Catalyst for dehydrogenation of paraffin hydrocarbons

 

(57) Abstract:

The invention relates to the field of catalysts for dehydrogenation of paraffin hydrocarbons. The catalyst contains chromium oxide, alkali metal oxide, aluminum oxide, and optionally zirconium oxide and boron oxide at the following content, wt.%: CR2O3- 10-25; IU2O - 0,5-2,0; ZrO2- 0,5-2,0; B2O3- 0,1 - 1,0; Al2O3- else, where Me is an alkaline metal. The catalyst may also contain 0.5 to 1.5 wt.% silicon oxide. As the oxide of the alkali metal catalyst preferably contains an oxide of potassium. The catalyst has high activity with a small number of adverse reactions. 2 C.p. f-crystals, 1 table.

The 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 year).

Closest to the present invention is a catalyst for dehydrogenation of paraffin hydrocarbons, including the>3- Rest

where Me is an alkaline metal.

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

Both of these catalysts have low activity in the process of dehydrogenation of paraffin hydrocarbons.

The present invention is to obtain a catalyst with increased efficiency.

Offered the catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, alkali metal oxide, aluminum oxide, and, optionally, zirconium oxide and boron oxide at the following content, wt.%:

Cr2O3- 10,0 - 25,0

Me2O - 0,5 - 2,0

ZrO2- 0,5 - 2,0

Br2O3- 0,1 - 1,0

Al2O3- Rest

where Me is an alkaline metal.

The new catalyst can also optionally contain an oxide of silicon with the following content, wt.%:

Cr2O3- 10,0 - 25,0

Me2O - 0,5 - 2,0

ZrO2- 0,5 - 2,0

B2O3- 0,1 - 1,0

SiO2- 0,5 - 1,5

Al2O3- Rest

As the oxide of the alkali metal catalyst preferably contains an oxide of potassium.

The difference between the new catalyst from the prototype is Savelyeva combination of components in a number of promotes more rapid and complete oxidation-reduction reactions. This reduces the proportion of adverse reactions, increasing the catalyst activity. Work at higher conversions and almost the same selectivity reduces the recycle paraffin hydrocarbons and thereby save energy. The process of obtaining a new catalytic system consists in the dispersion of the chromium compounds, alkali metal and boron on the carrier consisting of oxides of aluminum and zirconium or dispersion of chromium compounds and alkali metal on a carrier consisting of oxides of aluminum, zirconium, and boron.

If the content in the new catalyst of silicon oxide a process for the catalytic system consists in the dispersion of the chromium compounds, alkali metal and boron on the carrier consisting of oxides of aluminum, zirconium and silicon, or the dispersion of chromium compounds and alkali metal on a carrier consisting of oxides of aluminum, zirconium, silicon, and boron.

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, boron and potassium, followed by drying and calcining, and the>Preferably the conducting impregnation method "initial humidity of the carrier with a solution containing all of the precursors of the active components.

As for boron are other techniques by which it can be added to the catalytic system:

the addition of boron to the media before applying the precursors of the oxides of chromium and potassium;

treatment of solids containing the oxides of chromium and potassium solution containing the boron compounds using ion exchange, impregnation, etc.;

the deposition of boron compounds by parasitemia media to Supplement predecessors of chromium oxide and potassium, using volatile substances;

the deposition of boron compounds by parasitemia solid substance containing: oxide of aluminum, chromium oxide and potassium oxide, using volatile substances.

Among these methods, preferred are the carrier impregnated with a solution containing the precursors of the active elements: oxides of chromium, potassium and boron and boron additive to the carrier before applying the precursors of the oxides of chromium and potassium.

As a precursor of boron oxide can be used as inorganic and organic boron compounds.

From the EPR particles 5 - 250 μm, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA). Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 3 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%) and 1.0 g of boric acid (H3BO3; and 99.8 wt.%) at 80 - 85oC for 2 hours, the Suspension is filtered on the filter. The residue left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 135 m2/g, a porosity of 0.34 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, 0,58% ZrO2and 14% B2O3.

200 g of this alumina impregnated, using the technique of "initial" moisture, aqueous solution (68 cm3containing 67,9 g CrO3(and 99.8 wt.%) and 4.94 g of KOH (92 wt.%) in deionized water at 85oC. the Impregnated product left at room temperature for 1 hour, then dried at 90oC for 6 hours the Dried product is activated in a stream of air at 700oO -1,5; ZrO2TO 0.6; B2O3- 0,1; Al2O3- the rest.

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane, carried out at 560 - 590oC, space velocity of the raw material 400 l of reagent/(l 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 hydrocarbons are served for 30 min; phase blowdown, when nitrogen is passed for 10 min 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 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 was carried out at 650oC, whereas the dehydrogenation was carried out at 560 - 590oC. the results are shown in tableau hydrated product of thermochemical activation of aluminum hydroxide (product of THA). Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 6 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%) and 2.7 g of boric acid (H3BO3; and 99.8 wt.%) when 80-85oC for 2 hours, the Suspension is filtered on the filter. Sample pseudoboehmite left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 145 m2/g, porosity of 0.41 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, to 1.15% ZrO2and 0.39% B2O3.

200 g of the resulting aluminum oxide impregnated according to the method described here previously, aqueous solution (82 cm3containing 67,9 g CrO3(and 99.8 wt.%) and 4.94 g of KOH (92 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 20,2; K2O - 1,5; ZrO2TO 0.9; B2O3to 0.3; Al2O3- the rest.

The resulting catalyst was tested in the processes dihydrofurane media having a particle diameter of 5 to 250 μm, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA). Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 9.6 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%) within 2 hours the Suspension is filtered on the filter. Sample pseudoboehmite left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 150 m2/g, a porosity of 0.4 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, 1.9% of ZrO2.

200 g of the resulting aluminum oxide impregnated according to the method described here previously, aqueous solution (82 cm3containing 67,9 g CrO3(and 99.8 wt.%), 4.94 g KOH (92 wt.%) and 4.5 g of H3BO3(and 99.8 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 20,0; K2O - 1,4; ZrO2TO 1.5; B2O3- 1,0; Al

Example 4. 200 g microspherical alumina, obtained as described in example 2, impregnated according to the method described here previously, aqueous solution (82 cm3) containing 30 g CrO3(and 99.8 wt.%) and 5.9 g of KOH (92 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 10,0; K2O - 2,0; ZrO2- 0,1; B2O3- 0,4; 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 5. 200 g microspherical alumina, obtained as described in example 2, impregnated according to the method described here previously, aqueous solution (82 cm3containing 90 g CrO3(and 99.8 wt.%) and 1.7 g of KOH (92 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 25,0; K2O - 0,5; ZrO2TO 0.9; B2O3to 0.3; Al2O3- the rest.

The resulting catalyst was tested in the process of dehydrogenation of isobutane and propane as described in STIC 5 - 250 μm, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA).

Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 6 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%) and 5.5 g boric acid (H3BO3; and 99.8 wt.%) at 80 - 85oC for 2 hours, the Suspension is filtered on the filter. Sample pseudoboehmite left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 145 m2/g, a porosity of 0.42 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, 1.2% of ZrO2and 0.8% B2O3.

200 g of the resulting aluminum oxide impregnated according to the method described here previously, aqueous solution (84 cm3containing 49 g CrO3(and 99.8 wt.%) and 3.1 g of KOH (92 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 15,5; K2O - 1 is up in the process of dehydrogenation of isobutane and propane as described in example 1. The results are shown in the table.

Example 7. Microspheric carrier having a particle diameter of 5 to 250 μm, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA). Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 3 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%), 1.5 g of boric acid (H3BO3; and 99.8 wt.%) and 3.9 g of SiO2in the form of a 30% aqueous solution of silicates at 80 - 85oC for 2 hours, the Suspension is filtered on the filter. Sample pseudoboehmite left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 145 m2/g, porosity of 0.41 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, 0.6% of ZrO2AND 0.22% B2O3and 1.6% SiO2.

200 g of the resulting aluminum oxide impregnated according to the method described here previously, aqueous solution (82 cm3containing 67,87 g CrO2(and 99.8 wt.%) and 4.94 g of KOH (92 wt.%) in desi composition, wt.%: Cr2O3- 20,2; K2O - 1,5; ZrO2- 0,5; B2O3- 0,2; SiO2- 1,3; 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 8. Microspheric carrier having a particle diameter of 5 to 250 μm, obtained from pre-hydrated product of thermochemical activation of aluminum hydroxide (product of THA). Hydration 270 g of the product THA spend aqueous solution (1000 ml) containing 6 g of nitric acid Zirconia (ZrO(NO3)22H2O; and 99.8 wt.%, 2.7 g of boric acid (H3BO3; and 99.8 wt.%) and 2 g of SiO2in the form of a 30% aqueous solution of silicates at 80 - 85oC for 2 hours, the Suspension is filtered on the filter. Sample pseudoboehmite left in air at room temperature for 6 h, and then subjected to heat treatment consisting of heating at 140oC for 5 h and calcination at 800oC for 4 h in air flow.

The product obtained has a specific surface area of 138 m2/g, a porosity of 0.40 g/cm3and consists mainly of gamma-, Delta - and theta-transition oxides of aluminum and contains, in addition, 1.2% of ZrO23
containing 67,87 g CrO3(and 99.8 wt.%) and of 6.65 g of KOH (92 wt.%) in deionized water at the same temperature as in example 1.

Obtain a catalyst having the following composition, wt.%: Cr2O3- 20,0; K2O - 2,0; ZrO2TO 0.9; B2O3to 0.3; SiO2- 0,5; 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.

1. Catalyst for dehydrogenation of paraffin hydrocarbons, including chromium oxide, alkali metal oxide and alumina, characterized in that it further contains zirconium oxide and boron oxide at the following content, wt.%:

Cr2O3- 10 - 25

Me2O - 0,5 - 2,0

ZrO2- 0,5 - 2,0

B2O3- 0,1 - 1,0

Al2O3- Rest

where Me is an alkaline metal.

2. The catalyst p. 1, characterized in that it further contains an oxide of silicon with the following content, wt.%:

Cr2O3- 10 - 25

Me2O - 0,5 - 2,0

ZrO2- 0,5 - 2,0

B2O3- 0,1 - 1,0

SiO2- 0,5 - 1,5

Al

 

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