Catalyst for dehydrogenation of olefinic hydrocarbons

 

(57) Abstract:

Catalyst for dehydrogenation of olefinic hydrocarbons contains the following components, wt.%: the potassium oxide 10 to 20; the oxide of rubidium or cesium oxide is 0.1 to 5.0; the silicon oxide 0.5 to 1.2; chromium oxide 2,0 - 5,0; zirconium dioxide 1,0 - 3,0; aluminum oxide is 0.1 to 5.0; magnesium oxide and/or calcium oxide is 1.0 - 10.0; copper oxide 0,05 - 2,0; iron oxide rest. The composition can improve the activity and selectivity of the catalyst and its durability. table 2.

The invention relates to the production of catalysts, namely the production of catalysts for the processes of dehydrogenation of olefinic hydrocarbons.

Known catalyst for dehydrogenation of olefinic hydrocarbons containing, wt.%:

Fe2O3- 55

K2CO3- 35

Cr2O3- 3

Al2O3+SiO2- 7

(Kotelnikov, R., Strunnikova L. C., Putanov C. A., Arapov I. P. Catalysts for the dehydrogenation of lower paraffinic, olefinic and alkylaromatic hydrocarbons. M: Tsniiteneftehim, 1978).

Conversion of butylene this catalyst is between 28 and 30% with selectivity 81 - 82%.

Closest to the present invention is kata is
The potassium oxide - 10 - 20

The oxide of rubidium or cesium - 0,1 - 5,0

The silicon oxide is 0.5 to 1.2

The chromium oxide - 2,0 - 5,0

The Zirconia - 1,0 - 3,0

Aluminum oxide is 0.1 to 5.0

Iron oxide - Rest

(RF patent N 1608917 from 20.09.88, publ. B. I. N 25, 1996, B 01 J 23/86, C 07 C 5/333).

This catalyst gives the reaction of dehydrogenation of isoamylenes yield of isoprene 38,0 - to 39.6 wt.% when selectivity 86,2 - 88,2%. In the reaction of dehydrogenation of n-butylenes - 32,5% and 83%, respectively. Such indicators are insufficient for effective use in an industrial process. Also known catalyst has a low mechanical strength.

Pilot testing of this catalyst showed that the strength of granules is crucial in maintaining long term operation. So, having an initial strength 100 - 130 n/cm2the catalyst after 1000 hours of operation in the process of dehydrogenation had the strength 60 - 70 n/cm2. The decrease in strength during operation leads to a deterioration in the distribution of the raw gas stream over the catalyst layer and the increase of pressure in the reactor, which reduces the efficiency of the catalyst in industry and life.

Problem solved.

Offered the catalyst for dehydrogenation of olefinic hydrocarbons containing iron oxide, potassium oxide, rubidium oxide or cesium oxide, silicon oxide, chromium oxide, zirconium dioxide, aluminum oxide, magnesium oxide and/or calcium oxide and copper oxide at the following content, wt.%:

The potassium oxide - 10 - 20

The oxide of rubidium or cesium oxide is 0.1 to 5.0

The silicon oxide is 0.5 to 1.2

The chromium oxide - 2,0 - 5,0

The Zirconia - 1,0 - 3,0

Aluminum oxide is 0.1 to 5.0

Magnesium oxide and/or calcium oxide - 1,0 - 10

The copper oxide - 0,05 - 2,0

Iron oxide - Rest

Distinctive features of the prototype feature is the additional content of magnesium oxide and/or calcium oxide and copper oxide in the indicated quantities.

The use of the new catalyst declare section components in a certain number allows you to increase the activity and selectivity of the catalyst. In addition, the new catalyst composition has a significantly higher strength. Compared with the prototype it increases 1.4 - 2.5 times.

The proposed catalyst is prepared by mixing oxides of iron, chromium, zirconium, aluminum, copper, magnesium and/or calcium or legkorazmyvaemykh to oxv, containing soluble compounds of potassium, rubidium or cesium and potassium silicate. Formed plastic catalyst mass is molded, dried and calcined.

Example 1. The catalyst is prepared by a mixture of 79.5 g of hydrated ferric oxide with 3.5 g of green chromium oxide, 1.0 g of Zirconia, 5,2 g perezajennogo aluminum hydroxide, 7.5 g of basic magnesium carbonate and 0.5 g of copper oxide. The mixture of dry ingredients is stirred for 1 h until a uniform distribution of components; after which the mixture is impregnated with 2.5 ml of a solution of alkali promoters with a total concentration of 850 g/l and the ratio of the oxide of potassium oxide, rubidium : silica = 12:2:1. After impregnation mixture is stirred for another 1.5 hours to obtain the plastic paste; then molded by extrusion in "worm", is dried at a temperature of 120oand calcined at 650o. The resulting catalyst has the following composition, wt.%:

The oxide of potassium - 15

The cesium oxide - 2,6

The silicon oxide - 1,2

The chromium oxide is 3.5

The Zirconia - 1,0

Aluminum oxide - 2,6

Magnesium oxide - 5,0

The copper oxide - 0,5

Iron oxide - 68,6

Example 2. The catalyst was prepared according to the technology described in example 1, but for making use of 82.5 g of iron oxide, 2.0 g of oxide HRG potassium carbonate, 0.15 cesium carbonate and 0.9 g of potassium silicate.

The catalyst has the following composition, wt.%:

The potassium oxide - 20,0

The oxide of cesium - 0,1

The silicon oxide - 0,5

The chromium oxide - 2,0

The Zirconia - 2,0

Alumina - 5,0

Magnesium oxide - 1,0

The copper oxide - 1,0

Iron oxide - 68,4

Example 3. The catalyst is prepared as in example 1, but for making use 69 g pre-calcined at 600oC micaceous iron pigment with a specific surface area of 10 m2/g, 5 g of chromium oxide, 1 g of Zirconia, 0.5 g of aluminum oxide obtained by thermo-chemical activation (product THA), 15 g of basic magnesium hydroxide, 2 g of copper oxide. For impregnation use 28 ml of a solution of alkali promoters containing of 15.4 g of potassium carbonate, 7.9 g of rubidium nitrate and 1.4 g of potassium silicate.

Thus obtained catalyst has a composition, wt.%:

The potassium oxide - 10,0

The oxide of rubidium - 5,0

The silicon oxide - 0,85

The chromium oxide - 5,0

The Zirconia - 1,0

Alumina - 0,1

Magnesium oxide - 10,0

The copper oxide - 2,0

Iron oxide - 66,05

Example 4. The catalyst is prepared as in example 1, but for making use of 72.3 g of iron oxide, obtained thermoregulated magnesium, 0.65 g of copper oxide; a mixture of dry ingredients is impregnated with a solution containing of 23.2 g of potassium carbonate, 5,4 g of rubidium carbonate and 3.6 g of potassium silicate. The catalyst after calcination has a composition, wt.%:

The potassium oxide - 15,0

The rubidium oxide - 2,6

The silicon oxide - 1,2

The chromium oxide is 3.5

The Zirconia - 3,0

Alumina - 5,0

Magnesium oxide - 1,0

The copper oxide - 0,65

Iron oxide - 68,65

Example 5. The catalyst is prepared as in example 1, but instead of magnesium oxide it contains calcium oxide and has the following composition, wt.%:

The potassium oxide - 15,0

The cesium oxide - 2,6

The silicon oxide - 1,2

The chromium oxide is 3.5

The Zirconia - 1,0

Aluminum oxide - 2,6

Calcium oxide - 5,0

The copper oxide - 0,5

Iron oxide - 68,6

Example 6. The catalyst is prepared as in example 1, but for making use 81,1 g yellow micaceous iron pigment, 3.5 g of chromium oxide, 1.0 g of Zirconia, 5,2 g perezajennogo aluminum hydroxide, 0.5 g of copper oxide, 6.3 g of magnesium carbonate and 5.4 g of calcium carbonate. The mixture is impregnated with a solution containing 23.1 g of potassium carbonate, 0.15 g of cesium carbonate and 3.6 g of potassium silicate. The catalyst has the following composition, wt.%:

The potassium oxide - 15,0

The oxide of cesium - 0,1
Magnesium oxide - 3,0

The copper oxide - 0,5

Iron oxide - 70,1

Example 7. The catalytic activity of the catalysts prepared according to examples 1 to 6, is determined in isothermal reactor fixed bed of catalyst. The volume of the loaded catalyst 20 cm3the size of the granules 2,5x3,0 mm. Test of the catalyst is carried out at 600oC, space velocity of isoamylenes 1,0-1h, (liquid), diluted with water vapor in a molar ratio of hydrocarbon: water vapor = 1:10,0 - 15,0. The method of determining the mechanical strength based on the determination of effort that must be applied to the granule (l = 4 mm = 4 mm) for its destruction by forming the side surface. The results of the activity, the strength of the catalysts are given in table. 1.

Example 8. The catalysts prepared according to examples 2, 5 and 6 experience in the reaction of dehydrogenation of n-butylenes at 620oC, flow rate of the raw material (gas) 600-1h, diluted with water vapor in a molar ratio of hydrocarbon : water vapor of 1:13.

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

Catalyst for dehydrogenation of olefinic hydrocarbons, including iron oxide, potassium oxide, rubidium oxide or hydroxy which contains magnesium oxide and/or calcium oxide and copper oxide in the following components, wt.%:

Oxide

potassium - 10,0 - 20,0

rubidium or cesium - 0,1 - 5,0

silicon - 0,5 - 1,7

chromium - 2,0 - 5,0

The Zirconia - 1,0 - 3,0

Oxide

aluminum - 0,1 - 5,0

magnesium

and/or calcium oxide - 1,0 - 10,0

copper - 0,05 - 2,0

iron - Rest

 

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