RU1780831C - Catalyst for converting hydrocarbons - Google Patents

Abstract

A catalyst for the conversion of hydrocarbons. The inventive catalyst (CT) contains, wt.%: Nickel or cobalt oxide 1.2-10.2; alumina 0.8-20.0; metal oxide into subgroups 0.021-2.0; metal oxide IV in the subgroup of 0.003-0.43; ceramic carrier based on alumina, the rest in the mass ratio of nickel or cobalt oxide (alumina, metal oxide into subgroups) metal oxide IV into subgroups (0.5-3.12): 1: (0.006- 0.100) (0.00008- 0.045). Characteristic: increased CT activity. 5 tab. next to

Description

The invention relates to supported catalysts for the processes of incomplete catalytic conversion of hydrocarbons in reactions with steam, carbon dioxide, air, oxygen or mixtures thereof at temperatures from 450 to 1350 ° C and pressures from O, 1 to 5.0 MPa, and can be used in the chemical, petrochemical, metallurgical, engineering and food industries to produce gas mixtures for the production of ammonia or alcohols, industrial hydrogen, or reducing gases for various purposes purpose (controlled and protective reducing environments, fumigants, etc.).

Known nickel catalysts for the conversion of hydrocarbons (1 2) supported

type using alumina, chromium or magnesium oxide as a stabilizing promoter.

The main disadvantage of these catalysts is that the applied mass ratio of the main% of the components of the supported part, namely, the ratio of the oxide of the reducing active metal to the oxide of the non-reducing meta / fa selected as a stabilizing promoter, was within rather high values (3-10 ): 1, that there was direct lack of activity, thermal stability and selectivity (resistance to carbonization).

A known catalyst for the conversion of hydrocarbons containing supported active part, including nickel oxide and

 with about

00 CJ

aluminum and calcium oxide promoters; and an alumina carrier modified with barium, calcium, and titanium oxides. The composition of the deposited part corresponds to the ratio of the deposited components: MU / A12Oz / CaO 3.0 / 1.0 / 0.05 (3).

However, the known catalyst, due to the insufficiently low ratio of the main active components No. 0 / A1203, does not meet current requirements for activity and selectivity.

The closest to the proposed invention in terms of technical nature and the achieved effect is a hydrocarbon conversion catalyst (4) containing a supported active part, including nickel or cobalt oxides, a stabilizing promoter in the form of alumina, a promoter of carbon gasification reactions in the form of alkaline-earth oxide metal Subgroups of elements of the periodic system selected from the group of oxides of magnesium, calcium, strontium and barium, and a ceramic carrier based on alumina with the following content the indicated components, wt.%:

Alumina 6.99-39.76

Metal Oxide On

subgroups of elements

periodic

systems 0.17-70.39

Nickel oxide or

cobalt

and a ceramic carrier based on alumina. Moreover, these components of the applied part correspond to the following mass ratio: NiO or CoO / A 20z 1.5-8.0, and NiO or CoO / Me aO 1.5-100.0.

The disadvantages of the known catalyst are insufficient activity, thermal stability and resistance to carburization.

The aim of the invention is to increase activity, thermal stability and resistance to carbonization.

This object is achieved in that the catalyst for the conversion of hydrocarbons contains an active part, including nickel or cobalt oxides, a stabilizing promoter in the form of alumina, a promoter of carbon gasification reactions in the form of alkaline earth metal oxide To a subgroup of elements of the periodic system selected from the group of magnesium oxides , calcium, strontium and barium, metal oxide IVe subgroups of the elements of the periodic system, selected from the group of oxides of titanium, zirconium, hafnium with the following content of these components ., Wt%:

Nickel oxide or

cobalt38.27-75.80

Metal oxide Pa subgroups of the elements of the periodic system 0.27-6.17

Magnesium oxide selected from the group 0.51-2.5

Calcium oxide 0.34-6.17

Strontium oxide 1.85-5.2

0 Barium oxide 0.27-5.2

Metal dioxide IVB subgroup of the elements of the periodic system 0.03-2.44 selected from group 5 Titanium dioxide 0.03-2.44

Zirconia 0.03-2.44

Hafnium dioxide 0.03-2.44

Alumina Else

and a ceramic carrier based on aluminum oxide 0 with the following content of components in the catalyst, wt.% (per calcined mass):

Nickel or cobalt oxide 1.2-10.2

5 Aluminum oxide 0.8-20.0

Specified metal oxide per gTodgroup of elements of the periodic system 0.021-2.0 The above dioxide 0 metal IVe subgroups

elements of the periodic system 0.003-0.43

5 aluminum oxide ceramic carrier

Moreover, the indicated components of the applied part correspond to the following mass ratio: NiO or CoO / A12Oz / Me aO / Me | Uv02 (0.5-3.12) :( 1.0) :( 0 0, 006-0,100): (0 , 0008-0.045).

A significant difference between the proposed catalyst and the known one lies in the fact that the supported active part additionally contains metal dioxide IVe 5 of a subgroup of elements of the periodic system selected from the group of titanium, zirconium, hafnium oxides with the following content of these components, wt.%:

Alumina 24.20-61.73

0 Metal Oxide

subgroups of the elements of the periodic system 0.27-6.17 selected from the group

Magnesium Oxide 0.51-2.50

5 or

Calcium oxide 0.34-6.17

or

Strontium oxide 1.85-5.20

or

Barium oxide 0.27-5.20

Metal dioxide IVe

subgroups of elements

periodic

systems selected from the group

Titanium dioxide or

Zirconium dioxide or

0.03-2.44 0.03-2.44 0.03-2.44 0.03-2.44

Hafnium dioxide

Nickel oxide or

cobalt

with a total content of components in the catalyst, wt.% per calcined mass:

Nickel oxide or

cobalt 1.2-10.2

Alumina 0.8-20.0

Metal Oxide On

subgroups of elements

periodic

systems0.021-2.0

Metal dioxide IVe

subgroups of elements

periodic

systems 0.003-0.43

Based Media

alumina rest

The components of the applied part correspond to the following mass ratio: NiO or CoO / A1203 / Me aO / Me1Uv02 (0.5-3.12): 1.0: (0.006-0.10) :( 0.0008-0.045). These differences make it possible to increase activity 2.5–7.5 times, selectivity 1.6–2.6 times, and thermal stability 1.2–2.3 compared to the known catalyst (4) (examples I and III) times.

Example 1. The catalyst used mainly for autothermal mine conversion of gaseous and light liquid hydrocarbons under pressure up to 2.5 MPa, consists of nickel, aluminum, magnesium and zirconium oxides deposited on a porous ceramic carrier based on industrial alumina.

The carrier is obtained from fine grinding technical alumina grade G-00 (residue on a sieve of 40 microns no more than 1 wt.%, The content of aA 20z 40-50 wt.%) By mixing it with wood flour grade 400, taken in an amount of 10 -12 wt.% By weight of alumina, and with a 20% solution of nitric acid. The flow rate of the solution is about 56 dm3 / 100 kg of alumina. The mass is mixed for 40 minutes in a mixer with Z-shaped blades, after which it is molded on a high-pressure extrusion press (10.0 MPa) in the form of ring-shaped granules 19x19x8 mm, dried in a heating mode in an elevator dryer at 40-130 ° C for 18-28 hours. Dried media with

the index of losses during calcination at 800 ° C (SPP) of not more than 13.0 wt.% is calcined in a shaft calcining furnace at a temperature of 1400 ° C with holding for 5 10-14 hours. The rate of water absorption of the resulting carrier is of the order of 24-26 wt. % The carrier has the following composition, wt.%: Calcium oxide 0.120

Magnesium Oxide 0.025

0 Barium Oxide Traces

Zirconia Traces

Titanium dioxide

Silica 0.140

Iron trioxide

5 Chromium trace trioxide

Manganese monoxide traces Amount of potassium and sodium oxides 0.400

α-alumina The rest 0 The carrier is repeatedly impregnated in a salt solution containing per 1000 dm3 of water: 830.2 kg of nickel nitrate M (MOH) 2 6H2O, 1045.2 kg of aluminum nitrate A1 (MOH) sx x9H20,

5 27.1 kg of magnesium nitrate Md (MOH) a-4H20,

2.30 kg of zirconyl nitrate 2gO (MOH) 2-2H20.

This formulation corresponds to the ratio

oxides of the deposited part equal to MU / уAI203 / MgO / Zr02 - 1.50 / 1.00 / 0.030 / 0.007 and

0 to its following composition, wt.%:

Nickel Monoxide 59.09

y-alumina 39.42

Magnesium Oxide 1.22

5 Zirconia 0.27

After each impregnation, the carrier is calcined at a temperature of 500 ° C with a holding time of at least 2 hours.

The finished catalyst has the following 0 composition, wt.%:

Nickel monoxide 7.75

y-alumina 5.17

Magnesium Oxide 0.16

Zirconia 0.036

5 Media specified

composition of the rest

The catalyst has an open porosity of 54-56 vol.%, The total specific surface is 7-8 m2 / g, the surface of metallic nickel is 0 l, 1.5-1.8 m2 / g. The temperature resistance of the catalyst is about 26 cycles of heat exchange of 1200-20 ° without destruction of the granules.

Example 2. The catalyst, used mainly for autothermal mine and secondary reforming of naphtha under a pressure of 4.0 MPa, consists of cobalt, aluminum, calcium, and zirconium oxides deposited on a porous ceramic carrier based on technical alumina doped with additives of calcium and titanium oxides.

The carrier is prepared according to the method described in Example 1. with the difference that in addition to the molding composition, calcium carbonate and titanium dioxide are added, taken respectively from the calculation of 0.52% CaO and 0.12% TiO2 in the finished carrier. At a temperature of the order of 1300 ° C, the water absorption index of the carrier is 26-28% by weight.

The carrier has a composition, wt.%: Calcium oxide 0.520

Magnesium Oxide 0.030

Barium Oxide Traces

Zirconia Traces

Titanium dioxide 0.120

Silicon Dioxide 0.008

Iron trioxide .100

Chromium trioxide

Manganese Monoxide Traces Sum of Potassium and Sodium Oxides 0.400

a-alumina Else

The carrier is repeatedly impregnated in a nitrate solution with the following salt ratio per 1000 kg of condensate:

883.8 kg of cobalt nitrate Co (MO3) a - 6H20, 1045.2 kg of aluminum nitrate A (MO3) sx x9N20,

17.9 kg of calcium nitrate Ca (MOH) 2-4HaO; 2.3 kg of zirconyl nitrate ZrO (N03) 2X x2H20.

This corresponds to the ratio of the oxides of the deposited part of CoO / y-Al203 / CaO / Zr02 1.60 / 1.00.0.030 / 0.007 and the following composition of the deposited part of the catalyst, wt.%:

Cobalt Monoxide 60.67 y-Alumina 37.92

Calcium oxide 1.15

Zirconium dioxide 0.26

After each impregnation, the support is calcined at a temperature of 570 ° C (holding for 2 hours). The finished catalyst has a composition, wt.%: Cobalt monoxide 7.36 y-Alumina 4.60

Calcium oxide 0.14

Zirconia 0.032

Conveyor carrier

The catalyst has an open porosity of 52-54 vol.%, The total specific surface area of 6-7 m2 / g, the surface of cobalt metal is 1.2-1.5 m / g. The thermal stability of the catalyst is of the order of 60 heat exchangers of 1200-20 ° C without breaking the granules.

Example 3. The catalyst used for the cyclic reforming of hydrocarbons under pressure up to 2.0 MPa consists of nickel, aluminum, calcium and zirconium oxides supported on a porous ceramic carrier prepared on the basis of sintered aluminum hydroxide doped with calcium oxide additives (0.305%) and titanium (1.55%). Can also be used for cracking ammonia. The support is prepared from freshly precipitated aluminum hydroxide modified with additives of finely dispersed calcium and titanium oxides, taken in a CaO / TiO2 ratio of 1/5. A wet mixture of oxides containing a burn-out organic additive is tableted in the form of Raschig rings, dried and calcined in a tunnel oven at a temperature of about 1350 ° C (holding time is at least 3 hours). The calcined support has a granule size of 19 x 19 x 9 mm and a moisture absorption index of about May 21. % The carrier has a composition, wt.%: Calcium oxide 0.305

Magnesium Oxide 0.040

Barium Oxide Traces

Zirconia Traces

Titanium dioxide

Silica 0.120

Iron trioxide

Chromium trioxide

Manganese Monoxide Traces Sum of Potassium and Sodium Oxides 0.205

α-alumina and γ-alumina Else The support is repeatedly impregnated in a molten salt with the following composition: 145.5 kg of nickel nitrate M (NaO3) 2 bN20, 550.5 kg of aluminum nitrate A (NaO3) z-9N20, 31, 5 kg of calcium nitrate Ca (NaO3) 2-4H20 and

3.44 kg of zirconyl nitrate 2gO (MOH) 2 2I20.

This corresponds to the ratio of supported oxides equal to NiO / y-Al203 / CaO / Zr02 0.50 / 1.00 / 0.100 / 0.020, and the composition of the supported part of the catalyst, wt.%:

Nickel monoxide 30.87

y-alumina 61.73 calcium oxide 6.17

Zirconium dioxide 1.23

After each impregnation, the catalyst is calcined at a temperature of 570 ° C (2 hours).

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 10.0

y-alumina 20.00

Calcium oxide 2.00

Zirconia 0.40

The carrier of the above

composition of the rest

The finished catalyst has an open porosity of 55-58 vol.%, The total specific surface area of 8-9 m2 / g, the surface of metallic nickel 1.1-1.4 m / g, heat resistance 55 of the heat transfer agent 1200-20 ° C without breaking the granules.

Example A. The catalyst used for the endothermic air conversion of natural gas or liquefied propane-butane to produce controlled atmospheres used for heat treatment of machine parts consists of cobalt, aluminum, magnesium and zirconium oxides supported on a large-porous corundum carrier based on technical alumina. The carrier is prepared according to the method described in Example 1, with the difference that in addition to the molding composition there is an addition of calcium carbonate (taken from the calculation of 0.365% CaO) and a coarse grain that burns out, for example, polystyrene grain with a diameter of 2 mm, taken in an amount of 20 , 0% of the charge volume. The flow rate of the nitric acid solution should be increased to 66 dm / 100 kg of alumina. After calcining in a tunnel oven at a temperature of about 1450 ° C, the support is water-absorbed. spacing equal to 32 wt.%.

The carrier has a composition, wt.%: Calcium oxide 0.365

Magnesium Oxide 0.040

Barium Oxide Traces

Zirconia 0.010

Titanium dioxide

Silica 0.136

Iron trioxide 0.059

Chromium trioxide

Manganese monoxide 0.005 Sum of potassium and sodium oxides 0.360

a-Alumina Remaining The carrier is repeatedly impregnated in a solution of salts containing 100 dm3 of water:

83.16 kg of cobalt itta nitrate Co (N Oz) 2 BNaO, 51.90 kg of aluminum nitrate A1 (MOH) s-9H20, 4.04 kg of magnesium nitrate Md (MOH) 2-6H20 and

0.16 kg of zirconyl nitrate 2gO (MO3) 2-2H20, which corresponds to the following ratio of the components of the applied part: CoO / y 12Oz / MdO / 2g02 3.03 / 1.00 / 0.090 / 0.010 and the following composition of the applied part of the catalyst, wt. %:

Cobalt Monoxide 73.38 y-Alumina 24.20 Magnesium Oxide 2.18

Zirconia 0.24

After intermediate and final piercing of the impregnated carrier at a temperature of 520 ° C (2 hours), the finished catalyst 5 has the composition, wt.%:

Cobalt monoxide 8.66 y-alumina 2.86 magnesia 0.26

Zirconia 0.029

0 Carrier of the above h

composition of the rest

The catalyst has an open porosity of 52-54 vol.%, The total specific surface is 6-8 m2 / g, the surface of metallic cobalt 5 is 1.0-1.3 m2 / g, the heat resistance is 48, and the heat exchange is 1200-20 ° C without destroying the granules. .

Example 5. The catalyst used for steam reforming of petroleum gas, such as liquefied propane, consists of nickel, alumina TT TTrnci and zirconium oxides supported on a porous ceramic support prepared on the basis of aluminum hydroxide modified with 5 addition of calcium aluminate.

A moistened mixture consisting of aluminum hydroxide and containing a burnable organic plasticizer, for example polyvinyl alcohol, is tabletted in the form of Rashig rings, dried and calcined in a tunnel oven at a temperature of 1450 ° C (holding time is at least 6 hours).

The finished carrier in the form of annular granules with dimensions of 15.0 x 12.0 x 6.5 mm 5 has a water absorption index of the order of 26.0 wt.%.

The carrier has a composition, wt.%: Calcium oxide 15,300

Magnesium Oxide 0.060

0 Barium oxide, Traces

Zirconia Traces

Titanium dioxide

Silica 0.120

Iron trioxide

5 Chromium Trioxide Traces

Manganese Monoxide Traces Sum of Potassium and Sodium Oxides 0.350

α-alumina The rest 0 The carrier is repeatedly impregnated in a salt solution containing 100.0 dm3 of water:

182.6 kg of nickel nitrate 1M1 (1MO3) 2-bNaO. 585.8 kg of aluminum nitrate A1 (MOH) z-9H20, 5 6.55 kg of strontium nitrate Sr (N03J2-4H20, 1.28 kg of zirconyl nitrate 2O (MOH) 2 2H20. - After each impregnation, the support is calcined at a temperature of 450 ° C, and after final impregnation at a temperature of 570 ° C

until complete decomposition of nitrates. The ratio of oxides in the supported part of the catalyst is equal to NiO / y-Al203 / SrO / Zr02 0.589 / 1,000 / 0.030 / 0.007, which corresponds to the following composition of the supported part of the catalyst, wt.% Nickel monoxide 36.22

y-Alumina 61.50 Strontium oxide 1.85

Zirconia 0.43

The resulting catalyst has a composition, wt.%:

Nickel monoxide 6.00

y-alumina 10.19

Strontium oxide 0.306

Zirconia 0.071

The carrier of the above composition

The catalyst has an open porosity of 50-53 vol%, a total specific surface area of 15-18 m2 / g, a nickel metal surface of 2.5-3.0 m2 / g, and heat resistance of about 50 heat exchange of 1200-20 ° C without breaking the granules.

Example 6. The catalyst used mainly for autothermal mine conversion of gaseous hydrocarbons under a pressure of 4.0 MPa consists of nickel, aluminum, calcium and zirconium oxides supported on a porous ceramic carrier prepared from a mixture of aluminum hydroxide with the addition of calcium oxides (1, 00% CaO) and titanium (0.50% TiO2) taken in a CaO / TiO2 ratio of 2/1.

The carrier is prepared by a method similar to example 4, and has the following composition, wt.%:

Calcium oxide 1.004

Magnesium Oxide Traces

Barium Oxide Traces

Zirconia Traces

Titanium dioxide 0.502

Silica 0.100

Iron trioxide

Chromium trixide

Manganese Oxide

The sum of potassium and sodium oxides 0.219

c: -Aluminium oxide The rest The carrier is repeatedly impregnated in a salt solution containing 1000 dm3 of water:

T746, nickel nitrate Ni (N03) 2 6H20, 5500.0 kg of aluminum nitrate A (W3) s-9H20, 276.3 kg of calcium nitrate Ca (MOH) 2-4H20, 2.93 kg of zirconyl nitrate 7gO (LiO2 2H20, which corresponds to the ratio of supported oxides NiO / y-Al203 / CaO / Zr02 0,600 / 1,000 / 0,0877 / 0,0017 and the composition of the deposited part of the catalyst, wt.%:

Nickel Monoxide 35.51

y-Alumina 59.19 Calcium oxide 5.20

Zirconia 0.10

After each impregnation, the support is calcined at a temperature of 570 ° C (holding for 2 hours).

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 6.32

y-Alumina 20.53 Calcium oxide 0.92

Zirconia 0.018

Carrier of specified composition

The catalyst has open porosity.

43-45 about. %, total specific surface 57 m2 / g, metallic nickel surface

1.1-1.4 m / g, heat resistance of the order of 50 heat exchange 1200-20 ° C without destruction of the granules

Example 7. The catalyst used for the initial endothermic reforming of gaseous hydrocarbons under pressure up to 4.0 MPa consists of nickel, aluminum, barium and zirconium oxides supported on a large-porous ceramic carrier prepared on the basis of industrial alumina with calcium oxide additives (3.00 % CaO and 1.50% MdO). A carrier with a water absorption index of 42.0 wt.% Is obtained by a method similar to that described in Example 4, with the difference that the mixture, in addition to Ca and Md oxides, contains a large-pore burnable additive in an amount up to 50% of the volume of the molding material.

The carrier has a composition, wt.%: Calcium oxide 3,000

Magnesium Oxide 1,500

Barium Oxide Traces

Zirconia Traces

Titanium dioxide

Silicon dioxide 0.109

Iron trioxide

Chromium trioxide

Manganese Oxide

The sum of potassium and sodium oxides 0.320

a-alumina Else

The support is impregnated twice in a solution containing 1000 dm3 of water: 856.70 kg of nickel nitrate Ni (N03) 2-6HaO, 519.00 kg of aluminum nitrate A1 (MOS-9HaO, 1.34 kg of anhydrous barium nitrate Ba (MOS) 2 and

0.21 kg of zirconyl nitrate 2U (SH3) 2-2H2O. The ratio of oxides supported on the resulting catalyst is NiO / y-Al20s / BaO / Zr02 - 3.12 / 1.00 / 0.0112 / 0.0012,

which corresponds to the following composition of the applied part of the catalyst, wt.%:

Nickel Monoxide 75.52

y-Alumina 24.21

Barium oxide 0.27

Zirconia 0.03

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 7.58

y-Alumina 2.43

Barium oxide 0.027

Zirconium Dioxide 0.003

Media above

composition of the rest

The catalyst has an open porosity of 57–59 vol%, a total specific surface of 14–17 m / g, an active metal surface of 2.7–3.2 m2 / g, heat resistance of the order of 80, and a heat exchange of 1200–20 ° C without destruction of granules .

Example 8. The catalyst used in the process of endothermic steam reforming of natural gas to produce hydrogen, carried out under pressure up to 4.0 MPa, consists of cobalt, aluminum, strontium and zirconium oxides supported on a porous alumina-based ceramic carrier. Carrier obtained by a similar method described in example 5, has a water absorption of 42.0 wt.%.

It has the following chemical composition, wt.%:

Calcium oxide 0.250

Magnesium Oxide 1,500

Barium oxide 5,500

Zirconia 0.010

Titanium dioxide

Silica 0.160

Iron trioxide

Chromium trioxide

Manganese Oxide

The amount of potassium oxides

and sodium 0.392

a-alumina Else

The carrier is soaked twice in a salt solution containing 1000 dm of water:

685.64 kg of cobalt nitrate Co (NaO3) 2 6H20,

519.00 kg of aluminum alumini nitrate A (MOH) z-9N20,

13.82 kg of strontium nitrate 5g (MOH) 2-4H20,

0.174 kg of zirconyl nitrate 2U (MO3) 2-2H20.

The ratio of oxides in the supported part of the catalyst is CoO / y-Al2Q3 / SrO / Zr02 2.50 / 1.00 / 0.0715 / 0.0011, which corresponds to the following composition, wt.%:

Cobalt monoxide 69.98

y-alumina 27.99

Strontium oxide 2.00

Zirconia 0.03

After intermediate and final calcination of the impregnated carrier at a temperature of 550 ° C (holding for 2 hours), the obtained catalyst has the composition, wt.%: Cobalt monoxide 7.50 y-alumina 3.00 Strontium oxide 0.032

The carrier of the above composition

The catalyst has an open porosity of 48-59 vol.%, A total specific surface area of 10-12 m / g, a surface of cobalt metal of 1.5-2.0 m2 / g, a heat resistance of the order of 45, heat exchange of 1200-20 ° C without breaking the granules.

Example 9. The catalyst used for endothermic steam reforming of natural gas, carried out under pressure up to 4.0 MPa and at low vapor / gas ratios in the initial reaction mixture of the order of 2.4-2.6, consists of nickel and aluminum oxides , calcium and zirconium deposited on a ceramic alumina carrier are prepared in the form of cylindrical granules of complex geometric profile (perforated cylinders with coaxial holes, the thickness of the partitions is 1-2 mm).

The support is made by high pressure extrusion (up to 30.0 MPa) from a pulp consisting of freshly precipitated aluminum hydroxide, zirconia additives, plasticizers and a burnable organic binder. When a mass is extruded through a die, it is shaped like a long cylinder with many coaxial holes inside it, which in cross section may take the form of circles, sectors, and other geometric shapes. The dried cylindrical extrudates are cut into granules using rotating diamond disk knives with a height to diameter ratio of N / A of 1.5-2.0. The carrier is calcined in a tunnel furnace at a temperature of about 1550 ° C (holding time for at least 4 hours). The water absorption rate of the finished carrier is 26-28 wt.%.

The carrier has a composition, wt.%:

Calcium oxide Magnesium oxide Barium oxide Zirconia titanium dioxide Silicon dioxide Iron trioxide Chromium oxide Manganese oxide The sum of potassium and sodium oxides a-alumina

0.510

0,027

Footprints

0,500

0.019

0.105

0,030

Footprints

Footprints

0.202 Else

The carrier is repeatedly impregnated in a salt solution containing 1000 dm3 of water:

2222.9 kg of Nickel M nitrate ((MOH) 2 bNeO,

6000.0 kg of aluminum nitrate A (OZE ENZO,

20.6 kg of calcium nitrate Ca (Gyuz) 2-4N20,

78.8 kg of zirconyl nitrate ZrOfNOa) 2H20.

The ratio of oxides in the applied part

catalyst equals NiO / y-Al203 / CaO / Zr02

0.700 / 1,000 / 0.006 / 0.042, which corresponds

the following composition, wt.%:

Nickel Monoxide 40.03

y-alumina 57.19

Calcium oxide 0.34

Zirconium dioxide 2.44

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 2,500

y-alumina 3,570

Calcium oxide 0.021

Zirconia 0.150

Conveyor carrier

The finished catalyst has an open porosity of 51-53 vol.%, The total specific surface area of 5-7 m / g the surface of metallic nickel is 1.0-1.3 m / n, the heat resistance is more than 100 heat exchangers 1200-20 ° C without destroying the granules.

Example 10. The catalyst for endothermic steam-carbon dioxide reforming of natural gas under pressure up to 3.5 MPa consists of oxides of nickel, aluminum, strontium and zirconium deposited on a porous ceramic carrier, prepared on the basis of sintered aluminum hydroxide doped with calcium oxide additives (0.28% CaO), magnesium (1.5% MdO) and manganese (0.25% MnO). The carrier is prepared by tabletting a mixture containing aluminum hydroxide, alloying additives, oxides, graphite lubricant and a burnable organic plasticizer, for example, a 10% aqueous solution of polyvinyl alcohol or an emulsion of PVA-M polyvinyl acetate. The dried carrier, in the form of Raschig rings or flat perforated cylinders, is calcined in a tunnel oven at a temperature of about 1380 ° C (8 hours exposure). The water absorption rate of the finished carrier is 18-20 wt.%.

The carrier has a composition, wt.%: Calcium oxide 0.275

Magnesium Oxide 1,500

Barium Oxide, Traces

Zirconia 0.010

Titanium dioxide

Silica 0.120

Iron trioxide 0.160

Chromium trioxide

Manganese Oxide 0.250

The sum of potassium and sodium oxides 0.268

a-alumina Else

The support is repeatedly impregnated in a salt solution containing 1000 dm3 of water: 1325.2 kg of nickel nitrate Ni (NOa) 2 6NgO, 5000.0 kg of aluminum nitrate A (MO3) 9H20, 15.8 kg of strontium nitrate Sr (NOsJ2-4H20,

39.1 kg of zirconyl nitrate 7gO (MO3) 2 2H20. This corresponds to the ratio of oxides in the supported part of the catalyst, equal to Ni / y-Al203 / SrO / Zr02 0,500 / 1,000 / 0.0085 / 0,0250 and the following composition, wt.%:

Nickel monoxide 30.80

y-Alumina 61.50

Strontium oxide 5.20

Zirconia 1.54

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 5.10

y-alumina 10.20

Strontium oxide 0.086

Zirconia 0.255

The carrier of the above composition

The finished catalyst has an open porosity of 50-53 vol. %, the total specific surface area is 8-1 Ohm / g, the surface of metallic nickel is 1.1-1.3 m / g, heat resistance is on the order of 55, heat exchange 1200-20 ° C. Example 11. The catalyst used to produce hydrogen in the process of endothermic steam reforming of natural gas under a pressure of up to 2.5 MPa consists of nickel, aluminum, magnesium and titanium oxides supported on a large-pore alumina support obtained by extrusion molding and sintering of the mass on based on technical alumina.

The carrier obtained by a method similar to that described in Example 1 has a water absorption of 22.0 wt.%.

The carrier has a composition, wt.%: Calcium oxide 2,000

Magnesium Oxide Traces

Barium Oxide .0,500

Zirconia 4,500

Titanium dioxide

Silicon dioxide 0.022

Iron trioxide

Chromium trioxide

Manganese Monoxide Traces Sum of Potassium and Sodium Oxides 0.420

cz-alumina Else

The carrier is impregnated repeatedly in a solution of salts containing 1000 dm3 of water:

1400.0 kg of nickel nitrate M MOZ1 H20.

2645.2 kg of aluminum nitrate A1 (MOz) s - ENaO,

23.48 kg of magnesium nitrate Md (MOz} 2-6N20,

0.83 kg of anhydrous titanium nitrate T1 (MOH) 2. The ratio of supported oxides in the resulting catalyst is NiO / y-ALO3 / MdOYu2-1.000 / 1,000 / 0.0103 / 0.0010, which corresponds to the composition of the supported part, May. %:

Nickel Monoxide 49.72

y-alumina 49.72

Magnesium Oxide 0.51

Titanium Dioxide 0.03.

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 8.08

y-alumina 8.08

Magnesium Oxide 0.083

Titanium dioxide 0.0081

The carrier of the above

composition of the rest

The finished catalyst has an open porosity of 48-52 vol.%, A total specific surface area of 5-7 m / g, a nickel metal surface of 0.8-1.2 m / g, a heat resistance of the order of 60 heat exchangers of 1200-20 ° C without breaking the granules.

Example 12. The catalyst used in the initial reforming of natural gaseous hydrocarbons under pressure up to 4.0 MPa and at low vapor / gas ratios in the initial reaction mixture of the order of 2.5-2.8 consists of nickel and aluminum oxides. , calcium and hafnium deposited on a porous ceramic carrier prepared on the basis of technical alumina.

The carrier is prepared by a method similar to that described in Example 1, with the difference that in the initial mass of the additive carbonates are 0.525% CaO, 1.550% MdO and 3.000% ZrOa in a calcined carrier. At a calcination temperature of the support of the order of 1300 ° C, the water absorption index is 32-34% by weight.

The carrier has a composition, wt.%:

Calcium oxide 0.525

Magnesium Oxide 1,550

Barium Oxide Traces

Zirconia 3,000

Titanium dioxide

Silicon dioxide 0.143

Iron trioxide

Manganese Monoxide Traces

The amount of potassium oxides

and sodium 0.380

a-alumina Else

The support is repeatedly impregnated in a salt solution containing per 1000 dm of water: 968.18 kg of nickel nitrate M (MO3) 2 6H20, 1045.20 kg of aluminum nitrate A1 (Sch3 ENgO, 16.77 kg of calcium nitrate Ca (MO3) a 4HaO and

0.21 kg of hafnil nitrate НГО (МОз) 2-2Н20. The ratio of the oxides supported on the carrier g is NIO / y-A120s / CaO / NYU2 1.75 / 1.00 / 0.028 / 0.0008, which corresponds to the following composition of the supported part of the catalyst, wt.%: Nickel monoxide 63.04

y-alumina 36.02

Calcium oxide 1.01

Hafnium dioxide 0.03 The composition of the obtained catalyst, wt.%:

Nickel Monoxide 10.20

y-Alumina 5.83 Calcium oxide 0.163

Hafnium dioxide 0.005

The carrier of the above composition

The finished catalyst has an open porosity of 56-58 vol.%, A total specific surface area of 9-11 m2 / g, a nickel metal surface of 2.0-2.3 m2 / g, a heat resistance of about 75 heat exchangers of 1200-20 ° C without breaking the granules.

Example 13. The catalyst used for the autothermal mine conversion of light gasoline (naphtha) under a pressure of up to 3.5 MPa consists of nickel, aluminum, barium and titanium oxides supported on a ceramic alumina carrier containing additives of calcium, magnesium and titanium oxides. The carrier is prepared by a method similar to that described in Example 2, with a water absorption rate of 27.0% by weight.

The carrier has a chemical composition, wt.%:

Calcium oxide 0.825

Magnesium Oxide 0.250

Barium Oxide Traces

Titanium dioxide

Zirconia Traces

Silica 0.121

Iron trioxide

Chromium trioxide

Manganese monoxide 0.075 The sum of potassium and sodium oxides 0.396

a-alumina. The rest. The support is repeatedly impregnated in a salt solution containing 1000 dm3 of water: 414.93 kg of nickel nitrate M (MOH) 2 6H2O, 1045.24 kg of aluminum nitrate A (MOH 9НзО.

14.38 kg of barium nitrate Ba (NaO3) 2 NgO and

13.77 kg of anhydrous titanium nitrate TlfNOsb

The ratio of supported oxides in the resulting catalyst is equal to МУ / у-А12Оз / ВаО / ТУ2 0.75 / 1.00 / 0.055 / 0.045, which corresponds to the following composition of the deposited part, wt.%:

Nickel monoxide 40.53

y-alumina 54.03

Barium oxide 3.00

Titanium dioxide 2.44

The resulting catalyst has a composition, wt.%:

Nickel Monoxide 6.67

y-Alumina 8.89

Barium Oxide 0.493

Titanium Dioxide 0.400

Media above

composition of the rest

The finished catalyst has an open porosity of 52-54 vol.%, A total specific surface area of 6-7 m / g, a nickel surface of 0.9-1.1 m / g, a heat resistance of 58 heat exchangers of 1200-20 ° C without degradation of gra

zero.

25

Example 14. The catalyst used for endothermic steam reforming of light gasoline (naphtha) under pressure up to 3.5 MPa consists of nickel, aluminum, magnesium and hafnium oxides supported on a ceramic alumina carrier.

The carrier is prepared according to the method specified in Example III, with a water absorption index of 32.0% by weight. The composition of the carrier 35 is indicated in Example IV. The carrier is repeatedly impregnated in a solution of salts containing 100.0 dm3 of water:

160.20 kg nickel nitrate Ni (N03) 2 bNaO,

550.00 kg of aluminum nitrate A1 (MOz) s-ENaO, 40

19.42 kg of magnesium nitrate Md () 2- bNzO,

5.14 kg of hafnyl nitrate NGO (MOZ) 2-2H20.

This corresponds to the ratio of supported oxides NiO / y-А12Оз / МдО / НГО2 0,550 / 1,000 / 0,0408 / 0,039 45 and the composition of the deposited part of the catalyst, wt.%:

Nickel Monoxide 33.73

y-alumina 61.33

Magnesium Oxide 2.5050

. Hafnium dioxide 2.44

After intermediate and final calcination at a temperature of 500 ° C (holding for 2 hours), the resulting catalyst has a composition, wt.%: 55

Nickel monoxide 6.00

y-alumina 10.90

Magnesium Oxide 0.45

Hafnium dioxide .0.43

0

5

0

5

0

5

0

5

0

5

The carrier of the above composition

The finished catalyst has an open porosity of about 55 vol%, a total specific surface area of about 17.5 m / g, a heat resistance of at least 40 heat exchangers of 1200-20 ° C without breaking the granules.

Example 15. The catalyst used as an input protective layer in the process of autothermal mine conversion of light liquid hydrocarbons under pressure up to 4.0 MPa, containing nickel, aluminum, calcium and zirconium oxides supported on a porous ceramic carrier based on alumina modified with oxide additives calcium, titanium and chromium. The carrier is prepared by a method similar to that described in Example 1, with the difference that 5.0 wt.% Chromium trioxide, 0.15 wt.% Calcium oxide and 0.30 wt.% Titanium dioxide are added to the mass. The resulting carrier has a water absorption of 17.0 wt.%. The carrier has a composition, wt.%: Calcium oxide 0.152

Magnesium Oxide 0.033

Barium Oxide Traces

Titanium Oxide 0.300

Silicon dioxide 0.203

Zirconia Traces

Iron trioxide 0.134

Chromium trioxide 5,000

Manganese Monoxide Traces Sum of Potassium and Sodium Oxides 0.284

a-alumina. The rest. The support is repeatedly impregnated in a solution of salts containing 1000 dm3 of water: 423.00 kg of nickel nitrate M (MOH) 2-6H20, 532.29 kg of aluminum nitrate A NaOH EN O, 10.19 kg of calcium nitrate Ca (Moh) 2 4H20, 1L 6 kg of zirconyl nitrate ZrOfNOsh 2NgO. This formulation corresponds to the following ratio of supported oxides: МУ / у-AI203 / CaO / Zr02 1,500 / 1,000 / 0,030 / 0,007, which corresponds to the composition of the supported part of the catalyst, wt.%:

Nickel Monoxide 59.12

y-Alumina 39.42 Calcium oxide 1.18

Zirconium dioxide 0.28

After intermediate calcinations at a temperature of 565 ° C, the resulting catalyst has a composition, wt.%:

Nickel Monoxide 1.20

y-Alumina 0.80 Calcium oxide 0.024

Zirconia 0.0056

The carrier of the above composition

The finished catalyst has an open porosity of 37.0 vol.%, A specific surface of about 0.5 m2 / g, a surface of metallic nickel of about 0.1 m2 / g, a heat resistance of at least 80 heat exchangers of 1200-20 ° C without breaking the granules.

Example 16. The catalyst used in the process of endothermic primary reforming of naphtha under pressure up to 4.0 MPa consists of nickel, aluminum, calcium and zirconium oxides supported on a ceramic alumina carrier modified with calcium, magnesium, barium and zirconium oxides .

The carrier is prepared according to the method described in example 1, with the difference that additional additives of calcium, magnesium, barium and zirconium oxides are added to the mass, as well as the addition of 10 wt.% 560 wood flour. After calcination at a temperature of about 1350 ° C. the carrier has a moisture absorption of 32.0 wt.% and composition, wt.%: calcium oxide 0.216

Magnesium Oxide 15,000

Barium Oxide .500

Zirconia 0.300

Titanium dioxide

Silicon dioxide 0.145

Iron trioxide 0.148

Chromium trioxide

Manganese Monoxide Traces Total potassium oxides - - and sodium 0.390

a-Alumina Remaining The carrier is twice impregnated in a salt solution containing 1000 dm3 of water:

912.85 kg of nickel nitrate Ni (NOs) 2 6H20, 1045.20 kg of aluminum aluminum nitrate A (MOH) z-9H20, 11.98 kg of calcium nitrate Ca (MOH) 2 4H20, 1.64 kg of zirconyl nitrate 2gO (MOH ) g - 2H20. This formulation corresponds to the ratio of supported oxides: NiO / y-A120s / CaO / gg02 1.650 / 1,000 / 0.020 / 0.005 and the following composition of the supported part of the catalyst, wt.%:

Nickel Monoxide 61.68

y-alumina 37.38 calcium oxide 0.75

Zirconia 0.19

After intermediate and final calcination of the catalyst at a temperature of 570 ° C, it has a composition, wt.%:

Nickel Monoxide 6.26

y-Alumina 3.79 Calcium oxide 0.076

Zirconia 0.019

Media above

0

5

0

5

0

5

0

5

0

5

composition of the rest

The finished catalyst has an open porosity of about 66 m2 / g, a specific surface area of metallic nickel of about 15 m / g, a heat resistance of at least 50 heat exchangers of 1200-20 ° C without breaking the granules.

The compositions of the proposed catalysts in examples 1-16 are presented in table. 1 and 2, and physico-chemical characteristics are given in table. 3.

In order to compare with the prototype catalyst and the foreign analogue, the Megan Conversion Reaction Test was conducted. Each 8.0 L catalyst sample was charged into a tubular reactor made of heat resistant steel. The outer diameter of the reactor is 130 mm, the wall thickness is 16 mm, and the length is 2500 mm. The tubular reactor is mounted vertically in the chamber of a gas furnace, the two side walls of which consist of 500 x 500 mm panel burners, three burners on each side. Hot flue gases from the bottom of the chamber are released into the atmosphere. The natural gas of the Urengoy field used is refined to a residual sulfur content in the vapor-gas mixture of not more than 0.5 mg / nm3.

The test was carried out under conditions of Zral conversion of natural gas at a reduced steam / gas ratio (2.9-3.1): 1, a pressure of 3 MPa, a temperature of a gas-vapor mixture at the reactor inlet, 480-510 ° С, and an outlet temperature from the catalyst bed 790-800 ° C., test duration 10 days.

During the test, the following was determined: the composition of the converted gas, the degree of conversion of equivalent methane, the pressure drop in the catalyst bed. After every 48 hours of the test, a pressure drop in the reactor was recorded. After completion of the test, the catalyst was unloaded, the degree of destruction and the content of deposited carbon (wt.%) Were determined, and the physicochemical properties of the spent catalyst were studied.

The test results are presented in tables 4 and 5.

The data presented show that the activity of the proposed catalyst is 3.0 times, heat resistance is 2 times, selectivity is 2.3 times higher than the corresponding indicators for the English catalyst brand Dycat-873.

Claims (2)

1. A catalyst for the conversion of hydrocarbons containing an supported active part, including nickel or cobalt oxides, a stabilizing promoter in the form of alumina, a promoter of carbon gasification reactions in the form of alkaline earth metal oxide To a subgroup of elements of the Periodic system, selected from the group of oxides of magnesium, calcium, strontium and barium, and a ceramic carrier based on alumina, characterized in that, in order to increase the activity of thermal stability and resistance to carbonization, the active part of the additive dioxide but contains metal IVe subgroup elements of the periodic system, selected from the group consisting of titanium dioxide, zirconium and hafnium with the following contents of these components, wt.%: Nickel oxides or cobalt38.27-75.80 Metal Oxide Pa subgroups of elements The periodic system 0.27-6.17 selected from the group: Magnesium Oxide 0.51-2.5 Calcium oxide 0.34-6.17 Strontium oxide 1.85-5.2 Barium oxide 0.27-5.2 Metal dioxide IVB subgroups of elements Periodic System 0.03-2.44 5 0 5 selected from the group: Titanium dioxide 0.03-2.44 Zirconia 0.03-2.44 Hafnium dioxide 0.03-2.44 Alumina Else with the following content of components in the catalyst, wt.% (on calcined mass): Nickel oxides or cobalt 1.2-10.2 Alumina 0.8-20 Specified Metal Oxide To subgroups of elements Periodic systems0.021-2.0 Specified Metal Dioxide IVs subgroups of elements Periodic systems 0.003-0.43 Ceramic carrier oxide based aluminum rest 2. The catalyst according to claim 1, with the fact that the specified components of the active part corresponds to the following mass ratio: nickel or cobalt oxide: alumina: metal oxide into subgroups: metal oxide IVe subgroups 0 5-3.12: 1.0: 0.006-0.100: 0.0008-0.045. Table I Tables 2 Physio-chemical property of the proposed and known catalyst Measured by The famous catalanzate Of properties catalysis-,., --..--. “.“ „„ ““ -. “.....„ .. „-........-......-... .............. „..., ..... J ... ..J..i .... l..J.J.i ... k..U-.J.L..IjJ-24JS lll L2.Ll..J.ttJjS.JjJ..Lj ... L Porosity, vol. 52-5 55-58 52-5 50-53 57-59 8-53 51-53 50-53 48-52 52-5 55 57 "83-W Obza specific surface,  d7-b & 7 8-9 6-8 15-18 5-7 14-17 10-12 5-7 8th 5-7 5-M 6-717.5 0.5 15 "-15 0.5 -3; 0 Surface k-,, TIVNY metal , 5-1.8 1,2- (5, -. T.0-IJ 2.5-3.0 1.tt, 4 2.7-3.2 t, 5-2.0 t, 0-t, 3 1.1-1.3 0.8-1.2 2.0-2.3 0.9-1.1 - Ot | i0.2 0.6 Heat-resistant. . bone, heat number, f ,,,,, -. ". shift, 1200 ° С 26 60 55 W 50 50 80 «5 100 55 (075 80 50 -28 Physico-chemical characteristics of the tested catalysts This indicator is inversely proportional to selectivity (persistence and carbonization). TablmecaE The famous catalanzate . j ... L Table Catalyst Comparison Test Results Note. The equilibrium residual content of CH). and the degree of conversion respectively equal to 1.0 vol.% and 56.3%. Table 5