, etc. In principle, it is also possible to apply in this case, the cations of atoms of non-transition metals, i.e. metals of the main groups such as, for example, sodium, potassium, rubidium, etc. are also Possible lanthanum ions and noble metals such as gold and silver, which are in the form of salts can be added, usually in small the concentration of salts of transition metals. These ions (noble) metals could the t to provide a simultaneous doping mostly embedded transition metal ions.

Especially positively has proved in this case, the introduction of copper cations in the respective intermediate layers, since these cations capable of decomposing at a high temperature nitrogen oxides (NOx) mainly nitrogen (N2) and oxygen (O2). Thus, in principle, it is also possible to additionally use a reducing agent, such as methane. In any case, the main goal is selective catalytic chemical reduction gases NOxby using different reducing agents such as NA and/or CO and/or NH3.

If you describe in detail, the metal as the metal salt are mixed in dry form with a dry substance, previously prepared from layered silicates with the supports of metal atoms. This produced positive results in the form of salts of metals, in particular copper nitrate (Cu(NO3)2), copper acetate and copper sulfate (II) (CuSO4). If necessary, this dry mixture is crushed and then (in dry form) is heated, in particular, generally to a temperature above 300°With, typically, to a temperature of from 450 to 700°C. the result is a decomposition of a metal salt or a salt of copper with the release of oxides of nitrogen (nitrogen dioxide (NO2) or sulfur dioxide (SO2in the above example. Depending on supports formed from metal atoms which may occur in solid-phase exchange and/or the intermediate coating layers and/or internal/external surfaces of the necessary metal atoms or groups of these atoms.

Thus, unused still atoms or metal ions or copper and/or groups of atoms of the metal or copper, which are mostly embedded in the intermediate layer. The remaining atoms or metal ions or groups of atoms of the metal cover outer surface. Therefore, at least partially thermal replacement compensating the charge of the cations in the intermediate layers of the layered silicates of the above atoms or metal ions, contributing significantly the catalytic activity of the obtained layered silicate. In the intermediate layers are generally uniform distribution of the metal atoms.

In contrast to the known methods of production of catalytically active layered silicate is especially easy, as there is no need for the solution of the metal or transition metal, mixed with a pre-modified dry substance. Therefore, according to the invention does not require filtering and processing of the specified solution, as prepared dry mixture. In addition, provided the specified heating a dry mixture of a simultaneous calcination, i.e. also no need for a separate operation, provided in the prior art. As is known, when the calcination remove without an is, may be contained in a dry mix of crystallization water or other solvents and simultaneously decomposes carbon dioxide.

The resulting material or the final product is subject to moisture so that it could be optimal to take when necessary, any form after adding a binder or plasticizer. As binders may be used water, aluminum oxide or ceramic material. The final product is easily molded and processed, for example, by extrusion. Thus, it is possible to obtain a simple monolithic structure or so-called granules, i.e. small molded products which are suitable for direct use as catalysts for automotive exhaust gases. However, additionally requires that any resulting extrudate or molded articles previously subjected to heating and drying.

Monolithic structure and granules provide the advantage that they are catalytically active throughout its volume. The situation is different when prepared as described catalytically active layered silicate is used as a layer in combination with (inert) carrier, as, for example, the protective coating. This coverage can be obtained, for example, drip n is the carrying of a solution of layered silicate, according to the invention, to the media. Because the metal atoms are distributed in the intermediate layer in the form of large cells, there is no danger that the use of such media coverage as the catalyst can occur during operation of the unwanted processes of sintering, reducing the catalytic activity. This advantage becomes even more important if you apply the monolithic catalysts of the layered silicate or granules according to the invention, i.e. of more or less coarse-grained granulate.

As the layered silicate can, in principle, be applied to two-layer minerals, such as kaolinite or aluminosilicates. However, according to the invention, it is preferable to use a three-layer or even four-layer minerals. Suitable three-layer mineral proved to montmorillonite or bentonite. Other effective measures specified in 15 claims.

Example

As source material used bentonite, in particular calcium bentonite with the main component montmorillonite, consisting of about 57 wt.% SiO2about 23 wt.% Al2About3about 3 wt.% Fe2About3and about 10 wt.% H2O. This source material finely to grind to increase the specific inner surface. In the fine grinding efficiency of the prepared base material of the catalyst is increased.

This was followed by the so-called "education spacers" (Pillaring), i.e., wet chemical introduction of metal atoms to create spacers in both the intermediate layers used three-layer mineral. Pre-fine mineral powder was dispersible in the water, which, however, is not mandatory, as already in powder or dispersion is added a solution of aluminum hydroxide (AlOH). Through a solution of aluminum hydroxide can be determined and set at variance the relationship between the mass of the bentonite and the volume of the suspension. This ratio represents the concentration value of the interlayer system supports, i.e. the value of how many atoms in the form of supports required in the intermediate layers.

In this case, the content of aluminium in comparison with bentonite is of special significance. If the solution is too much aluminum in comparison with the content of the bentonite, it leads to the reduction of the inner surface due to the intensive educational supports made of aluminium atoms. Too low a content of aluminum in solution in comparison with the concentration of bentonite after dispersion leads to the fact that the intermediate layer does not have the necessary strength, which is particularly evident during the temperature increase.

Hence, there is an opt the normal range of ratios between aluminum and bentonite, which, basically, is determined on the basis of the obtained specific internal surface. Needless to say that in these experiments the ratio HE/Al must be maintained constant. In any case, the target products are evaluated on the basis of the specific internal surface and the resulting pore size that under the optimal ratio between aluminum and bentonite reaches the maximum value. This follows from the table below, in which the ratio between the aluminium and bentonite from about 3.0 to about 5.0 provides the maximum value of the specific inner surface and pore volume.

Table

The results for dierent values of the ratio between the aluminium and bentonite, mmol (6.8 g of bentonite 1 l)
The mmol, Al/gConductivity, MS/cmThe amount of deposition per day, mlSurface, m2/gPore volume, µl/gMicropore volume, µl/gIndicator d Å
1,02,319109976016,9
2,04,3221368875of 17.0
3,06,220 30927914318,6
5,0the 9.719290258131of 17.5
6,810,5182469913519,1
8,015,11712810611618,5
10,015,2161259566of 17.5

From the above table it can be seen that when the above-mentioned ratio between aluminum and bentonite equal to from about 3.0 to 5.0 and have already achieved a relative maximum, not only for the specific internal surface and pore volume, but the volume of micropores. Simultaneously, takes certain specified values, the thickness of the intermediate layer (d value), equal 17-19 Åthat favorably affects the subsequent introduction of copper atoms.

Additionally, it was found that already at the specified ratio between aluminum and bentonite from about 3.0 to 5.0mm optimum range of the thickness of the formed pillars of metal atoms. Here we mean that, given the more or less constant performance of the intermediate layer (d value) varies with the number of spacers and the metal atoms per unit area and almost follows a Gaussian distribution. This spectrum distribution of the thicknesses of the spacers of metal atoms contributes to the catalytic action, since the decomposition of oxides of nitrogen usually is not done in one step, but in several. The main importance of small pores, i.e. areas with a high surface density of the spacers of metal atoms, so that NO turned, first of all, NO2. In the presence of larger pores, i.e. at a lower surface density of bars of metal atoms is predominant conversion of NO2in the nitrogen (N2) and oxygen (O2). Naturally, the distribution density of the spacers of metal atoms, established at the specified ratio between aluminum and bentonite from about 3.0 to 5.0 and promotes multi-stage decomposition of oxides of nitrogen.

However, before will happen the introduction of copper atoms, the drying of bentonite modified by bars of aluminium atoms in the intermediate layer, in particular, therefore, as it was described. To the dry substance is admixed as a salt of the metal nitrate or copper sulfate in a dry form. In conclusion, the dry mixture is heated to a temperature of 450-550°With, resulting nitrogen dioxide or sulfur evaporates, and the remaining atoms or copper ions are introduced into the previously formed intermediate layer with bars of aluminium atoms./p>

The result is a modification of a known themselves layered silicates, providing a catalytic effect on the flow of exhaust gases and using this embedded in the intermediate layers of metal atoms such as copper atoms. These copper atoms in the electric field of the intermediate layer can cause decomposition, in particular, oxides of nitrogen. All this is achieved through a relatively simple wet and dry chemical processing methods and operations of grinding. Used in this layered silicate becomes large specific surface area.

Due to the fact that the catalytically active cations located in the electric field formed around the intermediate layer, firmly embedded in the crystal structure, the negative phenomena that may not resolve the prior art, are practically absent. I.e., obtained in the framework of the present invention the catalytically active layered silicates do not form harmful to the environment and health of emissions even at elevated temperatures, typically, the catalysts used for automobile exhaust gases.

The resulting substance is easily formed directly or after addition of the binder material, for example, by extrusion. Therefore, there is no need to use complex is x forming methods. Thus, receive the base material of the catalyst, which practically produces no emissions and, in addition, can cheaply be molded to give it almost any configuration.

In addition, it was found that obtained using the method according to the invention, the modified layered silicate is not only can be used as the base material of the catalyst, but also can serve to filter soot in diesel engine vehicles. In this case, the intermediate layers detain the individual particles of soot, while contained in the exhaust oxides of nitrogen (NOx) eliminate clogging the specified filter with soot, so as nitrogen oxides are oxidized at the current temperatures, the carbon soot particles in the carbon dioxide (CO2held in the form of gas through the respective diesel particulate filter. Thus, not only the decomposition of nitrogen oxides, but also soot particles are filtered and chemically converted.

Using the block diagram in the drawing again explains the individual steps of the method.

First of all layered or source material (the original bentonite) on stage 1.1 if necessary, sieved and dried. Phase 1.1 may also grinding.

After that, the source material is dispersed, for example, in water, as shown for stage 1.2. Thus, PR is maintained example receive bentonite dispersion.

At the same time on stage 2.1 prepare a solution of metal, while the salt of the metal (aluminium salt) is dissolved by adding sodium liquor and on stage 2.2 obtain the required solution of metal hydroxide solution of aluminum).

Then the original or bentonite dispersion stage 1.2, and the solution of the metal or a solution of aluminum hydroxide phase 2.2 mix among themselves for the formation of the interlayer spacer (pillaring). To improve the mixing can be applied or not applied to ultrasound, in particular, at step 3.1. Using this solution or mixture at the stage 3.2 washed, filtered and then on step 4.1 is dried or calcined. This occurs typically at a temperature of 400-600°C for 1-12 hours.

After this is done the screening, which was retrieved in step 4.2 dry matter is separated and the grain size less than 500 microns delay. Dry mix on stage 5.1 mix in completely dry salt of the metal, for example copper, or with salts of other metals.

Then catalytically active metal atoms or transition metal embedded in the intermediate layer at the stage 6.1 method in which a dry mixture is heated or calicivirus within 1-12 hours. In conclusion, spend another molding process at step 6.2 with or without additional use of binders or plasticizers. Finally get the monolithic target product in the form of granules or solution for coating the carrier. In any case, the final product has a special resistance to water vapor, which determines its use for the catalytic purification of the EXHAUST system of the car.

1. The way to obtain catalytically active layered silicates for the treatment of exhaust gases containing one or more intermediate layers, wherein at the step (3.1) education interlayer supports in layered silicate add a solution of the metal and the mixture obtained at step (4.1) drying/calcination heat with the formation of the intermediate support layer supports of metal atoms, prepared in the dry matter of the type of catalytically active salt of the transition metal with the receipt of the dry mixture and finally heated dry mixture to a temperature above 300°With the result that the atoms are catalytically active transition metal embedded in the intermediate layer and simultaneously is the calcination of the dry mixture.

2. The method according to 1, characterized in that as a solution of the metal solution using aluminum, titanium, iron, copper, chromium.

3. The method according to claim 1 or 2, wherein the dry mixture is heated to a temperature of 450-700°C.

4. The method according to claim 1, characterized in that the mixture of layered silicate and a solution of metal is first washed, then filtered and only then slowly heated, and the reactions the formation of the supports of metal atoms is carried out at room temperature.

5. The method according to claim 4, characterized in that after drying the substance is abruptly heated to a uniform distribution digitalisierung supports of metal atoms in the intermediate layer.

6. The method according to claim 5, characterized in that the temperature gradient at the sharp heat set such that the temperature rise was about 100°C/10 min or more, for example, from 100 to 500°30 min.

7. The method according to claim 1, characterized in that after the formation of the pillars of metal atoms in the intermediate layers of the layered silicate by an acid treatment is in the cationic state, and by alkaline treatment in anionic, then washed and dried.

8. The method according to claim 1, characterized in that the catalytically active salt of the transition metal is obtained on the basis of transition metals, such as, for example, copper, titanium, lanthanum.

9. The method according to claim 8, characterized in that the catalytically active metal salt used nitrate or copper sulfate.

10. The method according to claim 1, characterized in that obtained from the dry mixture the substance is formed, if necessary after addition of the binder, such as alumina, for example, by extrusion.

11. The method according to claim 10, characterized in that the extrudate is dried.

12. The method according to claim 1, characterized in that the layered silicate used two-layer and/or a three-layer mineral.

13. The method according to claim 1, characterized in that the inner surface of the obtained layered silicate is about 300 m2/g or more.

14. The method according to claim 1, characterized in that the catalytically active layered silicates used nanocomposite layered silicates, in particular, the clay interlayer pillars of Al and/or Ti.

15. The method according to claim 1, wherein the solution of metal used poly solution of metal.



 

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9 cl, 5 tbl, 9 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4-) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.

EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.

16 cl, 2 dwg, 2 tbl

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: invention relates to a method of preparing catalysts for middle-temperature conversion of carbon monoxide, which can be used in industry when producing nitrogen-hydrogen mix for ammonia synthesis. Preparation of catalyst for middle-temperature conversion of carbon monoxide with water steam, comprising precipitation of iron hydroxide from iron nitrate solution with ammonia-containing solvent, washing of iron hydroxide with water to remove nitrate ions, mixing with calcium and copper ions, mechanical activation of components, molding, drying, and calcination of granules, is characterized by that, in the component mixing step, lanthanum oxide is supplementary added, in which case molar ratio of components is as follows: Fe2O3/CaO/CuO/La2O3 = 1:(0.8-0.9):(0.045-0.08):(0.005-0.01).

EFFECT: increased catalytic activity and more than thrice reduced content of by-products in condensate.

1 tbl, 3 ex

FIELD: gas treatment.

SUBSTANCE: invention relates to processes of removing carbon monoxide from gas mixtures containing, except hydrogen, carbon dioxide. This process is an important step for production of pure hydrogen or hydrogen-containing gas, e.g. in ammonia synthesis. Catalyst for removing carbon monoxide from hydrogen-containing gas represents permeable composite material containing combination of phases of catalytically active group VIII metal or their alloy, oxide-type carrier, and metallic copper or copper metal containing alloy, composite-forming grain size being less than 0.5 mm and permeability of composite exceeding 10-14 m2. Catalyst preparation procedure as well as processes of removing carbon monoxide from hydrogen-containing gas using it are also described.

EFFECT: increased activity and selectivity of catalyst.

20 cl, 3 dwg, 8 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to chemistry of heterogeneous catalysts and is directed to production of high-octane gasoline component via alkylation of isobutane with butane-butylene fraction on heterogeneous catalysts. Solid catalyst represents porous superacid based on zirconium and/or hafnium metallosilicates promoted with salts of double- or triple-charged metal cations with double-charged anions and depicted by general formula (EO2·aSiO2)·b(McXd) wherein E = Zr and/or Hf, a=17-34; b=0.5 when c=1 and d=1, M= Ni2+, Zn2+, or ZrO2+, X=SO42- or ZrF62-; or b=0.1666 when c=2 and d=3, M=Sc3+, Y3+, or Ga3+ and X= SO42-, parameter "a" being allowed to deviate from indicated value to larger or lesser side by 20% and parameter "b" by 5%. High-octane gasoline component is produced as indicated above at temperature 348 to 375 K, pressure 1.7 to 2.5 MPa, isobutane-to-butenes molar ratio 10-15, and volume feed supply velocity between 6.4 and 8.5 g/mL catalyst/h. Catalyst can optionally be regenerated.

EFFECT: enhanced conversion, yield of alkylate, productivity, and prolonged catalyst lifetime.

7 cl, 4 tbl, 11 ex

FIELD: chemical industry; petrochemical industry; hydrogen power industry; metallurgy industry; coke industry; other industries; methods of production of hydrogen and the nanofibrous carbonic materials.

SUBSTANCE: the invention is pertaining to the catalytic productions of hydrogen and the carbonic materials of the nanofibrous structure out of the hydrocarbon. The invention may be used in the chemical industry, the petrochemical industry at utilization of the hydrocarbon gases, and also in the hydrogenous power industry, in metallurgy and the carbonic productions. The method of production of hydrogen and the nanofibrous carbonic material includes decomposition of the hydrocarbon material at the heightened temperature on the catalyst containing nickel, copper and the hard-to-restore oxides. In the capacity of the hydrocarbon material use methane and decomposition is conducted at the temperature of 700-750°С or use the gaseous hydrocarbons with the monatomic ratio of hydrogen : carbon - within 2-3 and decomposition is conducted at the temperature of 500-600°С. The invention allows realization of the catalytic decomposition of the gaseous hydrocarbons with production of hydrogen and nanofibrous carbon.

EFFECT: the invention ensures realization of the catalytic decomposition of the gaseous hydrocarbons with production of hydrogen and nanofibrous carbon.

3 cl, 4 dwg, 1 tbl, 9 ex

FIELD: disproportionation process catalysts.

SUBSTANCE: invention relates to generation of hydrogen through steam conversion of carbon monoxide and development of catalyst for indicated process. Invention provides carbon monoxide conversion catalyst showing high catalytic activity and heat-conductivity and a process of steam conversion of carbon monoxide using indicated catalyst. Catalyst is characterized by heat-conductivity at least 1 W(mK)-1, which enables performing process with low temperature gradient in direction transversal to gas stream direction.

EFFECT: increased catalytic activity and heat-conductivity.

7 cl, 4 dwg, 3 tbl, 10 ex

FIELD: carbon monoxide conversion catalysts.

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

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

1 tbl, 3 ex

FIELD: hydrogenation-dehydrogenation catalysts.

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

EFFECT: increased activity and selectivity of catalyst.

3 cl, 1 tbl, 8 ex

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