Vanadium-titanium catalyst preparation method

FIELD: redox reaction catalysts.

SUBSTANCE: invention relates to methods for preparing vanadium-titanium oxide catalysts for redox reactions, e.g. for industrial processes of production of phthalic anhydride via oxidation of o-xylene, selective reduction nitrogen oxides, and detoxification of organochlorine compounds. Method of invention comprises following stages: providing titanyl sulfate solution; adding ammonia and then vanadium peroxide solution to titanyl sulfate solution or adding to the same vanadyl sulfate or oxalate and then ammonia solution; optionally ageing suspension resulting after mixing of solutions; filtration; and calcinations at 450°C.

EFFECT: increased heat resistance of active chlorobenzene oxidation catalyst and reduced catalyst preparation time (10-12 h instead 72 h as in a known method).

1 tbl, 3 ex

 

The invention relates to methods of producing vanadium oxide-titanium catalysts of oxidation-reduction reactions, such as industrial processes of production of phthalic anhydride by oxidation of o-xylene, selective reduction of nitrogen oxides and disposal of chlorinated organic compounds.

A method of obtaining vanadium-titanium catalyst for the oxidation of chlorobenzene with a molar ratio of V:Ti=10. The catalyst was prepared by mixing metavanadate ammonium (NH4VO3and suspension of titanium oxide in an aqueous solution of urea with the addition of oxalic acid to a pH equal to 4, further heating up to 90°C for 20 hours then the slurry is dried and calcined at 500°10 h (Moon S.W., Lee G-D., Park, S.S. and Hong S-S. "Catalytic combustion of chlorobenzene over V2O5/TiO2catalysts prepared by the precipitation-deposition method", J. React. Kinet. Catal. Lett., vol.82, No2, p.303-310,2004).

The disadvantage of this method is the low activity of the resulting catalyst in the oxidation of chlorobenzene, due, in particular, its low specific surface (9 m2/g). So, when the volumetric gas flow rate 15000 h-1conversion of chlorobenzene is 90% at 327°C.

A method of obtaining vanadium-titanium catalyst by adding titanium dioxide (anatase) in an aqueous solution of metavanadate ammonium (NH4VO ), bringing the pH of the slurry to 7.0, and 7.1 (addition of NH4OH or NHO3), stirring for 48 h and filtered. The resulting product is dried at 60°C for 24 h and calcined in air at 500°C for 2 hours Then the powder catalyst can be deposited on an inert substrate (ER 1145762, MKI B01J 23/22, 2001).

The disadvantage of this method is the low activity of the resulting catalyst in the oxidation of chlorobenzene, due, in particular, its low specific surface area (29 m2/g). Thus, when the concentration of chlorobenzene in air 9000-900 ppm and volumetric gas flow rate 20000 h-1conversion of chlorobenzene is only 39% at 450°and at lower concentrations of chlorobenzene, equal to 265 ppm, and a lower volumetric gas flow rate equal to 15000 h-1the conversion of chlorobenzene equal to 90% at 327°C. in Addition to the disadvantages of this method include its considerable duration (more than 3 days) and low thermal stability of the obtained catalyst. Thus, already at 500°in the composition of the catalyst is observed the appearance of rutile phase, which significantly reduces its activity.

Thus, the authors was to develop a method for production of vanadium-titanium catalyst, providing the high activity of the catalyst at low temperatures, more in the high thermal stability and reducing the process time of its receipt.

The problem is solved in the proposed method for production of vanadium-titanium catalyst, which includes obtaining the solution of titanyl sulfate, adding to the resulting solution of aqueous ammonia and then the peroxide solution of vanadium or adding to the resulting solution vanadyl sulfate or oxalate and then ammonia solution may extract the resulting suspension after mixing the solutions, the subsequent filtering and calcining at 450°C.

At the present time of patent and technical literature is not a method of obtaining vanadium-titanium catalyst, in which process the catalyst is lead from a solution mixture of the source compounds.

All known methods for producing a vanadium-titanium catalysts involve the interaction of solutions of salts of vanadium solid powder of titanium dioxide with subsequent filtering and calcining. The result is an oxide catalyst, where the vanadium oxide deposited on the surface of titanium dioxide. The principal difference of the proposed method against known is the process in mixture solutions using deposition of ammonia. The result is the catalyst structure of anatase, which is embedded ions of vanadium.

The proposed method can be implemented as follows. Get solution of titanyl Sul the veil in the water, add with stirring an aqueous solution of ammonia and hydrogen peroxide solution of vanadium. The resulting suspension heated at 60-80°C for 1-2 h In the case of use as the source of a mixture of a mixture of solutions of titanyl sulfate and vanadyl sulfate or oxalate in water to the mixture an aqueous solution of ammonia. Formed in the first and second cases, the precipitate is filtered off, slowly heated to 450±5°C and maintained at this temperature for 10h. Then cooled to room temperature. The resulting product certificate of x-ray phase analysis. Specific surface area determined by the method of "BET" on the analyzer TriStar 3000 V6.03A.

The resulting catalyst was tested in the oxidation of chlorobenzene in a flow reactor and the temperature range 300-350°C. was charged To the reactor, 0.5 g of catalyst in powder form with a particle size less than 0.25 mm in a mixture of four volumes of silicon carbide with a particle size also less than 0.25 mm At a temperature of 300-350°in the reactor serves a vapor mixture of chlorobenzene with air (concentration of chlorobenzene in a mixture 9000-900 ppm) with a bulk velocity of 20000 h-1. In gases after the reactor determine the unreacted chlorobenzene by adsorption him on silica gel (particle size 0.25-0.5 mm), elution its acetone and chromatography was carried out with an internal standard of durene. Transformed the E. of chlorobenzene in the products of complete combustion (CO 2) is determined by the gravimetric method (absorption Astarita). The results are given in the table.

Table
The composition of the catalystThe concentration of chlorobenzene, ppmProcess temperature, °Conversion of chlorobenzene, %The output of the products of complete oxidation (CO2), %
Example 19000

9000

9000

9000

900
345

330

310

300

300
100

100

99

95

100
100

100

99

95

100
Example 2.9000

9000

9000

900
350

340

320

300
100

100

97

100
100

100

97

100
Example 3.9000

9000

900
340

320

300
100

99

100
100

99

100

According to x-ray analysis of the catalyst obtained by the proposed method, more thermally stable than known since the appearance of rutile phase is observed at 600°C.

The proposed method is illustrated by the following examples.

Example 1. Dissolve of 7.36 g TiOSO4·2H2About 200 ml of water; add with stirring to 5.9 ml vodno the ammonia solution with a content of 24% NH 3and the peroxide solution of 0.34 g V2About5in 30 ml of water. The resulting suspension is heated at 60°C for 2 hours. The precipitate is filtered off, slowly heated to 450°C and maintained at this temperature for 10 hours. After cooling to room temperature receive oxide vanadium-titanium catalyst with a molar ratio of V:Ti=1:10 with the structure of anatase and specific surface 92 m2/year

Example 2. In a solution with a concentration of 41,11 g/l TiOSO4and 4.19 g/l VOSO4add with constant stirring an aqueous solution of ammonia with 24% of NH3upon reaching pH=8. The precipitate is filtered off, slowly heated to 450°C and maintained at this temperature for 10 hours. After cooling to room temperature receive oxide vanadium-titanium catalyst with a molar ratio of V:Ti=1:10 with the structure of anatase and specific surface 66 m2/year

Example 3. In a solution with a concentration of 41,11 g/l TiOSO4and 3,984 g/l VOC2O4add with constant stirring an aqueous solution of ammonia with 24% of NH3upon reaching pH=8. The precipitate is filtered off, slowly heated to 450°C and maintained at this temperature for 10 hours. After cooling to room temperature receive oxide vanadium-titanium catalyst with a molar ratio of V:Ti=1:10 astructural of anatase and specific surface 76 m 2/year

Thus, the proposed method allows to obtain a heat-resistant catalyst of the oxidation of chlorobenzene with high catalytic activity. In addition, significantly reduced the duration of the process of preparation of the catalyst (10-12 hours versus 72 hours in a known way).

A method for production of vanadium-titanium catalyst, characterized in that it comprises the production of a solution of titanyl sulfate, adding to the resulting solution of aqueous ammonia and then the peroxide solution of vanadium or adding to the resulting solution vanadyl sulfate or oxalate and then ammonia solution may extract the resulting suspension after mixing the solutions, the subsequent filtering and calcining at 450°C.



 

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