Method for selective preparing acetic acid by catalytic oxidation of ethane and/or ethylene and catalyst for realization of method
FIELD: organic chemistry, chemical technology, catalysts.
SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.
EFFECT: improved preparing method.
14 cl, 1 tbl, 6 ex
This invention relates to a method for selective receipt of acetic acid catalytic gas-phase oxidation of ethane and/or ethylene in the presence of a catalyst containing molybdenum and palladium.
Oxidative dehydrogenation of ethane to ethylene in the gas phase at temperatures exceeding 500° it is known, for example, from the patent applications U.S. And 4250346 And 4524236 and 4568790.
Thus, the application at the U.S. patent And 4250346 described the use of a catalytic composition for the conversion of ethane into ethylene, containing the elements molybdenum, X and Y in the ratio a:b:C, where X is Cr, Mn, Nb, TA, Ti, V and/or W, and Y is Bi, CE, Co, cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, a=1, b=0.05 to 1, with=0-2. The total value of "C" for Co, Ni and/or Fe must be less than 0.5 in.
The reaction proceeds preferably in the presence of added water. The described catalysts can be used, if necessary, for the oxidation of ethane to acetic acid, the efficiency of conversion into acetic acid is about 18% conversion of ethane to 7.5%.
In these applications it is mainly about how to obtain ethylene, to a lesser extent on the target getting acetic acid.
In contrast, in EP-B-0294845 describes how selective obtaining acetic acid from ethane, ethylene or mixtures thereof with oxygen in the presence of a catalytic mixture which, at least, who will win:
A) a calcined catalyst of the formula MoxVyor MoxVyZzwhere Z can be one or more metals of Li, Na, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Sc, Y, La, Ce, Al, Tl, Ti, Zr, Hf, Pb, Nb, TA, As, Sb, Bi, Cr, W, U, Te, Fe, Co and Ni, x=0.5 and 0.9, y=0.1 to 0.4, and z=0.001 to 1, and
B) a catalyst for the hydration of ethylene and/or a catalyst for the oxidation of ethylene.
In the case of the second catalyst component (B) refers, in particular, about the molecular sieves as catalyst or oxidation catalyst containing palladium.
When applying the described catalytic mixture and the power of the reactor containing the catalyst, a gas mixture consisting of ethane, oxygen, nitrogen and water vapor, the maximum selectivity is 27% conversion of ethane to 7%. High speed conversion of ethane according to EP 0294845 achieved only with the described catalytic mixture, but not with a catalyst containing the individual components a and B.
Another way to obtain a product containing ethylene and/or acetic acid, described in European patent EP-B-0407091. When the gas containing ethane and/or ethylene and molecular oxygen, at elevated temperature in contact with a catalytic composition, which contains the elements A, X and Y. At the same time is a ModReeWf, X is Cr, Mn, Nb, TA, Ti, V and/or W and Y is Bi, CE, Co, cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U. Maxim is supplemented flax selectivity, which can be achieved with the application of the described catalyst in the oxidation of ethane to acetic acid, is 78%. As other byproducts carbon dioxide, carbon monoxide and ethylene.
In the Federal Republic of Germany patent 19620542 describes how selective obtaining acetic acid from a gaseous nutrient mixture containing ethane, ethylene or a mixture thereof, and oxygen, at elevated temperature, characterized in that the gaseous nutrient mixture is injected together with a catalyst, which contains elements of a:b:c:d:e in combination with oxygen: MoaPdbRecXdYewhile the symbols X, Y have the following values: X=Cr, Mn, Nb, V, TA, Ti, V and/or W; Y=Bi, CE, Co, cu, Te, Fe, Li, K, Na, Rb, Be, Mg, Ca, Sr, Ba, Ni, P, Pb, Sb, Si, Sn, Tl and/or U; the indices a, b, C, d and e denote the gram-atom ratios of the respective elements, this a=1, b>0, c>0, d=0.05 to 2, e=0-3. In these examples, at 280° and 15 bar conversion of ethane comes to 8%, and the selectivity of acetic acid to 91%.
In the Federal Republic of Germany patent 19630832 describes how selective obtaining acetic acid from a gaseous nutrient mixture containing ethane, ethylene or mixtures thereof and oxygen at elevated temperatures. Nutrient mixture when it interacts with a catalyst containing the elements Mo, Pd, X and Y in combination with oxygen.
This X means the one and the multiple members, selected from the group CR, Mn, Nb, TA, Ti, V, Te and W, and Y represents one or more elements selected from the group B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, and U. G-the atomic ratio of corresponding elements are indicated as follows: a (Mo)=1; b (Pd)>0, C (X)>0; d (Y)=0-2.
The catalysts described in the aforementioned patent, find the maximum performance of 149 kg/(FM3) when the selectivity of acetic acid >60 mol.%. Performance is characterized by the amount of acetic acid per unit time and volume of the catalytic Converter.
The object of the invention in the international patent application WO 9847850 is a selective way of obtaining acetic acid from a gaseous nutrient mixture containing ethane, ethylene or mixtures thereof and oxygen at elevated temperatures on the catalyst, which contains the elements W, X, Y, and Z in the gram-atom ratios a:b:c:d in combination with oxygen: WaXbYcZdwhere X is one or more elements selected from the group of Pd, Pt, Ag and/or Au, Y is one or more elements selected from the group V, Nb, Cr, Mn, Fe, Sn, Sb, cu, Zn, U, Ni and/or Bi, Z is one or more elements selected from the group Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and/or Te, a=1, b>0, c>0, d=0-2, and the catalyst. At 250°, 15 bar the contact time of 20 seconds selectivity of acetic acid 80% conversion of ethane 10%.
International patent application WO 00/14047 concerns a method for obtaining acetic acid, while ethane and/or ethylene react with a gas containing molecular oxygen in the reactor with a fluidized bed in the presence of solid fluidized microspherical catalyst oxidation, and at least 90% of the above-mentioned catalyst particles have a size less than 300 microns. As the catalyst described compound of the formula MoaWbAgcIrdXeYfwhile X is Nb, and V, Y represents an element from the group Cr, Mn, TA, Ti, In, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, cu, Ag, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, U, Re and Pd; a-f mean the gram-atom ratios of the elements with 0<and≤ 1; 0<b≤ 1; a+b=1; 0<(C+d)≤ 0,1; 0<e≤ 2; 0≤ f≤ 2. In these examples, the oxidation of ethane to acetic acid maximum performance acetic acid is 354, 4 kg(m3h), in the oxidation of ethylene to acetic acid productivity of acetic acid is 258,52 kg/(m3h).
In the Federal Republic of Germany patent 19745902 found that when using a catalyst containing the elements Mo and Pd, and one or more elements from the group Cr, Mn, Nb, TA, Ti, V, Te and/or W, it was possible in relatively mild conditions, simple way with high selectivity and significant capacity to oxidize ethane and/or the ethylene to acetic acid.
This invention patents Germany 19745902 also concerns the method for selective receipt of acetic acid from a gaseous nutrient mixture containing ethane, ethylene or mixtures thereof and oxygen at elevated temperature, while gaseous nutrient mixture is introduced with the catalyst, which contains the elements Mo, Pd, X and Y in the gram-atom ratios a:b:c:d in combination with oxygen: MoaPdbXcYd; and the symbols X and Y have the following meanings: X indicates one or more elements selected from the group of CR, Mn, TA, Ti, V, Te and W, in particular, V and W; Y represents one or more elements selected from the group of: B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Cu, Rh, Ir, Au, Ag, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl, and U, in particular, Nb, Ca, Sb and Li. The indices a, b, C and d mean gammatone ratio of the respective elements, with a=1, b=of 0.0001 to 0.01, C=0,4-1 and d=0.005 to 1. Since X and Y mean several different elements, the indices c and d can also accept multiple values.
Hereinafter called the invention concerns a catalyst for selective receipt of acetic acid, containing the elements Mo, Pd, X and Y in the gram-atom ratios a:b:c:d in combination with oxygen. The gram-atom ratios a:b:c:d is preferably lie in the following fields: a=1, b=0,0001-of 0.005, C=0.5 to 0.8, and d is 0.01 to 0.3.
The content of palladium in the catalyst above the top of the her borders, as described in the method of patent Germany 19745902, promotes the formation of carbon dioxide. In addition, high concentrations of palladium in General should be avoided because it unnecessarily increases the cost of the catalyst. In contrast, when the palladium content below the defined boundaries of the observed preferred formation of ethylene.
The catalyst used in the Federal Republic of Germany patent 19745902, preferably contains in addition to the elements molybdenum and palladium still vanadium, niobium, antimony and calcium in combination with oxygen. The gram-atom ratios a:b:C1:d1:d2:d3elements Mo:Pd:V:Nb:Sb:Ca preferably as follows: a(Mo)=1; b(Pd)=0,0001-0,005, in particular 0,0001-0,001;1(V)=0,4-1,0; d1(Nb)=0,01-0,2; d2(Sb)=0.01 to 0.3; d3(Ca)=0.01 to 0.3.
The performance achieved in example 7 of the patent Germany 19745902, 310°, 15 bar, and duration of contact 7 seconds is 470 kg/(h· m3).
In the international patent application WO 00/00284 described catalytic system based on MoVNbPd, MoVLaPd or their mixtures for obtaining acetic acid from ethylene. The above examples demonstrate the maximum performance, component 1291 kg(m3·h)when the conversion of ethylene 63,43% and the selectivity of acetic acid 78,03%.
In connection with the above-mentioned patents is ochevidnim that the oxidation of ethylene production is important for acetic acid can reach 1291 kg/(m 3h)that the oxidation of ethane due to its complicated activity compared with the activity of ethylene, the productivity of acetic acid remains, however, much lower than in the oxidation of ethylene. In the patent application Germany And 19745902 described is greatest at the present time, the productivity of acetic acid in the oxidation of ethane, a component of 470 kg/(m3h). Desired, however, higher performance, because it can be reduced the size of the reactor and the amount of gas in circulation.
Consequently, there is a task to provide a catalyst and method that would allow targeted to oxidize ethane and/or ethylene to acetic acid in a simple manner with high selectivity and productivity in the most mild reaction conditions.
The present invention describes a modified method of obtaining a composition similar to that described in the patent application of RGA-19745902 catalysts, which improves the catalytic properties of these catalysts. A feature of the invention, among others, is that by using the described catalyst along with the oxidation of ethylene proceeds also significantly difficulty oxidation of ethane in the optimal reaction conditions with a high conversion of ethane, highly the selectivity of acetic acid and, in particular, high performance acetic acid, compared to the above-mentioned patents.
Catalysts in the patent application Germany And 19745902 get traditional ways. The assumption of the suspension, in particular, aqueous solution, which contains a separate source components elements in accordance with their shares. The starting materials of the individual components for the preparation of the catalyst according to this invention along with the oxides are substances, preferably soluble in water, namely, ammonium salts, nitrates, sulfates, halides, hydroxides and salts of organic acids that can be converted into the corresponding oxides by heating. For mixing get and stirred aqueous solutions or suspensions of salts of the metals. In the case of molybdenum, based on commercial availability, are used as starting compounds corresponding molybdates, for example, ammonium molybdate. As the palladium compounds are used, for example, palladium(II)chloride, palladium(II)sulfate, palladium(II)-terminated, palladium(II)-nitrate, and palladium(II)-acetylacetonate.
The present invention describes obtaining a catalyst other methods using other raw materials in comparison with those described in patent application Germany And 19745902. So, instead of oxalate is IBIA use neobyasnimy salt, preferably niobiumtitanium, the composition X3NbO(C2O4)3+X2NbO(OH)(C2O4)2where X=N+or NH
The present invention concerns also containing niobium catalyst of the above type, which is obtained through the use of neobiasnimij salt, for example of niobiumtitanium, the quality is TBE source of niobium.
The resulting reaction mixture was stirred and then, in the interval from 5 minutes to 5 hours at a temperature of from 50 to 100° C. thereafter, water is removed and the remaining catalyst is dried at a temperature of from 50 to 150° With, in particular from 80 to 120° C.
When the resulting catalyst is then subjected to calcination, it is recommended to calcinate dried powdered catalyst at a temperature of from 100 to 800° With, in particular from 200 to 500° With, in the presence of nitrogen, oxygen or oxygen-containing gas. The calcination can be carried out in a muffle furnace, it is better, however, in a rotary tubular furnace, in which there is a continuous flow of catalyst suitable gas, which leads, in turn, to improved homogeneity of the catalyst in comparison with the catalysts described in the patent application of RGA-19745902. The duration of calcination is from 2 to 24 hours.
The catalyst can be used without appropriate support, or to mix with it, or be applied to it. Suitable are the usual carriers, such as porous silica, calcined silica, diatomaceous earth, kieselgel, porous or nonporous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, oxide olo is a, ceria, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitride or silicon carbide, as well as the grid of glass, carbon fibers, metal oxides or metals or the corresponding monoliths.
Preferred carriers have a surface of less than 100 m2/, Preferred carriers are silicon dioxide or aluminum oxide with a small specific surface area. The catalyst can be used as a heterogeneous oxidation catalyst in the form of an arrangement or disordered molded solid or powdered form.
The reaction may proceed in the fluidized bed or in a reactor with a fixed bed. For use in the fluidized bed, the catalyst is prepared commonly used methods, such as agglomeration, so that the preferred size distribution of the particles was in the range of from 10 to 200 microns.
Gaseous nutrient mixture contains ethane and/or ethylene, which in the form of pure gas or in a mixture with one or more other gases are fed into the reactor. As such additional gases or carrier gases are considered, for example, nitrogen, methane, carbon monoxide, carbon dioxide, air and/or water vapor. The gas containing molecular oxygen may be air, and more or less what it than air, saturated with molecular oxygen gas, for example oxygen. The proportion of water vapor can be from 0 to 50 vol.%. Higher concentrations of water vapor needless costs obtained aqueous acetic acid for technological reasons. Based on the water vapor concentration in the nutrient mixture in the examples of the present invention is reduced in comparison with the examples in the patent Germany 19745902, which leads to significant savings in the processing of acetic acid. The ratio of ethane/ethylene to oxygen preferably in the range from 1:1 to 10:1, preferably from 2:1 to 8:1. The higher content of oxygen is preferable, since this achieves a higher conversion of ethane and thus higher yield of acetic acid. The preferred additive is oxygen or gas containing molecular oxygen, in concentrations outside the limit under the reaction conditions, because this simplifies the process. Of course it is also possible to adjust the ratio of ethane/ethylene:oxygen within these limits.
The reaction is carried out at temperatures of from 200 to 500° C, preferably from 200 to 400° C. the Pressure may be atmospheric or above atmospheric, for example in the range from 1 to 50 bar, preferably from 1 to 30 bar.
The reaction can be carried out in a reactor with a stationary layer or pseudo is igennem layer. It is advisable to first mix ethane with an inert gas, namely nitrogen, or water vapor, before introducing the oxygen or gas containing molecular oxygen. The mixed gas is preferably preheated in heater to the reaction temperature before feeding the gas mixture to the catalyst. Of the reactor exhaust gas acetic acid is separated by condensation. The remaining gases are returned to the inlet of the reactor, where introducing oxygen or a gas containing molecular oxygen, as well as ethane and/or ethylene.
When comparing catalysts corresponding to this invention, the catalysts known from the prior art, it is found that the use of these catalysts under the same reaction conditions (incoming reaction gas, pressure, temperature) achieved higher productivity and selectivity of acetic acid.
When using the catalysts corresponding to this invention, the selectivity in the oxidation of ethane and/or ethylene to acetic acid is ≥ 70 mol.%, preferably ≥ 80 mol.%, in particular ≥ 90 mol.%, and performance >470 kg/(h· m3), in particular >500 kg/(h· m3), preferably >550 kg/(h· m3so that by way of the invention in comparison with prior art, simple is Ecodom can be achieved by increasing outputs of acetic acid while reducing the formation of unwanted side products.
The catalyst composition described in the examples, listed in relative atomic ratios.
The preparation of the catalyst:
The catalyst (I): the prepared catalyst of the following composition:
80 g of ammonium molybdate (NH4)6Mo7O24×4H2O (Riedel-de Haen) in 400 ml of water.
29,4 g metavanadate ammonium NH4VO3(Riedel-de Haen) in 400 ml of water.
19.1 g of nobelmuseet (firm ..Stark),
1.92 g of antimony oxalate Sb2(O2O4)3(Pfaltz &Bauer),
of 1.34 g of calcium nitrate CA(NO3)2×4H2O (Riedel-de Haen) in 200 ml of water.
0,078 g palladium(II)acetate (CH3CO2)2Pd (company Aldrich) in 200 ml of ethanol.
Aqueous solutions of 1-3 mixed separately at 70° C for 15 minutes. Then the third solution is combined with the second. The combined mixture was stirred at 70° C for 15 minutes before adding them to the first solution. Then add a solution of 4. The resulting mixture was stirred at 70° C for 15 minutes and then pariveda up to a volume of 800 ml of the Mixture is spray dried and calcined in a stationary state in air at 120° C for 2 hours and at 300° within 5 hours. The catalyst was slightly crushed in a mortar and pressed into tablets. Their sieved to obtain a fraction with sizes from 0.35 to 0.7 mm
Test method of the catalyst:
5 or 10 ml of the catalyst is placed in a steel reactor with an inner diameter of 14 mm, the Catalyst is heated in a stream of air at 250° C. Then install the pressure control initial pressure. The desired mixture of ethane:oxygen:nitrogen is dosed with water in the evaporation zone, where the water vaporizes and combines with the gases. The reaction temperature is measured in the catalyst bed by thermocouple. The reaction gas is analyzed online by gas chromatography.
In the examples, the following indicators are defined as:
The conversion of ethane (%): [WITH]/2+[CO2]/2+[P2H4]+[SN3COOH])/[CO]/2+[CO2]/2+[P2H4]+[C2H6]+[SN3COOH])of 100
The selectivity of ethylene (%):
([C2H4] //2+[CO2]/2+[P2H4]+[SN3COOH])100 Selectivity of acetic acid (%):
=concentration in mol.% and
[C2H6]=concentration of unreacted ethane.
The duration of the contact is defined as:
Θ (s)=bulk density of catalyst (ml)/volume of the current of gas (V) through the reactor in soo is under the reaction conditions (ml/s)
RZA means productivity in kg of acetic acid per hour per m of catalyst.
Carrying out the reaction:
The ratio of ethane/oxygen/nitrogen in the reaction gas is 5/1/4. The proportion of water vapor in the reaction mixture is established in the amount of ≤ 20%. Since the performance depends on the reaction pressure, all the experiments in the examples for comparison is carried out at 15 bar. The conditions of the reaction and the results are presented in table 1.
The results of catalytic tests the oxidation of ethane to acetic acid on the catalyst (I)
|The composition of the reaction Gas||Conversion||Selectivity,%||RZA kg/FM3|
|Experience No..||So° C||Θ (C) ml/s||V(C2H6)ml/s||V(O2) ml/s||V(N2) ml/s||V(H2O) g/h||With2H6%||HOAc||With2H4||CO+CO2||HOAc|
From table 1 it follows that the reduced contact time with the same composition of the reaction gas and the reaction temperature 280° with a slight decrease of the conversion and the unknown the military selectivity of acetic acid leads, however, to single productivity (cf. experiments 2 and 3). Further reduction of the contact time at 300° With (cf. experience 4) at comparable conversions and selectively leads to a further increase performance. Compared with the experience of 4 in experiments 5 and 6 along with a further reduction in contact time and at comparable conversion and selectivity performance can further be increased up to 630 kg/(h· m3). Especially it should also be noted that the marked decrease in the selectivity of acetic acid compared with experiments 1-4 does not lead to increased formation of fully oxidized products, and due to the low water content in the nutrient mixture along with acetic acid preferably is formed of ethylene, which is a valuable product, is recycled and can be further oxidized to acetic acid.
1. Continuous process for the selective receipt of acetic acid by contacting at elevated temperature gaseous nutrient mixture containing ethane, ethylene or mixtures thereof, and oxygen, with a catalyst containing the elements Mo, Pd, X and Y in combination with oxygen having the General formula (I)
in which X is V, and optionally one or more elements selected from groups: One, Those who W
Y means Nb, Ca and Sb, and optionally one or more elements selected from the group of Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr, Hf,
the indices a, b, C and d denote the gram-atom ratios of the respective elements, with a=1, b=of 0.0001 to 0.01, C=0,4-1 and d=0.005 to 1, characterized in,using the catalyst, in which the niobium is introduced with the use of ammonium salts of niobium, and the duration of contractorowned and nutrient composition of gaseous mixture are chosen so that the performance of the oxidation in acetic acid was >470 kg/(m3h).
2. The method according to claim 1, wherein X means a few items, however, if necessary, the index c for different items take different values.
3. The method according to claim 1 or 2, characterized in that as the ammonium salt of niobium use ammoniacal niobium.
4. The method according to one of claims 1 to 3, characterized in that
the temperature lies in the region from 200 to 500°C.
5. The method according to one of claims 1 to 4, characterized in that the pressure in the reactor is from 1 to 50 bar.
6. The method according to one of claims 1 to 5, characterized in that the index b is from 0.0001 to 0.001.
7. The method according to one of claims 1 to 6, characterized in that the reactor serves ethane, mixed with at least one additional gas.
8. The method according to claim 7, characterized in that as an additional g which serves for nitrogen, oxygen, methane, carbon monoxide, carbon dioxide, ethylene and/or water vapor.
9. The method according to one of claims 1 to 8, characterized in that the use of catalyst present in the form of a mixture with a carrier or recorded on the media.
10. The method according to one of claims 1 to 9, characterized in that the selectivity of the oxidation of ethane and/or ethylene to acetic acid is equal to or more than 70 mol.%.
11. The method according to one of claims 1 to 10, characterized in that theuse a catalyst in which palladium is deposited in the form of an alcohol solution of palladium acetate.
12. Catalyst for the selective gaseous oxidation of ethane, ethylene or mixtures thereof in acetic acid containing the elements Mo, Pd, X and Y in combination with oxygen having the General formula (I)
in which X is V, and optionally one or more elements selected from the group of TA, Te and W,
Y means Nb, Ca and Sb, and optionally one or more elements selected from the group of Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr, Hf,
the indices a, b, C and d denote the gram-atom ratios of the respective elements, with a=1, b=of 0.0001 to 0.01, C=0,4-1 and d=0.005 to 1, characterized in that the catalyst obtained by using as a source of niobium ammonium salt of niobium and has a capacity of oxidation equal to >470 kg/(m3h).
13. It is talization indicated in paragraph 12, characterized in that as a source of niobium use ammoniacal niobium.
14. The catalyst according to item 12, palladium made to him in the form of an alcohol solution of palladium acetate.