Cobalt-based catalyst and utilization thereof in fischer-tropsch process

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

 

This invention relates to a catalyst based on cobalt, receiving and use in the Fischer-Tropsch process.

the Fischer-Tropsch process is well known and essentially consists in the hydrogenation of CO to obtain hydrocarbons. Reaction conditions are also described in the literature.

Catalysts that can be used in the Fischer-Tropsch process, usually consist of metals of group VIII supported on a carrier, preferably selected from aluminum oxide, silicon dioxide, titanium oxide and mixtures thereof.

Currently, research projects on the Fischer-Tropsch process is increasingly oriented towards improving the selectivity to hydrocarbons With9+in particular, C22+also known as paraffins Fischer-Tropsch process.

Among the catalysts for Fischer-Tropsch increasingly using cobalt, which is particularly effective in the direction of the reaction towards formation of paraffins.

Was found specific catalyst based on cobalt supported on alumina, which compared to conventional cobalt catalysts are more selective in part of primary education paraffins in the Fischer-Tropsch process.

Accordingly, this invention relates to a catalyst which can be used in the Fischer-Tropsch process and which essentially soteitis of cobalt oxide, deposited on an inert carrier essentially consisting of aluminium oxide, characterized in that the cobalt oxide is essentially composed of crystals having average size in the range from 20 to 80 And preferably from 25 to 60 And even more preferably from 30 to 40 A.

These crystals of cobalt oxide may be partially doped with Al atoms.

The special feature of this catalyst compared with the known catalysts lies in the fact that it consists of crystals is much smaller, namely 20-80 And the proposed catalyst compared with 120-180 And the catalyst obtained according to traditional methods. This allows you to achieve the best dispersion of cobalt on the media, and consequently, a better contact between the catalyst and reactants in the reaction phase.

In addition to the cobalt oxide catalyst according to the present invention may also contain metals, commonly known as promoters, such as Si, Zr, TA, Zn, Sn, Mn, Ba, Ca, La, Ve, W, is much smaller than the cobalt, quantities. Promoters are used to improve the structural stability of the media itself.

One or more promoter activity with different impact on the characteristics of the catalyst, as described in the literature (see, for example, .Jager, R.Espinoza, "Catalysis Today", 23, 1995, 21-22), perhaps also with otstavat together with cobalt. For example, such promoters as K, Na, Mg, Sr, Cu, Mo, TA, W, and metals of group VIII significantly increase the activity. Ru, Zr, rare earth oxides (RO), Ti increase the selectivity to hydrocarbons with high molecular weight. EN, RO, Re, Hf, CE, U, Th promote regeneration of cobalt catalyst.

As aluminum oxide, it may be in any crystalline phase of this, gamma, Delta, theta, alpha and mixtures thereof in the presence or without one or more promoters structural stability, selected from among the above. In a preferred embodiment of the invention, the aluminum oxide may be in the form γ, or δor mixtures thereof.

The surface area alumina such, which usually have a catalytic media, i.e. from 20 to 300 m2/g, preferably from 50 to 200 m2/g (BET), while the average size of the aluminum oxide are in the range from 1 to 300 μm

The content of cobalt in the catalyst of the present invention is in the range from 2 to 50 wt. -%, preferably from 5 to 20 wt. -%, 100% take the total weight of the carrier and cobalt (plus, possibly, promoters). If the promoters are present, their number does not exceed 20% of the mass. with respect to cobalt, preferably 10% of the mass.

Before use in the process of Fischer-Tropsch catalyst by nastasemarian need to activate any of the usual methods, for example, the recovery of cobalt oxide to cobalt metal in the presence of hydrogen.

Accordingly this invention relates to a process for the preparation of cobalt oxide deposited on an inert carrier essentially consisting of aluminium oxide, where the specified cobalt oxide essentially consists of crystals with an average size in the range from 20 to 80 A, and the method includes the following operations:

1) preparation of intermediate compounds deposited on the aluminum oxide and having the following General formula (I):

[With2+1-xAl+3x(OH)2]x+[Andnx/n]·mH2O (I)

where x is in the range from 0.2 to 0.4, preferably from 0.25 to 0.35; And anion; x/n is the number of anions required to neutralize the positive charge; m is in the range from 0 to 6; and preferably equal to 4;

2) annealing the intermediate compounds of General formula (I) with the formation of crystalline oxide of cobalt.

As for the anion Andnit can be independently selected from the group comprising inorganic anions (e.g., F-, Cl-, Br-I-, ClO4-, NO3-HE-IO3-, COC2-, SO42-WO42-), anions heteropolyacids (for example, Po 12O403-, PW12O403-), anions of organic acids (such as adipic, oxalic, succinic, malonic). In a preferred embodiment of the invention the anion Andnchoose from the NO3-HE-, COC2-. In the preferred embodiment, Andn-1is a CO32-.

Connection with General formula (I) can be produced by various methods known to experts in this field.

For example, you can use the so-called method of deposition, in accordance with which the Co2+and Al3+precipitated together on the aluminum oxide in the form of hydroxides. In accordance with this method the solution of an aluminum salt and a cobalt salt, preferably an aqueous solution of these salts, are added dropwise to the suspension, preferably aqueous, of aluminum oxide. This operation should be carried out, maintaining a pH range between 6.6 to 7.2, preferably from 6.8 to 7.1, for example, using an aqueous solution of bicarbonate or soda. Alternatively, you can add two separate solution, however, it is obvious that for the sake of simplicity it is better to use a single solution of the two salts. Connection with General formula (I) is recovered by filtration.

In accordance with another, less preferred, embodiment assests the tion of the invention, you can use the so-called hydrothermal method, which consists in processing svezheosazhdennoi hydroxides of cobalt and aluminum, or of mechanical mixture of the oxides with water.

Connection with General formula (I) may be amorphous or crystalline. The ratio between the amorphous portion and the crystalline part can be modified using known techniques (e.g., annealing). The crystalline part of the compounds with the General formula (I) has a structure similar to the structure of hydrotalcite.

Hydrotalcite is a naturally occurring mineral; it consists of hydroxycarbonate Al and Mg. Like hydrotalcite system has a similar structure, but contains other elements.

Group hydrotalcite can be represented by the following formula:

[M2+1-xM3+x(OH)2]x+[Andnx/n]·mH2O,

in the case of this hydrotalcite M2+=Mg2+M3+=Al3+andn=CO32-.

One of the main characteristics of this group of compounds is a layered structure: layers of type brucite, Mg(OH)2or [M2+1-xM+3x(OH)2]x+in which part of the divalent ions of M2+replaced by trivalent ions M3+alternate with anionic layers associated with different if what estom water [A nx/n]·mH2O. Anionic layers counterbalance the positive charge of the hydroxide layers, the latter is associated with the presence of trivalent ions.

In the General case of M2+and M+3can be ions of different nature, the only requirement for them is that they were able to fit in the cavities left by hydroxyl groups in a compact structure type brucite (in other words, their ionic radius should be close to the ionic radius of Mg2+). The value of x in the structural formula is in the range from 0.2 to 0.4, preferably from 0.25 to 0.35. Outside this interval, you can obtain a pure hydroxides or other compounds with different structures. For structures hydrotalcite type is characterized by the following ratio: M2+/M+3=2 and M2+/M+3=2, which limit the composition and does not lead to a change in lattice parameters and structure (just change the internal distribution of cations in the layer brucite). More detailed information about the connection type hydrotalcite can be found in the review "Hydrotalcite-type anionic clays: preparation, properties and applications (Catalysis Today, 11(1991) 173-301).

After the connection with the General formula (I) received and selected, preferably before the operation (2) to expose the connection of the drying operation to reduce the amount of absorbed water (or solvent).

About erace (2) is in the ignition connection with General formula (I) at a temperature in the range from 300 to 500° C, preferably from 350 to 450°C.

As already mentioned, before use in the Fischer-Tropsch process, the catalyst is subjected to recovery. In a preferred embodiment of the invention this operation is performed by treatment with hydrogen, possibly diluted with inert gases, for example nitrogen. The recovery operation is preferably performed at a temperature in the range from 300 to 500°S, more preferably from 320 to 450°C. to Perform a recovery as possible at high and at atmospheric pressure, the latter conditions are preferred. The duration of the recovery process depends on the experimental conditions (temperature, pressure, dilution or dilution of hydrogen).

The next task of the present invention relates to a method for producing predominantly of hydrocarbons22+or the so-called waxes, Fischer-Tropsch, characterized in that it is carried out in the presence of the catalyst described in claim 1 of the claims.

the Fischer-Tropsch process is well known reaction between CO and H2possibly diluted CO2and/or N2with obtaining mainly of hydrocarbons With22+.

Reaction conditions described in literature. For example, the temperature may be in the range from 170 to 400°C, preferably from 180 to 250°C,while the pressure may vary from 1 to 100 bar (0.1 to 10 MPa), preferably from 15 to 40 bar (1.5 to 4 MPa). The ratio of CO/H2may vary from 0.5/1 to 4/1, preferably from 1.87/1 to 2.5/1, preferably stoichiometric value (plus or minus 3%).

The catalyst according to the present invention can be applied either in the reactor with a fixed bed or in suspension reactor type.

Below are examples for a better understanding of this invention.

EXAMPLES

The examples fall into two catalysts based on cobalt, called a (catalyst comparison) and B. For both the media is γ-δ alumina Condea Scca 5-170. Morphological characteristics of the carrier are shown in table 1.

Table 1
The carrier - aluminum oxide (Al2About3)
Crystalline phase60% γ-40% δ
Surface area (m2/g)162
Specific volume of pores (cm3/g)0,46
Granulometric composition50%<82 A (dp)

Obtaining the CATALYST of COMPARISON AND

The catalyst was obtained by the method of initial wetting. 100 g γ-δ alumina Condea Scca 5-170 infused 100 cm3an aqueous solution of Co(NOsub> 3)2·6N2O (0.3 mol). Prochitannij media were left to dry in an oven at 80°C for 16 hours and then subjected to calcination in muffle the air flow in accordance with the following regime:

from 25 to 350° (10°C/min)

- isothermal conditions at 350°With (30 min)

from 350 to 400° (5°C/min)

- isothermal conditions at 400° (240 min)

from 400 to 25° (10°C/min).

The dried catalyst was examined by x-ray analysis (XRD).

The calcined catalyst was investigated by elemental analysis, x-ray analysis and x-ray photoelectron spectroscopy, XPS (XPS).

The STUDY of the DRIED SAMPLE AND

The dried sample was subjected to x-ray analysis. Spectrum testified to the presence of large crystals of hexavalent cobalt nitrate used during impregnation as a cobalt precursor, and the presence of carrier - γ-δ-phase alumina Condea Scca 5-170.

The STUDY CALCINED SAMPLE AND

The calcined sample was subjected to elemental analysis to determine the actual content of cobalt, entered at the time the sample is received. The content of cobalt corresponded exactly to 14.2% of the mass.

The sample was also subjected to x-ray the analysis, and spectrum testified to the presence, in addition to γ-δ-carrier phase, phase spinel, which can be attributed to the particles of Co(Co2-x, Alx)O4.

The percentage of aluminum was determined on the basis of structural analysis of the spectrum. This value refers to the percentage of cationic lattice sites in a pure phase spinel oxide of cobalt (Co3O4)occupied by ions of aluminum, and reflects the interaction between the precursor oxide and the media. Table 2 shows the data obtained from x-ray spectrum, related to the mass % of a spinel phase, the mass % of Al ions present in the spinel phase and the crystallite size; the latter was determined by the method of Scherer (Scherrer).

Table 2

X-ray analysis of the catalyst A.
Phase spinel, %Ions Al,%The crystal size (A)
20,37,2135

Finally, the calcined catalyst And subjected to x-ray photoelectron spectroscopy. This spectroscopic technique can give information about the composition and morphology of the system in the surface layers of the sample.

Table 3 shows the results of x-ray photoelectron spectroscopy.

Table 3

X-ray photoelectron spectroscopy of catalyst A.
AS With 2P3/2(eV)ΔF (2p1/2-2P3/2) (eV)With 2P / Al 2s
78015,10,15
AS - bond energy

The first two columns in table 3 indicate the presence of Co3O4on the surface of the catalyst, the composition of which has already been determined by x-ray analysis; the third column shows the ratio between the intensity of the XPS signal related to the cobalt 2P, and the intensity of the signal related to aluminum 2s media, and gives important information on the distribution of cobalt precursor on the media. The higher value of this ratio, the more uniform will be distributed containing cobalt phase on the surface of the carrier. In the case of the catalyst And the value of 0.15, which means that the cobalt oxide unevenly distributed on the surface of the carrier, but leads to the conclusion about the presence of Islands of cobalt, randomly distributed over the surface. This is generally true for systems where the carrier is alumina, obtained in accordance with conventional techniques, and is often confirmed by scanning electron images is microscopii.

The content of reduced cobalt defined analytically in the sample, which was subjected to recovery at 400°C for 16 hours in a stream of pure H2corresponds to 35%.

OBTAIN CATALYST B

In contrast to the catalyst And the catalyst B of the present invention was obtained in accordance with the method of synthesis, which gives compound with the General formula (I)having a structure of type hydrotalcite, with subsequent calcination.

There were prepared two water solution: one solution contained(NO3)2·6N2O and Al(NO3)3·N2About (the ratio of moles of Co/Al 3:1) at a concentration of 1 mol (Mn+)/liter, and the other NaHCO3at a concentration of 1.3 mol/liter.

These two solutions at room temperature slowly and simultaneously added dropwise in the same vessel in which was dispersed media from γ-δ alumina Condea Scca 5-170 (55 g in approximately 200 ml of distilled water). The goal was to achieve after annealing the cobalt content of 13 to 15% of the mass. During the addition of the two solutions the pH was controlled by means of a glass electrode and maintained constant between the 6.8 and 7.1.

The solid residue was isolated by filtration on a Buchner funnel with repeated and copious rinsing with distilled water; then it was left for about what the suturing in an oven at 80° C for 16 hours. Next were calcination in muffle in the air stream.

The annealing was performed under the following conditions:

from 25 to 350° (10°C/min)

- isothermal conditions at 350°With (30 min)

from 350 to 400° (5°C/min)

- isothermal conditions at 400° (240 min)

from 400 to 25° (10°C/min).

By analogy with the sample And the dried catalyst B was investigated by x-ray analysis, and calcined catalyst B was investigated by elemental analysis, x-ray analysis and x-ray photoelectron spectroscopy.

The STUDY of DRIED SAMPLE B.

After drying the catalyst B was subjected to x-ray analysis. Spectrum testified to the presence of crystalline phase type hydrotalcite, well-formed despite the relatively small size of the crystals. This phase can be represented by the following formula:

[With2+6Al+32(OH)16]2+[CO32]·4H2O

The results of radiographic studies are presented in Table 4.

The calculated amount hydrotalcite phase corresponds to the lower content of cobalt than the total amount determined by elemental analysis, and, therefore, conclude, condosta part of cobalt otherwise placed on an aluminum carrier and is undetectable part, well dispergirovannoyj in the media.

It cannot be excluded that there are still hydrotalcite phase present in the form of crystallites of such small size that they cannot be detected by x-ray analysis.

In any case, it should be noted that does not detect the presence of uranyl nitrate of cobalt in contrast to what was confirmed for the dried catalyst comparison.

The STUDY CALCINED CATALYST B.

The calcined catalyst B was subjected to elemental analysis to determine the actual content of cobalt, entered at the time the sample is received. The content of cobalt corresponded exactly to 14.7% of the mass.

The sample was also subjected to x-ray analysis, and a spectrum testified to the presence of two spinel phases: one - γ-Al2About3received from the carrier, and the other a mixed oxide of Co/Al/O. the Results are shown below in table 4.

Table 4

X-ray analysis of the catalyst B.
BPhasea (A)V (A3)The crystal size (A)
DriedHydrotalcite3,074of 188.365
CalcinedCo/Al/O 8,086528,745

In contrast to the dried sample, the number of mixed oxide corresponds to the possible content of cobalt.

The unit cell parameters of these two phases is extremely close to the value taken from reference (table 5).

Table 5

Comparison of unit cell parameters with literature data.
a (A)V(A3)
Co3O4literature data8,084consists 528.3
γ-Al2About3literature data7,924497,5
Co2AlO4literature data8,086528,7
Phase γ-Al2About3catalyst Bof 7.920496,8
Phase Co/Al/O catalyst B8,086528,7

Calculations based on three possible formulas lead to is given in the table 6 results.

Table 6
Hypothetical type phaseThe calculated content, %
Co3O417,6
Co2AlO4 13,5
CoAl2O48

Also according to elemental analysis the most probable formula is the Co2AlO4perhaps a little more enriched in cobalt and more accurately expressed as Co2+xAl1-xO4.

You can come to the conclusion that during annealing dispersed on the carrier cobalt, not detected rentgenograficheski, along with detektivami hydrotalcite contributes to the formation of Co/Al/O oxide.

The crystallite size of the phase Co/Al/O spinels present in the catalyst B, is significantly smaller crystallite size defined in the catalyst And spinel(CO(2), Alx)O4.

After calcination the catalyst B was subjected to x-ray photoelectron spectroscopy is analogous to the procedure for catalyst A. the Corresponding results are shown in table 7.

Table 7

X-ray photoelectron spectroscopy of catalyst B.
AS With 2P3/2(eV)ΔF (2p1/2-2P3/2) (eV)Co2p/Al2s
78115,21,73
AS - bond energy

As for catalyst A, the first two columns of the evidence is jut about the presence of the compound With the 3O4on the surface of the catalyst; however, the magnitude of ES related With 2P and equal 781 eV, much higher than the value specified for catalyst A, which can be explained by the presence of the "aluminized" connections (confirmed and is better described as a mixed Co/Al/O system by x-ray analysis). The most interesting fact connected with relationship Co2p/Al2s (third column), which is unusually high, 10 higher than the ratio marked for catalyst A. This high value can be explained only homogeneous distribution of cobalt precursor on the surface of the carrier. Predecessor covers media, masking the XPS signal.

The content of reduced cobalt defined analytically in the sample, which was subjected to recovery at 400°C for 16 hours in a stream of pure H2corresponds to 40%.

Description of the TEST CATALYST

Catalysts a and B used in the test reactivity in a tubular reactor with a fixed bed (FTR), which was continuously applied to the mixture of CO and H2under the conditions indicated below in table 8.

The total pressure
Table 8

The conditions for testing catalyst
The reaction temperature200-240°
21 abs. Bar (2.1 Naabs.)
The ratio of N2/CO2/1
The volumetric rate1,3-3,0 Tbsp/mlcat/h

A known amount of catalyst was placed in a tubular reactor with a fixed bed. Activation of the catalyst is carried out through the restoration in the stream of hydrogen (2 tbsp/h/lcat) and nitrogen (1 tbsp/h/lcat) at a temperature in the range of 320-450°and a pressure of 1 bar (0.1 MPa) for 16 hours. In the end the reactor was cooled in a stream of nitrogen.

During this phase, the pressure in the system is brought up to a final working pressure of 22 abs. Bar (2,2 MPa abs.). They injected a mixture of reactants consisting of H2and in the stoichiometric ratio of 2:1, introducing the mixture of CO-H2and reducing the supply of N2as reflected in table 9.

Table 9

Conditions of supply of reagents in the phase of activation.
The time interval (hours)Flow rate (tablespoons/h)The flow rate of H2(tbsp/h)The flow rate of N2(tbsp/h)
0-0,51020200
0-0,51020150
0-0,510 20100
0-0,5102050
0-0,510200

It turned out that in the late phase activation system not contained gaseous diluent (nitrogen) and was under pressure, flow rate, a ratio of N2/WITH that reflected in the table. The temperature in approximately 15 hours was raised to the reaction temperature. The resulting wax is collected in suitable containers at a temperature of 110°C. Leaving the reactor gas was passed through the dispenser and the subsequent sampling system for gas chromatography analysis. Coming out of the reactor liquid and solid substances were analyzed by gas chromatography on a suitable equipment for the final determination of the number. In order to normalize the data on the activity of the catalyst obtained in different tests, in relation to the actual content of cobalt, the yield of products containing carbon (hydrocarbons and CO2), were normalized with respect to the actual number of moles of cobalt present in the catalyst, and in relation to the time measurement unit, and as a parameter of comparison used the value of Co-HC (cobalt-specific output) = number of moles reacted WITH/total number of moles is about an hour.

EXAMPLE 1. Catalyst A (table 10)

Table 10

Characteristics of catalyst A.
The amount of catalyst (cm3)20
Lifetime (h) (T.O.S.)396730
Hourly average gas flow rate (tablespoons/Lcat/h)15001500
Temperature (°)206215
Test pressure (abs. bar/MPa, abs)21/2,121/2,1
The actual ratio of N2/CO2,012,01
% conversion Co33,351,8
Co-HC (mol proreader. WITH/h/mol Co)4,16,5
With2+performance (C2+/h/kgcat)109,8168,2
With9+performance (C9+/h/kgcat)41,7119,5
With22+performance (C22+/h/kgcat)23,353,1

EXAMPLE 2. Catalyst B

Data for testing the activity of the catalyst is presented in table 11 and compared for isocaloric with data from when the EPA 1 to assess the positive effect from the point of view of the performance of higher hydrocarbons (C 22+for the catalyst of the present invention.

Table 11

Characteristics of catalyst B.
The amount of catalyst (cm3)20
Lifetime (h) (T.O.S.)139187
Hourly average gas flow rate (tablespoons/lcat/h)15001500
Temperature (°)225235
Test pressure (abs. bar/MPa. abs.)21/2,121/2,1
The actual ratio of H2/CO2,082,08
% conversion Co33,346,6
Co-HC (mol proreader. WITH/h/mol Co)4,25,8
With2+performance (C2+/h/kgcat)123,3to $ 179.7
With9+performance (C9+/h/kgcat)96,0136,3
With22+performance (C22+/h/kgcat)50,266,2

SPECIFIC ACTIVITY

Table 12 indicates the values of the specific activity of the two catalysts in terms of frequency power is a (PE), i.e. reacted moles WITH one active site per unit time.

Table 12

Specific activity.
CatalystT°)PE×102with-1
And2224,0
B2195,8

CHARACTERISTICS OF THE CATALYSTS.

COMMENTS TO the TABLES 10-12.

The application of the proposed catalyst based on cobalt supported on a carrier of alumina, allows to obtain better performance of the catalyst in terms of selectivity to heavy products are compared with the characteristics of the catalyst obtained by the deposition of cobalt on the same aluminum oxide according to traditional methods, the initial wetting.

Example 2 shows that obtained by the proposed method, the catalyst B allows to achieve higher performance for more9+and C22+(table 11) compared with the amounts obtained when using catalyst a (example 1, table 10).

Comparison of catalysts a and B was carried out at the same level of CO conversion, equal to 30 and 50%.

In conclusion, the catalyst B of the present invention contributes clicks the application of hydrocarbon products with a higher molecular weight, that gives an additional advantage for the synthesis of products according to the process of making a Fischer-Tropsch process.

To assess the activity of the catalyst is necessary to take into account the specific activity, expressed in each case as PE - "transition frequency".

The comparison of PE (see table 12) homologous catalysts, i.e. a and B (same media) shows how much more the specific activity of the system B, obtained in accordance with the proposed method.

1. The catalyst used in the Fischer-Tropsch process, essentially consisting of cobalt oxide deposited on an inert carrier, which essentially consists of alumina, characterized in that the cobalt oxide is essentially composed of crystals with an average size in the range from 20 to 80 Å.

2. The catalyst according to claim 1, characterized in that the crystals of cobalt oxide have an average size of from 25 to 60 Å.

3. The catalyst according to claim 2, characterized in that the crystals of cobalt oxide have an average size of from 30 to 40 Å.

4. The catalyst according to claim 1, characterized in that the alumina is in the form of γ or δ and mixtures thereof.

5. The catalyst according to claim 1, characterized in that the content of cobalt is in the range from 2 to 50 wt.%.

6. The catalyst according to claim 5, characterized in that the content of cobalt is in the range from 5 to > 20.%.

7. A method of producing a catalyst essentially consisting of cobalt oxide supported on alumina, where the specified cobalt oxide essentially consists of crystals with an average size in the range from 20 to 80 Åand the method includes the following operations:

1) preparation of intermediate compounds deposited on the aluminum oxide and having the following General formula (I):

[With2+1-xAl+3x(OH)2]x+[Andnx/n]·mH2O (I)

where x is in the range from 0.2 to 0.4, a is the anion, x/n is the number of anions required to neutralize the positive charge, m is in the range from 0 to 6;

2) the annealing of the intermediate compounds with the General formula (I) with the formation of crystalline oxide of cobalt.

8. The method according to claim 7, characterized in that x is in the range from 0.25 to 0.35.

9. The method according to claim 7, characterized in that m=4.

10. The method according to claim 7, wherein A=CO3.

11. The method according to claim 7, characterized in that before operation (2) perform the operation of drying compounds with the General formula (I).

12. The method according to claim 7, characterized in that the operation (1) perform by adding dropwise the solution of an aluminum salt and a cobalt salt to a suspension of aluminum oxide at pH in the range from 6.6 to 7.2 and the allocation obtained in this way is m connection with General formula (I), deposited on the aluminum oxide.

13. The method according to item 12, wherein the pH is in the range from 6.8 to 7.1.

14. The method according to claim 7, characterized in that the operation (2) calcination is carried out at a temperature in the range from 300 to 500°C.

15. The method according to 14, characterized in that the annealing is carried out at a temperature in the range from 320 to 450°C.

16. The method of obtaining hydrocarbon waxes on the Fischer-Tropsch process, wherein it is carried out in the presence of a catalyst according to any one of claims 1 to 6.



 

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2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

FIELD: chemical industry; conversion of synthesis gas into alcohols and hydrocarbons.

SUBSTANCE: proposed catalyst contains the following constituents, mass-%: active component in terms of CO; promoter-fluorine, 0.1-1.0; the remainder being carrier-aluminum oxide.

EFFECT: enhanced conversion of CO.

1 dwg, 2 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.

3 cl, 1 tbl, 15 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing mainly C5+-hydrocarbons. Method involves contacting carbon monoxide with hydrogen at temperature 180-270°C and under increased pressure in the presence of catalytic composition comprising as measure for the total mass of catalytic composition from 5 to 30 wt.-% of cobalt, from 0.01 to 5 wt.-% of manganese and at least from 0.01 to 0.9 wt.-% of rhenium and/or ruthenium on a carried made of titanium dioxide. Invention provides reducing amount of carbon dioxide evolved in the process of hydrocarbons synthesis by Fisher-Tropsh to the level 2% vol./vol., not above, but preferably to 1% vol./vol., not above, and without reducing C5+-selectivity.

EFFECT: improved preparing method.

7 cl, 2 tbl, 4 ex

FIELD: cobalt-based catalysts used in Fisher-Tropsh reaction in reactors with gas-liquid-solid agent fluidized bed.

SUBSTANCE: diameter of particles of cobalt-based catalyst applied to carrier is measured by means of Coulter LS230 in interval of from 70 to 250 mcm, area of surface exceeds 175 m2/g and volume of pores exceeds 0.35 cm3/g as measured by BET method. Specification contains also description of Fisher-Tropsh method in reactor with gas-liquid-solid agent fluidized bed. This method includes chemical interaction of CO with H2 for obtaining C5+ hydrocarbons in presence of said catalyst.

EFFECT: enhanced activity of catalyst; facilitated procedure.

8 cl, 3 dwg, 10 tbl, 6 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 ex

FIELD: chemical industry; methods of production of zirconium oxides

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.

EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.

1 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO42-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO42- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.

EFFECT: increased specific surface area and heat resistance at simplified technology.

9 cl, 2 dwg, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

The invention relates to a method for producing a catalyst hydrobromide, to a catalytic composition obtained by the above method, and to use this catalytic composition in hydrobromide

The invention relates to the field of physical chemistry and can be used to regulate the speed of the auto-catalytic hydrogenation reactions

The invention relates to a method for preparing a multi-component catalyst for the oxidation of propylene to acrolein

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

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