Method of cleaning of lithium-7 hydroxide

FIELD: catalytic chemistry.

SUBSTANCE: the invention is dealt with the fields of catalytic chemistry. The invention offers a predecessor of the cobaltic catalyst, which contains a catalyst carrier impregnated with cobalt. All the restorable cobalt is present in the carrying agent in the form of a sustained cobalt oxide in accordance with a block formula CoOaHb, in which a ≥ 1.7 and b ≥ 0. The invention also offers alternatives of the method of preparation of the predecessor of the cobaltic catalyst. The technical result is production of a cobaltic catalyst with a higher activity.

EFFECT: the invention ensures production of a cobaltic catalyst with a higher activity.

20 cl, 10 ex, 12 tbl, 10 dwg

 

The present invention relates to the creation of cobalt catalysts. More specifically, it relates to the creation of the predecessor of the cobalt catalyst, preparation method predecessor of the cobalt catalyst and method of preparation of the cobalt catalyst.

The methods of preparation of cobalt catalysts are widely known. For example, in U.S. patent No.5733839 described the method of preparation of the impregnated catalyst Fischer-Tropsch process, which is a carrier of aluminum oxide and an active component selected from the group comprising cobalt, iron and mixtures thereof.

The present invention is the creation of a supported cobalt catalyst (cobalt catalyst on the carrier), which has a higher performance than the known cobalt catalysts.

In accordance with the first aspect of the present invention features a cobalt catalyst precursor, which contains a catalyst carrier impregnated with cobalt, together with all reducible cobalt, which is present in the media as a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0.

In other words, in accordance with the first aspect of the present invention, a cobalt precursor is a new catalyst, which contains a catalyst carrier which has been impregnated with cobalt and calcined, so that the whole is present in him recoverable cobalt, i.e. cobalt, which is combined with other elements such as hydrogen and oxygen, in the absence of a supported cobalt interaction, such as the formation of cobalt aluminate or silicate of cobalt, which could reduce its ability to recover, is present in the media as a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0.

Thus, for example, whole recoverable cobalt may be present in the form of Co2About3·H2Oh or COO(OH), that is, when a=2 and b=1. But instead, all recoverable cobalt may also be present, for example, in the form of a mixture of Co3O4with COO(OH) or Co2About3·H2Oh, when 45% of recoverable cobalt catalyst precursor, which is present as Co3O4and 55% of recoverable cobalt, which is present as COO(OH) or Co2About3·H2O. This could cause the catalyst precursor all reducible cobalt is present as a supported cobalt oxide in accordance with block formula COOaHbwhere a=1.7 and b0,55. Another example is a mixture of Co2About3with COO(OH) or Co2O3·H2O, with 60% recoverable cobalt, which is present as Co2About3and with 40% of recoverable cobalt, which is present as COO(OH) or Co2O3·H2A. It could cause in the catalyst precursor all reducible cobalt is present as a supported cobalt oxide in accordance with block formula COOaHbwhere a=1.7 and b=0,4.

The catalyst precursor may contain from 5 g From 100 g of the carrier to 70 g From 100 g of the carrier, mainly from 20 g From 100 g of the carrier up to 50 g With 100 g of the carrier, and better still from 25 g From 100 g of the carrier to 40 g With 100 g of carrier.

In accordance with the second aspect of the present invention proposes a method of preparing a cobalt catalyst precursor, which includes the following operations:

the impregnated powder porous catalyst carrier salt of cobalt and partial drying of the impregnated carrier, and

calcining the partially dried impregnated carrier to obtain a cobalt catalyst precursor, and calcining is carried out at conditions of calcination, chosen so that all reducible cobalt is present in the media as supported by the second cobalt oxide in accordance with block formula COO aHbin which a≥ 1.7 and b>0.

The ignition lead by heating the carrier and transmission of hot air to a temperature of from 95° With up to 400° and control the rate of heating so that first removed the residual moisture, and then occurred the decomposition of cobalt salts on products containing oxides and any water of hydration.

The cobalt salt is a nitrate of cobalt, so that the oxides which are formed as the decomposition products are nitrogen oxides, and the calcination is carried out in the calcinator fluidized bed, however, after annealing the concentration of nitrogen in the catalyst precursor is less than 1.0 weight. %.

The volumetric rate of air should be at least 1.0 m3n1 kg(NO3)2·6N2About an hour, and the heating rate meets the following criteria: when the volumetric rate of air is 1.0 m3n1 kg(NO3)2·6N2About an hour, the heating rate is ≤ 1° C /min; however, when the volumetric rate of air exceeds 1.0 m3n1 kg(NO3)2·6N2About an hour, the allowable heating rate increases to x° C /min, where x≥ 1.

At the stage of calcination can assests shall be the initial heating of the impregnated carrier, until it reaches the temperature of annealing of the Cu, and then maintain it at the temperature of annealing of the Cu during the time period tc. The heating rate to a temperature of annealing the Cu is non-linear. The period of time tc during which the conduct isothermal annealing at a temperature of annealing the Cu comprises from 0.1 to 20 hours.

Partially dried impregnated carrier from the stage of impregnation of the carrier does not store, and not heated or not previously cooled subsequent stage of annealing fluidized bed, so he was immediately sent to the step of annealing the fluidized bed.

In accordance with the present invention can be used any commercially available porous oxide catalyst carriers, such as alumina (Al2About3), silicon dioxide (SiO2), titanium dioxide (TiO2), magnesium oxide (MgO) and a mixture of silicon dioxide with aluminum oxide. The media mainly has an average pore diameter of from 8 to 50 nm, and mostly from 10 to 15 nm. The pore volume of the carrier may range from 0.1 to 1.0 ml/g, and mainly from 0.3 to 0.9 ml/g, the Average particle size is from 1 to 500 μm, predominantly from 10 to 250 μm, and better still from 45 to 200 microns.

As the carrier can be used protected modified catalyst carrier, which contains the inhabitants, for example, silicon as a modifying component, as shown in the publication WO 99/42214.

The impregnated catalyst carrier in principle can be carried out using any known method or procedure of impregnation, such as impregnation with rudimentary humidity or impregnation phase of the suspension. However, the stage of impregnation may, in particular, to provide for the use of such a method which is described in the publication WO 00/20116. At this stage of impregnation of the carrier may provide for the use of the method of impregnation phase suspension with two operations, the characteristics of which depend on the requirements of the desired loading of cobalt and from the pore volume of the catalyst carrier.

During any of the two operations impregnation phase of the suspension may be added water-soluble precursor salt of palladium (Pd), platinum (Pt), ruthenium (Ru), or a mixture thereof, as a dopant capable of enhancing the recoverability of cobalt. The mass ratio of palladium, platinum, ruthenium or a combination mixture of these metals, if used, the metal cobalt may be from 0.01:100 to 0.3:100.

The impregnation and drying of the carrier is usually carried out in a conical vacuum dryer with a rotating auger or rotary vacuum dryer.

At the stage of annealing, the annealing may include the transmission of grief is its air over partially dried by the media and around it, which leads to further drying the impregnated carrier by removing present therein residual moisture; and calcining the resulting dried impregnated carrier, which causes the decomposition of cobalt salts on the degradation products containing the oxide(s) and any water of hydration, and the degradation products are excreted in the form of vapor, which contributes to the formation of the supported catalyst precursor, which contains a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0.

In particular, as salt is cobalt is a cobalt nitrate, oxide(s) are nitrogen dioxide, with the balance between NO2and N2O4and nitric oxide (NO).

The process may include dilution of decomposition products, which are obtained in the course of annealing. In other words, the formation of a supported cobalt oxide in accordance with block formula COOaHbinwhich a≥ 1.7 and b>0, is enhanced by dilution of the products of decomposition during annealing.

The presence of phase supported cobalt oxide in accordance with block formula CoOaHbin which a≥ 1.7 and b>0, can be set through the use of programmed reduction temperature (SST) image quality is as determinative technique.

The minimum temperature at which conduct the calcination, is the temperature at which decomposition begins predecessor of cobalt, i.e. salts of cobalt, while the maximum temperature of the annealing is a temperature at which phase the predominant supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0, is converted to undesirable phase spinel Co3About4.

The calcination can be carried out using any known equipment for annealing, such as calcinator fluidized bed, drum kiln and calcinator or furnace with a bulk layer.

In particular, the calcination may be conducted in the calcinator fluidized bed, preferably the calcination carried out in air, at temperatures from 95° With up to 400° C. a Minimum temperature of calcination is the temperature at which decomposition begins nitrate, i.e. a temperature of about 120° S, while the maximum temperature of the annealing is a temperature at which the predominant cobalt oxide in accordance with block formula COOaHbconverted to undesirable phase spinel Co3About4. The maximum temperature of the annealing is usual ranges from 200° With up to 300° C. After annealing the concentration of nitrogen in the catalyst precursor is preferably less than 1.0 weight. %.

In accordance with a preferred embodiment of the present invention conducts the removal of oxide (oxides of nitrogen and water during calcination in air to enhance the stabilization phase of supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0.

During calcination in a fluidized bed can be controlled by the rate of heating of the impregnated and dried carrier and bulk velocity of the air so that first removed the residual moisture in the media, and then occurred the decomposition of cobalt nitrate.

Mostly use the minimum volumetric rate of air in order to achieve the maximum relative intrinsic activity of the cobalt catalyst with respect to the resulting catalyst; however, with minimal bulk velocity combine the maximum heating rate. In particular, the applicant has found that for a specific impregnated with cobalt nitrate media there is a minimum volumetric air velocity 1.0 m3n1 kg(NO3)2·6N2About an hour, which should be used in order to achieve m is xymalos relative intrinsic activity of the cobalt catalyst. If used, the minimum volumetric air speed is less than 1.0 m3n1 kg of Co(NO3)2·6N2About an hour, then you cannot achieve the maximum relative intrinsic activity of the resulting cobalt catalyst. However, the applicant also found that the maximum heating rate 1° C/min, mainly 0,5° C/min, and typically from 0.1 to 0.5° C/min, can be used in combination with a minimum volumetric rate of air is 1.0 m3n1 kg (NO3)2·6N2About an hour. In other words, if the heating rate of the carrier exceeds 1°C/min while maintaining a minimum flow rate equal to 1.0 m3n1 kg (NO3)2·6N2About an hour, it could have a harmful effect on the initial activity of the catalyst.

However, if you use the volumetric rate exceeding 1.0 m3n1 kg(NO3)2·6N2About an hour, for example, the volumetric rate of 100 m3n1 kg(NO3O)2·6N2About an hour, then this can be used combined with it a higher maximum or threshold heating rate, namely 100° C/min, Thus, can be applied the instant the ignition in the line who communicate sufficiently high bulk velocities.

The method may include, at the stage of annealing the initial heating of the impregnated carrier, until it reaches the temperature of annealing of the Cu. Thus, the heating medium to a temperature of annealing the Cu can be carried out while maintaining the flow rate of at least 1.0 m3n1 kg (NO3)2·6H2O in h and the corresponding speed of the heating layer, combined with a bulk velocity, as described previously. The method may also include thereafter maintaining the temperature of calcination of the carrier Vehicle during the time period tc.

Control of the rate of heating may be effected by control of the pre-heater feed gas (air)through which the air necessary for fluidization (create a fluidized bed) and calcination, and/or by controlling the wall temperature of the calcinator. While temperatures up to TC is linear (with constant speed), it can be assumed that the increased activity can be achieved with non-linear heating rate, which allows you to adjust the profiles of liberation (exit) oxide (oxides of nitrogen and water.

The period of time tc during which the conduct isothermal annealing at the temperature of annealing T, may be from 0.1 to 20 hours, provided that the nitrogen content in prokalivaem the catalyst is less than 1.0 weight. %.

Partially dried impregnated carrier from the stage of impregnation of the carrier mainly kept not, and also not heated or not previously cooled subsequent stage of annealing fluidized bed, so that it (immediately) lead to the stage of calcination fluidized bed, mostly at the same temperature at which it leaves the stage of impregnation of the carrier. Thus, the partially dried impregnated carrier exits the stage of impregnation of the carrier at a temperature of from 60° to 95° and usually about 75° and comes to the stage of calcination fluidized bed at approximately the same temperature, without the storage media between the two stages. Stage calcination fluidized bed mainly done using calcinator fluidized bed, which is directly connected to a vacuum dryer.

Fluid environment, which is used in the calcinator, represents the air required for combustion, and the linear velocity of air through the calcinator, of course, must be sufficient to ensure proper fluidization.

The present invention also relates to the creation of the catalysis of the Torah, which is obtained using the method in accordance with the third aspect of the present invention or obtained by the recovery of the catalyst precursor in accordance with the first aspect of the present invention or the catalyst precursor obtained using the method in accordance with the second aspect of the present invention.

The proposed method is particularly suitable for the preparation of cobalt catalyst for Fischer-Tropsch phase of the suspension, that is, such a catalyst which is suitable for accelerating the conversion of synthesis gas containing carbon monoxide and hydrogen in the hydrocarbon products are carried out at elevated temperature and pressure.

These and other features of the invention will be more apparent from the subsequent detailed description of examples that do not have restrictive and described with reference to the accompanying drawings.

Figure 1 shows schematically the installation, which is used for the preparation of the catalyst of Example 1, at the stage of pilot production.

Figure 2 shows a picture of a programmable temperature reduction (PST) catalyst R. APC experiment was carried out using a heating rate of 10° C/min and a mixture of hydrogen with argon containing 10% of hydrogen.

Figure 3 shows a picture of programmable reduce the temperature of the catalyst N. APC experiment was carried out using a heating rate of 10°C/min and a mixture of hydrogen with argon containing 10% of hydrogen.

Figure 4 shows the relative internal specific activity of the catalysts of the Fischer-Tropsch process in accordance with Examples 1, 2 and 8, flow rate, during annealing in the fluidized bed.

Figure 5 shows the relative internal specific activity of the catalysts of the Fischer-Tropsch process in accordance with Examples 1, 2 and 8, as a function of heating rate during the annealing in the fluidized bed.

Figure 6 shows the performance of junk, preferred and most preferred catalysts for Fischer-Tropsch, volumetric flow rate and heating rate during calcination in a fluidized bed.

7 and 8 shows the results of thermogravimetric analyses (TGA) of the catalyst of Example 1, after impregnation and vacuum drying media, but before calcination in air, with:

7 shows the loss in mass of the catalyst as a function of time, using a heating rate of 0.40° C/min and holding time at a temperature of 250° With average of 6 hours;

on Fig shows the loss in mass of the catalyst as a function of time, using a heating rate of 5° C/min from 30° When about 75° C and heating rate of 0.4° C/min from 75° to 130° and then the holding time of 4 hours at a temperature of 130° C, heating rate of 0.17° C/min from 130° 160° and heating rate of 0.7° C/min from 160°, 250° and then the holding time of 4 hours at a temperature of 250° C.

Figure 9 shows a picture of a programmable temperature reduction catalyst Q. the SST experiment was carried out using a heating rate of 10° C/min and a mixture of hydrogen with argon containing 10% of hydrogen.

Figure 10 shows a picture of a programmable temperature reduction catalyst R. APC experiment was carried out using a heating rate of 10° C/min and a mixture of hydrogen with argon containing 10% of hydrogen.

EXAMPLE 1

On the pilot plant shown in figure 1, was prepared in a series of cobalt-based alumina catalysts for Fischer-Tropsch, named a, b, C, D, E, G, H and I. These catalysts were prepared using the calcinator fluidized bed. Catalysts D, E, G, H and I are made in accordance with the present invention and the catalysts a, b and C are shown for comparison.

In figure 1 the position of the 10 identified in the General experimental setup that was used for the preparation of catalysts for Fischer-Tropsch. The installation 10 includes a conical vacuum schilk the 12 volume 100 DM 3with a channel load 14, provided with a valve 16. The specified channel 14 is directly connected with the section of the Department (division) 18 calcinator fluidized bed, which is indicated in General position 20.

Calcinator 20 includes a vent channel 22 leading from the section 18 in the scrubber (scrubber) (not shown). Section 18 is connected by means of flanges 24, 26 with the tubular component 28, which forms a cylindrical wall calcinator with an inner diameter of 350 mm and a height of 655 mm Heating element 30 covers the component 28, and a sensor and a temperature controller 32, positioned between the element 30 and the component 28.

At its lower end component 28 has a flange 34 connected to the flange 36 of the component in the form of a funnel 38. Between the flanges 34, 36 is a filter 40, which overlaps the output of the component 28. Component 38 has an inlet air channel 42 through which heated air is supplied to the calcinator.

The temperature sensor 44, which is mounted in the channel of the component 28 is used to measure the temperature inside the fluidized bed (not shown) of the dry powder impregnated material carrier, which is formed on the filter 40. The temperature sensor 44 is mounted above the filter 40 at a distance of about 35 mm, Similar to the temperature sensor 46 is installed under the filter 40.

Installed the 10 vacuum dryer 12, which is used for impregnation and vacuum drying of the carrier, directly connected to the calcinator fluidized bed 20.

The catalysts were prepared by impregnation procedure in phase suspension and vacuum drying. This procedure was identical for all catalysts in this Example.

In each case, in the first operation impregnation and calcination, to produce a stirring solution of 17.4 kg(NO3)2·6H2O, 9.6 g (NH3)4Pt(NO3)2and 11 kg of distilled water 20,0 kg media γ alumina (Puralox SCCa 5/150, pore volume of 0.48 ml/g, produced by Condea Chemie GmbH Uberseering 40, 22297 Hamburg, Germany) by adding media to the solution. Result

the suspension was introduced into the conical vacuum dryer 12 and continuously stirred. The specified temperature of the suspension was raised up to 60° and then created a vacuum of 20 kPa(a). During the first 3 hours of operation, the drying temperature was slowly increased and reached 95° after 3 hours. After 3 hours, the vacuum was reduced to 3-15 kPa(a). The impregnated catalyst carrier was dried for 9 hours, after which the specified impregnated catalyst carrier was immediately and directly loaded into the calcinator fluidized bed 20. The temperature of the dry impregnated catalyst carrier at boot time in the calcinator with Talala about 75° C. boot Time is approximately 1-2 minutes, so the temperature inside the calcinator was kept equal to the point setpoint and was about 75° C. To obtain a catalyst containing cobalt 30 g From 100 g of Al2O3performed the second operation impregnation and drying. To this stirred solution of 9.4 kg(NO3)2·6N2Oh, 15.7 g (NH3)4Pt(NO3)2and 15.1 kg of distilled water 20,0 kg impregnated and calcined material from the first operation impregnation and calcination by adding this solid intermediate material in the solution. The resulting suspension was introduced into the conical vacuum dryer and continuously stirred. The specified temperature of the suspension was raised up to 60° and then created a vacuum of 20 kPa(a). During the first 3 hours of operation, the drying temperature was slowly increased and reached 95° after 3 hours. After 3 hours, the vacuum was reduced to 3-15 kPa(a). The resulting impregnated catalyst carrier was dried for 9 hours, after which the specified impregnated catalyst carrier was immediately and directly loaded into the calcinator fluidized bed. The temperature of the dry impregnated catalyst carrier at boot time in the calcinator was about 75° C. loading Time is approximately 1-2 m the chickpeas, therefore, the temperature inside the calcinator was kept equal to its point setpoint and was about 75° C.

The volumetric rate of air in the calcinator and the rate of heating of the impregnated and dried material in the range from 75°, 250° changed in an attempt to obtain a catalyst with a maximum relative initial internal activity. The exposure time of 6 hours at a temperature of 250° were kept constant for all operations of preparation of the catalysts. The temperature of the fluidized bed controlled (component 44 in figure 1) during each cycle the ignition.

The conditions used during the direct calcination in a fluidized bed of impregnated and dried material, are listed in Table 1.

The nitrogen content in each prepared on a pilot plant of catalysts was less than or equal to 0.5 weight. %as shown in Table 2.

Table 2

The nitrogen content in the catalysts a, b, C, D and I, after annealing.
CatalystThe nitrogen content (weight. %)
And0,50
In0,45
0,45
D0,48
I0,0

EXAMPLE 2

In a laboratory setup was prepared by the series of cobalt-based alumina catalysts for Fischer-Tropsch, named K, L, M and O, using the same procedures as in the preparation of catalysts on the pilot plant described in Example 1, but starting with 50 g of the carrier instead of 20 kg Number of other chemicals was also reduced in the ratio of 0.05/20. These catalysts were also prepared with the ignition in the fluidized bed. The preparation of these catalysts produced in a laboratory setup, similar to installing 10 figure 1. Catalysts L and M are made in accordance with the present invention and the catalysts For and are given for comparison.

The conditions used during calcination in a fluidized bed catalysts carriers prepared on a laboratory scale, are shown in Table 3.

EXAMPLE 3

Using the impregnation suspension was prepared cobalt catalyst R, which does not correspond to the present invention. In the first operation impregnation and calcination was stirred solution 43,68 g Co(NO3)2·6N2Oh, 0,024 g (NH3)4Pt(NO3)2and 50 ml of distilled water with 50 g media γ alumina (Puralox SCCa 5/150, pore volume of 0.48 ml/g, made in the rotary firm Condea Chemie GmbH Uberseering 40, 22297 Hamburg, Germany) by adding media to the solution. The resulting suspension was introduced into a rotary evaporator (rotarvap) and continuously stirred. The specified temperature of the suspension was raised up to 60° and then created a vacuum of 25 kPa(a). During the first 3 hours of operation, the drying temperature was slowly increased and reached 95° after 3 hours. After 3 hours, the vacuum was reduced to 5 kPa(a). The impregnated catalyst carrier was dried for 9 hours, after which the catalyst carrier was immediately calcined. The annealing was conducted in a static kiln at a temperature of 250° Since, without the flow of air over the sample. To obtain a catalyst containing cobalt 30 g From 100 g of Al2O3was carried out the second operation impregnation and calcination. The solution 23,51 kg Co(NO3)2·6N2Oh, 0,039 g (NH3)4Pt(NO3)2and 50 ml of distilled water was mixed with 50 g of the impregnated and calcined material from the first operation impregnation and calcination by adding this solid intermediate material in the solution. The resulting suspension was introduced into a rotary evaporator and continuously stirred.

The specified temperature of the suspension was raised up to 60° and then created a vacuum of 25 kPa(a). During the first 3 hours of operation, the drying temperature is slowly ascending the was reached 95° With over 3 hours. After 3 hours, the vacuum was reduced to 5 kPa(a). The resulting impregnated catalyst carrier was dried for 9 hours, after which the catalyst carrier was immediately calcined. The annealing was conducted in a static kiln at a temperature of 250° Since, without the flow of air over the sample.

EXAMPLE 4

Catalysts A, N and P were tested Fischer-Tropsch synthesis. The experimental data and conditions of the Fischer-Tropsch synthesis are given in Table 4.

Previously carrying out the synthesis in a laboratory microreactor slurry Fischer-Tropsch when the real conditions of the Fischer-Tropsch synthesis calcined precursors of the catalysts were recovered in the laboratory using standard laboratory methods of recovery (heating rate 1° C/min from 25 to 425° C, holding for 16 hours at 425° C, GHSV 200 mlnhydrogen per 1 g of catalyst per hour, 1 bar of pure hydrogen), followed by unloading and waxing Fischer-Tropsch process.

When using known kinetic expressions Fischer-Tropsch to cobalt:

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

derive pre-exponential factor of Arrhenius equation AFT(that is, AFT=kFT/(e-Ea|RT)) for each of the C conducted runs.

The domestic relative specific activity of the Fischer-Tropsch process can be defined as ((pre-exponential factor of the catalyst x) / (pre-exponential factor of the catalyst (A))* 100, where the catalyst x is a catalyst of specific examples, that is, catalysts H and R.

Experiments with a Programmable Temperature Decrease (APC) were carried out on the catalysts N and P (figure 2 and 3) using a heating rate of 10° C/min and a mixture of hydrogen with argon containing about 10. % hydrogen.

The results of the Fischer-Tropsch synthesis show that catalyst H is much more active (as it is the domestic relative factor FT, $ 138)than the catalyst P (which is the domestic relative factor FT, equal to 62). Picture of TFP also show clear differences between these two catalysts. These differences can be typed according to the following parameters:

1. The ratio of the height of peaks, peak 2 and peak 4.

2. The width of peak 2 at half the height.

3. The presence or absence of the peak 3.

Picture PST catalyst H is typical for supported cobalt catalyst, which contains recoverable cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b>0, while the AK PST painting catalyst R says about the presence of undesirable phase spinel Co 3About4.

From this we can conclude that the catalyst, which was duly hardened, will have the SST pattern, typical for the desired phase of cobalt oxide block formula COOaHbin which a≥ 1.7 and b>0, and the desired high relative internal activity of Fischer-Tropsch.

EXAMPLE 5

All the catalysts a, b, C, D, E, G, H, K, L, M and O, which were prepared with the ignition in the fluidized bed, were tested Fischer-Tropsch synthesis. The experimental data and conditions of the Fischer-Tropsch synthesis are shown in Tables 5 and 6.

The catalysts were recovered and tested as described in Example 4. Relative internal factors of the activity of Fischer-Tropsch were also calculated as described in Example 4.

The domestic relative specific activity of Fischer-Tropsch all catalysts were plotted on a graph in function of flow rate during calcination in a fluidized bed (figure 4). Activity of catalysts a, b, C, D, E, G, H, K, L and M increase linearly relative to the internal specific activity of Fischer-Tropsch component 140, at flow rate of 1.02 m3n1 kg (NO3)2·6N About an hour after which you can expect to retain a level of relative intrinsic activity of Fischer-Tropsch 140.

It can be assumed that the positive influence of flow rate for a preferred calcined phase of cobalt oxide and the desired parameters of the catalyst caused by the fact that at higher space velocities are reduced levels of maximum concentrations of NO and water around the catalyst particles during calcination.

The domestic relative specific activity of Fischer-Tropsch catalysts for a, b, C, D, E, G, H, I, K, L, M and O were also plotted on a graph as a function of heating rate during calcination in a fluidized bed (figure 5). You can come to the conclusion that at a constant volume rate of air inside the catalyst Fischer-Tropsch does not depend on variations in the heating rate in the range of 0.1° 0.5° C/min, it was Found that at higher speeds the initial heating of internal activity may decrease (e.g., for catalyst, as shown by the dashed extrapolations. It can be assumed that this is caused by increasing concentrations of NOxand water around the catalyst particles due to the rapid decomposition of the nitrates of cobalt at high speed heating. Figure 5 shows the initial (after 15 hours in the stream when the real who's synthesis conditions) FT internal activity of catalyst I. Catalyst I shows that if the volumetric rate is very high, for example, 1000 m3n1 kg (NO3)2·6N2About an hour, you can make instant ignition, that is, the heating rate 100° C/min

As shown in Fig.6, choosing the right combination of speed heating with a volume velocity of air allows to obtain a catalyst with the desired internal activity of Fischer-Tropsch.

EXAMPLE 6

The decomposition of the volume of nitrate of cobalt, i.e. liberation of the amount of NOxoccurs at a temperature of from 130° 160° as shown in Fig.7. To suppress the maximum peak of the NOxi.e. to enhance the initial activity was carried out adjusting to this profile release NOxthen there was investigated the possibility of using non-linear heating rate, the purposes of which are the maximum removal of residual moisture and water of crystallization previously achieve approximately 130° With subsequent smoothing allocation NOxin the range from 130° 160° C. Imitation specified was carried out using a TGA experiment using the shutter speed at 130° C, low heating rate from 130° 160° and high is th heating rate from 160° With up to 250° as shown in Fig. Found that in this case the allocation of NOxcontinues for a much longer period of time, due to which the maximum concentration of NOxaround the catalyst is reduced.

EXAMPLE 7

Catalyst Q was prepared similarly to catalyst I of Example 1. The SST pattern for catalyst Q shown in Fig.9.

Part of the sample of this catalyst Q was further calcined at 450° C, i.e. at a higher temperature than that proposed in accordance with the present invention. This was done in order to verify the presence of Co3About4in this particular sample of catalyst R. TFP picture for catalyst R is shown in figure 10.

The relative consumption of hydrogen in the recovery stage, which is calculated from the areas under the peaks 1, 2 and 4, figures 9 and 10, it is possible to conclude that the catalyst R, which was not prepared in accordance with the present invention mainly contains Co3About4. In contrast, the catalyst Q, which was prepared in accordance with the present invention mainly contains Soo(HE). This can be seen also from Table 7.

Table 7

The relative consumption of hydrogen at various stages reset the setting catalysts Q and R
ReactionCatalyst QCatalyst R
Pic

on
Mol

H2*
Pic

on
Mol

H2*
Soo(HE)+0,5H2Co3O4+2H2O10,4  
Co3O4+H2COO+H2About21,121,1
Soo+3H23SD+3H2About43,043,0
* Number of hydrogen was calculated from the areas under the respective peaks of recovery.

EXAMPLE 8

In a laboratory setup was prepared by the series of cobalt-based alumina catalysts for Fischer-Tropsch when using the same procedures as used in Example 2. Applied conditions of annealing are shown in Table 8.

Catalysts V, W and Z prepared in accordance with the present invention and the catalysts X and Y are shown for comparison.

Table 8

The conditions used during the use of the management in the fluidized bed dry impregnated media
CatalystWeight (g)The heating rate (° C/min)The volumetric rate * *
V501,01,8
W501,04,5
X504,01,0
Y508,01,8
Z508,04,5
* All catalysts had the following composition: 30 From/ 0,075 Pt/ 100 Al2O3(weight percent)

* * space velocity expressed as 1 m3nair for 1 kg(NO3)2·6N2About an hour

All the catalysts were recovered and tested on the operating parameters of the Fischer-Tropsch synthesis as described in Example 4. Were also calculated relative internal factors of the activity of Fischer-Tropsch, as described in Example 4. The data obtained are presented in Table 9 and shown in figure 4-6.

EXAMPLE 9

Two catalyst (AA and AB) were prepared by impregnation with a rudimentary humidity at which 50 g of alumina with a pore volume of 0.48 ml/g was impregnated with 24 ml of an aqueous solution of nitrate was kobal is the which also contains ammonium nitrate and platinum. After impregnation of the obtained intermediate product was dried and calcined in the calcination fluidized bed to a temperature of 250° C. the Exact conditions of annealing are given in Table 10. After annealing the intermediate product was impregnated a second time with the help of impregnation to incipient wetness and calcined similarly to the first operation impregnation and calcination. After the second surgery impregnation and calcination has been the catalyst has the following composition: 30 From/ 0,075 Pt/ 100 Al2O3.

The catalyst AA made in accordance with the present invention, and the catalyst AB is shown for comparison.

Table 10

The conditions used during calcination in a fluidized bed of dry saturated media
CatalystWeight (g)The heating rate (° C/min)Air consumption (l/min)The volumetric rate * *
AA501,01,71,8
AB501,00,30,3
* All catalysts had the following composition: 30 From/ 0,075 Pt/ 100 Al2O3(the weight of the new interest)

* * space velocity expressed as 1 m3nair for 1 kg (NO3)2·6N2About an hour

All the catalysts were recovered and tested on the operating parameters of the Fischer-Tropsch synthesis as described in Example 4. Were also calculated relative internal factors of the activity of Fischer-Tropsch, as described in Example 4. The obtained data are presented in Table 11.

The results show that cobalt catalysts prepared by the procedures of impregnation with a rudimentary humidity, the annealing are carried out in conditions in accordance with the present invention, can be used to obtain a catalyst with improved performance for Fischer-Tropsch synthesis.

EXAMPLE 10

Thermogravimetric analysis (TGA) in air catalyst Q, conducted after the second operation of its impregnation and calcination, shows that the loss in mass in the range from 250° 550° To amount to 3.5-4.0 weight. %. Assuming that during TGA produces compound of cobalt Co3About4was calculated to determine the true connection of cobalt present after standard calcination of the catalyst at 250° C. Possible candidates are compounds Soo, With whom HE or Co 2O3·H2O, Co(NO3)2and/or Co2About3. Expected during the conversion of these compounds in Co3O4weight changes are presented in Table 12. Considering these data we can conclude that the connection of cobalt, which is present after annealing at 250° carried out using conditions in accordance with the present invention, is mainly UNSD or Co2About3·H2O.

Table 12

The change in mass of the compounds of cobalt during decomposition in Co3About4
ConnectionThe weight change during decomposition in Co3About4(%)The change in mass, if the connection is present in the catalyst with 20 wt. % cobalt (%)
Soo+6,6+1,8
UNSD or  
Co2About3·H2About-13-4,0
With(NO3)2-56-35
Co2About3-3,2-0,9

1. The predecessor of the cobalt catalyst containing the catalyst carrier, the PCC is subjected to the cobalt, characterized in that the entire recoverable cobalt is present in the carrier precursor in the form of a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b&γτ; 0.

2. The cobalt catalyst precursor according to claim 1, in which the reducible cobalt is present in the form of Co2About3·H2Oh or COO(HE).

3. The cobalt catalyst precursor according to claim 1, in which the reducible cobalt is present in the form of a mixture of Co3O4with COO(OH) or Co2About3·H2O.

4. The predecessor of the cobalt catalyst according to one of claims 1 to 3, which contains 5 to 70 g With the media.

5. A method of manufacturing a cobalt catalyst precursor, comprising the following steps: impregnating a powder of a porous catalyst carrier salt of cobalt and partial drying of the impregnated carrier, resulting in a gain partially dried impregnated carrier, having a residual moisture; calcining the partially dried impregnated carrier by passing hot air over the partially dried impregnated carrier and around him, and by heating the impregnated carrier to a temperature of 95 - 400° to get the cobalt catalyst precursor, and manage with what speed the heating of the impregnated carrier and bulk velocity of the air thus to first removed the residual moisture in the media, and then occurred the decomposition of cobalt salts on the degradation products containing the oxide(s) and any water of hydration, with all of recoverable cobalt is present in the carrier predecessor as a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b&γτ; 0.

6. The method according to claim 5, characterized in that the decomposition products are in the form of steam, and the method involves thinning or removing the decomposition products.

7. The method according to claim 5, wherein the cobalt salt is a nitrate of cobalt, so that the oxides which are formed as the decomposition products are nitrogen oxides, and the calcination is carried out in the calcinator fluidized bed, however, after annealing the concentration of nitrogen in the catalyst precursor is less than 1.0 weight. %.

8. The method according to claim 5, characterized in that the volumetric rate of air is at least 1.0 m3n1 kg(NO3)2·6N2About an hour, and the heating rate meets the following criteria: when the volumetric rate of air is 1.0 m3n1 kg(NO3)2·6N2About an hour, the heating rate status is made by ≤ 1° C/min, and when the volumetric rate of air exceeds 1.0 m3n1 kg(NO3)2·6N2About an hour, the allowable heating rate increases to x° C /min, where x≥ 1.

9. The method according to claim 5, characterized in that it provides at the stage of annealing the initial heating of the impregnated carrier, until it reaches the temperature of annealing Tc, and then maintaining it at a temperature of annealing the Cu during the period of time tc.

10. The method according to claim 9, characterized in that the heating rate to a temperature of calcination Tcis nonlinear.

11. The method according to one of PP and 10, characterized in that period of time tcduring which spend isothermal annealing at the temperature of calcination Tcis 0.1 to 20 hours

12. The method according to claim 5, characterized in that the partially dried impregnated carrier from the impregnation stage immediately sent to the step of annealing the fluidized bed directly without storage, heating or cooling, mainly at the same temperature at which it leaves the stage of impregnation of the carrier.

13. A method of manufacturing a cobalt catalyst, comprising the following steps: impregnating a powder of a porous catalyst carrier salt of cobalt and partial with the Cabinet impregnated carrier, in the result of which get partially dried impregnated carrier, having a residual moisture; calcining the partially dried impregnated carrier by passing hot air over the partially dried impregnated carrier and around him, and by heating the impregnated carrier to a temperature of 95 - 400° to get the cobalt catalyst precursor, and control the speed of heating of the impregnated carrier and bulk velocity of the air so that first removed the residual moisture in the media, and then occurred the decomposition of cobalt salts on the degradation products containing the oxide(s) and any water of hydration, with the entire recoverable cobalt is present in the carrier predecessor as a supported cobalt oxide in accordance with block formula COOaHbin which a≥ 1.7 and b&γτ; 0 and the recovery of the cobalt catalyst precursor to obtain a cobalt catalyst.

14. The method according to item 13, wherein the decomposition products are in the form of steam, and the method involves thinning or removing the decomposition products.

15. The method according to one of p and 14, wherein the cobalt salt is a nitrate of cobalt, so that the oxides which are formed as about what aktov decomposition, are oxides of nitrogen, and the calcination is carried out in the calcinator fluidized bed, however, after annealing the concentration of nitrogen in the catalyst precursor is less than 1.0 weight. %.

16. The method according to item 13, wherein the volumetric rate of air is at least 1.0 m3n1 kg(NO3)2·6N2O per hour, and the heating rate meets the following criteria: when the volumetric rate of air is 1.0 m3n1 kg(NO3)2·6N2About an hour, the heating rate is ≤ 1° C/min, and when the volumetric rate of air exceeds 1.0 m3n1 kg(NO3)2·6N2O per hour, the allowable heating rate increases to x° C /min, where x≥ 1.

17. The method according to item 13, characterized in that it provides at the stage of annealing the initial heating of the impregnated carrier, until it reaches the temperature of annealing Tcand then maintaining it at a temperature of calcination Tcduring the period of time tc.

18. The method according to 17, characterized in that the heating rate to a temperature of calcination Tcis nonlinear.

19. The method according to one of p and 18, characterized in that period of time tccis 0.1 to 20 hours

20. The method according to item 13, wherein the partially dried impregnated carrier from the impregnation stage immediately sent to the step of annealing the fluidized bed directly without storage, heating or cooling, mainly at the same temperature at which it leaves the stage of impregnation of the carrier.



 

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