Production of hydrocarbons from synthesis gas

FIELD: petrochemical process catalyst.

SUBSTANCE: invention, in particular, relates to precursors of catalysts used in production of hydrocarbons from synthesis gas. Preparation of catalyst precursor involves contacting crude catalyst carrier, which is partly soluble in aqueous acid solution and/or in neutral aqueous solution, with modifying component of general formula Me(OR)x, wherein Me is selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Ti, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, and W; R represents alkyl or alkoxy group; and x is integer from 1 to 5. Therefore, modifying component is introduced into catalyst carrier or deposited onto surface thereof to form protected modified catalyst carrier, which is less soluble and more inert in aqueous acid solution and/or in neutral aqueous solution than crude carrier. Resulting catalyst carrier is then subjected to heat treatment at temperature lower than 100° C so that calcination of the carrier does not take place. Non-calcined protected modified catalyst carrier is mixed with aqueous solution of cobalt, which is active component of catalyst or its precursor, to form slurry. Which is exposed to subatmospheric pressure to facilitate impregnation of the catalyst carrier with cobalt or its precursor. Impregnated carrier is then dried at subatmospheric pressure and finally calcined.

EFFECT: enhanced selectivity and activity of catalyst in Fischer-Tropsch synthesis and eliminated need to perform calcination step after contact of crude Carrier with modifying component and drying.

16 cl, 5 dwg, 1 tbl, 6 ex

 

This invention relates to the production of hydrocarbons from synthesis gas and the catalyst used. In particular, it relates to a method for processing raw catalyst carrier with obtaining a protected modified catalyst carrier, to a protected modified catalyst carrier thus obtained, to a method for producing the catalyst of the protected modified catalyst carrier, the catalyst thus obtained, the method of production of hydrocarbons and the hydrocarbons thus obtained.

According to the first aspect of the invention provides a method for processing raw catalyst carrier which comprises contacting the untreated catalyst carrier, which is partially soluble in an aqueous acid solution and/or in a neutral aqueous solution, with the modifying component precursor of the formula Me(OR)Xwhere Me is selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Tl, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, TA and W, R denotes alkyl or acyl and x is an integer from 1 to 5, in order to enter the modifier component on the surface or in the bulk of the catalyst carrier and get protected modified catalyst carrier that is less soluble and more inert in aqueous acid solution and/or in neutral the aqueous solution, than the untreated catalyst carrier, without annealing the catalyst carrier after processing of the modifying agent. Untreated catalyst carrier can be, in particular, in the form of particles. Modifying the component then is the mass of particles protected modified catalyst carrier, on the surface of the particles, namely, the modifying component chemically linked to the surface of the particles. The modifier component can be chemically linked to IT (hydroxyl groups) on the surface of the media.

By "annealing" refers to the processing of the catalyst carrier at an elevated temperature, at least at 100°for the decomposition of the organic groups of the modifying component in the air, and to remove all residual solvent used for impregnation of the modifying component for introducing it into the mass or on the surface of the catalyst carrier, as described below. Thus, the present invention is characterized by the fact that the protected modified catalyst carrier is not subjected to processing by heating at 100°C or higher. Of course, this does not exclude the possible processing of the protected modified catalyst carrier when heated above 100°during the subsequent transformation of the protected modified the nose is the body in the catalyst precursor or catalyst, as explained above.

Thus, the modifying component if it is present in the catalyst carrier, is able to reduce the solubility of the untreated catalyst carrier in an aqueous acid solution and/or in a neutral aqueous solution.

In principle, there may be used any commercially available dried, for example, spraying, untreated catalyst carrier, which is partially soluble in an aqueous acid solution and/or in a neutral aqueous solution.

Examples of the raw media catalyst, which can be used include aluminum oxide (Al2About3), titanium oxide (TiO2), magnesium oxide (MgO) and zinc oxide (ZnO). When the catalyst carrier is alumina, in principle, can be used with any suitable carrier is alumina. For example, the carrier may be aluminum oxide, sold under the trademark Puralox SCCa 2/150, SASOL Germany GmbH. Puralox SCCa 2/150 (trademark) is a spray dried alumina. Similarly, when the carrier of the catalyst is an oxide of titanium, in principle, you can use any titanium oxide as a carrier. For example, it may be a titanium oxide, sold under the trademark of Degussa P25.

Under "raw" catalyst carrier imply catalyst carrier, which is part of the solution is m in aqueous acid solution and/or in a neutral aqueous solution.

Contacting the untreated catalyst carrier with the modifying component precursor can be made by impregnation or deposition from the vapor phase, however, the preferred impregnation.

According to one variant of the invention, the modifying component precursor may be a precursor modifier component on the basis of silicon or silicon compound, for example, an alkoxide of silicon, while the modifying component is silicon (Si). The organosilicon compound can be tetraciclina ("TEOS", namely, Si(OC2H5)4or tetramethoxysilane ("TMOS", namely, Si(och3)4).

When the modifying component precursor on the basis of silicon is used in combination with the catalyst carrier is alumina, it can be used in such a quantity that the content of silicon in the resulting protected modified catalyst carrier will be at least 0.06 Si atoms/nm2raw media, preferably at 0.13 Si atoms/nm2raw media and more preferably at least atoms of Si 0,26/nm2raw media.

The upper limit of the content of the modifying component, such as silicon, in a protected modified media catalysis the ora can be set such parameters, as the porosity of the protected modified catalyst carrier and/or the average diameter of pores of the protected modified catalyst carrier. Preferably, the average pore diameter of the protected modified catalyst carrier described herein were at least 12 nm, as described in ZA 96/2759 included as references. In addition, if the goal is to obtain a protected modified catalyst carrier having a composition of 30 g Co/100 g Al2About3, pore volume raw media Al2About3and protected modified catalyst carrier should be at least of 0.43 ml/g, as described in U.S. patent 5733839, applications WO 99/42214 and/or WO 00/20116. Thus, the upper limit of the modifying component, such as Si, in a protected modified catalyst carrier is selected so that the geometry, for example, the average diameter of pores and the porosity of the protected modified catalyst carrier is not adversely affected to a significant degree.

Thus, when the spray dried alumina Puralox SCCa 2/150 (trademark) is used as the raw catalyst carrier, apply such amount of the modifying component precursor on the basis of silicon, so that the upper limit of the content of silicon in polucen the m protected modified catalyst carrier was 2.8 Si atoms/nm 2the surface of the untreated catalyst carrier, preferably 2.5 Si atoms/nm2the surface of the untreated catalyst carrier, as described in the application WO 99/42214.

The maximum amount of silicon that can be added to the raw media catalyst at the same stage of impregnation, is 2.8 Si atoms/nm2the surface of the untreated catalyst carrier.

When contacting the catalyst carrier with the modifying component precursor on the basis of silicon or silicon compounds is carried out in the impregnation process, the organosilicon compound is dissolved in a solvent for impregnation, having a boiling point less than 100°C at atmospheric pressure. The solvent used for impregnation is usually an organic solvent capable of dissolving the silicon compound, such as ethanol, acetone or propanol. Untreated catalyst carrier can then be mixed with the resulting solution to obtain a mixture and then to sustain this mixture at elevated temperature for a certain period of time required for penetration of the modifying agent in the catalyst carrier and/or on its surface. Fever may be the boiling point of the solvent used for impregnation or may be close to the boiling point. Impregnated the ku can be conducted at atmospheric pressure, and the time period within which the impregnation, may be from 1 minute to 20 hours, preferably from 1 minute to 5 hours. Then the excess solvent or solution is removed, that is, the impregnated carrier is dried to obtain a protected modified catalyst carrier. Drying can be conducted under pressure or under vacuum of 0.01-1 bar (a), more preferably 0.01 to 0.3 bar (a), and at a temperature equal to the boiling point of the solvent at a pressure of drying, for example, using known equipment, equipped with a stirrer, the temperature in the jacket of the apparatus above the boiling point of the solvent. However, the drying temperature is below 100°C.

According to another variant of the invention the modifying component precursor may be a zirconium alkoxide, such as isopropoxide zirconium (Zr(OCH(CH3)2)4), then the modifier component is zirconium (Zr). Contacting the untreated catalyst carrier with the alkoxide of zirconium can be similarly described above for the predecessor, the modifying component is silicon-based.

According to the second aspect of the invention provides a method for processing raw catalyst carrier, which includes:

the mixture of the raw catalyst carrier, which is partially astrim in aqueous acid solution and/or a neutral aqueous solution, with a solution of the modifying component precursor of the formula Me(OR)Xwhere Me is a modifying component selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Tl, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, TA and W, R denotes alkyl or acyl and x is an integer from 1 to 5, in a solvent for impregnation, having a boiling point at atmospheric pressure below 100°With the mixture for processing;

the extract mixture at the boiling temperature of the solvent or at a temperature close to her, within 1 minute to 20 hours for impregnation of the catalyst carrier of the modifying agent and

drying the impregnated carrier removing excess solvent or solution under a vacuum of 0.01 to 1 bar (a) to obtain the protected modified catalyst carrier, which is less soluble or more inert in aqueous acid solution and/or in a neutral aqueous solution than the untreated catalyst carrier, without annealing the catalyst carrier after processing the modifying component, and that the modifying component is contained in a protected modified catalyst carrier and/or on its surface, is able to reduce the solubility of the protected modified catalyst carrier in an aqueous solution.

The method may include washing the protected modified catalyst carrier with the goals of the completion of removal of all residual solvent to obtain a suspension, representing the washed catalyst carrier and washing liquid, and drying the suspension.

Flushing can be performed with an aqueous solution at a temperature of about 60°C for a certain period of time, such as within 1 hour.

The drying of the suspension can be performed at a temperature of approximately 95°and under vacuum of 0.03 to 0.2 bar (a).

The invention also covers the protected modified catalyst carrier obtained as described above.

In accordance with a third aspect of the invention provides a method of obtaining a catalyst precursor, which includes a mixture of the protected modified catalyst carrier described above, with an aqueous solution of the active catalyst component or its precursor with getting the suspension and impregnation protected modified catalyst carrier with the active catalyst component or its precursor with obtaining a catalyst precursor.

The active catalyst precursor may be a cobalt nitrate and then the active component of the catalyst on its surface or in the bulk of the cobalt. Untreated catalyst carrier, as described above, may be aluminum oxide.

A method of obtaining a catalyst precursor can be carried out according the U.S. patent US 5733839, applications WO 99/42214 and/or WO 00/20116. Thus, the mixture of the protected modified catalyst carrier and the solution of the active catalyst component or its precursor and the stage of impregnation can be performed by subjecting a suspension of the protected modified catalyst carrier or media, water and the active catalyst component or its precursor action subatmospheric below atmospheric negative pressure (destruction), then to drying the obtained impregnated carrier under the action of negative pressure and calcination of the dried impregnated carrier with obtaining a catalyst precursor, namely, to obtain the catalyst Fischer-Tropsch in unrestored form.

If necessary the catalyst with a high content of cobalt, after the first impregnation stage, then drying and calcination as described above, it is possible to carry out a second or even a third impregnation, drying and calcination.

In the impregnation process, you can add a water-soluble salt of platinum (Pt) or palladium (Pd) as an additive, contributing to the restoration of the active component. The mass ratio of this addition to the active component of the catalyst can range from 0.01:100 to 0.3:100.

The invention also covers the catalyst precursor obtained in the above way.

Still the way the catalyst precursor is in unrestored form and requires its restoration and activation before it can be used, it is necessary to restore or activate to turn it into a catalyst.

Therefore, according to a fourth aspect of the invention provides a method of producing a catalyst, which includes restoring or activating the catalyst precursor described above.

The invention also includes a catalyst obtained by the method described above.

According to the fifth aspect of the invention provides a method of producing hydrocarbons, which comprises contacting synthesis gas containing hydrogen and carbon monoxide at an elevated temperature between 180°, 250°and at elevated pressures of from 10 to 40 bar in the presence of the catalyst described above, with the preparation of hydrocarbons by the reaction of the Fischer-Tropsch process, involving the interaction of hydrogen with carbon monoxide in suspension.

This invention also covers the hydrocarbons obtained by the method described above.

It is known that the catalyst for Fischer-Tropsch, representing a catalyst based on cobalt on media, aluminum oxide, leads to the production of wax-like product used in the reaction of the Fischer-Tropsch process involving synthesis gas, containing the its hydrogen and carbon monoxide.

Such catalysts still preferably obtained by impregnation of alumina (media) aqueous solution of the precursor of cobalt nitrate, the pH of which may be equal 1-6. Aluminum oxide is partially soluble in an aqueous acid solution and a neutral aqueous solutions. After dissolution of the aluminum ions in the presence of cobalt ions can

i) parasagitta in the form of structures of type hydrotalcite, such as Co6Al2CO3(OH)16·4H2And/or

(ii) to parasagitta in the form of boehmite (AlOOH).

These pereosazhdeniya patterns based on aluminum are considered physically associated and freely adsorbed by the surface of the original alumina. Also detected the formation of irregular structures on the surface of the media, appearing after impregnation, respectively, of aluminum oxide with an aqueous solution of Nickel nitrate, magnesium oxide - aqueous solution of ruthenium chloride and titanium oxide - aqueous solution of chloride of platinum. Thus, this phenomenon is not limited to aluminum oxide of Al2About3and can be detected also when using alternative carriers, such as magnesium oxide (MgO), titanium oxide (TiO2) or zinc oxide (ZnO).

A serious problem that may occur when using such catalysts, obtained on raw n is the bearers of the catalyst, in the reactions of Fischer-Tropsch synthesis on units greater productivity, is undesirable high content of cobalt in a wax-like product. The implementation of the Fischer-Tropsch synthesis in slurry with the use of known cobalt catalysts on untreated aluminum oxide can produce a wax-like product containing more than 50 hours per million of cobalt, even after the second ex-situ filtration through filter paper Whatmans 42 (trademark) (in this specification, this product is called "secondary filtered wax product"). During the impregnation of the raw aluminum oxide using an aqueous solution of nitrate of cobalt, the latter will also be deposited on the freely associated presidency aluminium-containing structures. This cobalt on presidency aluminium-containing structures may be emitted during the reaction of the Fischer-Tropsch synthesis, possibly due to the impact of hydrothermal reaction conditions and contaminate wax-like product (hydrocarbons, which are liquid under the conditions of the Fischer-Tropsch synthesis and displayed in the form of liquid from the reactor) ultrafine particles of submicron-type, enriched with cobalt. These enriched with cobalt ultrathin particles of submicron type are removed from the reactor in the composition of the wax-like product. In the later high cost of cobalt, it is very undesirable problem, which was solved, at least to some extent, by the present invention. The specified media - alumina during the impregnation stage is secured by increasing the inertia of the surface of aluminum oxide, thus preventing the formation of ultra fine particles of cobalt in the process of the Fischer-Tropsch synthesis. This is achieved with the implementation of the present invention.

The invention will be further described in more detail with reference to the following examples without limiting the invention and to the accompanying drawings.

The Figure 1 shows the profiles of the solubility of the raw media is aluminum oxide and the same media, the modified silica according to Example 1.

The Figure 2 shows the profiles of the solubility of the raw media or titanium dioxide and the same media, the modified silica according to Example 2.

The Figure 3 shows the profiles of the solubility of the raw media is aluminum oxide and the same media modified with zirconium in Example 3.

The Figure 4 shows the profiles of the solubility of the raw media is aluminum oxide and the same media, the modified titanium in Example 4.

The Figure 5 shows the contents of contamination of cobalt in the secondary filtered wax product as a function of time of reaction of the synthesis of Fischer-the Ropsha in the pilot unit. Compares the catalysts of the Fischer-Tropsch synthesis on a cobalt obtained on the raw carrier - particles of aluminum oxide, known under the trademark Puralox SCCa 2/150 (catalyst b) and the modified silicon carrier - alumina (catalyst A) according to the invention.

Example 1.

Modification of aluminum oxide silicon.

Dried by spraying alumina Puralox SCCa 2/150 (trademark) in the form of spherical particles, produced by SASOL Germany GmbH, Uberseering, 40, 22297, Hamburg, Germany, was used as the carrier. Thus, the media was raw. The surface of the particles of the medium was modified silicon. To implement the modification method was used for the impregnation. The silicone in the form of TEOS (tetraethoxysilane) was added in ethanol at 60°C. Ethanol was used as solvent for impregnation. To this solution was added particles of aluminum oxide and then kept the mixture at 50°s-75°C for 1 hour. Then the solvent was removed under vacuum of 0.03 to 0.2 bar (a), the temperature in the jacket of the dryer was equal to 95°C. After drying, the annealing was not performed. The silicon content was equal to 2.5 Si atoms/nm2the surface of the raw media.

Example 2.

Modification of the carrier oxide titanium silicon.

Raw or cooked titanium dioxide (Degussa P25, Tova the cent sign) progulivali at 650° C for 16 hours, was spray dried and classified, selecting a fraction of 75-150 microns. The carrier is characterized by a content of rutile equal to 80%, and a surface area equal to 27 m2/year

This media modified as described in Example 1, the addition of TEOS and drying at 95°obtaining protected modified silica carrier. After drying, calcination is not performed. The silicon content was 4.5 Si atoms/nm2the surface of the raw media.

Example 3.

Modification of the carrier - alumina-Zirconia.

To isopropyl alcohol in an inert atmosphere was added zirconium in the form of its predecessor isopropoxide zirconium. Thus, the solvent used isopropyl alcohol. To the resulting solution was added particles of aluminum oxide (the same that used in Example 1) and then the mixture was stirred at 60°C for 1 hour. Then under a vacuum of 0.03 to 0.2 bar (a) the solvent was removed, the temperature in the jacket of the dryer was equal to 95°C. After drying, the annealing was not performed. Thus gained the protected modified carrier based on alumina. The amount of the modifying component is 0.1 atom Zr/nm2raw media.

Example 4.

Modification of the carrier - aluminum oxide titanium.

Particles of aluminum oxide, t is coy, which was used in Example 1 was modified by the method described in Example 1, using TEAT (tetraethylorthosilicate) as the precursor instead of TEOS, followed by drying at a temperature of 95°C. After drying, the annealing was not performed. Received protected modified titanium-based media aluminum oxide. The titanium content was 2.5 atom Ti/nm2raw media.

Example 5.

Conductivity measurements.

Aluminum oxide and titanium oxide are dissolved in water at low pH. The dissolution of aluminum oxide or titanium oxide leads to the formation of aluminum ions or titanium ions, respectively. The more aluminum oxide or titanium dioxide will dissolve, the greater the concentration of ions of aluminum or titanium. The increase in the content of ions of aluminum or titanium in time was accompanied by monitoring conductivity at constant pH equal to 2. The pH value was maintained constant by automatic addition of 10%aqueous solution of nitric acid.

The Figure 1 shows the curve of cumulative number Al (mg), dissolved in m2raw media, as well as protected modified silica carrier of Example 1, from time to time. You can see that the raw pure alumina dissolved faster than secured option is carovana silicon aluminum oxide.

The Figure 2 shows the dissolution profiles of raw oxide of titanium, and also protected the modified silicon oxide, titanium according to Example 2. This figure shows that the modification of raw titanium dioxide has led to increased resistance to dissolution.

The Figure 3 shows the profile of the solubility of the raw Puralox SCCa 2/150 (trademark) alumina and the profile of the solubility of the protected modified with Zirconia media based on aluminum oxide according to Example 3. Figure 3 shows that the addition of zirconium to the raw media improves the resistance of the raw media to dissolve and action of aqueous acid solution.

The Figure 4 shows the dependence of the cumulative number Al (mg), dissolved in m2raw media for unmodified alumina, as well as to secure the modified titanium aluminum oxide according to Example 4, from time to time. You can see that the raw pure alumina dissolved faster than the protected modified titanium oxide of aluminum.

Example 6.

1. Obtaining a catalyst.

The catalyst A.

The predecessor of the cobalt catalyst on the carrier received on the protected modified silica carrier on the basis of aluminum oxide obtained in Example 1. In the first stage impregnation/drying/proKLIMA the Oia solution of 17.4 kg(NO 3)2·6N2O, 9.6 g (NH3)4Pt(NO3)2and 11 kg of distilled water was mixed with 20,0 kg of the modified silica carrier based on alumina adding media to the solution. The suspension was placed in a conical vacuum dryer and continuously stirred. The temperature of this suspension was raised up to 60°C, after which he filed a pressure of 20 kPa (a). During the first 3 hours of the stages of drying, which began with the application of a pressure of 20 kPa (a), the temperature was slowly increased and after 3 hours had reached 95°C. After 3 hours, the pressure was lowered to 3-15 kPa (a) and applied the drying speed is equal to 2.5 m %/h at the point of initial moisture content. Impregnation and drying lasted 9 hours, after which the impregnated and dried catalyst carrier immediately loaded into the calcinator fluidized bed. The temperature of the dried impregnated catalyst carrier in the loading and in the calcinator was equal to about 75°C. Loading lasted about 1-2 minutes, the inside temperature of the calcinator remained equal to about 75°C. the Catalyst was heated from 75°, 250°at a rate of 0.5°C/min and with a bulk velocity of air is 1.0 m3/kg(NO3)2·6N2O/h and kept at 250°C for 6 hours. To obtain a catalyst composition 30 g Co/100 g Al2O3spent second stage p is opilki/drying/calcination. A solution of 9.4 kg Co(NO3)2·6H2O, 15.7 g (NH3)4Pt(NO3)2and 15.1 kg of distilled water was mixed with 20,0 kg once impregnated calcined intermediate product by adding this product to the solution. The suspension was placed in a conical vacuum dryer and continuously stirred. The temperature of this suspension was raised up to 60°C, after which he applied pressure of 20 kPa (a). During the first 3 hours of the stages of drying, which began with the application of a pressure of 20 kPa (a), the temperature was slowly increased and after 3 hours had reached 95°C. After 3 hours, the pressure was lowered to 3-15 kPa (a) and applied the drying speed is equal to 2.5 m %/h at the point of initial moisture content. Impregnation and drying lasted 9 hours, after which the impregnated and dried catalyst carrier immediately loaded into the calcinator fluidized bed. The temperature of the dried impregnated catalyst carrier in the loading and in the calcinator was equal to about 75°C. Loading lasted about 1-2 minutes, the inside temperature of the calcinator remained equal to about 75°C. the Catalyst was heated from 75°, 250°at a rate of 0.5°C/min and with a bulk velocity of air is 1.0 m3/kg Co(NO3)2·6H2O/h and kept at 250°C for 6 hours.

The catalyst Century

The cobalt precursor kata is Isadora on the media received by way similar to that described above for catalyst A, except that the catalyst precursor was obtained for untreated aluminum oxide.

2. The reaction of the Fischer-Tropsch synthesis on a pilot installation.

In the reaction of the Fischer-Tropsch using 5 kg of catalyst obtained on unmodified alumina, namely catalyst in the reactor column type with a height of 11 m re-filtered wax-like product was gray after about 10 days in the process and the content of cobalt was increased up to 350 h/million after 25 days in the process, as illustrated in Figure 5. Experiments were completed in real conditions of the Fischer-Tropsch synthesis:

The temperature in the reactor230°
The pressure in the reactor20 bar
% conversion (N2+CO)50-70%
The composition of the source gas
H2about 50 vol.%
COabout 25 vol.%
restAr, N2CH4and/or CO2

Obtained in the reaction of Fischer-Tropsch wax-like product was subjected to phase separation of solids and then re-ex-situ filtration through a paper filter, the brand Whatmans 42 with getting re-filtered wax-like product.

The presence of high content of cobalt in the re-filtered wax-like product, apparently caused by crystallites of cobalt, which were deposited on physically associated presidency structures of aluminum (for example, hydrotalcite, Boema)present in the catalyst after impregnation with an aqueous solution of compounds of cobalt, when the catalyst was prepared using untreated catalyst carrier.

The implementation of the reaction of the Fischer-Tropsch synthesis in the presence of a catalyst And obtained on a modified medium on the basis of aluminum oxide with silicon content 2.5 Si atoms/nm2the surface of the raw media led to a re-filtered wax-like product with a much lower content of submicron particles of cobalt, which can be seen on Figure 5. After 22 days of operation, the catalyst with 2.5 Si atoms/nm2the surface of the raw media has led to re-filtered wax-like product which does not contain cobalt.

The results of the reaction of synthesis pilot plant show that the increase in the inertia of the raw media on the basis of aluminum oxide by modification of silicon was also found to prevent the penetration of ultra fine particles of cobalt in the product that show the measurement results about the donosti.

3. The reaction of the Fischer-Tropsch synthesis on a laboratory scale.

Precursors of the catalyst based on cobalt were recovered prior to the reaction of the Fischer-Tropsch process in a tubular reactor at a flow rate of hydrogen 200 ml of N2/g catalyst/h and the atmospheric pressure. The temperature was raised to 425°at the rate of 1°C/min, then isothermal conditions were maintained for 16 hours.

10-30 g the recovered catalyst with particle size 38-150 microns suspended in 300 ml of molten wax and loaded into the CSTR reactor with an internal volume of 500 ml of the feed gas consisted of hydrogen and carbon monoxide with a molar ratio of N2/WITH from 1.5/1 to 2.3/1. The reactor had an electric heater and stirrer, providing high speed, which ensured the elimination of restrictions on the transfer of masses of gas/liquid. The filing of the original flow was regulated using a flow regulator Brooks, was used in flow rate from 2 to 4 m3/kg catalyst/h Gas chromatography of gases and volatile hydrocarbons coming from above, was used to characterize the products.

Experiments were completed in real conditions of the Fischer-Tropsch synthesis:

The temperature in the reactor220°
The pressure in the reactor20 bar
% conversion (N2+CO)50-70%
The composition of the source gas
H2about 50 vol.%
COabout 25 vol.%
restAr, N2CH4and/or CO2

Using known kinetic equation for catalyst Fischer-Tropsch cobalt-based

rFT=(kFTPH2PCO)/(1+CUCO)2

for each of the experiments was determined by pre-exponential factor kFTbred by Arrhenius. By determining the relative characteristic activity of Fischer-Tropsch (pre-exponential factor of the catalyst X after recovery)/(pre-exponential factor of the catalyst), where X is the catalyst a or b, you can compare the characteristic activity of the catalysts of the Fischer-Tropsch cobalt-based. The initial relative characteristic activity of Fischer-Tropsch was determined after 15 hours, as shown in Table 1. It is obvious that the modification of the medium does not affect the characteristic activity of Fischer-Tropsch when compared with cobalt catalyst on the raw carrier - catalyst Century

H2
Table 1

Comparison of catalysts prepared in the raw carrier based on alumina (catalyst b) and the modified silicon carrier based on alumina (catalyst A), when carrying out the reaction of the Fischer-Tropsch synthesis in the laboratory CSTR.
The catalyst AndThe catalyst In
The number of experience363F233S
The synthesis conditions:22,220,6
The weight of the calcined catalyst (g)
The temperature in the reactor (°)220,0221,0
Reactor pressure (bar)20,020,0
Work time (h)16,015,0
The composition of the source gas:
H2(vol.%)52,652,2
CO (% vol.)27,926,4
(Remainder = Ar, CH4+CO2)
The volumetric rate of synthetic gas (H2+CO) (m3/kg cat. PM)3,63,0
The partial pressure in the reactor (bar)
5,54,5
CO2,92,5
H2O4,54,8
CO20,30,3
Reaction parameter:
Conversion: % synthetic gas61,768,3
The initial attributes. characteristic1,01,0
activity FT
% Of the total number of,1,33,3
developed in CO2
% selectivity of C-atom, CH45,34,3

It was found that the catalyst according to the invention, obtained by impregnation of a protected modified catalyst carrier according to the invention has excellent characteristics in the process of the Fischer-Tropsch synthesis, which is manifested in the high activity and selectivity. Unexpectedly, it was found that the modified media does not require calcination after impregnation of the modifying component precursor and drying so as to be inert in the aquatic environment. Thus, these protected modified media and EUT increased reactivity to the aquatic environment during the subsequent impregnation in suspension. The use of the catalysts obtained in these protected modified media, has led to a sharp reduction in the formation containing active phase of ultrafine particles in the process of the Fischer-Tropsch synthesis. The process of the Fischer-Tropsch synthesis in slurry with the catalyst on a modified medium led to a re-filtered wax-like product containing less than 50 ppm, ultrafine particles of the active phase, which significantly reduces the cost of the catalyst used in the process of the Fischer-Tropsch synthesis in slurry. Due to the extraordinary difficulties associated with separation of submicron particles of a wax-like product, the problem of removal of solid particles from this wax-like product in large measure solved by the present invention.

1. A method of obtaining a catalyst precursor, which includes contacting the untreated catalyst carrier, which is partially soluble in an aqueous acid solution and/or in a neutral aqueous solution, with the modifying component of the formula Me(OR)Xwhere Me is a modifying component selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Tl, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, TA and W, R denotes alkyl or acyl group and x is an integer from 1 to 5 for the introduction of the modifying component on the surface is or in the composition of the catalyst carrier and for receiving protected modified catalyst carrier, which is less soluble and more inert in aqueous acid solution and/or in a neutral aqueous solution than the untreated catalyst carrier, a heat treatment is protected modified catalyst carrier to a temperature below 100°thus, there is no calcined catalyst carrier, mixing not calcined protected modified catalyst carrier with an aqueous solution of cobalt as the active catalyst component or its precursor, to obtain the suspension, the action on the suspension subatmospheric pressure for impregnation protected modified catalyst carrier cobalt or its precursor, drying the obtained impregnated carrier at subatmospheric pressure and calcining the dried impregnated carrier.

2. The method according to claim 1, characterized in that the raw catalyst carrier consists of particles, and the modifying component is contained in the particles of the protected modified catalyst carrier, on the surface of the particles being chemically combined with the surface of the particles.

3. The method according to claim 2, characterized in that the modifying component is chemically related to the hydroxyl groups on the surface of the particles of the medium.

4. The method according to any one of claims 1 to 3, characterized in that the contacting neo is Rabotnov catalyst carrier with the modifying component precursor is carried out in the impregnation process.

5. The method according to claim 4, characterized in that the modifying component precursor is a silicon containing compound and the modifying component is silicon.

6. The method according to claim 5, characterized in that the organosilicon compound is a tetraethoxysilane or tetramethoxysilane.

7. The method according to claim 5 or 6, characterized in that the raw catalyst carrier is a carrier on the basis of aluminum, and the modifying component precursor is applied in such a quantity that the content of silicon in the resulting protected modified catalyst carrier is at least 0.06 Si atoms/nm2the surface of the untreated catalyst carrier.

8. The method according to claim 7, characterized in that the raw catalyst carrier is a spray dried catalyst carrier based on alumina, and the predecessor of the modifying component on the basis of silicon used in such a quantity that the upper limit of the content of silicon in the resulting protected modified catalyst carrier is 2.8 Si atoms/nm2the surface of the untreated catalyst carrier.

9. The method according to claim 5, characterized in that the organosilicon compound is dissolved in a solvent for impregnation, having a boiling point at atmosfernom pressure less than 100° C, and the catalyst carrier is mixed with the resulting solution with the formation of the mixture and processing the mixture to be processed is maintained at an elevated temperature at the boiling point of the solvent used for impregnation or near this point for a period of time sufficient for the introduction of the modifying agent in the catalyst carrier or on its surface.

10. The method according to claim 9, characterized in that the impregnation is carried out at atmospheric pressure, and the impregnation time is from 1 minute to 20 hours

11. The method according to claim 9 or 10, characterized in that the drying of the impregnated carrier is carried out at a pressure of drying or under vacuum of 0.01 to 1.0 bar (a) and at a temperature equal to the boiling point of the solvent at a pressure drying, and less 100°C.

12. The method according to claim 4, characterized in that the modifying component precursor is an alkoxide of zirconium and the modifying component is Zirconia.

13. The method according to item 12, wherein the zirconium alkoxide is dissolved in a solvent for impregnation, having a boiling point at atmospheric pressure of less than 100°S, the carrier of the catalyst is mixed with the resulting solution with formation of a mixture for processing the mixture for processing is supported at an elevated temperature at the boiling point of the solvent used for impregnation or near this point for elapsed the time, sufficient for the introduction of the modifying agent in the catalyst carrier or on its surface.

14. The method according to item 13, wherein the impregnation is carried out at atmospheric pressure over a period of time from 1 minute to 20 hours

15. The method according to item 13 or 14, characterized in that the drying of the impregnated carrier is carried out at pressure or under vacuum of 0.01-1 bar (a) at a temperature equal to the boiling point of the solvent at a pressure drying, and less 100°C.

16. The method according to claim 1, characterized in that during the impregnation add a water-soluble salt precursor on the basis of platinum or palladium as an additive that promotes the recoverability of the active component, when the mass ratio of the additive to the active component of the catalyst is from 0.01:100 to 0.3:100.



 

Same patents:

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: lube fractions are brought into contact with N-methylpyrrolidone in extraction tower according to three-step countercurrent purification scheme to form raffinate and extract solutions. When distillate fraction II (300-400°C) is purified, of sulfoxide is preliminarily added in amount of 0.1-0.5% based on the weight of solvent. Distillate fraction III (350-420°C) is then purified after addition to solvent of 0.5-1.5% of extract obtained from purification of distillate fraction II.

EFFECT: deepened purification of raffinate, increased yield of raffinate as commercial product, and enabled qualified application of extract by-product.

11 tbl, 6 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: lube fractions are brought into contact with N-methylpyrrolidone in extraction tower according to three-step countercurrent purification scheme to form raffinate and extract solutions. When distillate fraction II (300-400°C) is purified, of sulfoxide is preliminarily added in amount of 0.1-0.5% based on the weight of solvent. Distillate fraction III (350-420°C) is then purified after addition to solvent of 0.5-1.5% of extract obtained from purification of distillate fraction II.

EFFECT: deepened purification of raffinate, increased yield of raffinate as commercial product, and enabled qualified application of extract by-product.

11 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: synthesis gas is subjected to conversion to produce liquid hydrocarbons in sequentially connected reactors containing catalytic slurry of at least one solid catalyst in a liquid phase. Reactors are triphase bubble column-type reactors provided with virtually full stirring characterized by liquid Peclet number below 8, gas Peclet number below 0.2, and diameter larger than 6 m. Last reactor at least partially receives at least part of at least one of the gas fractions collected at the outlet of at least one of other reactors. At least one reactor is supplied with stream of catalytic slurry coming directly out of another reactor, and at least one stream of catalytic slurry coming out of reactor is at least partially separated so as to receive liquid product substantially free of catalyst and catalyst-rich catalytic slurry, which is then recycled.

EFFECT: improved process technology.

10 cl, 8 dwg, 7 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: oxidation is performed at 20-60°C with hydrogen peroxide aqueous solution in presence of molybdenum-containing catalyst, in particular molybdenum bis-alkylsulfoxide peroxo complexes.

EFFECT: increased yield of sulfoxides, oxidation selectivity, and oxidation rate.

2 tbl, 6 ex

FIELD: chemical industry; petrochemical industry; gaseous industry; oil-producing industry; oil-processing industry; installation for purification of the hydrocarbon raw from methanol.

SUBSTANCE: the invention is pertaining to the technology of purification of the hydrocarbon raw from methanol and may be used in gaseous, petroleum, petrochemical and chemical industries. The installation includes the assembly of the preliminary separation of the raw connected with the block of the adsorbing purification, the pipeline links and the shut-off-adjusting fittings. The assembly of the preliminary separation includes: the block of the preheating of the raw consisting of the heat exchangers (1) and (2), the rectifying column (3) with the connecting pipes for feeding of the liquid hydrocarbon raw (4), withdrawal of the methanol with the light fraction of hydrocarbons (5) and the withdrawal of the hydrocarbon tailings (6) with the bottom heating, the cooler (10) and container(11). The block of the raw preheating is connected to the connecting pipe (4) of the raw feeding into the rectifying column (3), and the connecting pipe (5) for the raw withdrawal in series through the raw preheating block, the cooler (10) and the container (11) directly connected with the block of adsorbing purification. In the other version the block of the raw preheating is connected to the connecting pipe (4) of feeding of the liquid hydrocarbon raw into the rectifying column (3), and the connecting pipe (5) of withdrawal through the heat exchanger (1) and the cooler (10) is connected to the connecting pipe (23) of the inlet into the extraction column. The connecting pipe (25) of withdrawal of the methanol with the light fraction of hydrocarbons out of the extraction column (20) is connected to the inlet connection pipe (28) of the separator (21), and the connecting pipe (26) of withdrawal of the water-methanol mixture is connected with the intermediate container (22). The connecting pipe (29) of withdrawal of the methanol with the light hydrocarbons from the separator (21) is connected to the block of the adsorbing purification. The connecting pipe (29) of withdrawal of the water-methanol mixture of the separator (21) is connected to the intermediate vessel (22), which outlet is connected to the feeding line of the extracting liquid into the extraction column (20). The invention reduces the operational costs, increases the lifetime of zeolite.

EFFECT: the invention ensures reduction of the operational costs, the increased lifetime of zeolite.

2 cl, 2 dwg, 2 ex

FIELD: method for separating at least a fraction of non-acidic chemical products from at least a fraction of raw gaseous product received in Fischer-Tropsch reaction, or from condensate of said product.

SUBSTANCE: in accordance to method at least a fraction of raw gaseous product or its condensate is fed into feeding plate of distillation column, liquid flow is drained from aforementioned column from plate, positioned above feeding plate of the column. Received liquid flow is divided on water phase and saturated non-acidic chemical product phase and water phase is returned to distillation column onto plate positioned below plate from which liquid flow is drained.

EFFECT: increased efficiency of cleaning method.

23 cl, 1 dwg

FIELD: petrochemical industry; methods of production of the polyolefin bases of the synthetic oils.

SUBSTANCE: the invention is pertaining to the method of production of the polyolefin bases of the synthetic oils by cationic oligomerization of the olefinic raw and may be used in petrochemical industry. The developed method contains: the stages of preparation of the olefinic raw, preparation and batching in the reactor of the solutions and suspensions of the components of the catalytic system Al(0)-HCl-(CH3)3CCl (TBX), isomerization of alpha-olefins and oligomerizations of the highest olefins and their mixtures under action of the catalytic system Al (0)-HCl-TBX, extractions of the dead catalyst, separation of the oligomerizate for fractions and hydrogenation of the extracted fractions under action of the catalytic agent Pd (0.2 mass %)/Al2O3+NaOH. The invention ensures improvement of the stages of the developed method. For prevention of the corrosion activity of the products the method additionally contains the stage of dechlorination of the present in the oligomerizate chlorine-containing oligoolefins by the metallic aluminum, triethylaluminum, the alcoholic solutions of KOH or using the thermal dehydrochlorination of the chlorine-containing polyolefins at the presence or absence of KOH. For improvement of the technical-and-economic indexes of the method at the expense of the increase of the output of the target fractions of polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C the method additionally contains the stage of the thermal depolymerization of the restrictedly consumable high-molecular polyolefins with the kinematic viscosity of 10-20 centistoke at 100°C into the target polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C.

EFFECT: the invention ensures improvement of all the stages of the developed method.

1 cl, 15 tbl

FIELD: petrochemical industry; methods of oil and fuels desulfurization.

SUBSTANCE: the invention is pertaining to the field of the oil and fuels desulfurization by ultrasound action on them. The method of the continuous removal of sulfides from liquid mineral fuel provides for mixing of the fuel, water medium and the dialkyl ether having the boiling point at the normal pressure of 25°C or above, and having the following formula R1OR2, in which R1 and R2 are the separate univalent alkyl groups, and the total number of carbon atoms in R1 and R2 is from 3 up to 7, with formation of the multiphase reaction medium. The multiphase reaction medium is passing through the ultrasonic chamber in the continuous running mode, in which the ultrasound acts on the multiphase reaction medium during the time sufficient to stimulate the transformation of the sulfides in the sulfides-containing mineral fuel into sulfones. The outgoing from the ultrasonic chamber multiphase reaction medium is spontaneously laminated into the water and organic phases. The organic phase is separated from the water phase in the form of the mineral fuel with the removed sulfides. The invention allows to effectively decrease the contents of sulfur in the source raw.

EFFECT: the invention ensures the effective reduction of the contents of sulfur in the source raw.

19 cl, 1 ex

FIELD: oil processing industry; petrochemical industry; methods of production of bitumen.

SUBSTANCE: the invention is pertaining to the field of reprocessing of the wastes of the oil processing industry and the petrochemical industry, in particular, to reprocessing the acid sludges and can be used for production of the bitumens applied in the road construction, in production of roofing and insulating and other materials. Substance: the acid sludge preferentially with the contents of sulfuric acid, which is not exceeding 7 % from mass of the residual acid sludge, is heated in the flowing reactor at the temperatures of the cracking and below the temperature of the coke formation. The nonvolatile hydrocarbon fraction is withdrawn from the reactor. The components with the boiling point above 200°C are extracted from the vapor hydrocarbon fraction and mixed with the non-volatile hydrocarbon fraction.

EFFECT: the invention ensures production of the bitumens applied in the road construction, in production of roofing, insulating and other materials.

2 cl, 1 dwg, 2 ex

FIELD: petroleum industry.

SUBSTANCE: invention relates to methods for processing petroleum residues in aim for preparing refined raw used in different processes in petroleum processing and to methods for isolating and concentrating heavy metals representing the industrial profit by using adsorbent adding to the reaction mass as a powdered form. For preparing liquid petroleum products a synthetic material is used as adsorbent based on hydroxyapatite of the formula Ca10(PO4)6(OH)2 adding to the reaction mass as a suspension. Demetallization of heavy petroleum raw is carried out in the presence of adsorbent, and process is carried out at temperature 200-250°C. Invention provides enhancing effectiveness, decreasing cost and expanding assortment of contact materials used in processes for adsorption demetallization of heavy petroleum raw.

EFFECT: improved preparing method.

6 tbl, 9 ex

FIELD: catalyst production, in particular Fischer-Tropsch synthesis of C5-C10-hydrocarbons from CO and H2.

SUBSTANCE: claimed method includes two-stage impregnation of zeolite carrier with cobalt nitrate aqueous solution with intermediate annealing in air flow at 350-450°C and drying.

EFFECT: catalyst of increased selectivity and activity in respect of isoparafinic hydrocarbons.

2 tbl, 9 ex

FIELD: preparation of cerium-containing catalysts modified by palladium on granulated and monolithic carriers.

SUBSTANCE: proposed method of preparation of Pd-CeO2 applied catalysts is performed by self-spreading thermosynthesis in layer of high surface granulated or block carrier from precursors, for example cerium-ammonium nitrate or mixture of cerium nitrate with fuel additives; palladium is introduced into catalyst in form of palladium nitrate by application on cerium-treated carrier or by joint application of cerium and palladium precursors followed by self-spreading thermosynthesis. Used as carriers are granulated carriers, ceramic blocks or blocks with high specific surface of Al2O3.

EFFECT: enhanced rapidness of catalyst preparation process.

2 cl, 1 tbl, 8 ex

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to catalyst for steam cracking of hydrocarbons, which catalyst contains KMgPO4 as catalyst component. Catalyst is prepared by dissolving KMgPO4 precursor in water and impregnating a support with resulting aqueous solution of KMgPO4 precursor or mixing KMgPO4 powder or its precursor with a metal oxide followed by caking resulting mixture. Described is also a light olefin production involving steam cracking of hydrocarbons.

EFFECT: increased yield of olefins, reduced amount of coke deposited on catalyst, and stabilized catalyst activity.

21 cl, 4 tbl, 14 cl

FIELD: hydrocarbon conversion processes and catalysts.

SUBSTANCE: invention, in particular, relates to selectively upgrading paraffin feedstock via isomerization. Catalyst comprises support and sulfated oxide or hydroxide of at least one of the elements of group IVB deposited thereon; a first component selected from group consisting of consisting of lutetium, ytterbium, thulium, erbium, holmium, and combinations thereof; and a second component comprising at least one platinum-group metal component. Catalyst preparation process comprises sulfating oxide or hydroxide of at least one of the elements of group IVB to form sulfated support; depositing the first component onto prepared support; and further depositing the second component. Invention also relates to hydrocarbon conversion process in presence of above-defined catalyst.

EFFECT: improved catalyst characteristics and stability in naphta isomerization process to increase content of isoparaffins.

13 cl, 2 dwg, 1 tbl

FIELD: chemical industry; methods of manufacture of the deposited polymetallic catalytic agents.

SUBSTANCE: the invention is pertaining to the methods of manufacture of the oxidation catalytic agents based on any solid carriers by deposition on them of the metals solid solutions. The catalytic agents may be used in the various fields of the catalysis, for example, for realization of the photocatalytic, electrocatalytic, catalytic and other reactions. The invention presents the description of the method of manufacture of the deposited polymetallic catalytic agents by deposition of the metals on ceramics, plastics materials, metals, composite materials, oxides of the transition metals, the carbonic material, which includes the sequential stages of deposition of the previous layers carrying the cationic and anionic parts and for recovery. In the capacity of the previous layer carrying the cationic part use the substances of the following composition: [М(NH3)xАyz, where M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substance of the following composition: Еx2[M'Dy2Cz2], where М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; D - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying the cationic part use the substances having the following composition: [М(NH3)xАyz and/or [М1(NH3)x1Аy1z1, where M AND M1 - Cr, Со, Ni, Cu, Zn, Ru, Ag, CD, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substances having the following composition: Еx2[M'Dy2Cz2] and/or Еx3[M'1Dy3Cz3], where М' and М'1 - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Ag, Cd, Hf, Ta, W, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying both the cationic part and then anionic part use the substance having the following composition: [М(NH3)xАy]x1[M'Dy1Cz1]z, where: M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, 0s, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2. The technical result of the invention is the high activity of the produced catalytic agents.

EFFECT: the invention ensures the high activity of the produced catalytic agents.

14 cl, 3 tbl, 97 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides rhenium oxide catalyst on anion-containing gamma-alumina-based support: 0.1-10.0% Re2O3 and 0.2-4.0% fluorine based on the weight of alumina. Catalyst is prepared by impregnating alumina, including 0.2-4.0 wt % fluorine, with rhenium compound solution, drying resulting mass, and subjecting it to heat treatment in oxidative and/or inert medium at 600-900°C. Propylene synthesis process including metathesis of C2-C4-olefinic hydrocarbon blend or ethylene alone is also described.

EFFECT: increased catalytic activity and simplified technology.

7 cl, 2 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of primary amine by the hydrogenation reaction of nitriles. Method involves carrying out the conversion reaction in reaction mixture that contains: (a) at least one nitrile; (b) hydrogen; (c) ammonia, if necessary, and (d) at least one cobalt or nickel catalyst modified ex situ by adsorption of alkaline metal carbonate or alkaline metal hydrocarbonate that comprises alkaline metal carbonate or hydrocarbonate taken in the amount from 2 to 12 wt.-%. Also, invention relates to a catalyst used in the method by cl. 1 and representing modified cobalt or nickel catalyst prepared by adsorption of alkaline metal carbonate or alkaline metal hydrocarbonate taken in the amount from 2 to 12 wt.-% on usual cobalt or nickel catalyst.

EFFECT: improved method of synthesis.

24 cl, 6 tbl, 48 ex

FIELD: alternate fuels.

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

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

4 cl, 3 tbl, 9 ex

FIELD: fuel combustion catalysts.

SUBSTANCE: invention provides catalyst containing active aluminum oxide, magnesium oxide, at least one platinum-group precious metal, and also at least one material capable of accumulating nitrogen oxides, said magnesium oxide forming homogenous mixed oxide with aluminum oxide in concentration ranging form about 1 to about 40 wt % based on total weight of mixed oxide. The use of catalyst is also disclosed.

EFFECT: increased heat resistance of catalyst and accelerated conversion of nitrogen oxides.

24 cl, 14 dwg, 3 tbl, 8 ex

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