BG62164B1 - Method for the amoxydation of olefines - Google Patents

Abstract

By the method C3 to C5 monoolefines are amoxydated to theproduction of a,6-monononsaturated acrylonitriles having 3 to 5carbon atoms and HCN by the introduction of monoolefines,molecular oxygen and ammonia in a reaction zone in steam phasecontact with solid amoxydation catalyst. The mole ratio of themolecular oxygen and ammonia introduced was at least 1.5 and 1.0,respectively. The catalyst contains the elements included in theformulaV1SbaMnNnOxwhere a has the value from 0.5 to 2, M is one or more of theelements Sn, Ti, Fe and Ga, m takes the values 0.05 to 3,especially from 0.1 to 1; N means one more of the elements W, Bi,Mo, Li, Mg, P, Zn, Mn, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, B; n hasthe value 0-0.5. The catalyst is produced by the contact betweenvanadium and antimony compound in water dispersion, the vanadiumbeing in solution.

Description

(54) METHOD OF AMOXIDATION OF OLEFINS

Technical field

The invention relates to a process for catalytic amoxidation (oxidation in the presence of ammonia) of C ₃ to C ₅ olefins in the vapor phase, to α, 6-unsaturated mononitriles and HCN. In particular, the invention relates to a method for the catalytic amoxidation of: propylene to produce acrylonitrile and hydrogen cyanide, and isobutylene to produce methacrylonitrile and hydrogen cyanide, the process being carried out in a vapor phase. In the term a, b-unsaturated mononitriles, the term unsaturated means an unsaturated bond of the ethylene type, but does not include an unsaturated bond of the acetylene type.

In this method, an oxide catalyst containing V, Sb and one or more of the Sn, Ti, Fe, and Ga promoters that increase the catalyst activity is used.

BACKGROUND OF THE INVENTION

US 4 162 992 describes the oxidation of olefins, in particular propylene, using a catalyst of formula

Sb _i VTi _c O _x in which “a” means a number equal to or greater than 6, and c is a number such that the ratio s / a is at least 0.5. As can be seen by comparison with the process of the present invention, the amount of Sb is far beyond the catalyst used now.

US Patent No. 3,681,421 to Barclay et al. describe catalytic ammoxidation in the vapor phase of propylene using an oxide composition containing antimony, vanadium and one or more additional polyvalent metals selected from the group of tin, iron, cobalt and titanium in a ratio of 1 mg antimony atom to 0.12 to 0.5 mg atom vanadium and 0.25 to 0.5 mg atoms of each of these additional polyvalent metals. Thus, this catalyst contains at least 2 antimony atoms per 1 vanadium atom, plus at least 1/2 atom of each of the above-mentioned polyvalent metals, which is present in the composition, which is partly the same as the empirical formula of the catalyst composition used in the method according to the present invention. The empirical formula of the catalyst described by Barclay et al. in example 1 it is VSb ₂ Sn and in example 3 it is VSb ₂ Ti ₀₇₉ and this is partly overlaid with the empirical formula of the catalyst according to the present invention. However, the catalyst used in the present method is prepared by a method which is different from the method used to obtain the catalysts described above by Barclay et al. Similar catalytic compositions are also described in patents BE-A-766843 and EP-A-0031693.

SUMMARY OF THE INVENTION

According to the present invention, C ₃ to C ₅ monoolefins are amoxidated to a, 6-mono-unsaturated acyclic nitriles with 3 to 5 carbon atoms by introducing the monoolefins, molecular oxygen and ammonia into the reaction zone in a vapor contact with a solid amoxidizing catalyst, such as the molar the ratio of introduced molecular oxygen and ammonia to the introduced monoolefin is at least

1.5 and 1.0, respectively, wherein the catalyst contains the elements and ratios indicated in the empirical formula:

V, Sb Μ N O in which “a” is 0.5 to 2, M is one or more of the elements Sn, Ti, Fe and Ga, m is 0.05 to 3, usually at least 0.1 and at most 1, N means one or more of the elements W, Bi, Mo, Li, Mg, Ρ, Ζη, Μη, They, Ge, Nb, Zr, Cr, Al, Cu, Ce, B, n has a value from 0 to 0.5, obtaining the catalyst consists of contacting in aqueous dispersion a vanadium compound with an antimony compound, wherein the vanadium compound is in solution.

The term unsaturated above means an unsaturated olefin-type carbon-carbon bond. The nitriles produced do not contain unsaturated acetylene bonds.

In the process of the invention, the feed C ₃ to C ₅ olefin stream supplied to the reaction zone may contain up to 10 mol% C ₃ to C ₅ paraffins, calculated from the total molar amount of olefins and paraffins. For this reason, a relatively inexpensive olefin feed stream that is not highly purified may be used. Generally, however, a hydrocarbon feed stream is used which, in addition to small amounts of contaminants, contains almost entirely C ₃ to C ₅ olefins. Amoxidation of propylene with the catalyst of Example 28, which is a repetition of Example 1 of the patent of Barclay et al., Yields 0.09 lb / 40.82 g / acrylonitrile per lb / 453.6 g / catalyst per hour. This example is given to compare the performance of a catalyst of the same empirical formula and composition (Example 9), but which was obtained in the manner described in the present invention when used in propylene oxidation. Comparison can also be made using a catalyst of the same composition, which is a portion of the catalyst obtained in Example 9 which is not flushed (Example 10). Using this catalyst yields 136.08 g of acrylonitrile per 453.59 g of catalyst per hour.

The productivity of the catalyst of actual Example 1 in the patent of Barclay et al. was calculated and found to be only 13.6 g of acrylonitrile to 453.59 g of catalyst per h.

The catalysts described in US 5,008,427 and the catalysts according to the invention are substantially the same. They have been used for paraffin amoxidation in a process requiring a large excess of propane over oxygen and ammonia. It has also been disclosed that small amounts of olefins (such as propylene) may be contained in the feed stream, although no actual examples are given of the presence of olefins in the feed stream. The highest acrylonitrile productivity described in a number of specific examples is 27.56 g of acrylonitrile per 453.59 g of catalyst per hour.

In the preparation of the catalysts used in this method, the calcination temperature must be above 750 ° C, in particular at least 780 ° C. Typically, calcination temperatures are from 790 to 1050 ° C. The M elements are believed to increase the activity and stability of the crystalline phase of VSbO ₄ , which is formed upon preparation of the catalyst of this formula. Since calcination at high temperature of the starting composition of the catalyst is necessary in order to increase the selectivity of the catalyst according to the invention for the production of acrylonitrile, but at calcination temperatures above 750 ° C there is a tendency to decompensate the active VSbO ₄ phase, it is considers that the M-elements not only increase the activity of the catalyst, but also perform the important function of stabilizing the active VSbO ₄ crystalline phase.

While washing the learned calcined catalyst with lower alcohol, water, or ammonium hydroxide solution generally slightly increases the selectivity for the conversion of olefins, such a leaching is not necessary for the conversion of olefins such as propylene to acrylonitrile.

The ammoxidation reaction is carried out at a temperature of 350 ° C to 700 ° C, but most often in the interval fj 430 to 520 ° C. The latter indicated range is particularly suitable for use in the oxidation of propylene to acrylonitrile and hydrogen cyanide.

In the ammoxidation process according to the invention, the reaction is carried out in the gas phase upon contacting a mixture of olefin ammonia and molecular oxygen, and an inert diluent, if present, in a fixed catalyst bed, or in a gravity stream, in a fluidized bed, or by a method with fast transportation.

Examples of suitable gaseous inert diluents are N ₂ , No, CO ₂ and H ₂ O. In the present method, in all embodiments, the volume ratio of the gaseous diluent to the olefin feed stream is typically in the range of 0 to 8, most commonly from 0 to 4.

The average contact time is from 0.01 to 10 s, but more often from 0.02 to 5 s and most often from 0.1 to 2 s.

The pressure in the reaction zone is generally in the range of atmospheric to 75, most often to 50 psia.

It is unknown from the prior art that catalysts having the empirical composition described by Barclay et al. and prepared in the manner described by Brazdil et al. in US 5,008,427 can be used to oxidize olefins to nitriles. According to the invention, it has been found that a catalyst composition having the empirical formula as set forth in the claims and prepared in the manner described in the claims can catalyze the olefin amoxidation process by propylene in such a way that it exceeds from 2 to 5 or more times the productivity of the best catalysts that are produced that have an acrylonitrile productivity of about 45.36 g to 453.6 g of catalyst per hour. This result provides an acrylonitrile yield of over 65% and a propylene conversion of over 90%.

Another advantage of using the catalyst according to the invention over the known ones is that it produces significantly less acrolein, which facilitates the way of regeneration of acrylonitrile and hydrogen cyanide.

The catalysts used in the propylene ammoxidation method combined in the tables are prepared as described in the following examples. Some of the catalysts are washed after calcination with water or alcohol and then dried. In these specific examples, Naico means Naico Chem.Co. of Chicago, IL, Nyacol is Nyacol Products Inc., a subsidiary of PQ Corporation of Asland, MA. Degusa means Degussa Corp., Teterboro, New York, a subsidiary of Degusa AD, Frankfurt, Germany, Nissan is Nissan Chem. Ind. Ltd from Tokyo, Japan.

The alcohol or water washing step described in some specific examples is carried out by transferring the catalyst into a coarse glass frit funnel, pouring alcohol or water over the catalyst, stirring so that the catalyst spreads evenly to the bottom of the funnel, such as allows a certain amount of alcohol or water to pass over the catalyst without suction. It should be noted that a much larger amount of water is required to flush with water than the amount of alcohol required to flush the catalyst described in the examples. When water is used, it must be distilled and the washing will continue until the conductivity of the waste water reaches that of the distilled water.

Example 1. 16.33 g of V, O ₅ was added to a mixture of 540 cm ^{3 of} H ₂ O and 60.0 g of 30% H ₂ 0 ₂ in a two-liter beaker and stirred at room temperature for 15 minutes until a dark red peroxy complex was obtained . Then 31.24 g of Sb, O ₃ was added to the powder, the beaker was placed on a maximum heater, and covered with a watch glass. When heated, the color of the slurry changes from yellow to green and then to black. The mixture was heated at reflux for 3 hours, occasionally adding water to maintain a constant volume. 26.92 g of 20% sol of SnO ₂ (Naico 88SN123) was added, followed by 7.14 g of fuming TiO ₂ (Degusa, P25) and 100.0 g of sol 40% SiO ₂ (Naico 2327). The catalyst suspension was evaporated with heating and stirring constantly until it was compressed. It is then dried at 120 ° C overnight, then calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was last calcined at 810 ° C for 3 h. Before being used in the microreactor, 8.0 g of the calcined catalyst was extracted into a Soxhlet with MeOH for 1.5 h and then dried at 120 ° C. The composition of the catalyst is 60% VSb, ₂ Sn, ₂ Ti ₀₅ O _x - 40% SiO ₂ .

Example 2. A catalyst of composition VSb ₁₅ O _x was prepared as follows: To a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a two-liter beaker was added 29.53 g V ₂ 0 ₅ and the mixture was stirred at room temperature for about 15 min until a dark red peroxy complex is obtained. Then 70.63 g of Sb ₂ O ₃ was added to the powder, the beaker was placed at maximum, and covered with a watch glass. When heated, the color of the slurry changes from yellow to green to black. The mixture was heated for approximately 3 hours, occasionally adding water to maintain a constant volume. Then, with continuous stirring, the suspension was heated until it was thickened. It is dried overnight at 120 ° C and calcined at 650 ° C for 8 hours. The catalyst was then ground and sieved to a size of 20-35 mesh. The catalyst thus milled was subjected to final calcination at 810 ° C for 3 h. Prior to testing in the microreactor, 10 g of the calcined catalyst were washed with 2 L of water at room temperature and then dried at 120 ° C.

Example 3. A catalyst of composition VSb _{I 4} Sn _{0 2} 02ί ₀₂ Ο _χ was prepared as follows: 26.8 g V ₂ O ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a two-liter beaker. and stirred at room temperature for about 15 min until a dark red peroxy complex is obtained. 59.82 g of Sb ₂ O ₃ powder is added and the beaker is heated to the maximum, covered with a watch glass. During heating, the color of the slurry changes from yellow to green and to black. The mixture was heated at reflux for approximately 3 hours and water was added from time to time to maintain a constant volume. 44.18 g of 20% sol of SnO ₂ (Naico 88SN123) was added and then 4.68 g of TiO ₂ in powder. The suspension was evaporated with continuous stirring until it was thickened. It is dried overnight at 120 ° C.

The procedure described above was repeated three more times and the resulting four dried portions were mixed in one large portion, which was calcined at 650 ° C for 8 hours. The catalyst was then ground and sieved to a size of 20-35 mesh. This catalyst was subjected to final calcination at 790 ° C for 3 h. Before being tested in the microreactor, 10 g of the calcined catalyst were washed with 6 l of water at room temperature and then dried at 120 ° C.

There are cases where catalyst flushing is missed. Testing such a catalyst in the propylene ammoxidation process shows that it is active but less than the catalyst prepared as described in this example but is flushed.

Example 4. A catalyst of empirical formula VSb ₂ Sn _{Q 5} Ο _χ was prepared as follows: 7.93 g V ₂ O ₅ was added to a mixture of 360 cm ³ H ₂ O and 40 g 30% H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex was obtained. Then 25.30 g of Sb ₂ O ₃ ia powder is added, the beaker is placed on a heater at maximum and covered with a watch glass. When heated, the color of the slurry changes from yellow to green to black. The mixture was heated at reflux for approximately 3 hours, occasionally adding water to maintain a constant volume. 26.27 g of 249.% sol of SnO ₂ (Nyacol) was added. The slurry was evaporated with continuous stirring until thickened. It is then dried overnight at 120 ° C and calcined at 650 ° C for 8 hours. The catalyst was then ground and sieved through a 20-35 mesh sieve. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being used in the microreactor, 8 g of the calcined catalyst were washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 5. A catalyst of the empirical formula VSbj ₄ Sn _0J Ti ₀ ! ΑΙ _00010χ is prepared as follows:

27.43 g of V ₂ O ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a two-liter beaker and stirred for about 15 min to give a dark red peroxy complex. Then 61.25 g of Sb ₂ O ₃ is added to the powder and the beaker is placed on a heater, which is turned on to its maximum, covered with a watch glass. During heating, the color of the slurry changes from yellow to green and to black. The mixture was heated at reflux for approximately 3 hours, occasionally adding water to maintain a constant volume. 90.46 g of 10% SnO ₂ (sol / Naico 1160) was added, followed by 2.4 g of TiO ₂ in powder and 11.26 g of 1.0 wt% A1 / NO ₃ / j.9H ₂ O as a solution. The suspension was evaporated with constant stirring until thickened. It was then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8 g of the calcined catalyst were washed with 75 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 6. A catalyst of the empirical formula 85% VSb ₂₁ Sn _O2 - 15% SiO ₂ was prepared as follows: 27.61 g V ₂ O ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 minutes until a dark red peroxy complex is obtained. Then it is added

48.43 g of Sb ₂ O ₃ powder and beaker are covered with a watch glass and placed on a heater which is turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 85.08 g of 10.7% SnO ₂ (sol / Naico 1181D) was added and then 50 g of sol 30% SiO ₂ (Naico). The suspension was evaporated with constant stirring until it was compressed. It is then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved through a 20-35 mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8 g of the calcined catalyst was extracted with methanol in a Soxhlet apparatus with methanol for 1.5 h and then dried at 120 ° C.

EXAMPLE 7 A catalyst of empirical formula VSb _7J Cr 2 _J O _i was prepared as follows: 3.33 g V ₂ O ₅ was added to a mixture consisting of 60 cm ³ H2O and 30 g 30% H2O2 in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. 450 cm ^{3 of} H2O was then added, followed by 39.78 g of Sb ₂ O ₃ as a powder, followed by heating for 30 minutes. Then 9.1 g of CrO ₃ was added and the heating continued for 2 h. The suspension was evaporated with constant stirring until thickened. It was then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The resulting catalyst was ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h.

Example 8. The catalyst of the empirical formula VSb ₁₂ Ti ₁₅ O _x was prepared as follows: 1.5 g V ₂ 0 ₅ was added to a mixture of 30 cm ³ H2O and 15 g 30% H2O2 in a two-liter beaker and stirred at room temperature for approx. 15 min until a dark red peroxy complex is obtained. 450 cm ³ H2O and 28.78 g Sb ₂ O ₃ powder were added and the suspension was heated for 30 min. Then a suspension of 19.72 g of TiO ₂ powder was added in a small amount of water and the heating continued for another 2 h. The suspension was evaporated with constant stirring until thickened, then dried overnight at 120 ° C and calcined at 650 ° C for 8 h. The resulting catalyst was ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h.

Example 9. The catalyst with empirical composition VSb ₂ SnO _x was prepared as follows: 17.14 g V ₂ O ₃ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Add 54.68 g Sb ₂ O ₃ powder and heat to maximum heater with the glass covered with a watch glass. When heated, the color of the slurry changes from yellow to green to black. The mixture is heated at reflux for approximately 3 hours, with water being added from time to time to maintain a constant volume. Add 264.17 g of 10.7% SnO ₂ (sol) (Naico 1181 D). The suspension was evaporated with constant stirring until it was thickened. It was then dried overnight at 120 ° C and calcined at 650 ° C for 8 h. The resulting catalyst was ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8 g of the calcined catalyst were washed with

100 cm ³ isobutanol at room temperature and dried at 120 ° C.

EXAMPLE 10 This catalyst is a portion of the catalyst of the last example which has not been flushed.

Example 11. A catalyst with an empirical composition VSb, ₂ Sn _Q2 Ti _{0 5} 0 _χ was prepared as follows: 27.21 g V ₂ O ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ c. two-liter beaker and stir at room temperature for about 15 min until a dark red peroxy complex is formed. Add 52.07 g of Sb ₂ O ₃ powder and turn on the heater at maximum with the glass covered with a watch glass. When heated, the color of the slurry changes from yellow to green to black. The mixture was heated for approximately 3 hours, during which time water was added from time to time to maintain a constant volume. 83.85 g of 10.7% SnO ₂ (sol) was added (Naico 1181D) and then 11.89 g of smoking TiO ₂ (Degusa, P-25). The suspension was evaporated with constant stirring until it was thickened. It was then dried overnight at 120 ° C and calcined at 650 ° C for 8 h. The resulting catalyst was milled and sieved to a size of 20-35 mesh and then subjected to final calcination at 810 ° C for 3 h. Prior to testing in the microreactor, 8 g of the calcined catalyst were washed with 75 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

EXAMPLE 12 This catalyst is a portion of the catalyst obtained in the previous example which is not flushed.

Example 13. The catalyst of the empirical formula VSbj ₂ Sn ₀₂ TiO _x was prepared as follows: 24.32 g V ₂ 0 ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 minutes until a dark red peroxy complex was obtained. Then 46.53 g of Sb ₂ O ₃ was added to the powder, a watch glass was placed on the glass and the heating was maximized. When heated, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 74.94 g of 10.7% SnO ₂ (sol) (Naico 1181D) was added, followed by 21.26 g of smoking TiO ₂ (Degusa, P-25). The suspension was evaporated with constant stirring until it was thickened. It was then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The resulting catalyst was ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of the calcined catalyst was washed with 150 cm ^{3 of} isobutanol at room temperature and then the catalyst was dried at 120 ° C.

Example 14. A catalyst of empirical formula 85% VSb ₁₂ Sn ₀₂ Ti _{o 5} O _x 15% SiO ₂ was prepared as follows: 23.13 g V ₂ 0 ₅ was added to a mixture of 900 cm ³ H ₂ O and 100 g 30 % H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 minutes until a dark red peroxy complex is added.

44.26 g Sb ₂ O ₃ in powder, cover the glass with a clock glass and place on a heater at maximum. When heated, the color of the slurry changes from yellow to green to black. The mixture was heated for approximately 3 hours, occasionally adding water to maintain a constant volume. 71.27 g of 10.7% SnO ₂ (sol / Naico 1181 D) was added, followed by 10.11 g of fuming TiO ₂ (Degus, P-25) and 50.0 g of 30% sol of SiO ₂ (Naico). The catalyst suspension was evaporated on a hot plate until it solidified. It was then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8 g of the calcined catalyst were washed by extraction in a Soxhlet apparatus with methanol and dried at 120 ° C.

Example 15. A catalyst of empirical formula 60% VSb! ₂ Sn ₀₂ Ti _o5 0 _χ - 40% SiO ₂ is prepared as follows: 16.33 g V ₂ O ₅ is added to a mixture containing 540 cm ³ H ₂ O and 60 g 30% H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxide complex was obtained. Then, 31.24 g of Sb ₂ O ₃ was added to the powder and maximum heating was started, with the glass covered with a watch glass. When heated, the color of the slurry changes from yellow to green and to black. The mixture was heated for approximately 3 hours, occasionally adding water to maintain a constant volume. Then 50.31 g of 10.7% sol of SnO ₂ (Naico 1181D) was added, followed by 7.14 g of fuming TiO ₂ (Degus / P-25) and 133.3 g of 30% sol of SiO ₂ (Naico). The catalyst suspension was evaporated to a solid and dried overnight at 120 ° C, then calcined at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h.

Before being tested in the microreactor, 8.0 g of the calcined catalyst was washed with 150 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 16. A catalyst of empirical formula VSbj ₂ Sn _O2 Ti _OJ O _x was prepared as follows: 17.41 g of NH ₄ VO ₃ was dissolved in 1 l of hot water. Add 26.03 g of Sb ₂ O ₃ powder and reflux for approximately 3 hours. 41.92 g of 10.7% sol of SnO ₂ (Naico 118ID) and 5.95 g of fuming TiO ₂ (Degusa, P-25) were added. The suspension was heated under continuous stirring until it solidified. It is then dried overnight at 120 ° C and calcined at 650 ° C for 8 hours. The resulting catalyst was ground and sieved to 20-35 mesh sizes. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Prior to testing in the microreactor, 8 g of the calcined catalyst were washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 17. A portion of the calcined catalyst obtained in the manner described in the last example was subjected to a Soxhlet extraction apparatus with methanol for

1.5 h, instead of being washed with isobutanol.

Example 18. A catalyst with an empirical composition of 60% VSbj ₂ Sn ₀₂ Ti _07J O _x - 40 SiO ₂ was prepared as follows: 15.41 g V, O ₍ added to a mixture consisting of 540 cm ³ H ₂ O and 60 g 30% H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is added, then Sb ₂ O ₃ is added to the powder, the beaker is covered with a watch glass and placed on a heating plate During the heating, the color of the slurry changes from yellow to green and finally to black, and the mixture is boiled for> 3 hours, by reflux. me time, water was added in order to maintain a constant volume. Then, 25.40 g 20% sol of SnO ₂ / Naico 88SN123 /, followed by 10.1 g of fumed TiO ₂ / Degussa, P-25 / and 133.33 g 30% Sol of SiO ₂ (NaIco) .The suspension was evaporated under constant stirring until it solidified, then dried overnight at 120 ° C and calcined at 290 ° C for 3 h at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8 g of the calcined catalyst was washed with 125 cm ^{3 of} isobutanoal at room temperature and dried at 120 ° C.

Example 19. A catalyst of the empirical formula VSb] ₂ Sn ₀₂ Ti _OJ 0 _x was prepared as follows: a solution of 17.41 g of NH ₄ VO ₃ in 600 cm ^{3 of} hot water was added dropwise to a suspension of 26.03 g of Sb2O3 new powder in 400 cm ^{3 of} water, the addition being continued for 2 h. The resulting mixture was boiled for 1 h. Then 37.38 g of 12% SnO2 (sol) (Naico 1188) and 5.95 g of fuming TiO ₂ (Degusa, P-25) were added. The slurry was concentrated to evaporation. It was then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The resulting catalyst was then ground and sieved to a size of 20-35 mesh. The fused catalyst was last calcined at 810 ° C for 3 h. Prior to being tested in the microreactor, 8.0 g of the calcined catalyst was washed with methanol extraction in a Soxhlet apparatus for 1.5 h and then dried at 120 ° C.

Example 20. A catalyst of empirical formula 60% ^VSb 1.2 ^Sr 0.2 ^Ti 0.5 ^K 0 0Ol ⁰ x ^'40 7 ° ^S ' ^O 2 ^{Ce P} R ^I 'is prepared as follows: 16.3 g of V205 is added to a mixture containing 540 cm ³ H 2 O and 60.0 g of 30% H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is obtained. Add 31.24 g of Sb ₂ O ₃ powder, cover the glass with a watch glass and heat to a maximum hotplate. During heating, the color of the slurry changes from yellow to green and finally to black. The mixture was boiled for approximately 3 hours, occasionally adding water to keep the volume constant. A drop of suspension is tested on filter paper to see if it has started to fade. While not fading, 26.9 g of 20% sol of SnO ₂ (Naico 88SN 123) was added to the suspension, followed by 7.13 g of fuming TiO ₂ (Degusa, P-25), 0.18 g of 10% aqueous potassium nitrate and 100.0 g 40% silica sol / Naico 2327 /. The suspension was evaporated with constant stirring until it was thickened. It is then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before transferring to the microreactor for testing, 8.0 g of the calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and then dried at 120 ° C.

Example 21. 60% Empirical Catalyst Catalyst

VSb, ₂ Sn ₀₂ Ti _0J - 40% SiO ₂ is prepared as follows: 27.21 g V ₂ O ₅ is added to a mixture consisting of 900 cm ³ H ₂ O and 100 g 30% H ₂ 0 ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Then 52.07 g of Sb ₂ O ₃ was added to the powder, the glass was covered with a watch glass and heated to the maximum heater. During heating, the color of the slurry changes from yellow to green and then to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. Add 83.85 g of 10.7% sol of Sn0 ₂ (Nacco 1181D) and then 11.89 g of fuming TiO ₂ (Degusa, P-25). The suspension was heated for 0.5 h and then 222 g of 30% SiO ₂ (sol) (Nissan) was added. The suspension was evaporated with constant stirring until it was thickened. It was then dried at 120 ° C overnight and calcined at 290 ° C for 3 b, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being examined in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 22. 60% Empirical Catalyst Catalyst

VSb, ₂ Sn ₀₂ Ti _0Jx - 40% SiO ₂ is prepared as follows: 16.33 g V ₂ 0 ₅ are made into a mixture consisting of 540 cm ³ H ₂ 0 and 60.0 g 30% H ₂ 0 ₂ in a two-liter beaker and stirred for about 15 min until a dark red peroxy complex formed. Add 31.24 g of Sb ₂ 0 ₃ powder, cover the glass with a watch glass and heat to a maximum. During heating, the color of the slurry changes from yellow to green and to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain the volume constant. 26.92 g of 20% SnO ₂ (zol) (Naico 88 SN123) was added, followed by 7.14 g of powdered TiO ₂ and 133.33 g of 30% SiO ₂ (zol / Nissan). The resulting suspension was evaporated with constant stirring until it was thickened. It was then dried overnight at 120 ° C and calcined at 290 ° C for 3 hp at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at

120 ° C.

Example 23. 60% Empirical Formula Catalyst

VSb, ₂ Sn ₀₂ Ti _0J - 40% SiO ₂ is prepared as follows: 16.33 g V ₂ O ₅ is made to a mixture consisting of 540 cm ³ H ₂ 0 and 60.0 g 30% H ₂ 0 ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Then 31.24 g of Sb ₂ O ₃ was added to the powder, the glass was covered with a watch glass and placed on a heater at maximum. During heating, the color of the slurry changes from yellow to green and to black. The mixture is refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 26.92 g of 20% sol of SnO ₂ (Naico 88SN123) was added, followed by 7.14 g of fuming TiO ₂ (Degus, P-25) and 117.65 g of 34% SiO ₂ (sol) (Naico H-1034). The resulting suspension is subjected to standing with constant stirring until it thickens. It is then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being evaluated in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 24. Catalyst with empirical formula 60%

VSbSn ₀₂ Ti _OJ 0 _x -40% SiO ₂ was prepared as follows: 17.88 g V ₂ O ₅ was added to a mixture consisting of 540 cm ³ H ₂ 0 and 60 g 30% H ₂ 0 ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex formed. Then 28.51 g of Sb ₂ O ₃ is added to the powder, the beaker is covered with a watch glass and placed on a heating plate which is turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for about 3 hours, occasionally adding water to maintain a constant volume. Then 29.47 g of 20% Sn0 ₂ (sol /) was added successively to the mixture.

Naico 88SN123 /, followed by steaming TiO ₂ (Degus, P-25) and 133.33 g of 30% SiO ₂ / ash, Nissan /. The catalyst suspension was evaporated on a heating plate with continuous stirring until thickened, then dried at 120 ° C overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h, and at 650 ° C for 3 h. 8 h. The catalyst was then ground and sieved through a 20-35 mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of the calciner catalyst was washed with 100 cm ³ isobutanol at room temperature and dried at 120 ° C.

EXAMPLE 25 This catalyst was prepared in a manner similar to that described in Example 1 except that it was larger in size. It has the same composition as in Example 1, but after the formation of the slurry, the procedure is different in that the slurry, after being concentrated to a large extent by evaporation, is spray dried in a semi-industrial spray dryer to obtain a microspheroidal flowable catalyst. 2.025 kg of the catalyst thus obtained are withdrawn from the oven chamber and 1.575 kg are withdrawn from the cyclone.

A sample of 500 g of this product taken from the chamber was calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h and at 810 ° C for 3 h. Wash 100 g of this catalyst with 1500 cm ^{3 of} isobutanol and then dry.

Example 26. A catalyst of the empirical formula 60% VSb, ₂ Sn ₀₂ TiO _0J 0 _x was obtained as follows: 16.33 g V ₂ O ₅ was added to a mixture consisting of 900 cm ³ H ₂ 0 and 100 g 300% H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Then 31.24 g of Sb ₂ O ₃ powder is added to the mixture and the beaker is placed on a maximum heating plate and covered with a watch glass. During heating the color of the slurry changes from yellow to green to black. The mixture is refluxed for approximately 3 hours and water is added from time to time to maintain a constant volume. Then 50.3 g of sol per 20% SnO ₂ (Nsico 88SN123), 7.14 g of fuming TiO ₂ (Degusa, P-25) and 133.33 g of 30% sol of SiO (Naico) were added to the slurry. The catalyst suspension was evaporated until it was compressed with continuous stirring. It was then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved through a 2035 mesh sieve. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 27. A catalyst of the empirical formula 80% VSb] ₂ Ga ₀₂ Ti _0J 0 _x - 20% SiO ₂ was prepared as follows: 5.63 g V ₂ 0 ₅ was added to a mixture consisting of 450 cm ³ H ₂ O and 50.0 g of 30% H ₂ O ₂ in a beaker and stirred for about 15 min until a dark red peroxy complex is obtained. Then 10.87 g of Sb ₂ O ₃ was added to the powder, the glass was covered with a watch glass and placed on a heating plate, which was turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain the volume constant. After being dissolved in a small amount of water was added 5.15 g Ga / NO _3/3 .9H ₂ 0, followed by 2.46 g of fuming TiO ₂ / Degussa, P-25 / and 16.67 g 30% sol of SiO ₂ / Nissan /. The catalyst suspension was evaporated on a hot plate with continuous stirring until it was compressed. It was then dried for two days at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h at 650 ° C for 8 b. The catalyst was then ground and sieved through a 20-35 mesh sieve. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 75 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 28. A catalyst of the empirical formula VSb ₂ SnO _x was prepared as follows: 46.64 g of Sb ₂ O ₃ powder was added over 10 min to a mixture of 240 g of water and 80 g of concentrated / 70% / HNO ₃ with stirring. and temperature 95-100 ° C. Then 18.99 g of Sn powder (325 mesh size) was added over 30 minutes to the stirred suspension, during which time the temperature was maintained at 95-100 ° C. Stirring was continued at this temperature for another 15 min. The suspension was then cooled and centrifuged. The solid residue was resuspended in 240 g of water at 40 ° C. The pH of the suspension was raised to 7.0 by the addition of 80 cm ³ NH4OH solution containing 1/3 28% NH4OH and 2/3 H2O. The slurry was stirred again for 5 min. The pH was again adjusted to 7.0 and then the slurry was again centrifuged. The solid residue was suspended once more in 240 cm ^{3 of} water and centrifuged again. To the solid residue was added 14.63 g of V2O ₃ powder and stirred thoroughly. The resulting moist paste was dried in a thin layer at 120 ° C overnight. The resulting dry powder was calcined at 290 ° C for 2 h, 425 ° C for 2 h, at 650 ° C for 3 h and at 850 ° C for 16 h.

Example 29. This catalyst is a sample of the catalyst obtained in the previous example, which is washed with isobutanol using 75 cm ^{3 of} isobutanol to wash 8.0 g of catalyst and then dried overnight at 120 ° C. .

Example 30. A catalyst of the empirical formula 60% VSb ₁₂ Sn ₀₂ Ti _OJ O _x - 40% Si0 ₂ was prepared as follows: 8.16 g V ₂ 0 ₅ was added to a mixture consisting of 450 cm ^{3 of} water and 50 g 30 % H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is obtained. Then 15.62 g of Sb ₂ O ₃ is added to the powder, the beaker is covered with a watch glass and placed on a heating plate which is turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. Add 13.46 g

20% sol of SnO ₂ / Nacico 88SN123 / followed by 3.57 G of fuming TiO ₂ / Degusa, P-25 / and 33.33 g of 30% sol of SiO ₂ / Nissan / and 10.0 g of fuming / Aerosil / SiO ₂ . The catalyst suspension was evaporated on a heating plate with continuous stirring until thickened, then dried at 120 ° C overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h, and at 650 ° C for 3 h. 8 b. The catalyst was then ground and sieved through a 20-35 mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 31. A catalyst of empirical formula VSt ^ ₂ SnTiO _x was prepared as follows: 9.21 g V ₂ 0 ₅ was added to a mixture containing 450 cm ³ H ₂ 0 and 50 g 30% H ₂ O ₂ in a two-liter beaker and stirred. at room temperature for about 15 minutes to give a dark red peroxy complex. Then 17.62 g of Sb ₂ O ₃ was added to the powder, the glass was covered with a watch glass and placed on a heating plate, which was turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 75.89 g of 20% sol of SnO ₂ (Naico 88SN123), 8.05 g of fuming TiO ₂ (Degus, P-25) were added sequentially and the catalyst suspension was evaporated on a heating plate with continuous stirring until it was concentrated. The resulting catalyst was then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved through a 20-35 mesh screen. The crushed catalyst was subjected to the last calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and dried at 120 ° C.

Example 32. A catalyst of empirical formula VSb] ₂ Sn ₀₂ Ti _0J 0 _x was prepared as follows: 27.21 g V ₂ O ₅ was added to a mixture consisting of 900 cm ^{3 of} water and 100 g of 30% H ₂ O ₂ in two-liter beaker and stir at room temperature for about 15 min until a dark red peroxy complex is obtained. Add 52.07 g of Sb ₂ O ₃ powder, cover the beaker with a watch glass and place on a heating plate which is turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for about 3 hours, occasionally adding water to maintain a constant volume. 83.85 g of 10.7% sol of SnO ₂ (Naico 1181D) was added, followed by smoking TiO ₂ (Degusa, P-25). The suspension was evaporated on a heating plate with constant stirring until it was compressed, then dried at 120 ° C overnight and calcined at 650 ° C for 8 h. The resulting catalyst was ground and sieved through a 20-35 mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 75 cm ^{3 of} isobutanol at room temperature and then dried at 120 ° C.

Example 33. The catalyst of the empirical formula VSbj ₂ Sn ₀₂ Ti _w was obtained as follows: 11.99 g Y ₂ O _} was added to a mixture containing 450 cm ^{3 of} water and 50 g of 30% H ₂ O ₂ in a two-liter beaker and stirred. at room temperature for about 15 min until a dark red peroxy complex is obtained. Then 22.95 g of Sb ₂ O ₃ is added to the powder, the beaker is covered with a watch glass and placed on a heating plate which is turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for about 3 hours, occasionally adding water to maintain a constant volume. Then 49.42 g of 20% sol of SnO ₂ (Naico 88SN123) was added (followed by 5.24 g of fuming TiO ₂ (Degusa, P-25). The catalyst suspension was evaporated on a heating plate with continuous stirring until thickened, dried at 120 ° C overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h .

The catalyst was then ground and sieved through a 20-35 mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and then dried at 120 ° C.

Example 34 A 70% empirical catalyst of VSbSn ₀₂ O _x was prepared as follows: 13.46 g of V ₂ O ₅ was added to a mixture containing 450 ml of water and 50 g of 30% H ₂ O ₂ in a 1 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Then 32.18 g of Sb ₂ 0 ₃ was added to the powder, the glass was covered with a watch glass and placed on a heating plate, which was turned on to a maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 17.82 g of 25% sol of SnO ₂ (Nyacol) was added and the mixture was stirred for an additional 1 h. The suspension was then cooled and centrifuged to release unreacted Sb ₂ O ₃ to give a black water sol containing 10.02% solids.

123.1 g of it was mixed with 9.23 g of 40% SiO ₂ sol (Naico 41D01) and evaporated on a heating plate, after which the mixture was dried overnight at 120 ° C to give 15.58 g of product as a solid. which was heated at 425 ° C for 3 h and at 650 ° C for 8 h. The solid was ground to 20-25 mesh sizes 7.61 g, then heated at 810 ° C for 3 h and then washed with 22 l of water.

Example 35. Catalyst with Empirical Composition 60%

VSb, ₂ Sn ₀₂ Ti _0J - 40% SiO ₂ was prepared as follows: 15.02 g V ₂ 0 ₅ was added to a mixture containing 540 cm ^{3 of} water and SiO ₂ and 60 g of 30% H ₂ O ₂ in a two-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex formed. Then 33.54 g of Sb ₂ 0 ₃ is added to the powder, the beaker is covered with a watch glass and heated to a maximum hotplate. During heating the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. Was added 24.77 g 20% sol Sn0 ₂ / Naico 88SN123 /, followed by 6.57 g of fumed TiO ₂ / Degussa, P-25 / and 133.33 g 30% sol of SiO ₂ / Nissan /. The catalyst suspension was evaporated on a heating plate with continuous stirring until it was thickened, then dried overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h . The catalyst was then ground and sieved through a 20-35 mesh mesh screen. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of the calcined catalyst was washed with 100 cm ^{3 of} isobutanol at room temperature and then dried at 120 ° C.

Example 36. A catalyst of the empirical formula 85% VSb ₍₂ Sn _0J Ti _0i 0 _x was obtained as follows: 10.19 g V ₂ 0 ₅ was added to a mixture containing 450 cm ^{3 of} water and 50.0 g of 30% H ₂ O ₂ in beaker and stirred at room temperature for about 15 minutes until a dark red peroxy complex is formed, then 19.50 g of Sb ₂ O ₃ is added to the powder, the beaker is covered with a watch glass and placed on a heating plate, which is turned on to a maximum. during warm-up, the color of the slurry changes from yellow to green, and the mixture is refluxed for approximately 3 hours, occasionally adding water. In order to maintain a constant volume. Add 42.01 g 20% sol of SnO ₂ / Naico 88SN123 / followed by 4.45 g of fumed TiO ₂ / Degussa, p-25 / and 25.0 g 30% sol of SiO ₂ / Nissan /. The catalyst the suspension was evaporated on a heating plate with constant stirring until it was thickened, then dried overnight at 120 ° C overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. After the catalyst is ground and sieved to a size of 20-35 mesh. The ground catalyst was last calcined 13 at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 125 cm ^{3 of} isobutanol and then dried at 120 ° C.

Example 37. A catalyst with an empirical composition of 80% VSb ₁₂ Fe ₀₂ Ti _OJ - 20% SiO ₂ was prepared as follows: 11.42 g V ₂ O ₅ was added to a mixture consisting of 450 cm ³ H ₂ O and 50 g 30 % H ₂ O ₂ in a 2 liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. 21.85 g of Sb ₂ O _{3 is added} to the powder, the beaker is covered with a watch glass and placed on a maximum hotplate. During heating the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain the volume constant. Then 4.35 g of ferric acetate, 4.99 g of fuming TiO ₂ (Degusa, P-25) and 33.33 g of 30% sol of SiO ₂ (Nissan) were added. The catalyst suspension was evaporated on a heating plate with constant stirring until it was compressed, then dried overnight at 120 ° C and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The resulting catalyst was ground and sieved to 20-35 mesh sizes. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before subjecting the microreactor to the test, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol and then dried at 120 ° C.

Example 38. A catalyst of the empirical formula 80% VSb, ₂ Cr ₀₂ Ti _flJ 0 _x was prepared in the manner described in the preceding example, except that iron acetate is replaced by CrO ₃ in an amount corresponding to that indicated in the empirical formula formula.

Example 39. A catalyst with empirical composition VSbj ₄ Sn _{0 2} Ti _{0 3} < ₃ was prepared as follows: 26.10 g V ₂ O ₅ was added to a mixture consisting of 400 cm ³ H ₂ O and 100 g 30% H ₂ O ₂ in a 2-liter beaker and stirred at room temperature for about 15 min until a dark red peroxy complex is formed. Then 58.45 g of Sb ₂ O ₃ was added to the powder, the glass was covered with a watch glass and placed on a heater at maximum. During heating, the color of the slurry changes from yellow to green to black. The mixture was refluxed for approximately 3 hours, occasionally adding water to maintain a constant volume. 42.12 g of 20.58% sol of SnO ₂ was added followed by 6.87 g of fuming TiO ₂ (Degusa, P-25). The catalyst suspension was evaporated with constant stirring until it was concentrated, then dried overnight at 120 ° C and calcined at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was subjected to final calcination at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol and dried at 120 ° C.

The ash of SnO ₂ used in the preparation of this catalyst described above is prepared as follows: 1800 ml of water and 900 ml of concentrated nitric acid are placed in a 4 liter beaker equipped with a magnetic stirrer with a thermometer. For 2-

2.5 g of 300 g Sn metal (-20 mesh) was added while maintaining the reaction temperature of 5560 ° C (60 ° C should not be raised). The white suspension was stirred at room temperature overnight and centrifuged. In this way SnO ₂ is well separated and allows the supernatant to be separated from the solid by casting. The combined solids were suspended in water (2.5 l total volume). The suspension was then neutralized to pH 7 by the addition of 380 ml of concentrated NH ₄ OH. The suspension was diluted to 3500 ml and stirred overnight, then centrifuged again and the solid was separated, pooled and diluted to 3500 ml with fresh water (first washing with water). This suspension was stirred overnight and then centrifuged a third time. The water was removed and the solid was washed a second time with water (a second wash) by a fresh suspension in the centrifuge tubes. After shaking to disperse the solid, the dishes were weighed and centrifuged a fourth time. The clear wash water is removed. Check with Aldrich indicator paper / JPB / found that the flushing water still contained> 0.5 g / l nitrate ions. Therefore, a third wash is made by resuspending the solid in water in the centrifuge tubes. This wash water is diluted milk sol after centrifugation. The solid is only 0.113% and indicator paper indicates the presence of approximately 1 g of nitrate (1 / the wash water is diluted 1:10 before using the paper). Further washing would peptide more SnO ₂ so that the process stops at this point. After final washing, 1564.2 g of a wet SnO ₂ residue is recovered. A 20% sol solution was prepared by adding 117.8 g of a 40% methylamine solution to the wet solid, grinding the powder to give a translucent gray paste, and diluting the paste with 2122 g of water. Grinding is not easy due to the formation of lumps of the substance into which the solvent partially penetrates. These lumps are sticky and slippery and difficult to spread. The most difficult to break lumps are removed from the vessel and dipped in a wide evaporation vessel, using the bottom of the vessel to crush the pieces on it. The sol sometimes has a little gray unreacted Sn metal in suspended form, which is why it is last centrifuged for 30 min. It separates the metal, but the sol cannot be decanted well from the metal. Therefore, the sol is filtered through a glass microfiber filter on a Buchner funnel to remove this dispersed metal. The sol obtained in this way is light gray-green with a solids content of 20.58%.

Example 42. The starting slurry for the preparation of the catalyst of Example 1 was prepared as described in this example, except that the amounts were greater. A small portion of this catalyst suspension is then taken and evaporated on a heating plate with continuous stirring until it is thickened. This catalyst was dried at 120 ° C overnight and calcined at 290 ° C for 3 h, at 425 ° C for 3 h and at 650 ° C for 8 h. The catalyst was then ground and sieved to a size of 20-35 mesh. The ground catalyst was last calcined at 810 ° C for 3 h. Before being tested in the microreactor, 8.0 g of calcined catalyst was washed with 100 cm ^{3 of} isobutanol.

The catalysts described above are tested in the ammoxidation cycles grouped in the following tables. In these experiments, the catalyst obtained according to the example given in the leftmost column of the tables was tested in a fixed stainless tubular stainless steel reactor with an inside diameter of 9.52 mm. The test pressure is slightly higher than the atmospheric pressure. The reactor is equipped with a heating elbow and immersed in a temperature controlled bath with molten salt. The feed stream is passed over the catalyst for at least one and a half hours before sampling of the product begins; test each catalyst of the appropriate example, sampling the product for analysis within the last 30-60 min.

The examples described above illustrate the invention without limitation.

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Claims (11)

Claims 1. A method for the oxidation of C ₃ to C ₅ monoolefins to obtain α, 6-monounsaturated acyclic nitriles of 3 to 5 carbon atoms and HCN by introducing monoolefins, molecular oxygen and ammonia in the reaction zone into vapor contact with a solid ammoxidating catalyst , the molar ratio of introduced molecular oxygen and ammonia to the introduced monoolefin is 1.5: 1.0, characterized in that the catalyst contains the elements and their ratios indicated in the empirical formula: V.Sb Μ N О 1 a m n x in which a is a number from 0.5 to 2, M is one or more of the elements Sn, Ti, Fe and Ga; m is a number from 0.05 to 3; N means one or more of the elements V, Bi, Mo, Li, Mg, Ρ, Ζπ, Μη, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, B; and n has a value of 0.0 to 0.5 and is obtained by contacting the vanadium compound with an antimony compound in aqueous dispersion, the vanadium compound being in solution. A process according to claim 1, characterized in that they are obtained by the oxidation of propylene or isobutylene by acrylonitrile or methacrylonitrile. A method according to claim 1, wherein m is at least 0.1. 4. The method of claim 2, wherein m is at least 0.1. 5. The method of claim 1, wherein m is at most 1. A method according to claim 2, characterized in that me is at most 1. The method of claim 1, wherein m is in the range of 0.1 to 1. A method according to claim 2, characterized in that it is in the range of 0.1 to 1. A method according to claim 2, characterized in that propylene is subjected to amoxidation. 10. The method of claim 9, wherein m is in the range of 0.05 to 1. 11. The method of claim 9, wherein m is in the range of 0.1 to 1.