Catalyst for dehydrogenation of paraffin hydrocarbons

 

(57) Abstract:

The invention relates to the production of catalysts for dehydrogenation of paraffin hydrocarbons, the catalyst comprises chromium oxide, aluminum oxide and tin oxide, in addition it contains zinc oxide and platinum at the following content, wt.%: CR2ABOUT310,0-30,0, ZnO 30,0-45,0, SnO20,1-3,0, Pt Of 0.005 To 0.2, Al2ABOUT3the rest of it. The technical result - the efficiency of the catalyst. table 1.

The present invention relates to the production of catalysts for dehydrogenation of paraffin hydrocarbons. Known catalyst for dehydrogenation of paraffin hydrocarbons (containing % wt.)

Cr2ABOUT3- 12,2

K2O - 1,4

SiO2- 2,0

Al2O3- rest

(U.S. Pat. RF 1366200, publ. Bull. from. 2 15.01.1988,)

Closest to the present invention is a catalyst for dehydrogenation of paraffin hydrocarbons, including, wt.%

Cr2O3- 6,0-30,0

SnO - 0,1-3,5

Me2O - 0,4-3,0

SiO2- 0,08-3,0

Al2O3- rest

where Me is an alkaline metal (U.S. Pat. RF 2127242, publ. Bull. from. 7 10.03.1999,)

Both pointed to by inovah hydrocarbons.

The present invention is to increase the efficiency of the catalyst.

Offered the catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, aluminum oxide, tin oxide, and optionally zinc oxide and platinum on the next component content, % wt:

CR2ABOUT3- 10,0-30,0

ZnO - 30,0-45,0

SnO2- 0,1-3,0

Pt - 0,005-0,2

Al2O3- rest

The difference between the new catalyst from the prototype is the content of zinc oxide and platinum at the specified content component.

The use of the catalyst of the inventive combination of components in a number of promotes more rapid and complete oxidation-reduction reactions, reducing the formation of coke. This reduces the proportion of adverse reactions, increasing the efficiency of the catalyst.

The process of obtaining a new catalytic system consists in the dispersion of chromium compounds and platinum on a carrier consisting of oxides of aluminum, zinc and tin.

The preparation of the catalyst may be, for example, by impregnation of the specified carrier with a solution containing PressTV is ansii in the column of spray drying. The sample calcined catalyst in the activator when 680-750oC for 2-5 hours. The invention is illustrated by the following examples.

Example 1.

Media obtained from 212,8 g perezajennogo hydrate of aluminum oxide (residue on ignition = 65,5%), 139,7 g of zinc oxide, 0.5 g of tin oxalate and 600 g of water by mixing in a ball mill for 16 hours at a temperature of 20oC. the resulting suspension is subjected to heat treatment consisting of heating at a temperature of 120oC for 6 hours and calcination at 1100oC for 4 hours in air flow. Catalysts having a particle diameter of from 5 to 250 microns, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, 113 g of chromium trioxide 0.04 g of Pt in the form of a solution of hexachloroplatinic acid and 700 ml of water in a bead mill with stirring for 3 hours at a temperature of 30oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 720oC for 4 hours in air flow. The resulting product has the following composition, % wt:

CR2O3- 30,0

ZnO - 35,1

SnO2- 0,1

Pt - 0,01

Al2ABOUT3- rest

The resulting catalyst ispytav is oresti feed 400-600 l reagent/l catalizadores in laboratory quartz reactor. The catalytic cycle that simulates carrying out the reaction in an industrial reactor consists of a reaction phase, in which the hydrocarbons are served within 30 minutes; phase blowdown, when nitrogen is passed for 10 minutes to release the catalyst from the adsorbed reaction products of dehydrogenation; regeneration phase, when in the regenerator the gas is fed to the regeneration air for 30 minutes (in these experiments) and again the blowdown phase when nitrogen is passed for 10 minutes to release the catalyst from the adsorbed reaction products of regeneration. Specifications industrial process dehydrogenation in a fluidized bed of catalyst require regeneration at temperatures above the reaction temperature; in this case, regeneration and restoration is carried out at 650oSecond, whereas the dehydrogenation when 560-610oC. the results are shown in the table.

Example 2

Media obtained from 130 g of the product of thermochemical activation of hydrate of aluminum oxide (residue on ignition = 87,8%), which is 100.8 g of zinc oxide, 2.64 g of tin oxalate and 600 g of water by mixing in a ball mill for 16 hours at a temperature of 20oC. the resulting suspension under the 1050oC for 3 hours in air flow. Catalysts having a particle diameter of from 5 to 250 microns, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, 46.4 g of chromium trioxide, 0,013 g Pt in the form of a solution of hexachloroplatinic acid and 500 ml of water in a bead mill with stirring for 5 hours at a temperature of 20oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 680oC for 5 hours in air flow. The resulting product has the following composition, % wt:

CR2O3- 15,0

ZnO - 39,5

SnO2- 0,8

Pt - 0,005

Al2ABOUT3- rest

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane, as described in example 1. The results are shown in the table.

Example 3.

Media obtained from 130 g of the product of thermochemical activation of hydrate of aluminum oxide (residue on ignition = 87,8%), g zinc oxide, 7,31 g of tin dioxide and 600 g of water by means of hanging in a ball mill for 16 hours at a temperature of 20oC. the resulting suspension is subjected to heat treatment consisting of heating at a temperature of 120oC for 6 hours and calcination at 1050oWith the Ute spray-drying the suspension, obtained from 200 g of the carrier, 30 g of chromium trioxide, 0,49 g Pt in the form of a solution of hexachloroplatinic acid and 550 ml of water in a bead mill with stirring for 1 hour at a temperature of 40oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 750oC for 3 hours in air flow. The resulting product has the following composition, % wt:

CR2O3- 10,0

ZnO - 43,7

SnO2- 3,0

Pt - 0,2

Al2O3- rest

The resulting catalyst was tested in the dehydrogenation process of isobutane and propane as described in example 1. The results are shown in table 1.

Example 4.

Media obtained from 130 g of the product of thermochemical activation of hydrate of aluminum oxide (residue on ignition = 87,8%), g zinc oxide, with 3.79 g of tin dioxide and 600 g of water by stirring in a bead mill for 2 hours at a temperature of 50oC. the resulting suspension is subjected to heat treatment consisting of heating at a temperature of 120oC for 6 hours and calcination at 1100oC for 4 hours in air flow. Catalysts having a particle diameter of from 5 to 250 microns, produced by the method of spray-drying the suspension, procedi in the bead mill under stirring for 2 hours at a temperature of 50oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 760oC for 3 hours in air flow. The resulting product has the following composition, % wt:

CR2O3- 20,0

ZnO - 34,8

SnO2- 1,5

Pt - 0,1

Al2O3- rest

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane, as described in example 1. The results are shown in the table.

Catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, aluminum oxide and tin oxide, characterized in that it additionally contains zinc oxide and platinum at the following content, wt. %:

Cr2O3- 10,0-30,0

ZnO - 30,0-45,0

SnO2- 0,1-3,0

Pt - 0,005-0,2

Al2ABOUT3- The rest

 

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