Cobalt-based catalyst precursor preparation method and fischer-tropsch catalyst preparation method

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

 

This invention relates to catalysts based on cobalt. Specifically, the present invention relates to a method for producing a catalyst precursor Fischer-Tropsch cobalt-based, to a method for producing such a catalyst based on cobalt and to a method for producing hydrocarbons using a catalyst based on cobalt.

Known methods for producing precursors of catalysts based on cobalt, which include the impregnated catalyst carrier suspension cobalt salts, drying the impregnated catalyst carrier, and calcining the dried impregnated catalyst carrier with obtaining the desired cobalt content on the media. The obtained precursor is then activated by restoring them with obtaining catalysts of the Fischer-Tropsch cobalt-based. These catalysts can exhibit high activity when used in the processes of Fischer-Tropsch synthesis; however, catalysts with high or excellent activity cannot easily be obtained by known methods. Thus, the purpose of this invention is to provide a catalyst Fischer-Tropsch cobalt-based, with characteristic high initial and/or stable activity in the processes of Fischer-Tropsch synthesis, and method of preparation of such a catalyst.

The agreement is but the first aspect of the present invention provides a method of obtaining a catalyst precursor on the basis of cobalt, which includes: in the first stage of impregnation of the carrier/drying/calcination of the impregnated porous particles of the catalyst carrier salt of cobalt, partially drying the impregnated carrier, and calcining the partially dried impregnated carrier with obtaining a calcined product; partial recovery of the calcined product and the second stage impregnation media/drying/calcination treatment partially restored product salt of cobalt, partially drying the impregnated product, and calcining the partially dried impregnated product with obtaining a catalyst precursor cobalt-based.

The resulting precursor of the catalyst based on cobalt can then be recovered by obtaining catalyst for Fischer-Tropsch cobalt-based. Unexpectedly, it was found that this catalyst has a characteristic of high or excellent initial and stable activity in the processes of Fischer-Tropsch synthesis.

Therefore, according to the second aspect of the invention provides a method of producing catalyst for Fischer-Tropsch cobalt-based, which includes:

at the first stage of impregnation of the carrier /drying / calcination of the impregnated porous particles of the catalyst carrier salt of cobalt, partially drying the impregnated carrier, and calcining the partially misuse the aqueous saturated media with obtaining a calcined product;

partial recovery of the calcined material;

in the second stage impregnation media /drying / calcination treatment partially restored product salt of cobalt, partially drying the impregnated product, and calcining the partially dried impregnated product with obtaining precursor catalyst based on cobalt and

the recovery of the precursor of the catalyst based on cobalt with obtaining catalyst for Fischer-Tropsch cobalt-based.

In this description, unless otherwise specified, the weight of the catalyst means the weight of the calcined catalyst, i.e. the weight of catalyst before its restoration.

During the partial recovery of the calcined product of the cobalt oxide contained in the calcined product, i.e. the initial phase of cobalt oxide is partially restored to cobalt oxide containing less oxygen than the original phase of cobalt oxide. Not limited to any theory, it should be noted that, as I believe, this is the phase containing less oxygen than the original phase of cobalt oxide, is a phase similar to the COO. Within this description, when reference is made to the phase Soo, I mean, what does it mean phase partially restored oxide of cobalt.

Effective partial recovery calcined what the product can be evaluated by carrying out x-ray analysis or when carrying out experiments on the restoration of the calcined material at the programmed temperature.

Partial recovery of the calcined product can be performed at a temperature between a minimum temperature, which is defined as the lowest temperature at which the partial recovery of the initial phase of cobalt oxide, and the maximum temperature, which is defined as the lowest temperature at which begins the recovery phase COO to metallic cobalt. Thus, the minimum temperature can be 100°C, preferably 130°C, the maximum temperature may be equal to 300°C, preferably 250°C.

Partial recovery of the calcined product can be performed by contacting the calcined product gas containing hydrogen and/or carbon monoxide, forming the exhaust gas.

After partial recovery, which occurs at the stage of partial recovery or the container (S) can be unloaded in an inert atmosphere at a temperature of partial recovery. Instead, you can unload in the air after the first cooling, or cooling temperature partial restore to room temperature. Phase Soo is stable in air at room temperature. Stage a partial recovery can be achieved by shielding pricelinemortgage with gaseous reducing agent, for example, in the fluidized bed of particles of calcined material with a gaseous reducing agent, acting as sigalda environment; in a fixed layer of particles of calcined material, through which pass the gas-reducing agent, etc.

Salt of cobalt can be, in particular, cobalt nitrate, Co(NO3)2·6N2O.

The modified catalyst carrier in the form of particles may be any commercially available porous oxide catalyst carrier, for example, alumina (Al2About3), silicon oxide (SiO2), a mixed oxide of silicon-aluminum (SiO4×Al2About3), titanium oxide (TiO2) and magnesium oxide (MgO).

The media can be protected modified catalyst carrier containing, for example, silicon as a modifying component, as described in the application WO 99/42214 included in this description by reference.

The carrier impregnated as impregnation partially recovered product can, in principle, be carried out by any suitable known method of impregnation, for example, by impregnation with wetting or impregnation suspension. Similarly, calcining the impregnated carrier, and calcining the partially recovered material that has been impregnated, can be implemented in any suitable device for annealing, for example, in pseud the liquefied layer, in the fixed layer in the furnace, in a rotating chamber dryer and/or calcinator preferably at temperatures between 150 and 300°C. In particular, the annealing can be performed as described in the application PCT/IB 00/01745 included in this description by reference.

The calcination may be in the fluidized bed, as described in the application PCT/IB 00/01745.

The carrier impregnated and partially restored product, drying and calcination can in particular be implemented in accordance with the method described in our related application WO 00/20116, which is incorporated in this description by reference. Getting predecessor may, therefore, enable two-step impregnation method suspension, partial drying and calcination, as described in the application WO 00/20116 which is affected by the magnitude of the desired content of the active component (cobalt) and pore volume of the porous carrier oxide catalyst.

The impregnation of the support and drying usually can be performed in a conical vacuum dryer with a rotating auger or vacuum drum dryer.

The catalyst precursor may contain 5-70 g Co/100 g of carrier, preferably 20-50 g Co/100 g of carrier.

During one or both stages of impregnation may be added water-soluble salt of palladium (Pd) or platinum (Pt) or a mixture of such salts as dopasowywa supplements, FPIC is stuudy recovery of cobalt.

It is preferable to add this depireux additive mass ratio of palladium, platinum or a mixture of palladium and platinum and cobalt, equal to from 0.01:100 to 0.3:100.

The invention relates also to a catalyst for Fischer-Tropsch cobalt-based, obtained by the process according to the second aspect of the present invention, and the precursor of the catalyst based on cobalt, obtained by the method according to the first aspect of the present invention.

According to a third aspect of the invention provides a method of producing hydrocarbons, which comprises contacting synthesis gas containing hydrogen (H2) and carbon monoxide (CO), at an elevated temperature between 180 and 250°and increased pressure between 1 and 40 bar with a catalyst based on cobalt according to the invention in suspension by the reaction of the Fischer-Tropsch process - the interaction of hydrogen with carbon monoxide to obtain hydrocarbons.

The invention also covers hydrocarbons obtained by the method described in this application.

Below the invention will be described in more detail with reference to the following examples do not limit the invention, and drawings.

figure 1 shows the process of recovery of catalyst G with the programmed mode change temperature (TPR) after the first stage impregnation/drying and calcination;

figure 2 shows TPR catalyst G pic the e stage a partial recovery.

figure 3 shows the TPR catalyst G after the second and last stage of impregnation/drying/calcination.

Example 1.

The catalyst (30 g With /0.075 g Pt /100 g Al2O3) (not according to invention).

The receipt.

Promoted platinum catalyst was obtained with the application of the product SASOL Germany GmbH: Puralox SCCa 5/150 as the carrier is pre-formed Al2About3in accordance with the method of impregnation with an aqueous suspension and vacuum drying followed by calcination in a fluidized bed; in accordance with Example 1 of the application WO 00/20116 or one of the catalysts D, E, G or H in the application PCT/IB 00/01745.

The preparation used in the process of the Fischer-Tropsch synthesis on a laboratory scale in a continuously stirred reactor (CSTR) in suspensions of this calcined product, which was restored and covered with wax, was carried out by the following procedure:

27.5 g of the catalyst was restored in an atmosphere of pure hydrogen at a pressure of 1 bar (vhsv ≥200 ml of N2/g of catalyst/hour), the temperature was increased from 25 to 380-425°at the rate of 1°C/min, after which the temperature was held constant at this temperature 380-425°C for 16 hours.

The recovered catalyst was allowed to cool to room temperature, and the hydrogen was replaced by argon, the catalyst was unloaded in RA the melted wax is Fischer-Tropsch process in an argon atmosphere. The catalyst with a coating of wax was then transferred into the reactor, where the formed suspension.

The process of the Fischer-Tropsch synthesis (CSTR).

This process of Fischer-Tropsch synthesis (CSTR) (room 106F) was performed in the presence of a catalyst C. This experience lasted about 90 days, during which was supported by the following synthesis conditions:

the temperature in the reactor:220,5°
the pressure in the reactor:20,3 bar
amount of catalyst:20,8 g
space velocity (H2+CO)2169 ml/g catalyst/h
the volumetric rate of APG2452 ml/g catalyst/h

where APG denotes Arge Pure Gas, i.e. industrial synthesis gas obtained Schümann-Sasol (Pty) Limited in Sasolburg, South Africa, according to the method of coal gasification with subsequent cleaning method Rectisol.

The composition of the injected gas:

H2:49,1%vol.
WITH:25,9%vol.
CH4:9,3%vol.
CO2:0,5%vol.
Ar:15,2%vol.

The parameters obtained in this experiment (106F), are presented in Table 1.

Factor relative (Fischer-Tro is Sha) is the characteristic activity (RIAF) was defined as follows.

The catalyst for the Fischer-Tropsch cobalt-based was characterized in the process of the Fischer-Tropsch synthesis:

rFT=Z moles WITH, turned into the products of the Fischer-Tropsch synthesis per gram of catalyst per second, at T=γ Kelvin at the next partial pressure:

PHZ=ν bar

PCO=τ bar

RIAF is equal to:

RIAF=[Z(1+ 1,82 τ)2] / [49480,9 e(-11113,4/γ)ντ]

The initial characteristic activity of Fischer-Tropsch (aiof catalyst based on cobalt suspension is defined as follows:

andi=RIAF after 15 hours (i.e. ti=start time) continuous mezhrajjonnogo synthesis in suspension: 220°C, 20 bar, % conversion (N2+JI) above 50%, the initial gas mixture had the composition: about 50 vol.% H2and about 25 vol.% And the rest - Ar, N2CH4and/or CO2.

Example 2.

An example of the preparation of the catalyst based on cobalt on the media Al2O3in the suspension according to this invention (catalyst G), which is characterized by high initial characteristic activity of Fischer-Tropsch.

Catalyst G (30 g With/0.075 g Pt /100 g Al2O3)

Promoted platinum catalyst based on cobalt cook on medium SASOL Germany GmbH: Puralox SCCa 5/150 in accordance with the method of impregnating water with which spezie and drying in vacuum, followed by calcination in a fluidized bed, described in U.S. patent 5733839, applications WO 99/42214 and WO 00/20116. The catalyst was prepared as follows.

44,6 g With(NO3)2·6N2Oh was dissolved in 40 ml of distilled water and 0,0248 g (NH3)4Pt(NO3)2was dissolved in 10 ml of distilled water. These two solutions were mixed in a round bottom flask of 500 ml in rotary evaporator at 60°and atmospheric pressure and added 50 g of the carrier Puralox SCCa 5/150. Impregnation in aqueous suspension and vacuum drying was carried out under the following conditions:

The oil bath temperature (°)The pressure in a rotary evaporator (mbar)Time(min)
60Naturally10
6024030
7024490
8524260
8550240

The obtained intermediate product, dried under vacuum, was immediately subjected to calcination in a fluidized bed under the following conditions:

Continuous air flow of 1.7 DM3/min;

Temperature range:

25°-(1°C/min)→250°-(6 hours)→250°

This calcined intermediate product of the first stage impregnation with cobalt/is Latino and annealing was then subjected to a second impregnation stage a partial recovery. For this purpose, this intermediate product was recovered pure hydrogen under a pressure of 1 bar (volumetric rate of 2000 ml of N2/g/h), the temperature was increased from 25 to 230°at the rate of 1°C/min, after which the temperature was maintained equal to 230°C for 2 hours.

35,0 g this partially restored the intermediate product was placed in an aqueous impregnating solution in the second stage impregnation of cobalt/ platinum in an atmosphere of argon, and the impregnating solution was prepared as follows:

22,7 g With(NO3)2·6N2Oh was dissolved in 28 ml of distilled water, 0,0401 g (NH3)4Pt(NO3)2was dissolved in 7 ml of distilled water. These two solutions were mixed together in a round bottom flask of 500 ml in rotary evaporator at 60°and atmospheric pressure.

Impregnation in aqueous suspension and vacuum drying was carried out as follows:

The oil bath temperature (°)The pressure in a rotary evaporator (mbar)Time(min)
60Naturally10
6030030
7030790
8530160
85 50240

The obtained intermediate product, dried under vacuum, was immediately subjected to calcination in a fluidized bed under the following conditions:

Continuous air flow of 1.7 DM3/min;

Temperature range:

25° - (1°C/min)→250° - (6 hours)→250°

Recovery when the programmed temperature was performed using the intermediate products after the first stage of impregnation and calcination, after a partial recovery, and after the second stage impregnation and calcination. Figure 1 shows that the curve TPR intermediate product for the preparation of the catalyst after the first stage impregnation and calcination is characterized by multiple areas, reflecting the recovery stage. The first two peaks recovery may reflect a recovery to the COO, and the last broad peak characterizes the restoration of COO to metallic cobalt. Mode TPR sample of the catalyst after stage a partial recovery (i.e. Figure 2) is characterized by only a broad peak recovery COO to metallic cobalt. Thus, partial recovery caused recovery of oxides of cobalt with the formation of COO. Mode TPR product, which is an intermediate for the preparation of the catalyst, after the second impregnation stage and procelian is I (Figure 3) is again characterized by several peaks recovery similar to the peaks on the curve TPR for the sample after the first impregnation and calcination.

The calcined catalyst precursor was recovered and got on it a wax coating in accordance with the procedure described for catalyst B, with the purpose of use for the synthesis CSTR in the slurry Fischer-Tropsch process at laboratory scale.

The catalyst G was experienced in the implementation of the Fischer-Tropsch synthesis as described in Example 1.

The results are shown in Table 1.

The data in Table 1 allow us to conclude the following.

Catalyst G, namely 30 g With/0.075 g Pt/100 g Al2About3obtained with the use of stage a partial recovery, which is an additional stage in the process of obtaining, characterized by an initial RIAF, equal to 4.7, which is approximately 70% higher than the initial RIAF (2,8) catalyst, namely 30 g With/0.075 g Pt/100 g Al2About3obtained without the use of stage a partial recovery.

This invention has unexpectedly allowed to establish that the catalysts of the Fischer-Tropsch cobalt-based showed increased characteristic catalytic activity, when these catalysts were prepared with the use of stage a partial recovery, which is an additional stage in the process of preparation of the catalyst, is about the last stage of impregnation/drying and calcination, that is, stage a partial recovery carried out between the first and second stage impregnation/drying and calcination.

1. A method of obtaining a catalyst precursor on the basis of cobalt, including the impregnation of the porous carrier particles for catalyst cobalt salt, partially drying the impregnated carrier, and calcining the partially dried impregnated carrier with obtaining a calcined product containing the original cobalt oxide; partial recovery of the calcined product at a temperature of from 100 to 300°obtaining partially recovered product and treatment partially restored product salt of cobalt, partially drying the impregnated product, and calcining the partially dried impregnated product with obtaining a catalyst precursor cobalt-based.

2. The method according to claim 1, wherein the partial recovery of the calcined product conduct when contacting the calcined product gas containing hydrogen and/or carbon monoxide with obtaining off-gas.

3. The method according to claim 1, wherein the salt of cobalt, which is used in both stages of impregnation/drying/calcination, is a nitrate of cobalt, and a porous catalyst carrier is an aluminum oxide, silicon oxide, a mixed oxide of silicon, aluminium, titanium oxide or the oxide of m is fester.

4. The method according to claim 1, wherein the carrier is a protected modified catalyst carrier containing silicon as a modifying component.

5. The method according to claim 1, wherein the precursor of the catalyst based on cobalt contains 5 g Co /100 g of the carrier - 70 g Co /100 g of carrier.

6. The method according to any one of claims 1 to 5, wherein during one or both stages of impregnation add a water-soluble salt of palladium (Pd) or platinum (Pt) or a mixture of these salts as additives to facilitate recovery of cobalt.

7. The method of producing catalyst for Fischer-Tropsch cobalt-based, including the impregnation of the porous carrier particles for catalyst cobalt salt, partially drying the impregnated carrier, and calcining the partially dried impregnated carrier with obtaining a calcined product containing the original cobalt oxide; partial recovery of the calcined product at a temperature of from 100 to 300°obtaining partially recovered product and treatment partially restored product salt of cobalt, partially drying the impregnated product, and calcining the partially dried impregnated product with obtaining precursor catalyst based on cobalt and recovery of the catalyst precursor on the basis of cobalt with obtaining catalyst Fischer-Tro is Sha cobalt-based.

8. The method according to claim 7, wherein the partial recovery of the calcined product conduct when contacting the calcined product gas containing hydrogen and/or carbon monoxide with obtaining off-gas.

9. The method according to claim 7, wherein the salt of cobalt, which is used in both stages of impregnation/drying/ calcination, is a nitrate of cobalt, and a porous catalyst carrier is an aluminum oxide, silicon oxide, a mixed oxide of silicon, aluminium, titanium oxide or magnesium oxide.

10. The method according to claim 7, wherein the carrier is a protected modified catalyst carrier containing silicon as a modifying component.

11. The method according to claim 7, wherein the precursor of the catalyst based on cobalt contains 5 g Co /100 g of the carrier - 70 g Co /100 g of carrier.

12. The method according to any of claims 7 to 11, wherein during one or both stages of impregnation add a water-soluble salt of palladium (Pd) or platinum (Pt) or a mixture of these salts as additives to facilitate recovery of cobalt.



 

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2 cl, 3 tbl, 2 ex

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55 cl, 4 dwg

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