Catalyst for synthesis of hydrocarbons from co and h2

FIELD: petrochemical processes catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.

EFFECT: increased selectivity and productivity.

2 cl, 3 tbl, 2 ex

 

The invention relates to the production of catalysts, in particular catalysts for the synthesis of aliphatic hydrocarbons5-C25from carbon monoxide and hydrogen (synthesis Fischer-Tropsch). The resulting products are components of motor fuels (gasoline and diesel), as well as intended for further processing in the processes of chemistry.

Known catalyst for synthesis of hydrocarbons From5-C25of CO and Hz, representing With the media Al2About3prepared by coprecipitation, with the following composition, wt.%: 3-40 With and 60-97 Al2About3. The media used in the form of powder. In his presence when the conversion FROM 40-80% of a mixture of N2+SO+I (vol.%) hydrocarbons With5-C25get with selectivity 36-59%. The main disadvantage of this catalyst is its low selectivity for the target products and high methane (20-30%).

Also known catalyst for synthesis of hydrocarbons, C5-C25of WITH and of the following composition, wt.%: 20-44, 0-3 MgO, 80-53 of calcium aluminate (Cao· Al2About3and Cao· 2l2O3in the ratio 1:1) [2]. The catalyst is prepared by coprecipitation. The media used in the form of powder. “Synthesis is carried out in a flow catalytic installation at atmospheric pressure. Pre-catalyst is srabatyvayut in a stream of hydrogen at 550° C for 5 hours At 220° With conversion of FROM 70%, and the selectivity of hydrocarbons5-C25from a mixture of 2H2+- 62%. The disadvantages of this catalyst is the low selectivity for the target products and high temperature activation of cooking.

The closest analogue is the catalyst for synthesis of hydrocarbons From5-C25from CO and H2[3] composition, wt.%: 55-72, 2-5 C, 23-43 monoaluminate calcium (Cao· Al2About3). The catalyst is prepared by wet mixing,” in which use of the powder reagent. The finished catalyst is activated with hydrogen 5 h at 400° C. as a result, when the atmospheric pressure and 220° With conversion WITH is 54-80%, the selectivity to hydrocarbons5-C25- 50-60%, and the methane - 20-35%.

The disadvantages of the described catalyst are low selectivity for the target products, high - methane, as well as high Co content (>55%) and, consequently, low productivity - ~ 0,1· 10-3g5-C25/g WITH/h

The aim of the present invention is to provide a highly selective and highly efficient catalyst for synthesis of hydrocarbons From5-C25from CO and H2.

The goal is to reach a catalyst containing cobalt and promoters on the medium - granular alumina, when, after the ith component, wt.%:

With 20-30

ALUMIN 70-80

The proposed catalyst may contain additives selected from the group of metal oxide (ZrO2or fO2) in an amount of 3 wt.% or metals (Ru, or Pd, or Pt) in the amount of 0.5 wt.%.

The composition used alumino are given in table. 1.

Table 1.

The composition and specific surface area of aluminu
GalyninChemical composition, wt.%Specific surface area, m2/gXRF

(main phase)
Al2About3CaO
189,710,3184γ -Al2About3, CaO· 2l2About3, CaO· Al2About3that α -· Al2About3, CaO· 6l2About3Caso3graphite
289,310,7172γ · Al2About3, CaO· 2l2About3, So· Al2About3·6N2O, caso3graphite

Example 1.

Sample preparation of the catalyst.

The catalyst composition, wt.%: 20, 80 ALUMIN-1, prepared in two stages. On the first take of 11.1 g of Co(NO3)2·6N2O and RA is tworay in 15 ml of distilled water. The resulting solution was poured with stirring to 18 g pre-calcined at 450° With the current air carrier with a grain size of 0.11 to 0.25 mm, Incubated 15 min and dried in a water bath with constant stirring for 30 minutes and Then the resulting powder was mixed with quartz (particle diameter quartz - 3-4 mm) in a volume ratio of 1:1 and calcined in a stream of air (space velocity of 1000 h-1) at 450° C for 1 h, the Sample is cooled to room temperature and separated from the quartz.

In the second stage of 11.1 g of Co(NO3)2·6N2O dissolved in 15 ml of distilled water and poured to the calcined sample with constant stirring. Stand 15 min and dried on a water bath for 1 hour

Get the catalyst composition, wt.%:

20

ALUMIN 80

Example 2.

The catalyst composition, wt.%: 20, 3 ZrO2and 77 ALUMIN-2, is prepared in three stages. On the first take of 1.2 g ZrO(NO3)2·2H2O and dissolved in 15 ml of distilled water. The resulting solution was poured with stirring to 18 g pre-calcined at 450° With the current air carrier with a grain size of 0.11 to 0.25 mm, Incubated 15 min and dried in a water bath with constant stirring for 30 minutes and Then the resulting powder was mixed with quartz (particle diameter quartz - 3-4 mm) in a volume ratio of 1:1 and calcined in a stream of air (about the lending rate of 1000 h -1) at 450° C for 1 h, the Sample is cooled to room temperature and separated from the quartz.

In the second stage take 11.1 g of Co(NO3)2·6N2O and dissolved in 15 ml of distilled water. The resulting solution was poured with stirring to the cooled sample coated with ZrO2. Further operations are the same as described above.

At the third stage of 11.1 g of Co(NO3)2·6N2O dissolved in 15 ml of distilled water and poured to the calcined sample containing ZrO2and 10%, with constant stirring. Stand 15 min and dried on a water bath for 1 hour

Get the catalyst composition, wt.%:

20

ZrO23

ALUMIN 77

The catalyst was tested in the process of obtaining hydrocarbon, C5-C25from CO and H2in the following conditions: a temperature of 190-230° C, the pressure is atmospheric, the volumetric rate of synthesis-gas - 100 h-1. Testing of the catalyst is carried out by loading into the reactor 23-25 g of the catalyst mixed in the volume ratio with quartz (particle diameter quartz - 2 mm) 3:1. The sample was then treated with hydrogen at a temperature of 400-600° C for 1 h with a bulk velocity is 3000 h-1. After restoration processing portion of the catalyst is treated synthesis gas composition, mol.%: 66-68 H2and 32-34 WITH with gradual increase in the pace of the atmospheric temperature from 160 to 240° With increments of 10° With every 5 h of treatment. The process is conducted in a stationary catalyst bed.

The results of the tests of the catalysts are given in table. 2 and 3.

62
Table 2.

The results of laboratory tests of the catalyst With/ALUMIN
IndicatorsALUMIN-1ALUMIN-2
The binder content, wt.%2030202020
Temperature recovery, °450450400450500
The temperature of the synthesis, °230210230220210
Conversion,%7077595855
Performance · 103g5-C25/GSO/h0,280,30,270,290,28
The release of hydrocarbons, g/m3112138115121108
Selectivity for hydrocarbons5-C25,%66706364
The selectivity for methane,%1715161716

Table 3.

The results of laboratory tests of the catalyst 20%/promoter/ALUMIN - 2 (Conditions repair: the volumetric rate of hydrogen - 3000 h-1temperature - 450° C, duration - 1 hour)
Indicators     
The promoterZrO2fO2PdENPt
The content of the promoter, wt.%330,50,50,5
The temperature of the synthesis, °230230200200200
Conversion,%6766545289
Performance · 103GS5-C25/GSO/h0,290,290,270,270,3
The release of hydrocarbons, g/m3137127108107 165
Selectivity for hydrocarbons, C5-C25, %7472727474
The selectivity for methane,%13129711

As can be seen from the above data, the proposed catalyst has several advantages:

- high performance (3 times higher compared to the prototype);

high selectivity for the target products (up to 74%);

- low selectivity to methane (up to 7%);

- used media represents granules, which facilitates the preparation of the catalyst, increases the mechanical strength of the catalyst and its life.

Sources of information

1. The UK patent WO 0187480, class C 07 C 1/04, published. 2001.

2. the Federal Republic of Germany patent No. 2536488, class C 07 C 1/04, published. 1982.

3. USSR author's certificate No. 1160629, class B 01 J 23/17, C 07 C 1/04, published. 1997 (prototype).

1. Catalyst for the synthesis of aliphatic hydrocarbons5-C25from CO and H2containing cobalt on the carrier, characterized in that as the carrier is used granulated ALUMIN, and the catalyst has the following composition, wt.%:

With 20-30

ALUMIN Else

2. The catalyst according to claim 1, characterized in that it further contains an additive is of promotora, selected from the group of metal-oxide - ZrO2or HfO2or metals Ru, or Pd, or Pt, and the catalyst has the following composition, wt.%:

With 20-30

Additive promoter of 0.5-3

ALUMIN Else



 

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