The method of producing the catalysts based on antimonate vanadium using sno2xh2o

 

(57) Abstract:

The invention relates to a method for producing a tin-containing vanadium-antimony catalysts suitable for the catalytic ammoxidation3-C5-paraffins or olefins, more specifically, to obtain catalysts for the ammoxidation of propane or isobutane, or propylene, or isobutylene with obtaining relevant ,-unsaturated mononitriles, Acrylonitrile or Methacrylonitrile. The described method of producing a catalyst containing vanadium, antimony, tin and titanium in the oxidized state, including the production of aqueous suspension of a mixture of original substances, the components of the boot containing compounds of elements to be included in the final catalyst, drying the mixture and calcining to form the active catalyst, with downloadable source of tin is a solution which contains SnO2xH2Oh, where x0, dispersed in of tetraalkylammonium hydroxide, defined by the formula (C2H2n+1)4NOH, where 5n1. Also described is a method of obtaining a catalyst having a specific empirical formula and providing for drying and calcination to 500oWith, as well as methods of obtaining the result increasing the activity and selectivity of the catalyst. 5 S. and 11 C.p. f-crystals.

The scope of the invention

The invention relates to a method for producing a tin-containing vanadium-antimony catalysts suitable for the catalytic ammoxidation3-C5-paraffins or olefins, more specifically, to obtain catalysts for the ammoxidation of propane or isobutane, or propylene, or isobutylene with obtaining relevant ,-unsaturated mononitriles, Acrylonitrile or Methacrylonitrile. In addition, the catalyst may be used in the ammoxidation methylpyridine, m-xylene or respectively in the oxidation of o-xylene in cyanopyridine, isophthalonitrile or phthalic anhydride.

More specifically the invention relates to the use of SnO2HN2Oh, where x0, dispergirovannom in the solution of tetraalkylammonium hydroxide, as tin-containing reagent upon receipt of catalysts containing vanadium and antimony, and tin in the oxide form. These types of catalysts are presented, for example, in U.S. patents 3 681 421, 4 788 317, 5 008 427 and in the descriptions of the patents great Britain 1 366 135 and 1 366 136, published in November 1973

Not all sources of tin are equally and ammoxidation of saturated3-C4-alkanes, in particular for ammoxidation. In fact, in the U.S. patent 5 214 016 and EPO 691 306-A1 indicates that the source of tin, which promoter is critical for the operational properties of the final catalyst. I believe that in order for the tin was reactive during the passage of the reaction in the solid phase during annealing of a mixture of catalyst precursor, it must be present in a very finely dispersed form in the predecessors of such catalysts. Upon receipt of the catalysts of the present invention suitable source is the Sol of tin oxide (see U.S. patent 5 008 427). However, the crushed tin oxide or tin oxide, obtained by reacting metallic tin with nitric acid, are certainly less efficient sources upon receipt of the catalyst. Although in circulation commercially available Sol of tin oxide is effective, it has a significant drawback, because it is very expensive source of tin.

The essence of the present invention

The purpose of this invention is the provision of a method of obtaining an excellent oxidation catalyst (especially amlove.

Another objective of the invention to provide a less expensive catalyst through the use of cheaper component tin in comparison with outstanding commercially available Sol of tin oxide, is used as the source of tin in the catalyst precursor.

Other objectives, aspects, features and advantages of the invention will become more apparent when reading the description with specific examples.

The above and other objectives are achieved by the present invention in accordance with which is provided a method of producing a catalyst containing vanadium, antimony and tin in the oxidized state, which includes obtaining water suspension of a mixture of original substances, the components of the load containing compounds of elements to be included in the final catalyst, subsequent drying and calcination of the mixture with the formation of the active catalyst, where the download source of the tin is a solution which contains SnO2HN2Oh, where x0, dispersed in of tetraalkylammonium hydroxide, where the hydroxide of tetraalkylammonium defined by the following formula:

(C2H2n+1)4NOH, where 5n1.

In prettybig suitable organic or inorganic compounds predecessor, containing V and Sb, and the compounds used for the introduction of other optional elements in the final catalyst, which is known in this field, such as salts, oxides, hydroxides or ORGANOMETALLIC compounds of these elements, while tin is introduced into the loading raw material used for making such catalysts, in the form of a solution SnO2HN2Oh, dispersed, as indicated earlier, of tetraalkylammonium hydroxide. Downloadable mixture of the foregoing substances are heated and calcined in a known manner to the formation of the final catalyst. Examples of the basic substances that make up the load, here shown in the specific working examples.

It is particularly effective in the production of catalysts is presented in U.S. patent 4 784 979, 4 879 264, 3 860 534 and 5 094 989, which are included here for reference. In addition, the catalyst may be optionally processed by one or more methods disclosed in U.S. patent 5 432 141 and 5 498 588, which is also included for reference.

Upon receipt of the catalysts of the present invention, the upper limit of the temperature of calcination is usually at least 500oBut for amoxicilline least 780oC.

The catalyst may be in the media or not to have such media. Preferably the catalyst is supported on such a carrier, such as silica, alumina, silica-alumina, Zirconia or mixtures thereof.

The preferred method of the invention consists in obtaining a catalyst having the elements and proportions indicated empiricheskoi formula

VSbmAaDdOx< / BR>
where a is one or more elements selected from Ti, Sn, and Sn is present always,

D is one or more elements selected from Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn, where:

m has a value from 0.5 to 10,

and is a number greater than 0

10>a>0,

d is a number from 0 to 10,

x is determined by the oxidation state of the cations present.

The method includes obtaining a water suspension of a mixture of original substances, the components of the load, containing compounds of the above elements to be included in the final catalyst, subsequent drying and thermal annealing mixture to obtain an active catalyst, where the loaded history is trialkylamine, this of tetraalkylammonium hydroxide defined by the following formula:

(C2H2n+1)4NOH, where 5n1,

and drying the slurry and calcining is carried out until the upper limit of the temperature of calcination, is equal to at least 780oC. the Upper temperature limit of the annealing can be up to 1200oWith, but more preferably it is not more than 1050oC.

In accordance with another aspect of the present invention provides a method of obtaining a ,-unsaturated mononitriles selected from Acrylonitrile and Methacrylonitrile by catalytic reaction in the vapor phase of a paraffin selected from propane and isobutane with molecular oxygen and ammonia and optionally a gaseous diluent, by catalytic contact of the above reagents in the reaction zone with a catalyst, where the initial reaction mixture fed to reaction zone has a molar ratio of paraffin to ammonia in the range from 2.5 to 16, preferably from 4 to 12, especially preferably from 5 to 11) and the molar ratio of paraffin to O2in the range from 1 to 10 (preferably 2 to 9, particularly preferably from 3 to 9), and the catalyst has em is the accordance with the last preceding paragraph.

The catalyst may also be used in the ammoxidation methylpyridine and m-xylene with getting cyanopyridine and isophthalonitrile or in the oxidation of o-xylene with obtaining phthalic anhydride. The molar ratio of NH3to pyridine and oxygen to methylpyridine respectively from 1 to 5 and from 1 to 10. Molar ratio of NH3to m-xylene and O2to m-xylene, respectively from 1 to 5 and from 1 to 10.

In the reaction of phthalic anhydride attitude ABOUT2to o-xylene may be in the range from 1 to 10.

The catalyst obtained by the method of the present invention can also be used in the ammoxidation of propylene or isobutene ammonia and oxygen to obtain Acrylonitrile or Methacrylonitrile. In this reaction at conventional temperatures and conditions, well known in this field, the molar ratio of NH3the olefin may range from about 1 to 5, and the molar ratio of O2the olefin may be in the range from 1 to 10.

Detailed description of the invention

The following examples of the preparation of catalysts and ammoxidation reactions carried out with the use of these catalysts serve only as an example>/P>A catalyst having the composition VSb1,4Snof 0.2Tia 0.1Ox(Catalyst 17388-79), obtained by mixing 27,30 g powder V2O5with a solution consisting of 100 ml of 30% H2ABOUT2in 900 ml of water in a two-liter beaker. After the reaction powder V2O5was completed, added 61,25 g Sb2O3and then 2,40 g powder TiO2(Degussa P-25). Chemical beaker covered with watch glass and the mixture was mixed and heated for about 3 hours. In a separate beaker to 100 ml of water and 8 ml of 25 wt.% hydroxide solution of Tetramethylammonium added 10,13 g SnO2HN2O ("acid tin oxide by Magnesium Electron Inc., (Magnesium Electron Inc.), received 06.07.91). The mixture was heated on a hot plate with constant stirring to the formation of the translucent mixture. This tin-containing dispersion is then added to the above dispersion of vanadium, antimony and titanium. To reduce the amount of evaporation of water, the mixture was mixed when heated in an open beaker. When the mixture could be stirred, it was dried in an oven at a temperature of 120oC. After that, she was progulivali for 1 hour at 325oWith, then for 8 hours at 650oC, then cooled and 820oWith, then for a further 3 hours at 650oC.

Then, the calcined catalyst is contacted with Isobutanol using about 6,25 ml of Isobutanol per 1 g of the catalyst by placing the catalyst in a funnel with a porous glass plate, pouring Isobutanol on the surface of the catalyst, mixing the catalyst in Isobutanol to ensure an even distribution of the catalyst on the bottom of the crater and then passing through the funnel without suction. This washing was carried out for 3 times. After the last washing Isobutanol missed through the funnel, the catalyst was heated in an oven at 120oC, the catalyst was removed, the residue of Isobutanol.

The catalyst was tested for the ammoxidation of propane using U-shaped titanium tubular reactor with a fixed bed and the tube size 1/4 " (0,635 cm). Gaseous source mixture fed to the reactor, had a molar ratio propane/ammonia/oxygen/nitrogen at a pressure of 15 pounds/inch2(1,0547 kg/cm2) 3:1:2:5. When the temperature of the reactor 490oWith time and contact 1.4 seconds selectivity for Acrylonitrile was 61.8% when the degree of conversion of propane to 19.2%. When the temperature of the reactor 495o

Example 2.

A catalyst having the composition VSb1,4Snof 0.2Tia 0.1Oxreceived by mixing 27,30 g powder V2O5with a solution consisting of 100 ml of 30% H2ABOUT2in 900 ml of water in a two-liter beaker. After the reaction powder V2O5was completed, added 61,25 g Sb2O3and then 2,40 g powder TiO2(Degussa P-25). Chemical beaker covered with watch glass, the mixture was mixed and heated for approximately 3 hours. In a separate beaker to 100 ml of water and 300 ml of 25% solution of hydroxide of Tetramethylammonium added 10,13 g SnO2HN2("Acid tin oxide" from the firm Magnesium Electron Inc., received 06.07.91). The mixture was heated on a hot plate with constant stirring to the formation of the translucent mixture. This tin-containing dispersion is then added to the above dispersion of vanadium, antimony and titanium. To reduce the amount of evaporation of water, the mixture was mixed when heated in an open beaker. When the mixture could be stirred, it was dried in an oven at a temperature of 120oC. then it was probalily for 1 hour at a temperature of 325oWith, then for 8 hours at 650oC, then cooled and ismalic the>who, then for a further 3 hours at 650oC.

Then, the calcined catalyst is contacted with Isobutanol using about 6,25 ml of Isobutanol per 1 g of the catalyst by placing the catalyst in a column with a porous glass plate, pouring Isobutanol on the surface of the catalyst, mixing the catalyst in isobutyl alcohol with the purpose of uniform distribution of the catalyst on the bottom of the crater and then passing through the funnel without suction. This washing was carried out for 3 times. After the last washing Isobutanol missed through the funnel, the catalyst was heated in an oven at 120oC, the catalyst was removed, the residue of Isobutanol.

The catalyst was tested for the ammoxidation of propane using U-shaped titanium tubular reactor with a fixed bed and the tube size 1/4 " (0,635 cm). Gaseous source mixture fed to the reactor, had a molar ratio propane/ammonia/oxygen/nitrogen at a pressure of 15 pounds/inch2(1,0547 kg/cm2) 3:1:2:5. When the temperature of the reactor 495oWith time and contact 2.4 seconds selectivity relative to the Acrylonitrile was 55.6 wt.% when the degree of conversion of propane of 13.18%.

1. The method of obtaining the suspension of a mixture of original substances, the components of the boot containing compounds of elements to be included in the final catalyst, drying the mixture and calcining to form the active catalyst, wherein the download source of the tin is a solution which contains SnO2HN2Oh, where x0, dispersed in of tetraalkylammonium hydroxide, the hydroxide of tetraalkylammonium defined by the following formula:

(C2H2n+1)4NOH, where 5n1.

2. The method according to p. 1, characterized in that the SnO2HN2About dispersed in the hydroxide of Tetramethylammonium.

3. The method according to p. 1, characterized in that the annealing is carried out at a temperature equal to at least 500oC.

4. The method according to p. 3, characterized in that the temperature of calcination of the catalysts for ammoxidation of paraffins is at least 750oC.

5. The method according to p. 3, characterized in that the temperature of calcination is at least 780oC.

6. The method according to p. 1, characterized in that the catalyst is supported on an inert carrier.

7. The method according to p. 6, characterized in that the medium is selected from the group consisting of silicon dioxide, aluminum oxide, dioceses elements and proportions, these empirical formula

VSbmAaDdOx,

where a is one or more elements selected from Ti, Sn, and Sn is always present;

D is one or more elements selected from Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn,

where m has a value from 0.5 to 10;

and is a number greater than 0,

10>a>0;

d is a number from 0 to 10;

x is determined by the oxidation state of the cations present,

including the production of aqueous suspension of a mixture of original substances, the components of the load, containing compounds of the above elements to be included in the final catalyst, subsequent drying and thermal annealing mixture to obtain an active catalyst, wherein the download source of the tin is a solution which contains SnO2HN2Oh, where x0, dispersed in of tetraalkylammonium hydroxide, the hydroxide of tetraalkylammonium defined by the following formula:

(C2H2n+1)4NOH, where 5n1,

while drying the slurry and calcining the mixture is carried out until the upper limit of the temperature of calcination, is equal to at least 500 who, 750oC.

10. The method according to p. 9, characterized in that the temperature of calcination is at least 780oC.

11. The method according to p. 8, characterized in that the catalyst is supported on an inert carrier.

12. The method according to p. 11, wherein the inert carrier is selected from the group consisting of silicon dioxide, aluminum oxide, Zirconia, silica - alumina or mixtures thereof.

13. The method according to p. 8, characterized in that the SnO2HN2About dispersed in the hydroxide of Tetramethylammonium.

14. The method of obtaining the ,-unsaturated mononitriles selected from Acrylonitrile and Methacrylonitrile the ammoxidation of paraffins in the presence of a catalyst obtained by the method according to p. 1, selected from propane and isobutane with molecular oxygen and ammonia by catalytic contact of the above reagents in the reaction zone with a catalyst having the following formula:

VSbmAaDdOx,

where a is one or more elements selected from Ti, Sn, and Sn is always present;

D is one or more elements selected from Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, BR>
d is a number from 0 to 10;

x is determined by the oxidation state of the cations present,

where the initial reaction mixture fed to reaction zone has a molar ratio of paraffin to the NH3in the range from 2.5 to 16 and a mole ratio of paraffin to oxygen in the range from 1 to 10, characterized in that the catalyst was prepared by the method according to p. 1.

15. The method of obtaining the ,-unsaturated mononitriles selected from Acrylonitrile and Methacrylonitrile the ammoxidation of paraffins in the presence of a catalyst obtained by the method according to p. 8, selected from propane and isobutane with molecular oxygen and ammonia by catalytic contact of the above reagents in the reaction zone with a catalyst having the following formula:

VSbmAaDdOx,

where a is one or more elements selected from Ti, Sn, and Sn is always present;

D is one or more elements selected from Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn,

where m has a value from 0.5 to 10;

and is a number greater than 0,

10>a>0;

d is a number from 0 to 10;

x is determined by Klenow zone, has a molar ratio of paraffin to the NH3in the range from 2.5 to 16 and a mole ratio of paraffin to oxygen in the range from 1 to 10, characterized in that the catalyst was prepared by the method according to p. 8.

16. The method of obtaining the ,-unsaturated mononitriles by ammoxidation of an olefin in the presence of a catalyst obtained by the method according to p. 1, selected from propylene and isobutene, with ammonia and oxygen-containing gas by catalytic contact of the above reagents in the reaction zone with a catalyst having the following formula:

VSbmAaDdOx,

where a is one or more elements selected from Ti, Sn, and Sn is always present;

D is one or more elements selected from Li, Mg, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn,

where m has a value from 0.5 to 10;

and is a number greater than 0,

10>a>0;

d is a number from 0 to 10;

x is determined by the oxidation state of the cations present,

where the initial reaction mixture fed to reaction zone has a molar ratio of ammonia to olefin in the range from 1 to 5 and the molar ratio of oxygen to olefin in di

 

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