RU2650495C1 - Catalyst for vapor hydrocarbon conversion - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst of vapor hydrocarbon conversion comprising active part, containing nickel (Ni), copper (Cu), platinum (Pt), palladium (Pd) rhodium (Rh), ruthenium (Ru), gold (Au), and aluminum oxide based carrying agent containing magnesium oxide, calcium / magnesium aluminate. Active part of catalyst further includes calcium, aluminum, potassium. Content of components in the catalyst, weight %: nickel oxide 5–60; potassium oxide 0–5; magnesium oxide 0–5; calcium oxide 0–5; aluminum oxide 0–5; copper oxide 0–5; platinum 0–2; palladium / rhodium / ruthenium / gold 0–0.5; rest is carrying agent up to 100. Proportion of X-ray amorphous elements of main active component is at least 0.4.

EFFECT: increase in initial activity, long-term stability.

8 cl, 3 tbl, 16 ex

Description

The invention relates to catalytic chemistry, in particular to the composition of catalysts for steam, carbon dioxide, oxygen reforming, pre-reforming, and can be used in the chemical and petrochemical industries.

It is known that catalysts for steam reforming of hydrocarbons are usually Ni-containing supported type with a substrate of refractory oxide material (calcium aluminate, magnesium aluminate, alpha-alumina). It is shown that in the preparation of hydrocarbon conversion catalysts, in addition to the nickel-containing active component, various structure-forming additives are used (kaolin, cement, clay, graphite, etc.).

In the preparation of hydrogen-containing gas mixtures for fuel cells and in the generation of synthetic gas from biomass during steam reforming, noble metal catalysts such as Rh or Pt are used. Catalysts based on Cu or Pd are used for steam reforming of methanol.

Most often, these catalysts are prepared by impregnation-calcination — the active metal is introduced into the porous substrate in the form of an aqueous solution, often metal nitrate, and then calcined to convert the metal nitrate to the oxide of the corresponding metal. Before use, the metal oxide is reduced, usually with hydrogen gas, to produce an active catalyst.

The amount of active component in the catalysts ranges from several percent to several tens of percent for Ni and from hundredths of a percent to several percent for Cu, Pt, Pd, Rh, Ru, Au. Due to the different activities, noble metals such as Pt, Pd, Rh, Ru and Au are preferably contained in an amount of 0.01-5 mass. %, a Ni or Cu - in the amount of 10-60 mass. %

The catalytically active components of the catalyst are preferably metal or metal oxide crystallites well dispersed in the bulk / surface layer of the carrier granules. The enlargement of the structural formations of the active components of the catalyst occurs during long-term operation and is referred to as sintering, which is accompanied by a decrease in the specific surface area of the active component and a decrease in the reaction activity of the catalyst. This process in the form of crystallite enlargement can be recorded and evaluated by x-ray diffraction. From copyright certificate No. 1659807 (SU class G01N 23/20, publ. 06/30/1991.) It is known that the modeling of sintering - structural deactivation of catalysts is carried out by high-temperature x-ray diffraction.

The extrudates, pellets, or granules of the catalyst carrier may be those that are commercially available or are prepared from suitable powders by methods known to those skilled in the art. Alpha-alumina, calcium or magnesium aluminate substrates are preferred.

Molded substrates and catalyst granules may have different geometric shapes and sizes, which depends on the shape or mouthpiece of the extruder used in their manufacture and may include lubricants or binders. For example, the granules may be in the form of spheres, cylinders, rings, corrugated rings, or elements with a plurality of holes, for example 2-10 through holes, which may be multi-leaf or corrugated, for example having a section such as a clover leaf. Complex forms of catalyst granules with high porosity are preferred. Their use provides a smaller drop in the working pressure of the steam reforming process due to the low gas-dynamic resistance. The restriction in the use of geometric shapes of the granules of the substrate and the catalyst is imposed by the requirement of their mechanical strength. Granules with crush strengths of 400-600 N are preferred.

It is known that the Topsoe hydrocarbon steam reforming catalysts are a seven-hole cylinder (C. Satterfeld. A Practical Course of Heterogeneous Catalysis, M .: Mir, 1984, pp. 361-371), and the catalysts obtained according to US Pat. RE 32.044, B01J 021/04; B01J 023/74; 12/03/1985, are also cylinders, but already with many channels oriented parallel to their axis, having the shape of a segment, circle, square, hexagon, oval or sinusoid.

In A.S. N 383347 (SU B01J 11/32, 02.25.1979.) Describes a nickel-based catalyst for the conversion of hydrocarbons with water vapor. The catalyst contains 10-60 mass. % nickel, has a mechanical strength of 600-700 kg / cm ² , a specific surface area of 50-70 m ² / g, withstands the number of heat exchangers of at least 40 (1000-20 ° C).

The method of preparation of the catalyst is carried out by mixing magnesium oxide (10-20 wt.%) And preliminarily calcined at 1200-1400 ° C alumina (20-50 wt.%). In addition, barium oxide (1-2 wt.%) Is introduced into the charge. Calcium mono- and dialuminate (30-40 wt.%) Are used as a binder. The finished catalyst has a ring shape.

The catalyst was tested for 160 hours on a model installation in conditions of steam conversion (pressure 30 ati, vapor / gas ratio 3.8 nm ³ / nm ³ , space velocity 800 h ^-1 , methane content in the source gas 7.4-8.0 vol.%). Activity at 800 ° C is 0.0-0.2 vol. % (residual methane content in the converted gas).

The main disadvantages of this catalyst are low coke resistance in view of the absence of promoters in its composition that provide resistance to carbonization and loss of strength of granules during operation.

Patent No. 2048909 (RU IPC ⁶ B01J 23/78, C01B 3/38 B01J 23/78, B01J 101: 32, B01J 103: 26, publ. 11/27/1995.) Describes a catalyst for steam conversion of hydrocarbons, which contains the following active components mass. %: nickel oxide 5.9-12.5; alumina 1.25-2.45; magnesium oxide 0.15-0.66; lanthanum oxide 0.49-1.96; cobalt oxide 0.20-1.02; or neodymium oxide 0.46 or cobalt and neodymium oxides 0.27-0.55.

The preparation method consists in creating a supported type of catalyst having, in the composition of the active component, cobalt and / or neodymium oxides additionally as promoters, which significantly increase the coke resistance and stability of the oxidative functions of the catalyst. As a carrier, the catalyst contains α-Al ₂ O ₃ or α-Al ₂ O ₃ containing, by weight. % 1.5 CaO and 0.5 MgO used to optimize the crystallites α-A ₂ O ₃ . Or the catalyst contains Al ₂ O ₃ as a support. This catalyst allows for steam conversion of raw materials containing 15 mass. % aromatic hydrocarbons, at 500 ° C, with loads up to 4 l / h in raw materials with a low content of H ₂ O / C without coking.

The disadvantages of the catalyst are the use of expensive lanthanum and neodymium and the duplication of the hydrogenating function of cobalt, which is implemented in hydrocarbon conversion plants as a separate stage.

The patent No. 2048910 (RU IPC ⁶ B01J 23/78 C01B 3/38, publ. 1995.11.27.) Describes a catalyst for steam reforming of naphtha and refinery gases, which includes the following active components of the mass. %: oxides of nickel (3.0-8.0), aluminum (0.65-1.80), magnesium (0.45-1.65), calcium (0.35-1.40), potassium (0 , 75-3.35) and the carrier (the rest). As a carrier, alumina is used containing kaolin - Al ₄ (Si ₄ O ₁₀ ) (OH) ₈ , with the following content of components, mass. %: kaolin - 2.0-8.0; aluminum oxide - the rest.

For the preparation of the catalyst, a support with a porosity of 0.25-0.32 cm ³ / g is used, which is twice impregnated with aqueous solutions of nickel, nitrate, hexahydrate Ni (NO ₃ ) ₂ ⋅ 6H ₂ O, aluminum, nitrate nitrate, nine-hydrate Al (NO ₃ ) ₃ ⋅ 9H ₂ O, calcium nitrate tetrahydrate Ca (NO ₃ ) ₂ ⋅ 4H ₂ O, magnesium nitrate hexahydrate Mg (NO ₃ ) ₂ ⋅ 6H ₂ O and potassium nitrate anhydrous KNO ₃ . After each impregnation, the catalyst is dried and calcined at 450 ° C for at least 4 hours

To test the coke resistance of the catalysts in the steam reforming of liquid hydrocarbons, a mixture of normal hexane and benzene containing 15% benzene is used as raw material, which is close to naphtha in coke content. Reforming is carried out at 500 ° C, a molar ratio of H ₂ O / C = 2.5 and atmospheric pressure in an installation with a flowing microreactor at a contact load of 4 l / h in liquid feed. The activation of the catalyst is carried out with hydrogen (0.2 mol / cm ³ cat. H) at 550 ° C for 2 hours

Coke resistance, characterized by a relative change in the pressure drop in the catalyst bed (P _con / P _beg ), is 1.00-1.10.

Stability, characterized by a relative change in the temperature gradient (T _con / T _beg ), is 1.28-1.74 (test duration 4 hours). The degree of conversion of raw materials is 38.6-53.3%. The residual hydrogen content (conversion at 500 ° C) is approximately 22.0-39.6 vol. %

The disadvantages of the catalyst are lower technical and economic characteristics, lack of activity at a low content of the Nickel component (3-6 wt.%) And the limited effective life of the catalyst. The disadvantage is the presence of silicon in the catalyst in the case of using kaolin, which at high temperatures sublimates from the catalyst and has a negative effect on expensive process equipment in operating conditions.

Patent No. 2132228 (RU IPC B01J 23/72, C01B 3/38 C01B 3/38, publ. 06/27/1999.) Describes a nickel catalyst on a carrier for steam conversion of hydrocarbons, which additionally contains copper in the following ratio of components, mass. %: nickel - 5-50; copper - 0.03-0.5; the carrier is the rest.

This supported nickel catalyst can be prepared by any known method, for example, by impregnating the refractory support with an aqueous solution containing nickel and copper, and then calcining the impregnated support in air. In addition, the catalyst can also be obtained by coprecipitation of soluble salts of the carrier, Nickel and copper. Such salts are, for example, chlorides, nitrates, carbonates, acetates and oxalates, which, as a result of heating in air, are converted to metal oxides. Suitable materials for carrying out the carrier are, for example, oxides of aluminum, magnesium, beryllium, lanthanum, calcium, titanium dioxide, silicon, zirconium, compounds of these metals and mixtures thereof. Preferred support materials are alumina or magnesia-alumina spinel (MgAl ₂ O ₄ ).

The resulting catalyst is activated by heating to 800 ° C in a medium of a mixture of the same amounts of steam and hydrogen at atmospheric pressure. During the activation process, the nickel and copper oxides on the support are reduced to a metallic state. The temperature of 800 ° C is maintained for an additional 150 hours in order to ensure sintering of the catalyst, as is the case in industrial operation. After sintering, the catalyst is removed from the reactor and crushed to a particle size of 3.4-5.0 mm.

After 450 hours of operation of the catalyst, the gaseous product has the following composition (vol.%, Calculated on dry gas): 2.86-2.90 CH ₄ ; 14.48-14.84 CO; 7.50-7.56 CO ₂ ; 0.83-0.84 N ₂ and 73.93-74.26 H ₂ .

The main disadvantage of the catalyst is its low coke resistance, since it does not contain alkali and alkaline earth metals in the active part. And this makes it necessary to use it in combination with a standard supported nickel catalyst. The disadvantage is the use among the materials of the carrier of silicon oxide, adversely affecting the processing equipment in operating conditions. The relevance of the use of the catalyst is limited to the infrequent cases of the presence of significant amounts of nitrogen in the feed.

From the patent No. 2532924 (RU IPC B01J 23 / 10,40,42,44,46 B01J 21 / 02,06,10 publ. 11/20/2014.) A catalyst for the oxidative conversion of hydrocarbon gases to produce carbon monoxide and hydrogen containing platinum metals groups and an oxide composition, while the platinum group metals include Pt, Pd and Rh, and the oxide composition is obtained from a mixture of sols of hydroxides Al, Si and Zr with particles of Ni, Mg and / or Ce oxides of size 5-30 nm obtained by the spray method pyrolysis of a solution of salts of Ni, Mg and / or Ce.

The preparation of catalysts includes the following steps:

1. Prepare a sol of mixed aluminum-zirconium oxyhydrosol from aqueous aluminum oxyhydrogel and zirconyl nitrate.

2. An aqueous sol of orthosilicic acid is obtained by hydrolysis of tetraalkylorthosilicate.

3. Get a mixture of oxides of Ni, Mg and / or Ce by spray pyrolysis.

4. Get a homogeneous mixture of sols of hydroxides Al, Si and Zr with particles of oxides of a given composition.

5. A porous oxide coating is formed on a metal-porous carrier: a homogeneous mixture is applied to the metal-porous carrier, dried, and subjected to thermocouple treatment.

6. At least one platinum group metal from the series Pd, Pt, Rh is applied to the porous oxide coating of the metal-porous support.

The catalysts exhibit high activity (methane conversion 91-97%) and selectivity for hydrogen (87-95%) and carbon monoxide (over 90%) in the partial oxidation of methane (initial process temperature 300-400 ° C, and then 800-950 ° C)

The disadvantages of the catalyst are the presence of very large amounts of silicon in the catalyst, which sublimes from the catalyst at high temperatures and adversely affects expensive process equipment in operating conditions, complicated multi-stage catalyst preparation technology using specific apparatuses non-traditional for catalyst production, and limited dispersion of active components in the range 5-30 nm.

Porous catalysts for reforming methane with water vapor are known from patent No. 2239100 (RU IPC B01J 23 / 83.755 B01J 21 / 02.06.10 B01J 37/00 B01J 35/02 publ. 07.20.2008.) The substrate (carrier) phase is one or more components that are selected from Al ₂ O ₃ , SiO ₂ , ZrO ₂ , TiO ₂ , ZnO, MgO, MgAl ₂ O ₄ , CoAl ₂ O ₄ and CeO ₂ . The metal of the active phase is selected from transition metals (e.g., Co, Ni, Cu, Fe), noble metals (e.g., Pt, Rh, Ru), lanthanides (e.g., La, Ce), as well as other elements of the Periodic Table that may act as stabilizers or promoters (alkaline earths, for example, Na, Mg, K, Cs) or other trivalent non-reducing metals (for example, Al, Ga). The active phase precursor is one or more compounds selected from acetates, nitrates, sulfates, oxalates, acetylacetonates, preferably acetates. The cations of the active phase can be complexed with the organic phase before being added to the suspension. It is also possible to carry out partial complexation of cations, which is carried out to prevent the formation of large crystals. Processing aids may include dispersants, binders, plasticizers, lubricants, pH modifiers, etc. This catalyst is characterized by a uniform distribution of the active phase and uniform and controlled porosity.

A method for producing porous substances on a substrate for catalytic applications is described, in which one or more soluble (s) precursor (s) of the active phase metal is added to a suspension consisting of an insoluble phase of the substrate in water or an organic solvent, the suspension is subjected to wet grinding to reduce particle size substrate phases to less than 50 microns, add additives that facilitate processing before or after grinding, add a pore-forming substance and a suspension, the viscosity of which is maintained at 100-5000 cP, dust drying, pressed, subjected to heat treatment to remove pore-forming substances and sinter.

The activity of the known catalyst Ni / Al ₂ O ₃ (nickel content: 16.6 wt.%) Was determined in methane reforming at various feed ratios of H ₂ O / CO ₂ / CH ₄ . At 650 ° C, the methane conversion is 26%.

The disadvantages of the method for producing porous substances on a substrate are associated with the low technological level of the industrial process: the need to remove pore-forming substances in a controlled atmosphere, which is associated with the huge consumption of inter-gases when calcining the catalysts on an industrial scale and the risks of temperature flashes and overheating in the calcining apparatus; the need to prevent sedimentation of the suspension during the entire long process of its preparation by vigorous mixing + PVA additives + heating; risk of ignition of the catalyst powder at spray drying temperatures above 400 ° C. In addition, with a high concentration of the active phase in the granules of the catalyst, large crystals of the catalytic substance are formed, which negatively affects the activity and duration of the catalysts.

The closest (prototype) in technical essence is the catalyst described in patent No. 2580548 (RU IPC B01J 23 / 10,40,46,52.72,755 B01J 21/02,06,10 B01J 35/00 B01J 37/02 publ. 10.04 .2016.), Which is used in the steam reforming reaction. The catalytic metals are selected from the group consisting of Ni, Cu, Pt, Pd, Rh, Ru and Au. The formed support (carrier) comprises an oxide selected from the group consisting of alumina, cerium dioxide, magnesium oxide, titanium dioxide or zirconia, calcium aluminate or magnesium aluminate, and mixtures thereof.

A method of preparing a catalyst includes the steps of: (i) spraying a suspension containing one or more of the above catalytic metals onto the surface of a molded support (carrier) in a tank coating device to obtain a molded coated support material containing a catalytic metal in a surface layer ( solids content in suspension is in the range of 10-60 wt.%); (ii) drying and optionally calcining the coated coated support material to form a catalyst precursor; and (iii) optionally reducing the metal or metals in the catalyst precursor to a state of less oxidation to form a catalyst.

Pellet activity (a catalyst containing Rh in an amount of 0.15 wt.%) Was investigated in the process of steam reforming of methane. Pellets were placed in a reaction tube with a diameter of 1 inch and a length of 2.2 inches of a tubular reactor. Steam reforming of methane was carried out at a steam: carbon ratio of 3.25, at a pressure of 1 atm, in the temperature range 500-600 ° C. The maximum achieved methane conversion is 42% (residual methane is 58%).

The main disadvantage of the coated catalyst obtained in the tank device is the limited period of its effective operation. This is due to the fact that:

1. The small thickness of the catalytic coating layer (5-250 microns) limits the total content of catalytically active metal in granules (pellets, extrudates). When pellets are usually used in steam reforming processes with sizes of 15-18 mm and the maximum coating thickness (0.25 mm) according to the invention and the active metal content in the coating composition (50 wt.%), The total active metal content in the granule (and the entire volume of the loaded catalyst ) does not exceed 5 mass. %, which is insufficient for nickelactive catalytic contact even in the initial state and, moreover, does not provide a “reserve” of active centers for a long run.

2. The concentration of active metals in a thin surface layer of granules in the case of poisoning of the catalyst by even a small amount of a deactivating substance removes the entire catalyst layer from a healthy state.

3. The method of spraying suspended matter in a tank device onto substrates of complex geometric shapes, in particular with many holes, does not allow the inventive coating layer to be created on the surfaces of the internal channels. Moreover, the advantages of a higher surface available for reagent molecules associated with the complex geometry of the granules and the internal macroporosity of the entire volume of the granules of the substrate are not used.

4. For catalysts of the crust type, the acute problem is the peeling of the coating of active components from the substrate during operation, especially during shutdowns with temperature changes from operating (700-1000 ° C) to ambient temperatures due to the difference in thermal expansion coefficients of the substrate material and coverings. According to this invention, when a water suspension of particles of a catalyst compound is sprayed, only a weak van der Waals bond of the coating to the substrate is realized, in contrast to the much stronger chemical bond in the case of acidic or alkaline solutions of active components. Losses of the active part of the catalyst due to peeling, cracking and entrainment of the coating reduce activity and shorten the service life.

5. The abrasion of a thin surface active layer of granules in a moving gas stream is accompanied by ablation of the catalyst itself and a rapid loss of activity.

The objective of the patented invention is to expand the range of catalysts that long retain high catalytic activity in the processes of steam conversion of hydrocarbons with the production of hydrogen-containing gases.

The set of essential features in the claimed invention allows to obtain the following technical result:

- increase in initial catalytic activity;

- prevention of a decrease in catalytic properties (long-term preservation (stability) of catalytic properties at a level close to the initial one);

- increasing the dispersion of active particles in a thermostable oxide matrix, providing a proportion of X-ray amorphous elements of the main active component of at least 0.4;

- increasing the degree of dispersion of one or more catalytically active components selected from the group of Ni, Cu, Pt, Pd, Rh, Ru, Au, in the volume / surface layer of granules of a structurally heat-resistant carrier, consisting of one or more components from the group of calcium aluminate, aluminate magnesium, alumina, calcium / magnesium oxide;

- optimal morphological restraint of the migration processes of the structural elements of the active components in the volume / surface of the carrier for a long time.

The claimed technical result from the implementation of the catalyst for the steam conversion of hydrocarbons, including the active part containing nickel (Ni), copper (Cu), platinum (Pt), palladium (Pd) rhodium (Ph), ruthenium (Ru), gold (Au), and an alumina-based carrier containing magnesium oxide, calcium / magnesium aluminate, or mixtures thereof, is achieved due to the fact that the active part of the catalyst further includes potassium, magnesium, calcium, aluminum in the following components in the catalyst, mass. %:

nickel oxide 5-60 potassium oxide 0-5 magnesium oxide 0-5 calcium oxide 0-5 aluminium oxide 0-5 copper oxide 0-5 platinum 0-2 palladium / rhodium / ruthenium / gold 0-0.5 carrier the rest is up to 100

The proportion of X-ray amorphous elements of the main active component is not less than 0.4, and the carrier additionally includes calcium oxide (CaO) in the following ratio of components, mass. %:

calcium / magnesium oxide 0-10 calcium / magnesium aluminate 0-90 aluminium oxide the rest is up to 100

The composition of the raw materials for the preparation of the carrier includes a structure-forming additive (SOD), alumina, reprecipitated aluminum hydroxide, calcium / magnesium aluminate, calcium / magnesium oxide in the following ratio of components, mass. %:

structure-forming additive 5-30 reprecipitated aluminum hydroxide 0-30 calcium / magnesium aluminate 0-30 calcium / magnesium oxide 0-40 alumina the rest is up to 100

As a structure-forming additive, wood flour, carbon black, petroleum paraffin, polyvinyl alcohol, graphite are used with an alumina: structure-forming additive ratio of 10: 0.5 ÷ 10: 3.

In one embodiment of the invention, it is proposed:

- Pre-perform joint grinding of alumina and structure-forming additives, which lead at least 6 hours to a fineness of grinding - the residue on a sieve of 0.05 mm is not more than 5 mass. %

- When preparing the carrier and catalyst, the carrier should be dried at a temperature of 40-50 ° C for 12-36 hours, dried at a temperature of 110-130 ° C for 4-24 hours and calcined at a temperature of 1100-1400 ° C for 3- 24 hours.

- Heat treatment of the catalyst as follows: at the beginning of drying, the temperature is maintained no more than 200 ° C, then raised at a speed of no more than 50 ° C per hour to a value of 250-270 ° C and at this temperature is kept for 4-12 hours, after which the catalyst is maintained at a temperature of 450-500 ° C for 6-12 hours.

In another embodiment of the invention, it is proposed to use a finished carrier in the form of granules of complex geometric shape as a carrier.

In a third embodiment of the invention, it is proposed:

- Pre-grind alumina with calcium oxide additives, then mix with dissolved salts of the active components.

- The resulting mass is molded in the form of granules.

- Dry and calcinate the granules at a temperature of 350-400 ° C.

- From the calcined granules to prepare the mixture for tabletting by grinding them and adding SOD and lubricants.

- The granules (tablets) obtained by pressing are steamed and calcined at a temperature of 400-600 ° C.

In a fourth embodiment of the invention, it is proposed:

- Pre-crushed alumina mixed with additives of calcium / magnesium oxide, oxides of active components, SOD and lubricants.

- Tableted the resulting mixture, pre-compacted, crushed and sieved.

Technological methods for producing the inventive catalyst are not limited to the above methods and may include other known methods for the preparation of catalysts, for example, by coprecipitation of soluble salts of active components on a carrier, by impregnating a carrier in a rotating reactor with the filing / spraying of the required amount of activator solution calculated from the carrier absorption, etc. .

A comparative analysis of the prototype and the inventive catalyst shows that the catalysts include an active part containing nickel (Ni), copper (Cu), platinum (Pt), palladium (Pd) rhodium (Ph), ruthenium (Ru), gold (Au), and alumina-based carrier containing magnesium oxide, calcium / magnesium aluminate.

A distinctive feature of the inventive catalyst is that the active part of the catalyst further includes potassium, magnesium, calcium, aluminum in the following components in the catalyst, mass. %:

nickel oxide 5-60 potassium oxide 0-5 magnesium oxide 0-5 calcium oxide 0-5 aluminium oxide 0-5 copper oxide 0-5 platinum 0-2 palladium / rhodium / ruthenium / gold 0-0.5 carrier the rest is up to 100

The proportion of X-ray amorphous elements of the main active component is not less than 0.4, and the carrier additionally includes calcium oxide (CaO) in the following ratio of components, mass. %:

calcium / magnesium oxide 0-10 calcium / magnesium aluminate 0-90 aluminium oxide the rest is up to 100

The composition of the raw materials for the preparation of the carrier includes a structure-forming additive (SOD), alumina, reprecipitated aluminum hydroxide, calcium / magnesium aluminate, calcium / magnesium oxide in the following ratio of components, mass. %:

structure-forming additive 5-30 reprecipitated aluminum hydroxide 0-30 calcium / magnesium aluminate 0-30 calcium / magnesium oxide 0-40 alumina the rest is up to 100

As a structure-forming additive, wood flour, carbon black, petroleum paraffin, polyvinyl alcohol, graphite are used with an aluminum oxide: structure-forming additive ratio of 10: 0.5 ÷ 10: 3.

In one embodiment of the invention, it is proposed:

- Pre-perform joint grinding of alumina and structure-forming additives, which lead at least 6 hours to a fineness of grinding - the residue on a sieve of 0.05 mm is not more than 5 mass. %

- When preparing the carrier and catalyst, the carrier should be dried at a temperature of 40-50 ° C for 12-36 hours, dried at a temperature of 110-130 ° C for 4-24 hours and calcined at a temperature of 1100-1400 ° C for 3- 24 hours.

- Heat treatment of the catalyst as follows: at the beginning of drying, the temperature is maintained no more than 200 ° C, then raised at a speed of no more than 50 ° C per hour to a value of 250-270 ° C and at this temperature is kept for 4-12 hours, after which the catalyst is maintained at a temperature of 450-500 ° C for 6-12 hours.

In another embodiment of the invention, it is proposed to use a finished carrier in the form of granules of complex geometric shape as a carrier.

In a third embodiment of the invention, it is proposed:

- Pre-grind alumina with calcium oxide additives, then mix with dissolved salts of the active components.

- The resulting mass is molded in the form of granules.

- Dry and calcinate the granules at a temperature of 350-400 ° C.

- From the calcined granules to prepare the mixture for tabletting by grinding them and adding SOD and lubricants.

- The granules (tablets) obtained by pressing are steamed and calcined at a temperature of 400-600 ° C.

In a fourth embodiment of the invention, it is proposed:

- Pre-crushed alumina mixed with additives of calcium oxide, magnesium oxide, oxides of active components, SOD and lubricants.

- Tableted the resulting mixture, pre-compacted, crushed and sieved.

The essence of the present invention is further described using the following examples 1-16. The comparative composition of the media are presented in table 1.

Table 2 presents the comparative composition of the active part of the catalysts.

Example 1

Media Preparation

Pre-carry out the preparation of a mixture consisting of alumina, calcium oxide and structure-forming additives (wood flour) based on dry matter by grinding them. For this, 350 kg of alumina, 40 kg of wood flour, 10 kg of calcium oxide are loaded into a ball mill. 3.5 dm ^{3 of} water was added to the mixture stirred for 0.5 hours. Grinding is carried out for at least 12 hours to a fineness of grinding - the residue on a sieve of 0.05 mm is not more than 5 mass. %

Pre-prepared peptizer solution. To do this, using a pump in the receiving tank-collector serves 30-50 DM ³ nitric acid. From the collection, nitric acid is pumped to the measuring device, where it is diluted with water to a concentration of 210-230 g / dm ³ .

The preparation of the carrier is as follows.

130 kg of the grinding obtained above as described above, including alumina, calcium oxide and wood flour, are loaded into the mixing machine. The mixture with continuous stirring in several stages moisten 40 DM ³ solution of nitric acid concentration of 210 g / DM ³ . Stirring is carried out for 1.5 hours. From the mass of the finished batch by extrusion, granules are formed in the form of corrugated rings. The formed carrier is sent to the drying-drying chamber. The carrier is dried at a temperature of 40-50 ° C for 24 hours. Then the carrier is calcined in a shaft furnace at a temperature of 1100-1150 ° C for 6-8 hours. The calcined carrier is discharged and cooled.

The water absorption of the carrier is 31 vol. %

Catalyst Preparation

Pre-prepared solution for the impregnation of the media as follows.

935 kg of aqueous nickel nitrate, 180 kg of aqueous aluminum nitrate, 41.5 kg of potassium nitrate (per 1 m ^{3 of} solution) are dissolved in water in a solvent reactor at a temperature of 50 ° C and with continuous stirring with compressed air and steam. The resulting impregnation solution is analyzed for the content of active components. In the finished impregnating solution, the following component composition is obtained in terms of metal oxides: NiO: Al ₂ O ₃ : K ₂ O = 1: 0.1: 0.08.

The production of the catalyst is as follows.

The finished solution from the solvent is fed into the measuring device. 200 kg of the carrier are loaded into the impregnation-calcination apparatus and, depending on its water absorption and the weight of the carrier, the calculated amount of the impregnating solution from the measuring device is fed into the impregnator until the granules are completely immersed. After exposure for 1.5 hours, the solution is drained. The impregnated catalyst granules are purged with air, dried at a temperature of 260 ° C for 12 hours, cooled to a temperature of 45-50 ° C. Then re-impregnation is carried out according to the described procedure. After the second impregnation and drying, the catalyst is calcined - incubated at a temperature of 455 ° C for 12 hours. The calcined catalyst is cooled to a temperature not exceeding 50 ° C, screened out from dust and fines.

The resulting catalyst has a chemical composition, mass. %:

nickel oxide 11,4 potassium oxide 0.9 aluminium oxide 1,2 carrier (Al ₂ O ₃ ) containing calcium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 2.7 mass. %, and the proportion of the X-ray amorphous part of the active component is 0.45.

Example 2

According to example 1 with the difference that the impregnation of the media is carried out 4 times.

The resulting catalyst has a chemical composition, mass. %:

nickel oxide 17.3 potassium oxide 1,2 aluminium oxide 1.9 carrier (Al ₂ O ₃ ) containing calcium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 2.7 mass. %, and the proportion of the X-ray amorphous part of the active component is 0.4.

Example 3

According to example 1, with the difference that:

- To prepare the carrier, 340 kg of alumina, 6.5 kg of calcium oxide, 6.5 kg of magnesium oxide are loaded into a ball mill.

- Mix 120 kg of grinding containing alumina, calcium oxide, magnesium oxide and 16 kg of carbon black.

- Add 36 dm ³ nitric acid solution.

- The granules are calcined at a temperature of 1200-1250 ° C.

The water absorption of the carrier is 26 vol. %

- To prepare an impregnating solution at a temperature of 40 ° C, 973 kg of aqueous nickel nitrate and 216 kg of aqueous aluminum nitrate (per 1 m ^{3 of the} solution) are dissolved in water.

- Get the following component composition of the solution in terms of metal oxides: NiO: Al ₂ O ₃ = 1: 0.12.

- The calcined carrier is impregnated 2 times with the solution prepared in Example 3, dried and calcined according to a technology similar to Example 1.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 10.1 aluminium oxide 1,1 carrier (Al ₂ O ₃ ) containing calcium oxide and magnesium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 1.8 mass. %, magnesium oxide 1.8 wt. %, the proportion of the X-ray amorphous part of the active component is 0.5.

Example 4

According to example 1 with the difference that:

- To prepare the carrier, 185 kg of alumina, 50 kg of reprecipitated aluminum hydroxide, 18 kg of calcium oxide, 3 kg of magnesium oxide are loaded into a ball mill. Grinding the mixture is 6 hours.

- Mix 125 kg of grinding containing alumina, aluminum hydroxide, calcium oxide, magnesium oxide, 12.5 kg of carbon black, 10 dm ³ solution of polyvinyl alcohol concentration of 10 mass. % Mixing of the charge is carried out for 0.5 hours.

- The mixture is compacted and tableted in the form of rings.

- The granules are dried at 120 ° C to a residual moisture content of not more than 2 mass. % and calcined at 1300-1350 ° C.

The water absorption of the carrier is 23 vol. %

- To prepare an impregnating solution at a temperature of 60 ° C, 584 kg of aqueous nickel nitrate are dissolved in water, then 120 dm ³ of a calcium nitrate solution of a concentration of 165 g / dm ³ in terms of CaO (per 1 m ³ of impregnation solution) is added.

- The component composition of the finished solution in terms of metal oxides has the following ratios: NiO: CaO = 1: 0.13.

- The calcined carrier is impregnated 2 times with the solution prepared in Example 4, dried and calcined according to a technology similar to Example 1.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 6.9 calcium oxide 0.9 carrier (Al ₂ O ₃ ) containing calcium oxide and magnesium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 7.0 mass. %, magnesium oxide 1.2 wt. %, the proportion of the X-ray amorphous part of the active component is 0.55.

Example 5

Preparation of media according to example 4.

The preparation of the catalyst according to example 4 with the difference that:

- The impregnation of the media is carried out 4 times.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 9.1 calcium oxide 1,2 carrier (Al ₂ O ₃ ) containing calcium oxide and magnesium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 7.0 mass. %, magnesium oxide 1.2 wt. %, the proportion of the X-ray amorphous part of the active component is 0.5.

Example 6

Preparation of media according to example 4.

The preparation of the catalyst according to example 1 with the difference that:

- To prepare an impregnating solution at a temperature of 60 ° C, 584 kg of aqueous nickel nitrate and 32.3 kg of potassium nitrate (per 1 m ³ of impregnation solution) are dissolved in water.

- The component composition of the finished solution in terms of metal oxides has the following ratios: NiO: K ₂ O = 1: 0.1.

- Annealed carrier 3 times impregnated with a solution prepared according to example 6, using a technology similar to example 1.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 8.0 potassium oxide 0.9 carrier (Al ₂ O ₃ ) containing calcium oxide and magnesium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 7.0 mass. %, magnesium oxide 1.2 wt. %, the proportion of the X-ray amorphous part of the active component is 0.3.

Example 7

According to example 1 with the difference that:

- To prepare the carrier, the alumina, aluminum hydroxide and technical calcium aluminate previously ground in a ball mill are mixed in a ratio of 600 g / 400 g / 300 g, respectively. Grinding lead at least 6 hours.

- To a mixture containing alumina, aluminum hydroxide and technical calcium aluminate, add 100 g of graphite and with continuous stirring 150 cm ³ solution of polyvinyl alcohol concentration of 10 mass. % Stirring is carried out for 0.5 hours.

- The carrier granules are dried in air for 24 hours, steamed for 4 hours, dried at 120 ° C, and then calcined at 1350 ° C.

The water absorption of the carrier is 18 vol. %

- To prepare the catalyst, an impregnation solution is prepared in a flask by dissolving in a small amount of water at a temperature of 65 ° C and continuously stirring 465 g of aqueous nickel nitrate, 37 g of aqueous aluminum nitrate, 11 g of potassium nitrate and adding 30 cm ^{3 of a} solution of calcium and magnesium nitrates concentration 85 g / dm ³ CaO and 85 g / dm ³ MgO (per 1 dm ³ impregnation solution).

- The composition of the finished solution in terms of metal oxides: NiO: Al ₂ O ₃ : K ₂ O: CaO: MgO = 1: 0.04: 0.04: 0.02: 0.02.

- The carrier prepared as described above is poured with an impregnating solution until the granules are completely submerged. After exposure for 0.5 hours, the solution is drained, the impregnated granules are laid out on filter paper to remove residual impregnation solution.

- The granules are dried at a temperature of 260 ° C for 4 hours, cooled to room temperature. Then re-impregnation is carried out according to the described procedure.

- After the final impregnation and drying, the catalyst is calcined - incubated at a temperature of 455 ° C for 6 hours.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 4.3 potassium oxide 0.2 aluminium oxide 0.2 calcium oxide 0.1 magnesium oxide 0.1 carrier (Al ₂ O ₃ ) containing calcium aluminate (calcium oxide) the rest is up to 100

moreover, the content of calcium aluminate (calcium oxide) in the carrier is 23 (8) mass. %, and the proportion of the X-ray amorphous part of the active component is 0.8.

Example 8

Preparation of media according to example 7.

The preparation of the catalyst according to example 7 with the difference that:

- The impregnation of the media is carried out 5 times.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 8.8 potassium oxide 0.5 aluminium oxide 0.4 calcium oxide 0.25 magnesium oxide 0.25 carrier (Al ₂ O ₃ ) containing calcium aluminate (calcium oxide) the rest is up to 100

moreover, the content of calcium aluminate (calcium oxide) in the carrier is 23 (8) mass. %, and the proportion of the X-ray amorphous part of the active component is 0.55.

Example 9

A corundum finished carrier in the form of cylinders with convex ends and 7 holes (TU 2163-003-07620772-2006) obtained by slip casting is used as a carrier.

The composition of the raw materials of the carrier, mass. %: alumina - 88, oil paraffin - 12.

The impregnating solution is prepared according to example 1 with the difference that:

- In a small amount of water at a temperature of 70 ° C and continuous stirring, 972 g of aqueous nickel nitrate, 300 g of aqueous aluminum nitrate, 90 g of potassium nitrate (per 1 dm ^{3 of} solution) are dissolved.

- The composition of the finished solution in terms of metal oxides: NiO: Al ₂ O ₃ : K ₂ O = 1: 0.17: 0.17.

- Corundum carrier 3 times impregnated with a solution prepared according to example 9, the technology of impregnation of the carrier, drying and calcination is similar to example 7.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 14.3 potassium oxide 2.5 aluminium oxide 2.6 carrier (Al ₂ O ₃ ) the rest is up to 100

the proportion of the X-ray amorphous part of the active component is 0.4.

Example 10

The preparation of the catalyst according to example 9 with the difference that:

- 30 g of the catalyst prepared according to example 8, is additionally impregnated with a solution of platinum chloride and ruthenium chloride by spraying the solution with slow stirring of the granules.

- The amount and concentration of the impregnation solution is calculated based on the water absorption of the sample (14.5 vol.%) And the required content of active components in the finished catalyst.

- The impregnated catalyst is dried and calcined at a temperature of 500 ° C.

The ratio of active components in the catalyst: NiO: Al ₂ O ₃ : K ₂ O: Pt: Ru = 1: 0.18: 0.17: 0.014: 0.028, and the resulting catalyst has a chemical composition, mass. %:

nickel oxide 14.2 potassium oxide 2.5 aluminium oxide 2.6 platinum 0.2 ruthenium 0.4 carrier (Al ₂ O ₃ ) the rest is up to 100

the proportion of the X-ray amorphous part of the active component is 0.4.

Example 11

To prepare the catalyst, the impregnation solution is prepared according to example 1 with the difference that:

- In a small amount of water, 233 g of aqueous nickel nitrate, 500 g of aqueous aluminum nitrate, 150 g of potassium nitrate are dissolved. Then add 310 cm ³ solution of calcium nitrate concentration of 200 g / DM ³ CaO (1 DM ³ impregnation solution).

- The composition of the finished solution in terms of metal oxides: NiO: Al ₂ O ₃ : K ₂ O: CaO = 1: 1.13: 1.17: 1.03.

- Corundum support for catalysts in the form of cylinders with convex ends and 7 holes (TU 2163-003-07620772-2006) is impregnated 4 times with the solution prepared according to example 11, the technology of impregnation of the support, drying and calcination is similar to example 7.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 4.6 potassium oxide 5.3 aluminium oxide 5.2 calcium oxide 5,0 carrier (Al ₂ O ₃ ) the rest is up to 100

the proportion of the X-ray amorphous part of the active component is 0.7.

Example 12

To prepare the catalyst, 1000 g of alumina mixed with 30 g of calcium oxide was ground in a ball mill for 6 hours.

To a mixture containing alumina and calcium oxide, 400 cm ³ of a nickel nitrate solution of a concentration of 250 g / dm ³ in terms of NiO and 20 cm ³ of a copper nitrate solution of a concentration of 250 g / dm ³ in terms of CuO are added in several stages.

The mass is kneaded for 0.5 hours with the addition of small amounts of water to impart thixotropic molding properties.

By extrusion, the mass is formed into granules with a diameter of 7 mm.

The granules are dried and calcined at a temperature of 400 ° C.

From calcined granules prepare the mixture for tabletting by grinding and adding 3.5 mass. % graphite and 2 mass. % water.

The granules (tablets) obtained by pressing are steamed for 6 hours, dried and calcined at a temperature of 500 ° C.

The ratio of active components in the catalyst in terms of metal oxides: NiO: CuO: CaO = 1: 0.05: 0.3.

The resulting catalyst has a chemical composition, mass. %:

nickel oxide 8.8 copper oxide 0.4 calcium oxide 2.5 carrier (Al ₂ O ₃ ) containing calcium oxide the rest is up to 100

moreover, the content of calcium oxide in the carrier is 2.9 mass. %, while the proportion of X-ray amorphous part of the active component is 0.5.

Example 13

To prepare the catalyst, 300 g of pre-ground alumina is mixed with 70 g of calcium oxide and 30 g of magnesium oxide.

To a mixture containing alumina (a structural additive providing texture characteristics of the catalyst), calcium oxide and magnesium oxide, 600 g of finely divided nickel oxide (NiO) are added. Stirring is carried out for 0.5 hours. Add 30 g of graphite and in several stages 60 cm of a solution of polyvinyl alcohol concentration of 10 mass. % Stirring is carried out for 0.5 hours.

The resulting mixture is compacted by preliminary tableting, crushed, sieved on a sieve and tableted in the form of cylinders 7 × 7 mm.

The ratio of active components in the catalyst in terms of metal oxides: NiO: CaO: MgO = 1: 0.11: 0.05.

The resulting catalyst has a chemical composition, mass. %:

nickel oxide 58.0 calcium oxide 6.8 magnesium oxide 2.9 carrier (structural additive) (Al ₂ O ₃ ) the rest is up to 100

the proportion of the X-ray amorphous part of the active component is 0.4.

Example 14

The preparation of the catalyst according to example 13 with the difference that:

- Pre-crushed in a ball mill alumina (a structural additive that provides texture characteristics of the catalyst) in an amount of 100 g, and then mixed with 900 g of finely dispersed nickel oxide (NiO) for 0.5 hours.

- To a mixture containing alumina and nickel oxide, add 30 g of graphite and in several stages 60 cm ³ solution of polyvinyl alcohol concentration of 10 mass. % Mixing of the charge is carried out for 0.5 hours. The mixture is compacted by preliminary tableting, crushed, sieved on a sieve and tableted in the form of cylinders 5 × 5 mm.

- The resulting catalyst has a chemical composition, mass. %:

nickel oxide 87.0 carrier (structural additive) (Al ₂ O ₃ ) the rest is up to 100

the proportion of the X-ray amorphous part of the active component is 0.2.

Example 15. The determination of the proportion of x-ray amorphous Nickel oxide.

10-20 granules of the nickel-containing catalyst are calcined at temperatures of 500, 600, 700, 800, 900, 950, 1000, 1050, 1100, 1200 ° C. For the initial fresh sample and each calcined sample by X-ray diffraction analysis on a Shimadzu XRD 7000 diffractometer (Cu-Kα radiation, tube voltage 40 kV, current 50 mA, scan area 2θ = 3-80 degrees, decryption and data processing in the Match program using PDF-2 bases) determine the quantitative content of crystallized NiO.

The X-ray amorphous part of C _{p / a} NiO in a fresh catalyst is determined by the formula:

With _{p / a} = (NiO _max- NiO _{fresh catalyst} ) / NiO _max .

Example 16. Tests of the activity and stability of the catalysts in the steam reforming reaction of hydrocarbon gas.

Testing the activity of the patented catalyst is carried out on a flow-through laboratory apparatus in the conversion of methane with water vapor at an initial volumetric ratio of steam: gas = 2: 1 and a space velocity of 6000 nm ³ / h of the source gas per 1 m ^{3 of} catalyst at temperatures of 600 and 800 ° C catalyst in an amount of 5.0 cm ³ granulation of 2-3 mm The component composition of the catalysts prepared according to examples 1-14 are presented in table 3.

The catalyst before the test is restored by heating to a temperature of 500 ° C and holding at 500 ° C for 3 hours in a stream of hydrogen (hydrogen consumption 10 ndm ³ / h).

The activity of the catalyst is characterized by the residual volume fraction of methane in the converted gas (calculated on dry gas). The converted gas is analyzed by gas chromatography.

To assess the stability associated with the structural deactivation of the main active component of the catalyst during prolonged use, an activity test is carried out for a sample previously calcined at 1000 ° C for 6 hours. The values of the activity of fresh (A _o ) and calcined at 1000 ° C (A) samples calculate the stability coefficient k = 1- (AA _o ) / 100.

The test results of the catalysts in examples 1-14 are presented in table 3.

The samples of the catalysts in examples 7 and 11 due to the low content of the active Nickel component (less than 5 wt.%) Have a low initial activity.

The samples of the catalysts according to examples 6, 14 are not sufficiently heat resistant (the proportion of X-ray amorphous nickel oxide is 0.3 and 0.2, respectively; the stability coefficient is 0.6 and 0.79, i.e., after test overheating, the samples decreased activity by 40 and 20%, therefore, in industrial conditions, the decrease in activity will occur much faster than samples with a higher stability coefficient of 0.9-1.0. The effective life of the inventive catalysts will be at least 5 years.

According to the prototype, studies of the activity of samples in steam reforming were carried out at a pressure of 1 atm, a steam: carbon ratio of 3.25 in the temperature range 500-600 ° C; the maximum achieved methane conversion is 42% (residual methane is 58%).

For all samples of the patented invention in tests at 1 atm and a temperature of 600 ° C under more stringent conditions, the ratio of pairs: carbon equal to 2.0 obtained a higher degree of conversion - residual methane does not exceed 55%.

The steam reforming catalysts are characterized by an extreme dependence of activity on the content of nickel oxide (in the activated catalyst, nickel). This is explained by the fact that, at a low content, nickel oxide (nickel) is evenly distributed over the surface / in the volume of the carrier in the form of a mono- and multimolecular layer. With a further increase in the content of nickel oxide (nickel), it forms three-dimensional structures — crystallites, in which internal atoms are not accessible to reagent molecules. As a result, the surface of the active nickel component and, accordingly, the activity of the catalyst are significantly reduced. The optimal amount of nickel oxide (nickel) in the catalyst depends on the properties of the carrier — its chemical composition, porous structure, the technology of applying / introducing active components onto / in the carrier, the qualitative and quantitative composition of the active part promoters, and the content of dispersants; those. for each catalyst formulation this is an individual quantity.

During operation of the catalyst is the formation and / or enlargement of crystallites of nickel oxide (Nickel). The rate of crystallite aggregation (sintering rate of the crystalline structure) depends on the process temperature, as well as the presence / absence of sintering and anti-sintering additives. Alumina as part of the active part of steam reforming catalysts acts as a dispersant of active particles and a structural stabilizer - it prevents the migration and coalescence of crystallites of nickel oxide (nickel); alkali metals accelerate the sintering of the active component. The role of calcium and magnesium oxides is ambiguous: at relatively low temperatures (up to 900 ° C) they interfere with sintering, and at high temperatures (above 1000 ° C) they contribute. The desired presence of alkali and alkaline earth metals in the catalysts is associated with their ability to inhibit the carbonization and, accordingly, deactivation of the catalyst.

This invention allows to obtain steam reforming catalysts of varying chemical composition with high initial activity and guaranteed long-term ability to maintain high activity during operation due to the thermal stability of the crystal structure.

When implementing the invention, from all possible combinations of the ratio of the components of the active part, their quantity and carrier composition within the stated ranges, only those are selected in which the proportion of X-ray amorphous particles of the predominant active component is not lower than 0.4.

Based on this, the amounts of each component of the active part are selected within the claimed concentrations, and the optimum ratios between the components are determined by the proportion of X-ray amorphous particles of the main active component, which objectively reflects the total multidirectional effect of all functional components and cooking technology.

This physical parameter of the catalyst — the X-ray amorphous fraction of the active component — objectively reflects the synergism of a complex multielement system: the multidirectional effect of additives, which are structural stabilizers, and additives, sintering the structure; the influence of the morphology and chemical properties of the carrier on the dispersion of the particles of the catalytically active part; catalyst production technologies, etc. In combination with the usually determined (in the prototype and analogues) index of initial activity of catalytic systems, a sufficient content of X-ray amorphous particles of the active component (nanoparticles with sizes <0.5 ÷ 1 nm) ensures not only high activity, but also long-term preservation high activity due to the “stock” of nanoscale structural elements, which are gradually involved in the process of recrystallization during long-term operation and ensure surface conservation up to step for reagent molecules, at a high, close to the initial level.

The present invention allows the use of forms having high porosity, large geometric surface area, low pressure drop.

The catalysts obtained in accordance with the present invention can be used in reforming processes, such as primary steam reforming, secondary reforming of a gas mixture subjected to primary reforming, autothermal reforming and pre-reforming. The catalysts can also be used for reforming by partial catalytic oxidation individually or in combination with steam reforming. Catalysts can also be used for methanation and hydrogenation reactions.

* - structure-forming additive.

For preforming catalysts 13-14, the test temperature is 600 ° C, the superheat temperature is 800 ° C.

Claims (12)

1. A catalyst for steam conversion of hydrocarbons, comprising an active part containing nickel (Ni), copper (Cu), platinum (Pt), palladium (Pd) rhodium (Ph), ruthenium (Ru), gold (Au), and a carrier based alumina containing magnesium oxide, calcium / magnesium aluminate or mixtures thereof, characterized in that the active part of the catalyst further includes potassium, calcium, aluminum in the following components in the catalyst, mass. % nickel oxide 5-60 potassium oxide 0-5 magnesium oxide 0-5 calcium oxide 0-5 aluminium oxide 0-5 copper oxide 0-5 platinum 0-2 palladium / rhodium / ruthenium / gold 0-0.5 carrier the rest is up to 100 while the proportion of X-ray amorphous elements of the main active component is at least 0.4. 2. The catalyst for the steam conversion of hydrocarbons according to claim 1, characterized in that the carrier further comprises calcium oxide (CaO) in the following ratio of components, mass. %: calcium / magnesium oxide 0-10 calcium / magnesium aluminate 0-90 aluminium oxide the rest is up to 100 3. The catalyst for steam conversion of hydrocarbons according to claim 1, characterized in that the composition of the raw materials for the preparation of the carrier includes a structure-forming additive, alumina, reprecipitated aluminum hydroxide, calcium / magnesium aluminate, calcium / magnesium oxide in the following ratio of components, mass. %: structure-forming additive 5-30 reprecipitated aluminum hydroxide 0-30 calcium / magnesium aluminate 0-30 calcium / magnesium oxide 0-40 alumina the rest is up to 100 4. The catalyst for the steam conversion of hydrocarbons according to claim 1, characterized in that wood-flour, carbon black, oil paraffin, polyvinyl alcohol, graphite are used as a structure-forming additive at a ratio of alumina: structure-forming additive equal to 10: 0.5 ÷ 10: 3 . 5. The catalyst for steam conversion of hydrocarbons according to claim 1, characterized in that they preliminarily co-grind alumina and structure-forming additives, which lead at least 6 hours to a grinding fineness - the residue on a sieve of 0.05 mm is not more than 5 mass. %, the support is calcined at a temperature of 1100-1400 - ° C, and the catalyst at the beginning is dried at a temperature of not more than 200 ° C, after which the temperature is raised at a speed of no more than 50 ° C per hour to a value of 250-270 ° C and at this temperature incubated for 4-12 hours, after which the catalyst is calcined at a temperature of 450-500 ° C for 6-12 hours. 6. The catalyst for the steam conversion of hydrocarbons according to claim 1, characterized in that the finished carrier is used in the form of granules of complex geometric shape. 7. The catalyst for steam conversion of hydrocarbons according to claim 1, characterized in that the alumina is preliminarily ground with calcium oxide additives, then mixed with soluble salts of the active components, the mass is formed into granules that are dried and calcined at a temperature of 350-400 ° C, after grinding and adding a structure-forming additive and lubricants, tablets are pressed, steamed and calcined at a temperature of 400-600 ° C. 8. The catalyst for steam conversion of hydrocarbons according to claim 1, characterized in that the pre-ground alumina is mixed with calcium oxide, magnesium oxide, active component oxides, structure-forming additives and lubricants, the resulting mixture is compacted by preliminary tabletting, crushed, sieved on a sieve and tabletted .