Catalyst for synthesis of hydrocarbons from co and h2 (fischer-tropsch synthesis)

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

 

The invention relates to the chemical industry, in particular to the composition of the catalysts, and can be used for the conversion of synthesis gas to alcohols and hydrocarbons.

Known catalytic composition consisting of cobalt in the amount of 1-50 wt.%, tantalum in an amount of 0.05-5 wt.% and supplements inert carrier up to 100%consisting of silicon dioxide, aluminum oxide, titanium dioxide and related compounds [1].

Closest to the invention to the technical essence and the achieved effect is the catalyst for the conversion of synthesis gas to hydrocarbons in the Fischer-Tropsch synthesis, representing the cobalt 12-40 wt.%; the platinum group metals: platinum, iridium, rhodium, or a mixture of 0.1-1.9 wt.%; else γ-alumina. When the catalyst contains 0.25-4.75% platinum group metal content of cobalt and 1% promoters of a mixture of oxides of rare earth elements [2].

The disadvantages are considered catalysts should be attributed to the low degree of conversion of CO to alcohols and hydrocarbons.

To eliminate this drawback is proposed catalyst consisting of an active component, promoter F with the addition of the promoters of the platinum group metals (platinum, palladium) or the first transition series (copper, chromium, zinc, titanium, or mixtures thereof and containing a carrier of aluminum oxide at the following content to the components, wt.%:

Active ingredient (in terms of Soo)10-20
The promoter F0,1-1,0
The promoter metals of the platinum group or the first
the transition series, or mixtures thereof0.3 to 1.0
Mediarest

It was found that the addition of fluorine in a concentration of from 0.1 to 1 wt.% the catalyst leads to a significant increase in CO conversion. Fluorine may be added at the time of receipt of the original media, and directly in the preparation of the catalytic composition.

Temperature holding readii can range from 150 to 300°as for conventional catalysts for Fischer-Tropsch synthesis, a pressure of from 1 to 100 ATM and a flow rate of synthesis gas from 100 to 2000 h-1.

The proposed catalytic composition may be prepared as the method of mixing and impregnation.

The method of preparation of catalysts by the method of mixing is that the reagents included in the composition, are mixed with the predecessor γ-Al2About3boehmite in a predetermined ratio in the form of an aqueous solution of nitrate salts of the respective metals (promoter) fluorine is added in the form of HF, followed by FD is the formation and calcination of the composition at t 450° C for 4 hours. Under these conditions, the boehmite goes in γ-Al2O3and nitric acid metal salts decompose to form oxides of the respective metals.

The method of preparation of catalysts by impregnation consists in the fact that in the beginning of boehmite by annealing at t 450°C for 4 h produced media γ-Al2About3. (The promoter) fluoride if it is used in the composition, is mixed with boehmite in the form of HF before annealing. Next, the calcined carrier is cooled to room temperature, and then applied to be used in the compositions of the ingredients in the form of aqueous solutions of nitrate salts of the metals. The obtained composition prokalyvayutsya at 450°C for 4 hours. Under these conditions, nitric acid metal salts decompose to form oxides of the respective metals.

Before testing, the catalysts are recovered in a stream of hydrogen at 200°C for 1 hour, then the temperature rises to 450°and the continuing recovery of the catalysts for a further 2 hours.

Testing of the obtained catalysts was carried out in a flow type reactor at P=10 ATM, T=175°V catalyst 25 cm3, the volumetric rate of the synthesis gas was 100 h-1. The composition of the synthesis gas was responsible hydrogen concentration of about 67. % concentration of FROM about 33. %.

Example 1

The catalytic composition is produced by impregnation containing 15 wt.% cobalt (in terms of Soo)deposited on alumina without fluorine. The rest is aluminum oxide.

Example 2

The catalytic composition made by the method of mixture containing 15 wt.% cobalt (in terms of COO) and 0.27 wt.% fluorine. The rest is aluminum oxide.

Example 3

The catalytic composition made by the method of mixture containing 15 wt.% cobalt in terms of COO and 0.1 wt.% fluorine, platinum, 0.3 wt.%. The rest is aluminum oxide.

Example 4.

The catalytic composition is produced by impregnation containing 15 wt.% cobalt in terms of COO and 1.0 wt.% fluoride, 1.0 wt.% palladium. The rest is aluminum oxide.

Example 5

The catalytic composition is produced by impregnation containing 10 wt.% cobalt in terms of COO and 1 wt.% fluorine. 1.0 wt.% copper. The rest is aluminum oxide.

Example 6

The catalytic composition made by the method of mixture, containing 20 wt.% cobalt in terms of COO and 0.27 wt.% fluoride and a mixture of 0.3 wt.% palladium and 0.7 wt.% chromium. The rest is aluminum oxide.

Example 7

The catalytic composition made by the method of mixture containing 15 wt.% cobalt in terms of COO and 0.27 wt.% fluoride and a mixture of 0.3 wt.% palladium and 0.7 wt.% zinc. The rest is aluminum oxide.

Use the 8

The catalytic composition is produced by impregnation containing 15 wt.% cobalt in terms of COO and 1 wt.% fluorine. 1.0 wt.% titanium. The rest is aluminum oxide.

In table 1 presents the results of the effects of fluoride and promoters consisting of platinum group metals, metals of the first transition series, or mixtures thereof, the conversion of CO in the synthesis gas obtained under the same conditions (T, °and linear velocities). As can be seen from comparison of example 1 and example 2 (table 1), the fluorine is a promoter for cobalt catalysts for Fischer-Tropsch synthesis, since its introduction has a significant impact on increasing CO conversion. From examples 2 and 3-9 (table 1) shows that the addition of platinum group metals, metals of the first transition series, or from mixtures significantly increases the conversion of CO in the SFT.

0
Table 1

The influence of fluorine on the conversion of CO in the synthesis gas
# exampleThe binder content, wt.%The promoterThe fluorine content, wt.%Conversion, %
NameQty wt.%
115--55,7
215--0,2771,6
315Pt0,30,2785,9
415Pd11,095,6
510Cu1,51,078,4
620Cr0,70,27of 89.1
Pd0,3
715Zn0,70,2775,3
Pd0,3
815Ti11,074,6
Table 2

Comparative data for the conversion FROM the known and the proposed catalytic composition
Known catalystThe proposed catalyst
Composition, wt.%Conversion, %Composition, wt.%Conversion, %
Co - 20 Pt - 0,1740Co - 15, Pt - 0.3, And F is 0.2785.9
Co - 20 Rh - 0,3353Co - 15, Pd - 1, F - 195.6
Co - 20 Ir - 0,3353Co - 20, Cr - 0,7, Pt - 0.3, And F is 0.2789.1

Comparative data for the conversion FROM the known and the proposed catalytic compositions are presented in table 2. As can be seen from a comparison of the data proposed catalytic composition and prototype, the introduction of the catalytic composition of fluorine, platinum group metals, metals of the first transition series, or mixtures thereof significantly increases the conversion of synthesis gas (table 2) in SFT.

Sources of information

1. EN 99107565, class B 01 J 23/847, 2001.

2. EN 2024297, class B 01 J 23/89, 1994.

Catalyst for synthesis of hydrocarbons from CO and H2(The Fischer-Tropsch synthesis), consisting of an active component, a promoter and a carrier, characterized in that th is as a promoter use F with the addition of the promoters of the platinum group metals, or metals of the first transition series, or mixtures thereof, and containing carrier - aluminum oxide at the following content, wt.%:

Active ingredient (in terms of Soo)10-20
The promoter F0,1-1,0
The promoter metals of the platinum group or of the first transition series, or mixtures thereof0.3 to 1.0
MediaRest



 

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