Catalyst for dehydrogenation of paraffin hydrocarbons

 

(57) Abstract:

The invention relates to the production of catalysts for dehydrogenation of paraffin hydrocarbons. Describes a catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, oxide of alkali and/or alkaline earth metal, silicon oxide and aluminum oxide. The difference of the catalyst is that it contains the addition of lead oxide at the following content, wt.%: Cr2O310,0-30,0, Me2O 0,5-3,0, SiO20,5-3,5, PbO 0.1 to 5.0, Al2O3- else, where Me is an alkaline and/or alkaline earth metal. The technical result - the efficiency of the catalyst. 2 C.p. f-crystals, 1 table.

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

Cr2O3- 12,2

K2O - 1,4

SiO2- 2,0

Al2O3- Rest

(U.S. Pat. RF N 1366200, publ. BI N 2, 15.01.1988,)

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

R>
where Me is an alkaline metal

(U.S. Pat. RF N 2127242. publ. BI N 7, 10.03.1999,)

Both of these catalysts have low activity and selectivity in the process of dehydrogenation of paraffin hydrocarbons. The present invention is to increase the efficiency of the catalyst.

Offered the catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, oxide of alkali and/or alkaline earth metal, silicon oxide, aluminum oxide, and optionally, lead oxide at the following content, wt.%:

Cr2O3- 10,0-30,0

Me2O - 0,5-3,0

SiO2- 0,5-3,5

PbO - 0,1-5,0

Al2O3- The rest,

where Me is an alkaline and/or alkaline earth metal

The new catalyst can also optionally contain boron oxide at the following content, wt.%:

Cr2O3- 10,0-30,0

Me2O - 0,5-3,0

SiO2- 0,5-3,5

PbO - 0,1-5,0

B2O3- 0,1-2,0

Al2O3- Rest

As the alkali metal catalyst preferably contains potassium.

The difference between the new catalyst from the prototype is the exception to the content of tin oxide, additional the Oia as an alkali metal.

The use of the catalyst of the inventive combination of components in a given volume can reduce koksoobrazovaniya, promotes more rapid and complete oxidation-reduction reactions. This reduces the proportion of adverse reactions, increasing the activity and selectivity of the operation of the catalyst.

The process of obtaining a new catalytic system consists in the dispersion of chromium compounds and alkali metal on a carrier consisting of oxides of aluminum, silicon and lead. The following are possible methods of preparation of the catalytic system.

The preparation of the catalyst can be carried out by impregnation of the specified carrier with a solution containing precursors of the oxides of chromium and potassium, with subsequent drying and calcination or ionic absorption with subsequent separation of the liquid, drying and calcination of the solid. Preferably the conducting impregnation method "initial humidity of the carrier with a solution containing all of the precursors of the active components.

The invention is illustrated by the following examples.

Example 1.

Microspheric carrier having a particle diameter of from 15 to 250 microns, recip is). Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 3.5 g of acetate of lead (Pb(C2H3O2)22H2O), 2 ml of acetic acid and 3 g of SiO2in 30% of silicates, at a temperature of 85-90oC for 3 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 800oC for 2 hours in air flow. 200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution containing of 67.1 g CrO3(and 99.8 wt.%) and are 5.36 g of KOH (85 wt. %) in deionized water at a temperature of 55oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 700oC for 4 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 20,0

K2O - 1,5

SiO2- 1,0

PbO - 0,7

Al2O3- Rest

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane, performed at a temperature of 560-590oC, space velocity of the raw material 400 l of reagent/l is Promyshlenno reactor, consists of the 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 650oC, whereas the dehydrogenation is carried out at 560-590oC. the results are shown in the table.

Example 2.

Microspheric carrier having a particle diameter of from 15 to 250 microns, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 0.5 g of acetate of lead (Pb(C2H3O2)22HoC for 4 hours and calcination at 850oC for 2 hours in air flow 200 g microspherical alumina, obtained as described in example 1, are impregnated by the method described herein before, with an aqueous solution containing 30,8 g CrO3(and 99.8 wt.%) and 9,86 g of KOH (85 wt. %), and deionized water at the same temperature as in example 1. The impregnated product is left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 800oC for 2 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 10,0

K2O - 3,0

SiO2- 3,4

PbO - 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.

Example 3.

Microspheric carrier having a particle diameter of from 15 to 250 microns, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

B>H3O2)22H20), 2 ml of acetic acid and 2.4 g of SiO2in 30% of silicates, at a temperature of 80-85oC for 4 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 750oC for 4 hours in air flow. 200 g microspherical alumina, obtained as described in example 1, are impregnated by the method described herein before, with an aqueous solution containing 113 g CrO3(and 99.8 wt.%), 2.1 g of KOH (85 wt. %), and deionized water at the same temperature as in example 1. The impregnated product is left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 750oC for 3 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 30,0

K2O - 0,5

SiO2- 1,6

PbO - 3,0

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.

Example 4.

Microspheric carrier having a particle diameter of from 15 to e (THA product).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 24 g of acetate of lead (Pb(C2H3O2)22H2O), 2 ml of acetic acid and 1.7 g of SiO2in 30% of silicates, at a temperature of 80-85oC for 4 hours. The precipitate was separated pas filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 720oC for 5 hours in air flow.

200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution containing 90 g CrO3(and 99.8 wt.%) and 3.7 g of KOH (85 wt. %), deinitialise water at 35oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at 720oC for 4 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 25,2

K2O - 1,0

SiO2- 0,5

PbO - 5,0

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.

Example 5.

Mikrosferotsitarnaja activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 3.5 g of acetate of lead (Pb(C2H3O2)22H2O), 2 ml of acetic acid, 3 g of SiO2in 30% of silicates and 3 g of boric acid, at 85-90oC for 3 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 780oC for 2 hours in air flow.

200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution containing of 67.1 g CrO3(and 99.8 wt.%) and are 5.36 g of KOH (85 wt. %) in deionized water at a temperature of 55oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 700oC for 4 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 20,0

K2O - 1,5

SiO2- 1,0

PbO - 0,7

B2)3- 1,1

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 what he receive from the pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 3.5 g of acetate of lead (Pb(C2H3O2)22H2O), 2 ml of acetic acid and 3 g of SiO2in 30% of silicates, at a temperature of 85-90oC for 3 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 800oC for 2 hours in air flow.

200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution containing 66,1 g CrO3(and 99.8 wt.%) in deionized water at a temperature of 50oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 700oC for 4 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 20,0

ZnO - 1,1

SiO2- 1,0

PbO - 0,7

Al2O3- Rest

The resulting catalyst was tested in the processes digidrirovanny/P> Microspheric carrier having a particle diameter of from 15 to 250 microns, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 3.5 g of acetate of lead (Pb(C2H3O2)22H2O, 8,1 g Mg(C2H3O2)2, 2 ml of acetic acid and 3 g of SiO2in 30% of silicates, at a temperature of 85-90oC for 3 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 800oC for 2 hours in a stream of air

200 g of this alumina impregnated, using the technique of "initial humidity", an aqueous solution containing 66 g CrO3(and 99.8 wt.%), in deionized water at a temperature of 50oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 700oC for 4 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 20,0

MgO - 0,8

SiO2- 1,0

PbO - 0,7

Example 8.

Microspheric carrier having a particle diameter of from 15 to 250 microns, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 3.5 g of acetate of lead (Pb(C2H3O2)22H2O), 3.2 g of Mg(C2H3O2)2, 2 ml of acetic acid and 3 g of SiO2in 30% of silicates, at a temperature of 85-90oC for 3 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 800oC for 2 hours in a stream of air

200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution containing 66,8 g CrO3(and 99.8 wt.%) and 3.1 g of KOH (85 wt. %) in deionized water at a temperature of 50oC. the Impregnated product left at room temperature for 1 hour, then dried at a temperature of 110oC for 6 hours. The dried product is activated in a stream of air at a temperature of 700oC for 4 hours. Get catalysis - 1,0

PbO - 0,7

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.

Example 9.

Microspheric carrier having a particle diameter of from 15 to 250 microns, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (900 ml) containing 15 g of acetate of lead (Pb(C2H3O2)22H2O), 2 ml of acetic acid and 2.4 g of SiO2in 30% of silicates, at a temperature of 80-85oC for 4 hours. The residue is separated on a filter and subjected to heat treatment consisting of heating at a temperature of 120oC for 4 hours and calcination at 750oC for 4 hours in air flow.

200 g microspherical alumina, obtained as described in example 1, are impregnated by the method described herein before, with an aqueous solution containing 113 g CrO3(and 99.8 wt.%), 2,05 g Cs2CrO4in deionized water at the same temperature as in example 1. The impregnated product is left at room temperature for 1 hour, C is the temperature 750oC for 3 hours. Obtain a catalyst having the following composition, wt.%:

Cr2O3- 30,0

Cs2O - 0,5

SiO2- 1,6

PbO - 3,0

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.

1. Catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, oxide of alkali and/or alkaline earth metal, silicon oxide and aluminum oxide, characterized in that it further contains an oxide of lead in the following content, wt.%:

Cr2O3- 10,0 - 30,0

Me2O - 0,5 - 3,0

SiO2- 0,5 - 3,5

PbO - 0,1 - 5,0

Al2O3- Rest

where Me is an alkaline and/or alkaline earth metal.

2. The catalyst p. 1, characterized in that it additionally contains boron oxide at the following content, wt.%:

Cr2O3- 10,0 - 30,0

Me2O - 0,5 - 3,0

SiO2- 0,5 - 3,5

PbO - 0,1 - 5,0

IN2ABOUT3- 0,1 - 2,0

Al2O3- Rest

3. The catalyst p. 1, characterized in that it contains as an oxide of the alkali metal oxide is potassium.

 

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