Spherical high-active supported metal catalysts

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to a method for preparing spherical supported metal catalysts with metal content from 10 to 70%, to spherical metal catalyst, to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical metal catalyst, and to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical supported metal catalyst.

EFFECT: increased activity and selectivity of catalyst having high porosity and uniform pore size distribution.

13 cl, 5 tbl, 12 ex

 

The invention relates to a spherical metal catalysts on the media, to the way they are received, as well as to a method for hydrogenation of aromatic compounds.

When using the catalysts in the reactors with a fixed layer of the spherical shape of the catalyst leads to uniform distribution of the load and thereby to prevent the formation of unwanted channels.

Obtaining spherical catalysts described in the literature in sufficient detail. Numerous examples of obtaining oxide media by addition of hydrosols is protected by various decisions in US-PS 4198318 described obtaining spherical Al2O3-media by addition of acidic Hydrosol in aqueous ammonia in the presence of non-ionic surface-active environment. In DE 4035089 perform the addition with the help of a vibrating plate of the die. In the US 2001/0012816 A1 describes the addition of mixtures of solutions of the polysaccharide with gidratirovannymi Al2O3-, SiO2Al2O3-, ZrO2Al2O3or TiO2Al2O3gels or with Al2About3-In2O3Al2O3or Br2About3SiO2Al2O3-hydrates in an aqueous solution of ions of CA2+, Al3+, Mg2+BA2+or Sr2+.

Everything described so far, the methods of the addition relative to the tsya, however, only the oxide carriers. Ways in addition to obtain metal catalysts on a carrier with a metal content >10 wt.%, after the addition, the drying and possible calcination you want to restore, so far described were not.

Another method of obtaining spherical catalysts is granulation, do not provide, however, a uniform size spheres. Other disadvantages of this method are the rough surface of the spheres and the uneven distribution of pore size in the cross section of the sphere.

Next spherical catalysts can be obtained through use of spheronizer". When this pre-obtained molded workpiece is formed on the rotating plate to obtain spheres, as described in the example of the oxide carriers in WO 99/58236. In these methods, the porosity strongly depends on the forming extrudates, and the uniformity of size and shape of the spheres to the same unsatisfactory.

The present invention is to obtain a highly active metal catalysts on a carrier for hydrogenation processes, which have a uniform size and shape of the spheres, and high dispersion of metal, high porosity and uniform pore sizes.

The present invention is, in addition, how is auchenia such catalysts.

The technical problem is solved according to the invention by a method of producing a molded spherical metal catalysts on a carrier with a metal content of 10 to 70 wt.%, while dissolved or suspended in a liquid medium mixture, of at least one polysaccharide and at least one compound of iron, cobalt, Nickel, copper or zinc from the group of oxides, hydroxides, basic carbonates, bicarbonates, silicates, zirconates, aluminates, titanates, chromite or aluminosilicates metal was added dropwise into a solution of metal salt, metal ions which are mainly part of the at least one selected metal link. As a solution of metal salt used according to the invention are preferably compounds other polyvalent cations, such as Mg2+, CA2+Sr2+BA2+, Mn2+, Al3+and Cr3+. Spherical molded workpiece catalysts obtained in the solution of metal salt from the mixture, after the exposure time from 1 to 180 min is separated, is dried at a temperature of from 80 to 150°and restore at a temperature of from 150 to 600°C. Then molded workpiece catalysts preferably stabilized in a known manner.

The method according to the invention receive the spherical fo bowannie preparation of catalysts, having a uniform spherical shape. Obtained by the process according to the invention catalysts are additionally higher uniform particle size.

Compared with catalysts obtained by methods known from the prior art, the catalysts obtained by the method according to the invention have a markedly increased volume of pores with a noticeably large number of macropores larger than 50 nm. According to the invention a high proportion of macropores leads to rapid destruction of the recovery of water from the formed billet catalyst. A particular advantage of the method according to the invention is therefore also in a very high dispersion of metal recovered catalysts.

Another advantage obtained according to the invention molded blanks catalysts is high even after the restoration of mechanical strength with simultaneously high pore volume.

Due to the selection of at least one compound of iron, cobalt, Nickel, copper or zinc in the mixture and/or by the ratio of solids of this connection, at least one added polysaccharide structure is then obtained according to the invention catalysts can be specifically set. According to the invention are preferred ratio of solids (calculated on the remainder of procelian the I) 4-15, in particular, from 4.4 to 8.5. According to the invention as a polysaccharide used preferably alginate. According to the invention as the liquid medium used is preferably water.

In one preferred form of execution of the mechanical strength of the spheres is raised by at least one solid and/or liquid additive, which is added at least one compound of iron, cobalt, Nickel, copper or zinc mainly before precapitalism and which acts as a binder. According to the invention is used preferably, at least one of the following additives: Tilos, bentonite, Amity, kaolin, silica, methylcellulose, silicon Sol and water glass. According to the invention are preferred ratio of solids (based on the residue from the calcination)at least one compound of iron, cobalt, Nickel, copper or zinc, at least one additive 4-14, in particular 10-12. In one embodiment, due to the number and nature of additives can be targeted to control the pore structure obtained according to the invention catalysts.

According to the invention the mechanical strength of the obtained catalyst is determined by the nature and concentration of at least one metal ion in the metal salt solution, in particular, in the drip column.

is according to the invention for iron catalysts on the carrier preferably use solutions of iron salts, for cobalt catalysts on the media - solutions of cobalt salts, Nickel catalysts on the media - solutions of Nickel salts, copper catalysts on the media - solutions of salts of copper and zinc catalysts on the media - solutions of zinc salts. The metal salt solutions may also contain other ions of polyvalent metals, or mixtures thereof, in particular, of such metals as magnesium, calcium, strontium, barium, manganese, aluminum or chromium, such as Mg2+, CA2+, Sr2+BA2+, Mn2+, Al3+or Cr3+.

In a preferred form of execution of at least one metal salt in the above-mentioned solution is present in the form of nitrate and/or acetate of a metal. In one embodiment, this preferred form of execution of at least one metal salt is present in solution in a quantity of 0.3-0.5 wt.%, preferably 1-2 wt.%.

In another preferred form of execution of the metals iron, cobalt, Nickel, copper and/or zinc optional add at least one alloying element from the group of magnesium, calcium, manganese, molybdenum, chromium, iron and zinc in the amount of 1-5 wt.%, preferably 1-3 wt.%. In a particularly preferred form of execution of the add manganese to the alloy in amounts of 2 wt.%.

In another preferred form of execution of the spherical molded zagotovitelnaja, received upon receipt of the catalyst in a solution of metal salt, after 1-180 min separated from the solution, and then dried at a temperature of 80-150°C, after which the first calicivirus before they will be recovered at a temperature of 150-600°C.

Mostly the reaction of recovery and stabilization of the dried or calcined catalysts is carried out in accordance with the prior art, as set forth in the examples.

In this regard, another object of the present invention is a spherical metal catalyst on the carrier with the above properties, we obtain one of the methods according to the invention.

Another object of the present invention is a method of hydrogenation is predominantly substituted and/or unsubstituted aromatic compounds and/or their mixtures with liquid or gaseous form, and these aromatic compounds hydronaut using a metal catalyst on the carrier according to the invention, obtained by one of the methods according to the invention.

In connection with the present invention of the following examples perform follow other benefits and other options perform, and explain the characteristics can be used not only in the specified combinations, but also in other combinations or by themselves.

Example 1 (according to the image the structure)

0.6 l of water is poured into a vessel with a stirrer, and then add 9 g of sodium alginate. After complete dissolution of the alginate with stirring add in 5.7 g of silicon dioxide in the form of a solution of sodium silicate in a concentration of 190 g of SiO2to 1 liter of solution. The resulting solution was continued to stir for 5 min and then the solution is injected 200 g obtained from a conventional deposition compound of Nickel and silicon dioxide with the remainder of the ignition (2 h at 800° (C) in an amount of 20 wt.% (corresponds to 40 g of the solid in the calculation of the residue from the calcination).

The ratio of compounds of the metal (calculated on the remainder of the ignition) and used alginate (solid) in the mixture is 4.4, and the ratio of metal joining and additives 7.

For a fluid suspension of the mixture (Slurry) homogenized using ultraturrax for 5 min (500 rpm), then continuously pumped into provided with slotted holes (3 mm diameter) ceramic drip head (volume 300 ml) and out perform the addition.

The addition of the solution occurs in the liquid column, containing an aqueous solution of Nickel nitrate (1% Nickel). The distance between the drip head and the liquid surface is about 10 cm, and the total solution volume of 1.5 L. Immediately after immersion of the droplets in a solution of Nickel is of heliobar the Finance. Uniformly molded spherical particles (beads) are deposited on the bottom of the tank. After complete addition the resulting material for another 30 min left in the solution for full cure.

Then the solution is decanted and molded catalyst particles are washed with about 5 liters of pure condensate.

Directly after this is dried molded billets at 130°C for 15 hours After drying the spherical catalyst material has a very uniform shape and size.

The dried catalyst calicivirus then in a suitable integral reactor in a stream of nitrogen at a temperature of approximately 350°and after conversion to hydrogen (gas load about 2000 rpm/about·h) recover for 6 h at a temperature of 400°C.

Stabilization of pyrophoric catalyst is then using an air-nitrogen mixture (starting with concentrations Of2from 0.1 to 2 vol.%).

Obtained according to the invention, the catalyst contains 58% Nickel and has a degree of recovery of 75%. Metal Nickel (determined by chemisorption) is 50 m21 g of the catalyst, the average crystallite size of the Nickel 3 nm, and the apparent density of 0.5 kg/liter

The catalyst according to the invention has, in addition, high uniformity of distribution of particle size: the average diameter is R is 2,15 mm All of the catalyst particles have a diameter of from 2.0 to 2.3 mm

Table 2 shows the mechanical and physico-chemical characteristics obtained according to the invention catalyst. It is seen that the catalyst differs extremely high volume of pores with high strength molded blanks catalyst.

Example 2 (according to the invention)

0.6 l of water while stirring dissolve 6 g of sodium alginate, and then add 3.5 g of silicon oxide in the form of silicon Sol solution at a concentration of 498 g of SiO2to 1 liter of solution. After about 5 minutes give 60 g of spray dried powder of the intermediate product of the catalyst residue on ignition (2 h at 800° (C) 75% (corresponding to 45 g of solid substance in the calculation of the residue from the calcination), which is known for the image obtained by co-deposition of Nickel, aluminium oxide and silicon dioxide with NaOH.

Used powder has a density of about 0.3 kg/l and the average particle size of about 8 microns.

The ratio of compounds of the metal (calculated on the remainder of the ignition) and used alginate (solid) in a mixture of 7.5, and the ratio of metal joining and additives 13.

After homogenization of the suspension by ultraturrax suspension as in example 1, pin in an aqueous solution of Nickel acetate (5% Nickel). ricepaddy material is left for 15 min in a solution of Nickel acetate.

After separation of the solution molded preform the catalyst is dried, and then without calcination restore in a stream of hydrogen at a temperature of 380°C.

Stabilization of pyrophoric catalyst is a mixture of nitrogen, air and carbon dioxide in a known manner. The content of CO2in the gas mixture is 1%vol.

Obtained according to the invention, the catalyst contains 55% Nickel and has a degree of recovery of 60%. Metal Nickel (determined by chemisorption) is 33 m21 g of the catalyst, the average crystallite size of the Nickel of 2.1 nm, and apparent density of 0.5 kg/liter

The resulting catalyst has, in addition, the high uniformity of the distribution of particle sizes with an average diameter of 2.6 mm, All of the catalyst particles have the diameter from 2.4 to 2.8 mm

The results of the mechanical and physico-chemical characteristics of the catalyst 2 according to the invention are also given in table 2. It is seen that the catalyst also has a very high volume of pores with good strength molded blanks.

Example 3 (according to the invention)

0.6 l of water while stirring dissolve 12 g of sodium alginate, and then add a mechanical mixture consisting of 80 g obtained in the usual manner powdered, dried and calcined Nickel-oxidal miniimage precipitated catalyst and 8 g of boehmite (Versal 250 by UOP, the residue from the calcination 74,7%, which corresponds to 6 g of solid substance in the calculation of the residue from the calcination). Oxide source material of the catalyst has an apparent density of 0.8 kg/l and an average particle size of 10 microns.

The ratio of compounds of the metal (calculated on the remainder of the ignition) and used alginate (solid) in the mixture is 6, and the ratio of metal joining and additives 12.

Pricipiaalu suspension of catalyst was prepared according to example 1. The addition of the solution is carried out in a 3%solution of Nickel nitrate. Priyanie catalyst particles are uniform in shape and size.

After drying and calcination taken of the material of the catalyst is carried out restoration at 420°in a stream of hydrogen. Stabilization of spherical particles of catalyst are described in example 1 conditions.

Obtained according to the invention, the catalyst contains 65% Nickel and has a degree of recovery of 70%. Metal Nickel (determined by chemisorption) is 28 m21 g of the catalyst, the crystallite size of the Nickel is 3.7 nm, and apparent density of 0.75 kg/l

The resulting catalyst has, in addition, the high uniformity of the distribution of particle sizes. The average particle size is 2 mm, All of the catalyst particles have a diameter of from 1.9 to 2.2 mm

Results m the mechanical and physico-chemical characteristics of the catalyst 3 according to the invention are listed in table 3.

Example 4 (according to the invention)

0.6 l of water while stirring dissolve 9 g of sodium alginate, and then add 8 g of conventional silica gel with the residue from the calcination 90%. After this exercise dosage 80 g powdered, dried and calcined cobalt-manganese-oxydiethanol precipitated catalyst residue from the calcination about 95%, which corresponds to a 76.5 g of solid substance in the calculation of the residue from the calcination. Powdery source material has a particle size less than 63 μm, and the density is 0.8 kg/liter

The ratio of compounds of the metal (calculated on the remainder of the ignition) and used alginate (solid) is 8.5. The ratio of metal joining and additives is 10.6.

Pricipiaalu suspension of catalyst was prepared according to example 1. The addition of a suspension of the catalyst is carried out in a 1.5%solution of calcium nitrate. Priyanie particles are uniform and round shape.

After drying and calcining the resulting catalyst material has a binder content of 30% and a manganese content of 2%.

The catalyst according to the invention prior to evaluation of its catalytic suitability for the hydrogenation of substituted aromatic compounds to restore at a temperature of 400°and stabilized in a known manner.

With a small spread and particle size material has an average particle size of 2.1 mm All of the catalyst particles have the diameter from 1.8 to 2.2 mm

Example 5 (according to the invention)

In 0.3 l of an aqueous solution of sodium silicate with the content of SiO261 g per 1 l of solution, which corresponds to 18.3 g of SiO2under stirring add 100 g of dried spray copper-dioxidine precipitated catalyst residue from the calcination of 73.5% (equivalent of 73.5 g of solid substance in the calculation of the residue from the calcination). Then add 300 g of 2%aqueous solution of sodium alginate, which corresponds to 6 g of alginate.

The ratio of compounds of the metal (calculated on the remainder of the ignition) and used alginate (solid) in the mixture is 12,25, and the ratio of metal joining and additives 4.

After homogenization of the suspension, it is heated with stirring to 60°and process for about 15 min at this temperature. After cooling, a homogeneous suspension and subsequent processing ultraturrax carry out the addition in 3%solution of nitrate of copper. After the addition of the spherical catalyst particles leave in the solution of nitrate of copper for another 10 minutes

After separation of the solution of nitrate of copper and washing of the material obtained catalyst are drying and calcining.

The resulting catalyst has an average particle size of 2 mm and different uniform size is ω and form.

After calcination the catalyst to restore the flow of nitrogen and hydrogen (2% H2) at a temperature of 200°and then stabilize in accordance with example 1.

The finished catalyst contains 65% copper and has a degree of recovery of 70%. The average size of copper primary particles is 8.7 nm.

The catalyst according to the invention has, in addition, a good uniformity of distribution of particle sizes. All of the catalyst particles have a diameter of 1.8-2.1 mm, the average particle diameter is 1.9 mm, and the apparent density of 0.4 kg/liter

Example 6 (comparative catalyst)

Dried and powdered Nickel-oxydrene source material with an average particle size of 10 μm and an apparent density of 0.7 kg/l mixed with telazol as a binder, and then peptizing in a laboratory mixer with the addition of the condensation water, nitric acid and silicon Sol solution. Additive tyloz is 2.5% (based on solids content of the mixture. After the mixing time of 15 min the entire mixture is molded in a laboratory extrusion press with a cutting device in the wiring size 3 mm

The obtained wet extrudates processed in the laboratory spheronizer (firm "Kalev", model 120, England) in the sphere. The obtained spherical material is dried subsequently at 130°and he is listed in the who L.1 particle size.

Table 1
Particle sizewt.%
>5-
4-50,1
3-410,7
2,5-3,039,9
2,0-2,525,8
1,6-2,016,1
1,0-1,67,4
<1,0-

In addition to a very wide range of sizes of the catalyst particles have different and somewhat irregular spherical shape.

The material obtained catalyst restore then at 400°in the stream of hydrogen and stabilize under standard conditions known manner.

The obtained comparative catalyst contains 55% Nickel and has a degree of recovery of 75%. Metal Nickel (determined by chemisorption) is 30 m21 g of the catalyst, the average crystallite size of Nickel and 4.5 nm, and the apparent density of 0.8 kg/liter

The catalyst has a wide distribution of particle sizes with diameters of 2-4 mm

Other indicators of physico-chemical characteristics of the comparative catalyst are given in table 2. It is seen that comparative catalyst has a significantly smaller volume of pores with a significantly lower macropores you the e 5 nm compared with catalysts, obtained according to the invention.

Example 7 (comparative catalyst)

The dried and calcined in accordance with example 4 cobalt-manganese-diocletianus source material of the catalyst is formed with the addition of graphite in tablet size 3×3 mm, Followed by molding the material of the catalyst is restored and stabilized as described in example 4.

The finished catalyst has an apparent density of 1.2 kg/l and the limit of compressive strength of 35 MPa.

The results of physico-chemical characteristics of the comparative catalyst are given in table 2.

Example 8 (comparative catalyst)

Used in example 5 copper-dioxidine source material of the catalyst calicivirus at 350°With, then peptizer in a suitable mixing unit with the addition of tylose, condensation of water and nitric acid, and then formed into extrudates (Trilobe-Extrudat) size 1.6 mm three-petal-shaped cross-section. After drying and calcination of the molded workpieces is carried out restoration and stabilization of the starting material described in example 5 conditions.

The finished catalyst contains 70% copper and has a degree of recovery of 75%. Apparent density of 0.85 kg/l, and the crystallite size of copper of 9.2 nm.

Example 9 (comparative catalyst)

To evaluate the catalytic suitability attractive gloss of leat the cabins also standard spherical Nickel-alumina catalyst having the following physical-chemical features:

The Nickel content (wt.%)55
The degree of recovery Nickel (%)60
Apparent density (kg/l)0,95
Average particle diameter (mm)2,5
The range of particle diameters (nm)1,6-4,7
The crystallite size of the Nickel (nm)5,1

In addition to the very wide distribution of particle sizes, this catalyst has a very inhomogeneous spherical shape. Thus, in addition to spherical particles of different sizes, it also contains the extrudates and pieces of extrudates.

td align="center"> 0,29
Table 2

Physico-chemical and mechanical properties obtained according to the invention and comparative catalysts
CatalystApparent density (kg/l)Wear resistance* (%)Total pore volume (cm3)Pore volume >50 nm (cm3/g)
1 (Fig.)0,50,80,840,52
2 (Fig.)0,41,00,950,64
3 (Fig.)0,750,70,60
4 (Fig.)0,50,30,450,29
5 (Fig.)0,41,20,820,58
6 (compare.)0,80,550,300,02
7 (compare.)1,20,50,270,14
8 (compare.)0,851,20,300,07
9 (compare.)0,950,80,350,04
* Standard test abrasion resistance (roller test, 25 g of the catalyst, 40 rpm, 30 min).

Example 10 (hydrogenation of aromatic compounds Nickel catalysts on the media)

For the catalytic properties of Nickel catalysts on the media in examples 1-3 as compared with the comparative catalysts in examples 6-9 apply hydrogenation of kerosene in the stationary layer by an integral flow reactor (inner diameter 25 mm).

Placed the amount of the catalyst is 50 ml 50 ml volume of catalyst placed on 10 servings 10 servings of SiC in a volume ratio of 1:1.

Before the catalytic reaction catalysts reactivit in a stream of hydrogen (50 l/h) during the 4 h at 250° C. as a seed used kerosene to the aromatic content of 18 wt.% and a sulfur content of 1.1 ppm reaction Conditions as follows:

The pressure of the reaction30 bar
The reaction temperature85°100°
The reaction time40 h80 h
LHSV1.3 ml/ml·h
The volumetric ratio of the gas/product H2/kerosene400:1

The results are shown in table 3.

Table 3
CatalystThe reaction temperature 85°The reaction temperature 100°
The proportion of aromatic compounds in the reaction product (ppm)The proportion of aromatic compounds in the reaction product (ppm)
1 (Fig.)1600150
2 (Fig.)1750160
3 (Fig.)1550152
6 (compare.)2640259
9 (compare.)3105298

The comparison of the results of ka is eliticism hydrogenation shows the advantage of the catalysts according to the invention: the degree of hydrogenation or decomposition of aromatic compounds in the presence of catalysts according to the invention is considerably higher than conventional catalysts.

Example 11 (hydrogenation of aromatic compounds cobalt-manganese catalysts on the media)

Cobalt-manganese-diocletianus catalyst (example 4) is subjected to catalytic testing in the hydrogenation of isocamphylcation to sandulovich alcohols. As a comparative catalyst was tested granular catalyst (example 7) of the same composition.

The catalytic test is carried out in a fixed bed by means of integral flow reactor (inner diameter 25 mm). Use amount of the catalyst 50 ml 50 ml volume of catalyst placed on 10 servings 10 servings of SiC in a volume ratio of 1:1.

Before the catalytic reaction catalysts reactivit in a stream of hydrogen (50 l/h) for 3 h at 300°C. diluted using a mixture of isocamphylcation and cyclohexanol (1:1). Other reaction conditions are the following:

The pressure of the reaction70 bar
The reaction temperature220°
The reaction time50 h
LHSV (itemfilename)0.5 ml/ml·h
The volumetric ratio of the gas/product H2/itemfilename4000:1

The results rolled the practical measurements are shown in table 4.

Table 4
CatalystThe shape of the catalyst

The pore
The output of sandalwood alcohol (%)The release of hydrocarbons (%)
4 (Fig.)Scope 2.1 mm82,17,9
7 (compare.)Tablet 3 mm68,910,8

The results show that the catalyst according to the invention with the same chemical composition has a higher activity and higher selectivity than gluteoplasty catalyst.

Example 12 (hydrogenation of aromatic compounds copper catalysts on the media)

Using the same reactor system as in example 11, catalytic characterization of copper-dioxidine catalyst (example 5) obtained when the hydrogenation of acetophenone. As a comparative catalyst is the catalyst of example 8. Diluted using a mixture of 70 wt.% of acetophenone and 30 wt.% methylphenylcarbinol. Other reaction conditions are the following:

The pressure of the reaction20 bar
The reaction temperature80°
The reaction time40 h
LHSV0.5 ml/ml·4
The volumetric ratio of the gas/product H2/seed250:1

The catalytic results of the measurements are shown in table 5.

Table 5
CatalystThe shape of the catalystThe output of methylphenylcarbinol (%)
5 (Fig.)Sphere76,4
8 (compare.)The extrudate three-petal-shaped cross-section66,9

The results show that the catalyst according to the invention with the same chemical composition has a higher activity than the comparative catalyst.

1. A method of obtaining a molded spherical metal catalysts on a carrier with a metal content of 10 to 70 wt.%, in which

is dissolved in a liquid medium, a mixture of alginate and at least one compound of a metal selected from the group consisting of

a) metal oxides;

b) silicates of metals;

in) aluminates of metals;

g) metal titanates;

d) metal aluminosilicate;

such as iron, cobalt, Nickel, copper or zinc, suspended in a specified environment pin in the metal salt solution consisting, for less than the least one multivalent metal ion selected from the group consisting of Ni2+, Cu2+, Mg2+, CA2+, Sr2+, Ba2+, Mn2+, Al3+and Cr3+;

obtained as a solution of a metal salt of a spherical catalyst particles after a time keeping from 1 to 180 min separated from him;

- dried at a temperature of from 80 to 150°C;

- restore at a temperature of from 150 to 600°C.

2. The method according to claim 1, and a solution of metal salt is at least one metal ion, at least one selected metal link.

3. The method according to claims 1 and 2, and the concentration of metal ions is 0.3-5 wt.%, preferably 1-2 wt.%.

4. The method according to one of claims 1 and 2, and the metal salt solution contains as anions nitrate and/or acetate.

5. The method according to claim 1, and the mixture is injected, at least one additive acting as a binder.

6. The method according to claim 5, and an additive selected from the group consisting of tylose, bentonite, boehmite, kaolin, silica gel, silicon Sol, methyl cellulose and liquid glass.

7. The method according to claim 5 or 6, and the ratio of solids present in the mixture at least one compound of a metal and at least one additive is 4-15 in the calculation of the remainder of the ignition.

8. The method according to claim 7, where the value t is erdich substances, present in the mixture at least one compound of a metal and at least one polysaccharide is 4-15 in the calculation of the remainder of the ignition.

9. The method according to claim 1, and to the mixture is added 0.1 to 5 wt.% one or more alloying elements.

10. The method according to claim 9, and alloying elements are Mg, CA, Mn, Mo, Cr, Fe or Zn.

11. The method according to claim 1, and the obtained spherical catalyst after drying and before restoring calcined at a temperature of 150-600°C.

12. Spherical metal catalyst on a carrier with a metal content of 10 to 70 wt.%, obtained by the method according to one of claims 1 to 11.

13. The method of hydrogenation of aromatic compounds in which aromatic compounds hydronaut using spherical metal catalyst on the carrier with a metal content of 10 to 70 wt.%, obtained by the method according to one of claims 1 to 11.



 

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6 cl, 2 ex

FIELD: waste water treatment.

SUBSTANCE: method comprising deposition of active components onto polymer carrier followed by washing with modifying solution and drying of resulting catalyst is characterized by that above-mentioned polymer carrier is a super-crosslinked polystyrene preliminarily washed with acetone and dried, deposition of active components onto polymer carrier is accomplished by impregnating it for 8-10 min with complex solution of platinum group metal chloride and/or gold-hydrochloric acid sodium salt in concentration 0.57-64.5 g/L in complex organo-alcohol-water solvent containing, in particular, tetrahydrofurane, methanol, and water, whereupon catalyst id dried to constant weight and then optionally washed with modifying solution of sodium carbonate, 2.76-136.74 g/L, and with distilled water to neutral pH = 6.8-7.2. Catalyst allows deep oxidation of phenol compounds at high degree of conversion.

EFFECT: enhanced phenol oxidation activity of catalyst, simplified catalyst preparation technology needing utilization of lesser amounts of expensive chemicals.

3 cl, 3 tbl, 18 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention concerns preparation of heterogeneous phthalocyanine catalyst for use in liquid-phase oxidation of sulfur-containing compounds and provides a method, which involves preparing nonwoven polypropylene carrier by treating it with boiling alkaline solution of sodium peroxycarbonate, 3.2-4.6 g/L, at pH 9-10 followed by treatment cobalt phthalocyanine-disulfonate, 3.2-4.6 g/L, and final treatment, which consists in washing preliminarily treated carrier with sodium hydroxide solution in concentration 0.1-0.5 g/L.

EFFECT: increased catalytic activity up to 92% and simplified catalyst preparation procedure.

2 cl, 1 tbl, 5 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep hydrofining of hydrocarbon feedstock, in particular diesel fractions, to remove sulfur compounds. Invention, in particular, provides catalyst for hydrodesulfurization of diesel fractions including active component selected from group VIII and VIB metal oxides dispersed on alumina carrier, which is, in particular, composed of aluminum oxides, 85-95%, and H form or cation-substituted form of zeolite ZSM-5, mordenite, zeolite BEA, or zeolite Y, 5-15%. Active component is selected from oxides of molybdenum and cobalt and/or nickel. Carrier preparation method comprises precipitation of aluminum hydroxide, incorporation of zeolite in H form or cation-substituted form in amount 5-15% (based on final product) and peptizing agent into aluminum hydroxide powder, extrusion of resulting mixture, drying, and calcination at 450-600°C. Preparation of catalyst includes impregnation of above-defined carrier with complex solution of group VIII and VI metal salts in air or nitrogen flow at temperature not higher than 200°C. Diesel fraction hydrodesulfurization process is also described.

EFFECT: enhanced purification of diesel fractions.

10 cl, 2 tbl, 14 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to a method of preparing ethylene oxide production catalyst containing silver deposited on alumina carrier originally having sodium and silicate ions on its surface. Carrier is preliminarily treated with aqueous solution of lithium salt at temperature below 100°C, after which at least 25% sodium ions are removed and replaced with up to 10 mln-1 lithium ions. Carrier is dried and then silver and promoters are precipitated on the pretreated and dried carrier.

EFFECT: achieved stability of catalyst.

7 cl, 11 tbl, 17 ex

FIELD: synthesis gas reaction catalysts.

SUBSTANCE: invention relates to catalyst for producing hydrocarbon from synthesis gas, which is suitable for hydrogenating carbon monoxide and obtaining hydrocarbon from carbon monoxide. Catalyst is composed of carrier, on which metal compound is deposited, catalyst containing impurities within a range from 0.02 to 0.15 wt %. Preparation of catalyst comprises preliminarily treating catalyst support to reduce concentration of impurities followed by depositing metal on support. Catalytic production of hydrocarbon from synthesis gas is also described.

EFFECT: increased activity, strength, and abrasion resistance of catalyst.

59 cl, 1 dwg, 1 tbl, 7 ex

FIELD: gas treatment.

SUBSTANCE: invention relates to novel catalysts, which can be, in particular, used in automobile engine exhaust treatment, in processes of deep oxidation of toxic organic impurities in industrial emission gases, and in other applications. Adsorption-catalytic system, including granules of sorbent capable of sorbing at least one of reagents and catalyst, represents geometrically structured system wherein catalyst is made in the form of microfibers 5-20 μm in diameter, sorbent granules are disposed inside catalyst, and size ratio of sorbent granules to catalyst microfibers is at least 10:1. Catalyst microfibers are structured in the form of woven, knitted, or pressed material. Gas treatment process involving use of such system is based on that gaseous reaction mixture to be treated is passed through above-defined system while periodically varying temperature of mixture, in particular raising it, to accomplish or regeneration of sorbent.

EFFECT: enhanced process simplicity and reliability (simple process government system, absence of mechanical stream switching devices, reduced power consumption, and enabled continuous gas treatment.

2 cl, 2 ex

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