The method of producing catalyst for fischer-tropsch

 

(57) Abstract:

The preparation method of catalyst for Fischer-Tropsch providing the application to the pulp, which includes a powder carrier of aluminum oxide, water, and cobalt (Co) as an active ingredient, vacuum. As a result, the carrier of aluminum oxide impregnated with an active component. Drying the impregnated carrier is made by the vacuum. In the calcination of the dried impregnated carrier receive the catalyst for Fischer-Tropsch. Thus, very active catalysts for the Fischer-Tropsch-based cobalt can be prepared relatively simply and inexpensively, as in accordance with the present invention does not require, for example, expensive promoter selectivity of paraffin. 14 C.p. f-crystals, 7 tab., 4 Il.

The invention relates to catalysts. In particular, it relates to a method for producing the catalyst for Fischer-Tropsch.

Widely known various methods of obtaining the specified catalyst. So in the patent US 5102851 described the manufacture of a catalyst suitable for the conversion of synthesis gas. Described that after impregnation of the carrier of aluminum oxide compound of cobalt, comodat using an aqueous solution, subjected to drying at a temperature of from 110oC to 120oC during the period of time from 3 to 6 hours. When the impregnation is done with the use of organic solvents, the initial drying can be carried out under low pressure in a rotary evaporator at a temperature of from 50oC to 60oC, and the additional drying is carried out at a temperature of from 110oC to 120oC in the course of time, several hours more (primary drying).

In the patent US 3591649 in the most General terms States that the impregnation of the support during the preparation process-based catalyst can be carried out at a pressure below atmospheric, and the fact that the drying of the impregnated carrier may be carried out at a pressure below atmospheric. However, these instructions are only General in nature. Mentions that the impregnation can be carried out under pressure in the range from, say, a pressure below atmospheric to 150 psig (pounds per square inch), and drying can be carried out at atmospheric pressure or in vacuum. Thus, in this patent is absolutely not recognized the criticality of the use of pressure below atmospheric impregnation and drying when using water propick and even suggested such information.

In the patent US 4413064 described manufacturing fluidized bed of catalyst, which is used to convert the synthesis gas into paraffins with rapid generation of gases in the range of diesel fuel. Say there can be used any suitable impregnation method for the deposition of cobalt on a substrate made of aluminum oxide, such as a method with the initial wetting or way of using excess solution.

Despite the popularity of these and other methods of obtaining catalysts of the Fischer-Tropsch process, continues to be an urgent task of creating more sophisticated methods, in particular, to increase the specific activity of the catalyst.

In accordance with this invention features a method of producing catalyst Fischer-Tropsch process, which includes

application to the pulp (slurry) including powder carrier of aluminum oxide, water and the active ingredient, which is used cobalt (Co), resulting in a carrier of aluminum oxide impregnated with an active component;

drying the impregnated carrier in a vacuum;

the calcination of the dried impregnated carrier, resulting in a gain catalyst for Fischer-Tr is Aquum during drying was less than 20 kPa, but mainly, less than 10 kPa.

Drying temperature is limited to the lower limit of the temperature of decomposition of the active component, which is typically a salt of nitrate, so that the drying temperature is usually 70 - 90oC.

The vacuum is created by placing the slurry in a suitable closed vessel and creates a vacuum in it.

Although the impregnation and drying in vacuum conditions can be implemented as two separate or different operations, they can be combined into a single operation, when the impregnation is carried out at a time when drying.

Drying under vacuum may continue until such time as the moisture content in the impregnated carrier will not be less than 20% by weight. After drying the impregnated carrier may not continue under vacuum to remove more water, especially water of crystallization. This additional drying can be carried out by passing a drying medium, such as air, over the impregnated carrier in counterflow or parallel flow. In this case, the drying temperature may be from 100oC to 180oC. for example, additional drying may be carried out using g the Torah, in this case, air flows in counter-current. Instead, additional drying may be carried out in the dryer with counter-current of air, which may be a spray dryer of the catalyst.

Due to the calcination of the dried impregnated carrier is the transformation or decomposition of the active component in its oxide form. For example, the active ingredient can be used in the form of a salt, for example, Co(NO3)2that falls into the oxide of the active component, for example, Co3O4. The calcination takes place in the kiln (the calcinator). For example, the kiln can be installed in the lower end of the spray dryers, mentioned earlier, with the dried carrier directly (by gravity) falls in the kiln.

If desired, the calcined catalyst can be re-converted to pulp, mixed with water and at least one of the following components: the active component, the other active component or additive, as described hereinafter, to obtain the resultant impregnated carrier, which is again subjected to calcination and drying, as described above.

Although the media aluminum oxide usually has no structural promoter, optionally, you can include the existence of a structural promoter, such as magnesium or cerium, for example, if you want to increase the abrasion resistance of the resulting catalyst obtained by the method in accordance with the present invention.

Regardless of, contains or not a carrier of aluminum oxide structural promoter, the method in accordance with the invention does not provide for is lnasty, such as potassium, chromium, magnesium, zirconium, ruthenium, thorium and rhenium, which could be added to the pulp or impregnated media. In the final catalyst will not contain such reinforcing synthesis promoters. As a result, the calcination of the dry impregnated carrier can be produced at relatively low temperatures, for example at a temperature below 350oC and even below 300oC.

In the case when the catalyst is intended for use in the reactor with a layer of the pulp, it can be washed after annealing the appropriate flushing means, for example, water to remove contaminants (contaminants), such as cobalt, which can form on the outer surface of the cobalt catalyst shell (shell), which does not contain aluminum oxide. This washing is performed with stirring, which can be implemented by boil water, which washed catalyst. Change from time to time water speeds up the procedure of washing.

The method in accordance with the present invention includes the restoration of the calcined catalyst, for example, by treatment with exposure to a reducing gas, such is m requirements in order to obtain the desired activity and/or selectivity, without the use of promoters enhance the synthesis, as will be described later. For example, the catalyst may have a specified minimum pore size, which is usually at least 12 nm. If the geometry of the carrier of aluminum oxide is that these geometric requirements of the resulting catalyst are not met, then the method may include appropriate pre-treatment of the carrier of aluminum oxide. For example, the method may include pre-processing of the powder carrier of alumina earlier education of the pulp with water and the active component, to change the average diameter (size) of its pores, and/or modify its chemical phase.

This pre-treatment may be a chemical pre-treatment of the carrier and/or its preliminary calcination earlier education of the pulp. In the case of chemical pre-treatment media may be handling ammonia. In particular the handling of ammonia may provide for the formation of a paste by mixing the carrier of aluminum oxide with water; spraying ammonia on aprimer, the kneading of the paste; extruding the paste, its drying, and finally calcining the paste. The specified annealing may be performed at a temperature of from 200oC to 1000oC, and mainly, from 500oC to 900oC. If desired, the paste can be added acid, such as acetic acid.

In that case, when the medium is pre-calcined without chemical pre-treatment, such as described above, this calcination can also be carried out at a temperature of from 200oC to 1000oC, and mainly, from 500oC to 900oC. More specifically, pre-processing in this case may include the mixing of the carrier of aluminum oxide with water and acid, such as acetic acid; an additional spray of water to the mixture while stirring, for example, by kneading the paste, extruding the paste, its drying, and finally calcining the paste. Water and acid, which are initially mixed with a carrier, can be a solution of diluted acid.

Naturally, extruding the paste may be optionally excluded, for example, in the case when the resulting catalyst should be used in re the soup sputtering techniques - drying, provided that it is subjected to specified temperature annealing, either in its manufacture or during preview processing, as described above. On sale are like a native oxide of aluminum, such as the carrier of the spray dried alumina, which can be purchased on the company CONDEA Chemie Gmbh, Germany.

Media aluminum oxide in accordance with the present invention differs in that it is used in a relatively pure form, contains at least only a small proportion of impurities and unwanted substances, such as titanium and/or silicon and/or a small proportion of the structural promoters, as previously mentioned. Moreover, the method in accordance with the present invention differs in that the carrier of aluminum oxide is the main or sole media, that is, the aluminum oxide is not used in combination with other media or substrates, such as titanium or silicon.

The proportion of the mass of the active component to the carrier of aluminum oxide in the slurry may range from 5:100 to 60:100, and usually from 10:100 to 45:100.

The method may include the additive in the slurry or impregnated noprobe enhance the recoverability of the active component. This additive may be instead or additionally added to the slurry, which is formed when the calcined catalyst reactivated in the slurry, as previously mentioned. The additive may contain platinum. The proportion by weight of the additive, if any, regarding the active component may comprise from 0.01:100 to 0.3:100.

The catalyst for the Fischer-Tropsch process, which is manufactured by the method in accordance with the present invention has a high specific activity and is suitable for selective conversion of synthesis gas using the reaction conditions of the Fischer-Tropsch fixed or consisting of a slurry of the catalyst; this conversion receive high molecular weight saturated hydrocarbons, for example paraffins.

The present invention will be described hereinafter in more detail with reference to the following examples that do not have restrictive data with reference to the accompanying drawings.

In Fig. 1 shows a graph of the selectivity of paraffin relative activity of the catalysts of examples 1-8.

In Fig. 2 shows a graph of the selectivity of wax relative to the pore size for catalysts of examples 5, 7, 9, 10, and 1 is reamers 36-59.

In Fig. 4 shows a graph of the conversion of CO relative selectivity for the catalysts of example 60.

In the following examples series installed on cobalt based catalysts alumina was prepared and tested for their activity in the conversion of synthesis gas into hydrocarbons.

Tests with a fixed layer

These tests were made using 40 ml of catalyst. The catalyst consisted of either milled and sifted extrudate with a particle size of from 1 to 1.7 mm or powdered dry product with a particle size of from 0.05 to 0.15 mm was Used tubular reactor with an inner diameter of 1 cm and length 100 cm of the Upper part of the reactor was filled with inert material, which acted as a pre-heater for the supplied gas. The source gas comprised of hydrogen and carbon monoxide in a molar ratio of 2:1. Hydrogen and carbon monoxide is about 84% (on a molar basis, the supply of gas. The remaining 16% are inert gases, mainly methane (14.5%) and nitrogen (about 1%). The reactor was enclosed in an aluminum jacket, which has been electric. Control of the feed flow was performed with the help of mass R is part of the full flow of power. Paraffin products were collected in the condenser with a pressure of about 1800 kPa and a temperature of 130oC. was standing Behind him with a condenser pressure of about 1800 kPa and a temperature of 20oC.

Tests with the pulp phase

From 10 to 30 g of the catalyst by spray - drying transformed into particles with a size of 38 μm to 150 μm, were suspended in 300 ml of molten paraffin and loaded in a tubular reactor, CSTR, having an internal volume of 500 ml Feed gas consisted of hydrogen and carbon monoxide in a molar ratio of 2:1. The reactor was heated electrically, and was used quite a high speed stirring, thereby to eliminate any restriction on the conversion of gas - liquid mass. Control of the feed flow was performed using a mass flowmeter of the brook, and were used in flow rate of the catalyst in the range from 1 to 3 m3/h/kg For spectrum analysis of the product was used gas chromatography as permanent gases, and volatile top of hydrocarbons.

Previously carrying out the synthesis of all the catalysts were recovered in the reactor with a fixed layer at a spatial velocity of pure hydrogen 2500 h-1and at a pressure in the range of the> at a speed of 1oC/min, then maintained isothermal conditions during the period of time from 6 to 16 hours.

Preparation of catalysts was carried out in accordance with the following examples.

Example 1

70 mm of distilled water was added 50 g of alumina powder. Then to this mixture was added 50 g of compound Co(NO3)26H2O (where Co is cobalt). The mixture is completely warmed up (mixed) and extraditables. The extrudates were dried in an oven for 2-3 hours at a temperature of 100oC, and then was hot at 350oC for 16 hours. Then received alumina powder, which can be purchased on the company Degussa FG called "Degussa aluminum oxide C".

Example 2

Similar to example 1 was prepared with the catalyst using impregnation, drying and calcination, except that a mixture of aluminum oxide with water was added 42.5 g instead of 50 g of compound Co(NO3)26H2O.

Example 3

Similar to example 1 was prepared with the catalyst, except that a mixture of aluminum oxide with water was added to 37.5 g instead of 50 g of compound Co(NO3)26H2O.

A CR compound Cr(NO3)39H2O (where Cr is chromium) as a promoter.

Example 5

70 mm of distilled water was added to 50 g of the same alumina powder as in example 1. Then to this mixture was added 50 g of compound Co(NO3)26H2O and 6.1 g of compound Mg(NO3)26H2O. the Mixture is completely warmed up (mixed) and extraditables analogously to example 1.

Example 6

Similar to example 1 was prepared with the catalyst, except that was added 0.35 g KNO3as a promoter.

Example 7

Similar to example 5 was prepared catalyst, except that was added 0.4 g KNO3instead of Mg(NO3)26H2O.

Example 8

Similar to example 1 was prepared with the catalyst, except that was added 4.9 g Th(NO3)45H2O as a promoter (where Th - thorium).

Characteristics of the catalysts of examples 1-8, as well as their properties during the synthesis of Fischer-Tropsch fixed layer are summarized in table 1.

You can see that there is a strong correlation between the selectivity of paraffin (defined here as the fraction of hydrocarbons, kondensierte promoter, as well as supplements promoter. This is more clearly seen in Fig. 1, which graphically shows the results of tables 1.

Catalysts with additional cobalt base were prepared in accordance with the following methodology in order to fully cover the entire range of pore sizes.

Example 9

Similar to example 1 was prepared with the catalyst, except that was added 12.5 g of Mg(NO3)26H2O as a promoter.

Example 10

Similar to example 5 was prepared catalyst, except that was added 4.0 g of acetylacetone Zirconia (zirconium - Zr (IV) instead of Mg(NO3)26H2O.

Example 11

Similar to example 1 was prepared with the catalyst, except that the added 0.85 grams KNO3as a promoter.

The obtained catalysts were dried, calcined and tested regarding their conduct during the synthesis of the fixed layer, similarly as it was done for the catalysts of examples 1-8. Physical characteristics and catalytic activity of the catalysts are presented in table 2.

From table 2 one can see that for a given activity (naprimer pores of the catalyst. This ratio does not depend on the type of added promoter. This is more clearly seen in Fig. 2, which graphically shows the results of table 2.

In examples 1-11 was used evaporated aluminum oxide, which was abstrogirovalsya together with the catalytically active components. An alternative approach is extruding (or spray drying and calcination of the carrier of aluminum oxide separately in the form of the first preparatory operations previously impregnation of the active component (components). This technique provides greater freedom regarding the selection of the geometry of the media.

In this application was used precipitated alumina supplied by the company Condea Chemie Gmbh under the brand names "Pural SB alumina", Puralox SCCa 5/150 or Puralox HP 5/180". The average pore size of the substrate was increased using the following techniques pre-treatment: annealing and/or chemical treatment with an alkaline compound such as ammonia. Examples 12-35 aimed at creating media with pre-processing.

Example 12

125 ml of acetic acid, diluted with 1.7 liters of distilled water were added to 2 kg of Pural SB alumina obtained by the company Condea. While kneading the mixture owls and calcined at a temperature of 600oC for 16 hours, to obtain in the media with pre-processing.

Example 13

The substrate was prepared analogous to example 12 by the way, except that the temperature of calcination was 700oC instead of the 600oC.

Example 14

The substrate was prepared analogous to example 12 by the way, except that the temperature of calcination was 800oC instead of the 600oC.

Example 15

125 ml of acetic acid, diluted with 1.4 liters of distilled water were added to the mixer to 2 kg Pural SB alumina obtained by the company Condea. Then over pasta with ammonia sprayed 250 ml of ammonia (volume of 12.5 percent). While kneading the mixture was additionally sprayed with 1.2 liters of water. The alumina was extruded, dried at 120oC for 12 hours and calcined at a temperature of 600oC for 16 hours.

Example 16

The substrate was prepared analogous to example 15 by the way, except that the temperature of calcination was 700oC instead of the 600oC.

Example 17

The substrate was prepared analogous to example 15 by the way, except that the temperature of calcination is therouanne water. In this solution were dissolved 20 g of Zr(NO3)45H2O. Then the resulting solution was sprayed onto 300 g of Pural SB alumina, while mixing in the mixer. While kneading the paste is then further sprayed 180 ml of 1.8% by volume of ammonia. The paste was extruded, dried at 120oC for 2 hours and calcined at a temperature of 750oC for 16 hours.

Example 19

A solution of 100 g 4Mg(CO3) Mg(OH)2) 4H2O, 160 ml of CH3COOH and 150 ml of distilled water was sprayed onto 300 g of Pural SB alumina, while mixing in the mixer. While kneading the paste is then further sprayed 220 ml of 12.5% by volume of ammonia. The paste was extruded, dried at 120oC for 2 hours and calcined at a temperature of 750oC for 16 hours.

Example 20

A solution of 30 g of Zr(NO3)45H2O in 210 ml of distilled water was sprayed onto 300 g of Pural SB alumina, while mixing in the mixer. While kneading the paste is then further sprayed 180 ml of a 3.5% by volume of ammonia. The paste was extruded, dried at 120oC for 2 hours and calcined at a temperature of 750oC for 16 hours.

Example 210 g of Mg(NO3)26H2O instead of 20 g of Zr(NO3)45H2O.

Example 22

The substrate was prepared analogous to example 18 by the way, except that there were used 9 g KNO3instead of 20 g of Zr(NO3)45H2O.

Example 23

The substrate was prepared analogous to example 18 by the way, except that there were used 20 g of Mg(NO3)24H2O instead of 20 g of Zr(NO3)45H2O.

Example 24

The substrate Puralox SCCa 5/150 was calcined at 750oC for 16 hours.

Example 25

The substrate Puralox SCCa 5/150 was calcined at 800oC for 16 hours.

Example 26

The substrate Puralox SCCa 5/150 was calcined at 900oC for 16 hours.

Example 27

The substrate Puralox SCCa 5/150 was calcined at 1000oC for 16 hours.

Example 28

The substrate Puralox HP 5/180 was calcined at 600oC for 16 hours.

Example 29

The substrate Puralox HP 5/180 was calcined at 700oC for 16 hours.

Example 30

The substrate Puralox HP 5/180 was calcined at 750oC for 16 hours.

Example 31

The substrate Puralox HP 5/180 was calcined at 800oC for 16 hours.

>The substrate Puralox HP 5/180 was calcined at 1000oC for 16 hours.

Example 34

The substrate Poralox HP 5/180 was calcined at 1100oC for 16 hours.

Example 35

The substrate was prepared analogous to example 15 by the way, except that there was used the temperature of annealing 750oC instead of the 600oC.

Physical properties of substrates with pre-processing examples 12-35 is given in table 3.

You can see that the temperature of the annealing leads to a decrease of the surface area of the carrier. This effect is very similar for both types of substrates, i.e. by treatment with ammonia and without it.

The average pore size increases with increasing temperature of annealing. Catalysts prepared with ammonia, have a greater average pore size than the catalysts prepared without ammonia.

Substrate examples 12-35 were impregnated with cobalt to determine the effect of mean pore size on the selectivity of paraffin. Was used the following methodology:

50 g of substrate were added to a solution containing 50 grams of Co(NO3)26H2O and 0.05 g of Pt(NH3)4(NO3)2(where Pt - pay the congestion was calcined at 350oC in the counter-current of air for 6 hours.

The average pore size and selectivity of the reactor wax, obtained in a tubular reactor with a fixed layer used in examples 1-11 in table 4.

From table 4 we can see that in this activity, the selectivity of the reactor wax is a function of the average pore size of the catalyst, regardless of the type of promoter used (for example, Zr, Mg, Mn, or K). This is more clearly seen in Fig. 3, which brought together the results of table 4.

Thus, these examples of synthesis in a tubular reactor with a fixed layer show that the main variable affecting the selectivity of the paraffin in the catalyst Fischer-Tropsch process with a cobalt is the average diameter of pores of the substrate or carrier, as well as the inherent catalyst activity.

In the following examples 60-65 was used commercially obtained by drying with spray and calcined alumina type Puralox SCCa 5/150. This material was calcined at a temperature of from 600oC to 700oC in the process of its manufacture. This substrate material aluminum oxide had a pore size of 12.5 nm, which, as seen in Fig. 3, javljaetsja material are given in table 5.

With the help of the media were prepared with 6 catalysts.

Example 60

40 grams of Co(NO3)26H2O were dissolved in 50 ml of distilled water and 50 g of Al2O3Puralox SCCa 5/150 were suspended in this solution. The resulting slurry was processed for about 2.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa in a rotary evaporator for impregnation of the carrier of aluminum oxide and drying the impregnated carrier. The dried impregnated carrier was further dried and calcined at a temperature of 230oC for 2 hours in air flow of 1.5 liters/min, the Resulting calcined sample was re-translated in suspension in the solution, which is prepared using dissolved in 50 ml of distilled water, 35 g of Co(NO3)26H2O and 50 mg of Pt(NH3)4(NO3)2. This pulp was re-treated in vacuum for about 1.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa to achieve free flow in a rotary evaporator. The dried impregnated carrier was further calcined at a temperature of 230oC for 2 hours in air flow of 1.5 liters/min.

Example 61

40 grams of Co(NO3is iravani in this solution. The resulting slurry was processed for about 2.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa in a rotary evaporator for impregnation of the carrier of aluminum oxide and drying the impregnated carrier. The dried impregnated carrier was calcined at a temperature of 380oC for 5 hours in air flow of 1.5 liters/min, the Resulting calcined sample was re-translated in suspension in the solution, which is prepared using dissolved in 50 ml of distilled water, 35 g of Co(NO3)26H2O. This slurry was re-treated in vacuum in a rotary evaporator for about 2.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa, followed by calcination at a temperature of 380oC for 5 hours in air flow of 1.5 liters/min. Annealed sample was re-translated in suspension in the solution, which is prepared using dissolved in 50 ml of acetone and 0.8 g of acetylacetone ruthenium (Rn (III). The resulting slurry was re-treated in vacuum, that is dried at a temperature of 75oC and at a pressure of from 2 to 5 kPa to achieve free flow in a rotary evaporator. The dried impregnated carrier was further calcined at t the SUB>26H2O and 1.2 g of rhenium acid (HReO4) were dissolved in 50 ml of distilled water, and 50 g of Al2O3Puralox SCCa 5/150 were suspended in this solution. The resulting slurry was treated in vacuum for approximately 2.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa in a rotary evaporator for impregnation of the carrier of aluminum oxide and drying the impregnated carrier. The dried impregnated carrier was calcined at a temperature of 350oC for 5 hours in air flow of 1.5 liters/min. Annealed sample was re-translated in suspension in the solution, which is prepared using dissolved in 50 ml of distilled water, 35 g of Co(NO3)26H2O and 0.8 g of rhenium acid. The resulting slurry was again dried in vacuum for approximately 2.5 hours at a temperature of 75oC and at a pressure of from 2 to 5 kPa to achieve free flow in a rotary evaporator, followed by calcination at a temperature of 350oC for 5 hours in air flow of 1.5 liters/min.

Example 63

29,6 g Co(NO3)26H2O and 30 mg of Pt(NH3)4(NO3)2were dissolved in 50 ml of distilled water, and 50 g of Al2O3Puralox SCCa 5/150 were WM and a temperature of 75oC and at a pressure of from 2 to 5 kPa in a rotary evaporator for impregnation of the carrier of aluminum oxide and drying the impregnated carrier. The dried impregnated carrier was calcined at a temperature of 230oC for 2 hours in air flow of 1.5 liters/min, the Resulting calcined sample was re-transferred to the solution, which was prepared by dissolving of 19.8 grams of Co(NO3)26H2O and 20 mg of Pt(NH3)4(NO3)2in 50 ml of distilled water. This slurry was again dried in vacuum for approximately 2.5 hours at a temperature of 75oC and a pressure of from 2 to 5 kPa to achieve free flow in a rotary evaporator. The dried impregnated carrier was further calcined at a temperature of 230oC for 2 hours in air flow of 1.5 liters/min.

Example 64

This example is similar to example 63 with the following changes:

1st impregnation: 30 grams of Co(NO3)26H2O were used instead of 40 g of Co(NO3)26H2O

2nd impregnation: 20 grams of Co(NO3)26H2O were used instead of 35 grams of Co(NO3)26H2O

3rd treatment: 0.55 g of acetylacetone ruthenium (Ru (III) were used in place of 0.8 g of acetylacetone ruthenium (Ru (III).

Example 65

26 kg Al2O3Puralox SCCa 5/150 were initially impregnated with 12.5 liters of an aqueous solution containing 13,9 kg Co(NO3)26H2O and 8.6 g of Pt(NH3)4(NO3)2. This impregnated sample was dried at a temperature of 80oC for 10 hours in air flow of 40 liters/min, followed by annealing at a temperature of 240oC for 4 hours in air flow 250 l/min During the initial impregnation was used, the volume of impregnating solution, that is, the above aqueous solution is equal to the pore volume of the carrier of aluminum oxide.

Then came the second operation initial impregnation, in which the obtained sample was soaked to 11.3 liters of an aqueous solution containing 12.1 kg of Co(NO3)26H2O and 8.6 g of Pt(NH3)4(NO3)2. Drying and calcination were carried out similarly to the first operation.

Then came the third and last operation in the initial impregnation, in which the obtained sample was soaked to 13.2 liters of an aqueous solution containing 14,2 kg Co(NO3)26H2O and 8.6 g of Pt(NH3)production example 60 was used successfully on a larger scale pilot plant, at approximately the same scale as in example 65. It was found that proper vacuum drying is an important parameter in case of the variant impregnation of the pulp in an enlarged scale. The final moisture content of this dried impregnated catalyst should be less than approximately 20 percent by weight. This allows to carry out the annealing, in which the dried impregnated catalyst is initially passed through a countercurrent air dryers (the residence time of approximately 1 min) with a temperature of 180oC, with an immediate drop in the tubular calcinator with temperature 250oC. the Flow of air through the calcinator set at the level of approximately 8 DM3/kg cat/min, with a surface speed of approximately 5 cm/sec. For complete calcination takes time more than 3 hours, and mostly about 6 hours.

In examples 60, 63 and 65 promoter was not used. Small amounts of platinum were added to facilitate the recovery of the catalyst. These amounts represent about 0.03 to 0.08 g Pt per 100 g of alumina, and is expected to co-impregnated with the operations of impregnation (for example, example 65) or to concentrate in the final aestii with examples 60 - 65 is shown in table 6.

From table 6 we can draw the following conclusions:

- The promoters of Ru or Re (ruthenium or rhenium), which are costly when required quantities not result in increased specific activity of Fischer-Tropsch when the content of cobalt is approximately 20% by weight (for example, 30 g Co/100 g Al2O3).

- The use of the catalysts with the basics of cobalt-known kinetic ratio of Fischer-Tropsch, such as

< / BR>
shows that characterized the activity is linearly proportional to the amount of cobalt in the catalyst: m Co/0,05 Pt/100 Al2O3(Al2O3Puralox SCCa 5/150), to levels m = 30 (i.e. constant use of cobalt). At high loadings of cobalt (i.e. m > 30) the use of cobalt decreases.

- The preparation of the catalyst: m Co/0,05 Pt/100 Al2O3the method of impregnation of the pulp (for example, example 60) is preferred compared to the initial wet impregnation (for example, example 65). The first impregnation method allows to obtain a catalyst with the inherent level of activity of Fischer-Tropsch, which is approximately 1.35 times higher than the last.

A study was conducted and modelirovanie 7 contains an example of the most suitable theoretical izbiratelnata Schulz-Flory this catalyst, under specified conditions of synthesis.

A graphical illustration of table 7 shown in Fig. 4, which emphasized the dependence of activity and selectivity, which is also visible in Fig. 1 for applications with a fixed layer.

As for the quality of the wax, the method impregnated pulp (for example, described in the preparation of example 60) has the advantage over option initial wet impregnation (for example, described in the preparation example 65).

The reaction paraffin, obtained using the catalyst of example 65, contains a suspension of submicron particles of Co3O4when the cobalt concentration is approximately 100 million-1that cannot be removed by filtering through filter paper Whatman 42. This also affects the color of the wax, which is color filtered reactor paraffin attributed to unwanted 16 categories (i.e. the darkest indicator).

The origin of these submicron particles of Co3O4pollution is caused by the presence of clearly defined shell that contains only Co without Al (studies using scanning electron microscope visible shell Tolomei full washing the calcined catalyst of example 65 able to successfully remove this enriched in cobalt material, without any effect on the specific activity of the Fischer-Tropsch process. This is despite the fact that approximately 8% of the original content of cobalt can be washed out.

Details of methods of washing water

Experiments accumulated at wash approximately 5 kg of catalyst according to example 65 (that is, after the operation of the final annealing and before recovery), show that requires at least 25 litres of water per one kg of catalyst.

When washing, you should observe the following:

- Water should be mixed to the highest degree that can be achieved by boiling.

- Change the water from time to time helps to speed up the procedure, while the recommended 25 liters per kg of catalyst eventually lightened.

Unwanted contamination of the wax is almost completely excluded in the case of catalysts impregnated in the pulp phase (for example, example 60), namely, catalysts with a more uniform distribution of cobalt in all particles have a smaller encapsulation shell of cobalt oxide.

Besides this, the operation of washing with water is recommended to obtain paraffin of high quality. Paraffin is only from 1 to 3 million-1cobalt, which leads to a color gradation of 10, after filtering through filter paper Whatman 42.

Thus, very active catalysts for the Fischer-Tropsch-based cobalt (fixed layer and phase slurry) can be prepared relatively simply and inexpensively, as in accordance with the present invention does not require, for example, expensive promoter selectivity of paraffin.

1. The method of producing catalyst Fischer-Tropsch process, wherein the pulp, which includes a powder carrier of aluminum oxide, water, and cobalt (Co) as an active ingredient, put the vacuum, resulting in a carrier of aluminum oxide impregnated with active ingredient, dried impregnated carrier in a vacuum, calcined dried impregnated carrier, resulting in a gain catalyst for Fischer-Tropsch.

2. The method according to p. 1, characterized in that the vacuum impregnation is less than 20 kPa.

3. The method according to p. 1 or 2, characterized in that the vacuum drying is less than 20 kPa.

4. The method according to one of paragraphs.1 to 3, characterized in that the impregnation and drying under vacuum is carried out at the same time.

5. Method one is ositelu will not be less than 20% by weight, after drying the impregnated carrier continue further transmission of the drying medium over the impregnated carrier in a countercurrent or concurrent flow with the drying temperature of 100 to 180oC.

6. The method according to one of paragraphs.1 to 5, characterized in that added to the pulp or impregnated 'green' media, in the form of an additive, a small amount of a substance capable of enhancing the recoverability of the active component.

7. The method according to p. 6, wherein the additive contains platinum (Pt), and the mass of the additive in relation to the active component is 0.005 : 100 to 10 : 100.

8. The method according to one of paragraphs.1 to 7, characterized in that the calcined catalyst re-convert the slurry when mixed with water and at least one of the following components: the active component, the other active component or in the form of additives, with a small amount of a substance that can increase the recoverability of the active component, obtaining the resulting impregnated carrier, which is again subjected to calcination and drying.

9. The method according to one of paragraphs.1 to 8, characterized in that the calcination of the dry impregnated carrier is produced when temperaturem means for removing pollutants.

11. The method according to one of paragraphs.1 to 10, characterized in that it envisages the formation of a slurry by dissolving in water a water-soluble compound of the active component, formerly the education of the pulp with a carrier of alumina powder, and the formation of the pulp associated with deep mixing media aluminum oxide and a solution of the compound of the active component.

12. The method according to p. 11, characterized in that conduct pre-treatment powder carrier of aluminum oxide to form a slurry with water and the active component, to change the average diameter of its pores and/or modify its chemical phase, and this pre-processing is a chemical pre-treatment of the carrier and/or the preliminary calcination media earlier education of the pulp.

13. The method according to one of paragraphs.1 - 12, characterized in that the mass of the active component in relation to the carrier of aluminum oxide in the slurry is from 5 : 100 to 60 : 100.

14. The method according to p. 1, characterized in that the pulp or impregnated carrier will not add a promoter selected from the group consisting of potassium, chromium, magnesium, zirconium, ruthenium, thorium, and rhenium, to enhance the activity of p so, what powder carrier of aluminum oxide has pores with a minimum diameter of 12 nm, and/or pre-treated with ammonia, and/or calcined at a temperature of from 200 to 1000oC.

 

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