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 in the following components: Cr2O3- 10.0 to 30.0 wt. %, ZnO - 30,0-of 45.0 wt. %, SnO2- 0.1 to 3.0 mass. %, Al2O3- the rest. The technical result is increased efficiency in the operation of the catalyst. table 1.

The invention relates to the production of catalysts for dehydrogenation of paraffin hydrocarbons. Known catalyst for dehydrogenation of paraffin hydrocarbons containing, by weight. %: Cr2O3- 12,2; K2On - 1,4; SiO2- 2,0; Al2O3- the rest. (U.S. Pat. RF 1366200, publ. B. I. 2, 15.01.1988,)

Closest to the present invention is a catalyst for dehydrogenation of paraffin hydrocarbons, comprising, by weight. %: Cr2O3- 6,0-30,0; SnO - 0,1-3,5; IU2On - 0,4-3,0; SiO2- 0,08-3,0; Al2O3- else, where Me is an alkaline metal. (U.S. Pat. RF 2127242, publ. B. I. 7 10.03.1999,)

Both of these catalysts have low activity and selectivity is the efficiency of the catalyst.

Offered the catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, aluminum oxide, tin oxide, and optionally zinc oxide in the following, wt. %: Cr2O3- 10,0-30,0; ZnO - 30,0-45,0; SnO2- 0,1-3,0; Al2ABOUT3- the rest.

The difference between the new catalyst from the prototype is the content of zinc oxide at the specified content components. 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 on the 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 precursors of chromium oxide with subsequent formation of microspheres by spray-drying the resulting suspension in the column of spray drying. A sample of catalyst calcined CLASS="ptx2">

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 h at 20oC. the resulting suspension is subjected to heat treatment consisting of heating at 120oC for 6 h and calcination at 1100oC for 4 h in air flow. Catalysts having a particle diameter of 5 to 250 μm, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, 113 g of chromium trioxide and 700 ml of water in a bead mill with stirring for 3 h at 30oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 720oC for 4 h in air flow. The resulting product has the following composition, wt. %: Cr2O3- 30,0; ZnO - 35,1; SnO2- 0,1; Al2O3- the rest.

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane, carried out 560-610oC, space velocity of the raw material 400-600 l reagent / l of catalyst h 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 catalyst from the adsorbed reaction products of dehydrogenation; regeneration phase, when in the regenerator the gas is fed to the regeneration air for 30 min (in these experiments), and again the blowdown phase when nitrogen is passed for 10 min 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 temperature of reaction: 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 h at 20oC. the resulting suspension is subjected to heat treatment consisting of heating at 120oC for 6 h and calcination at 1050oC for 3 h in air flow. Catalysts having a particle diameter of 5 to 250 μm, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, 46.4 g of chromium trioxide and 500 ml of water in a bead mill at plebania at 680oC for 5 h in air flow. The resulting product has the following composition, wt. %: Cr2O3- 15,0; ZnO - 39,5; SnO2- 0,8; Al2O3- the 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%), 91 g of zinc oxide, 7,31 g of tin dioxide and 600 g of water by mixing in a ball mill for 16 h at 20oC. the resulting suspension is subjected to heat treatment consisting of heating at 120oC for 6 h and calcination at 1050oC for 5 h in air flow. Catalysts having a particle diameter of 5 to 250 μm, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, 30 g of chromium trioxide and 550 ml of water in a bead mill with stirring for 1 h at 40oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 800oC for 3 h in air flow. The resulting product has the following composition, wt. %: Cr2O3- 10,0; ZnO - 43,7; SnO2- 3,0; Al2O3- the rest.

The floor of the tats in the table.

Example 4. Media obtained from 130 g of the product of thermochemical activation of hydrate of aluminum oxide (residue on ignition = 87,8%), 91 g of zinc oxide, with 3.79 g of tin dioxide and 600 g of water by stirring in a bead mill for 2 h at 50oC. the resulting suspension is subjected to heat treatment consisting of heating at 120oC for 6 h and calcination at 1100oC for 4 h in air flow. Catalysts having a particle diameter of 5 to 250 μm, produced by the method of spray-drying the suspension obtained from 200 g of the carrier, or 64.7 g of chromium trioxide and 550 ml of water in a bead mill with stirring for 2 h at 50oC. a Sample of the catalyst is subjected to heat treatment consisting of annealing at 780oC for 3 h in air flow. The resulting product has the following composition, wt. %: Cr2O3- 20,0; ZnO - 34,8; SnO2- 1,5; Al2O3- the 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 further comprises a hydroxy>- 0,1 - 3,0

Al2O3- The rest

 

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