The method of vapor-phase ammoxidation3- c5- monoolefins

 

(57) Abstract:

The way ammoxidation C3- C5-monoolefins to obtain , -monounsaturated acyclic NITRILES having from 3 to 5 carbon atoms, and HCN by introducing such monoolefins, molecular oxygen and ammonia in a reaction zone with a two-rail contact with a solid catalyst for the ammoxidation, in which the molecular ratio of the input molecular oxygen and ammonia to the mentioned input monoolefins is at least respectively of 1.5 and 1.0, in which the said catalyst contains elements and compounds, indicated by the empirical formula V1SbaMmNnOxwhere a = 0.5 - 2; M is one or more metal of Sn, Ti, Fe, and Ga; m = 0.5 to 3, usually at least 0.1 and not more than 1; N is one or more of: W, Bi, Mo, Li, Mg, P, Zn, Mn, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, B; n = 0.5, and in which the preparation of the catalyst involves contacting a water dispersion of vanadium compounds and compounds of antimony, with the said vanadium is in solution. 10 C.p. f-crystals, 2 tab.

The invention relates to a method for the catalytic vapor-phase ammoxidation3-C5olefins to obtain , - unsaturated mononitriles and HC is La get Acrylonitrile and HCN and (2) of isobutylene to obtain Methacrylonitrile and HCN. The term , -unsaturated mononitriles", "unsaturated" means ethylene unsaturation, and the term does not include acetylenic unsaturation.

In the present method using an oxide catalyst containing V, Sb and one or more promoters selected from Sn, Ti, Fe and Ga, which increase the activity of the catalyst.

U.S. patent N 4162992 reveals the ammoxidation of olefins, especially propylene using a catalyst having the formula SbaVTicOxwhere: a is at least 6, and c is a number such that the ratio C/a is equal to at least 0.5 in. As, however, it will be seen, the number of S1 is far beyond the amounts of catalysts used in the present inventive method.

In U.S. patent N 3681421 owned by Barclay et a1. disclosed a vapor-phase catalytic ammoxidation of propylene in the presence of an oxide composition containing antimony, vanadium and one or more polyvalent metals selected from tin, iron, cobalt and titanium in a ratio of 1 g-atom of antimony, from 0.12 to 0.5 g-atoms of vanadium and from 0.25 to 0.5 g-atom of each additional polyvalent metal. This catalyst, therefore, contains at least 2 atom, Sb atom V plus but consistent with empirical formulas of compounds catalysts, used in the method of the present invention. Empirical formula of example 1 according to the patent Barclay et a1. is the formula VSb2Sn, and example 3 VSb2Ti0,79and, thus, they partly coincide with the empirical formula of the catalyst of the present invention. The catalysts used in the present method, however, obtained in other ways than the catalysts according to the patent Barclay et a1. empirical formula which partly coincides with the empirical formula of the compositions of the catalysts of the present invention.

According to the present invention WITH3-C5monoolefinic amoxivet in a mono-unsaturated acyclic NITRILES having from 3 to 5 carbon atoms, by introducing such monoolefins, molecular oxygen and ammonia in a reaction zone in vapor contact with a solid catalyst for the ammoxidation, the molecular ratio of the input molecular oxygen and ammonia to the mentioned input monoolefins respectively, at least 1.5, and 1.0, where the said catalyst contains elements in the ratio given by the empirical formula:

V1SbaMmNnOx,

where

a 0.5 to 2,

M is one or more elements , o, Li. Mg, P, Zn, Mn, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, B,

n is not more than 0.5,

and where the preparation of the catalyst involves contacting a water dispersion of vanadium compounds and compounds of antimony, at that time, as mentioned vanadium is in solution.

The term "unsaturated" in the preceding paragraph means the carbon - carbon olefinic unsaturation. NITRILES have no acetylenic unsaturation.

In the present method, C3- C5olefinic raw materials fed to the reaction zone may contain up to 10 mol. C3- C5paraffins, if we take the total number of moles of olefins and paraffins. In this respect, can be used relatively inexpensive flows olefinic feedstock without a high degree of purification. However, usually the hydrocarbon feedstock fed to the reaction zone consists almost entirely of C3- C5olefins, in addition to minor amounts of impurities.

The importance of the last point in the previous approval of the invention is illustrated in the examples. The ammoxidation of propylene with the catalyst of example 28, which is a repetition of the catalyst of example 1 in patent Barclay et a1. led to the performance of 0.09 pounds of Acrylonitrile per hour per pound of Kostava (example 9), which is used in the ammoxidation of propylene, where the catalyst prepared according to the method of the present invention. Or the comparison can be made, however, when using a catalyst of the same composition, and thus part of the catalyst used in example 9, not washed (example 10). Performance in this case amounted to 0.30 pounds of Acrylonitrile per hour per pound of catalyst.

The calculated performance in actually existing example 1 of the patent Barclay et a1. amounted only to 0.032 pounds of Acrylonitrile per hour per pound of catalyst.

The catalysts of U.S. patent N 5008427 owned Brazdil et a1. and the catalysts of the present invention coincide to a large extent. They are used for ammoxidation of paraffins in the way of providing a large excess propane in comparison with oxygen and ammonia. Also revealed that small amounts of olefins (such as propylene) may be present in the feedstock, although in fact, current examples of the olefins in the feedstock are not. The highest performance in a large number of concrete examples was 0,068 pounds of Acrylonitrile per hour per pound of catalyst.

When cooking katalizatorami, 780oC. Typically, the temperature is ignited in the region from 790 to 1050oC. Not limited to any particular theory, we believe that the elements of M increase the activity and stability of the crystalline phase VSbo4which is formed during the preparation of the catalyst. Although to obtain increased selectivity of Acrylonitrile in the present invention requires a high temperature annealing of the source of catalyst, the temperature of annealing above 750oC leads to the decomposition of the active phase VSbO4and, hard to believe that the elements of M not only increase the activity of the catalyst, but also perform the important function of the stabilizer active crystalline phase.

Although calcined catalyst with a lower alcohol, water or ammonium hydroxide solution is usually to some extent increases the selectivity of the conversion of olefin, such as propylene, Acrylonitrile, such processing is not necessary when washing is finished.

The ammoxidation reaction is carried out at a temperature of from 350 to 700oC, but is usually in the range from 430 to 520oC. the Last area is especially suitable for the ammoxidation of propylene to obtain Acrylonitrile plus HCN.

In the method and, containing olefin, ammonia, molecular oxygen and an inert diluent, if appropriate in a fixed bed of catalyst, or when moving layer flow under the action of gravity, or in the fluidized bed, or in the reactor fast transfer.

Examples of suitable inert gaseous diluents are N2He, Co2and H2O. In the present method, in all its embodiments, the volumetric ratio of inert gaseous diluent to olefin entering the reaction zone is usually in the range from 0 to 8 (more often from 0 to 4).

The average contact time may be from 0.01 to 10 c, but is usually from 0.02 to 5 c, more usually from 0.1 to 2 c.

The pressure in the reaction zone generally varies from slightly above atmospheric to 75, more typically up to 50 pounds/inch2.

No one in the preceding field and remotely suggested the desirability of use of catalysts having the empirical composition on patent Barclay et a1. and prepared the way for U.S. patent N 5008427 belonging Brazdil et a1. We were truly amazed at the discovery that the compositions of the catalyst within the empirical formula presented in the claims, and prepared the way is the more than the best commercial catalysts, which have a capacity of about 0,10 pounds of Acrylonitrile per hour per pound of catalyst. This result is achieved when the outputs of Acrylonitrile over 65% and speeds the conversion of propylene over 90%

These remarkable results were extremely surprising and definitely unpredictable in the absence of valid data. The experimental results were totally unexpected discovery, the success of which we have not anticipated.

Another advantage of using these catalysts in comparison with the commercial catalysts is that typically receive much less acrolein, thus, simplifies the extraction of Acrylonitrile and HCN.

The catalysts used in the reactions ammoxidation of propylene, tabulated, compiled with reference to the subsequent examples. Some of the catalysts after calcination washed with water or alcohol, and then dried. In these specific examples, Nalco is The Nalco Chemical Company of Chicago, Illinois, Nyacol is Nyacol Products Inc. member of the PQ Corporation of Ashland M. A. De Gussa is Degussa Corporation, Teteboro N. J. branch Degussa AG, Frankfurt, Germany, Nissan is Nissan Chemical Industries, Ltd. Tokyo, Japan.

Example 1. 16,33 V2O5added to 2 liters of chemical glass to the mixture, consisting ie 540 cm3water and 60.0 grams of 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added 31,24 g Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is evaporated in a period of approximately 3 hours; from time to time added to the water to maintain a constant volume. Then added 26,92 g 20% Zola SnO2(Nalco 88SN123), then added 7,14 g fuming Ti0what annum stirring until thick. Then it was dried at 120oC all night and progulivali at 290oC for 3 h, at 425oC for 3 h, and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali for 3 hours at 810oC. Before being evaluated in the microreactor 8.0 g of calcined catalyst was extracted with MeOH by Soxhlet for 1.5 h, and then was dried at 121oC. the Catalyst had a composition of 60% VSb1,2Snof 0.2Ti0,5Ox-40% SiO2< / BR>
Example 2. The catalyst composition VSb1,5Oxprepared as follows: 29,53 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3H2O and 100 grams of 30% H2O2, and was stirred for 15 min to form a dark red peroxy complex. Then added br70.63 g powder Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass as it is heated the color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. The suspension is evaporated on a hot at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali for 3 hours at 810oC. Before being evaluated in the microreactor 10 g of the calcined catalyst was washed with 2 l of water at RT, and then was dried at 120oC.

Example 3. The catalyst composition VSb1,4Snof 0.2Tiof 0.2Oxprepared as follows: 26,8 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3H2O and 100 grams of 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added to 59.82 g powder Sb2O3set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 44,18 g 20% Zola SnO2(Nalco 88SN123), then added 4.68 g of powder TiO2). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night.

(Note that part of the catalyst is not washed. When it was tested in the ammoxidation of propylene, he showed himself as an active catalyst, but less active than the washed catalyst of this example).

Example 4. A catalyst having the empirical composition of the VSb2Sn0,5Ox, were prepared as follows: to 7.93 g V2O5added in 2 l of chemical glass to the mixture, consisting of 360 cm3H2O and 40 g 30% H2O2and mixed at RT for 15 min to form a dark red peroxy complex. Then added 25,30 g powder Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Then EXT is thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 5. A catalyst having the empirical formula VSb1,4Snof 0.2Tia 0.1A10,001Ox, were prepared as follows: 27,43 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3H2O and 100 grams of 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added 61,25 g powder Sb2O3set temperature control on hot plate "to the max" and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Then added 90,46 g 10% Zola SnO2(Nalco 1160), then added 2.4 g of powder TiO2and of 11.26 and 1 wt. solution A1(Singing). Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 75 cm3Isobutanol at RT, and then was dried at 120oC.

Example 6. A catalyst having the empirical formula of 85% VSb1,1Snof 0.215% SiO2, were prepared as follows: 27,61 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3H2O and 100 grams of 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added 48,43 g powder Sb2O3, set temperature control on hot plate "to the max" and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is evaporated in a period of approximately 3 hours; from time to time added to the water to maintain a constant volume. Then added 85,08 g 10.7% of Zola SnO2(Nalco 1181 D), and then added 50 g of 30% Zola SiO2(Nalco). The suspension is evaporated on a hot ri 290oC for 3 h, at 425oC for 3 h, and at 650oC-within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of calcined catalyst was extracted with methanol by Soxhlet for 1.5 h, and then was dried at 120oC.

Example 7. A catalyst having the empirical formula VSbthe 7.5Crthe 2.5Ox, were prepared as follows: 333 g V2O5added in 2 l of chemical glass to a mixture consisting of 60 cm3H2O and 30 g 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 450 cm3H2O, then added 39,78 g powder Sb2O3after which heating was continued for 30 minutes Then added to 9.1 g CrO3and heating continued for a further 2 hours, the Suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. Ground catalyst Aosta VSb12Ti15Ox, were prepared as follows: 1.5 g V2O5added in 2 l of chemical glass to a mixture consisting of 30 cm3H2O and 15 g 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added 450 cm3H2O and 28,78 g powder Sb2O3and the suspension was heated for 30 minutes and then added of 19.72 g of powder TiO2, raspolojennoe in a little water, and heating continued for a further 2 hours, the Suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 h

Example 9. A catalyst having the empirical composition of the VSb2SnOx, were prepared in the following way: 17,14 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3H2O and 100 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 54,68 g powder Sb2O3the additional glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 264,17 g 10.7% of Zola SnO2(Nalco 1181 D). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 10. This catalyst is part of the catalyst of the last example, which is not washed.

Example 11. A catalyst having the empirical composition of the VSb1,2Snof 0.2Ti0,5Ox, were prepared as follows: 27,21 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3water and 100 g of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 52,07 g powder Sb2O3, ustroitelem. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 83,85 g 10.7% of Zola SnO2(Nalco 1181 D), and then added 11,89 g fuming TiO2(Degussa, P-25). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC until thick and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 75 cm3Isobutanol at RT, and then was dried at 120oC.

Example 12. This catalyst is part of the catalyst of the previous example, which had not been washed.

Example 13. A catalyst having the empirical formula VSb1,2Snof 0.2TiOx, were prepared as follows: 22,32 V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3water and 100 g of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complo maximum", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 74,94 g 10.7% of Zola SnO2(Nalco 1181 D), and then added 21,26 g fuming TiO2(Degussa, P-25). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali for 8 h at 650oC. thereafter, the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 150 cm3Isobutanol at RT, and then was dried at 120oC.

Example 14. A catalyst having the empirical formula of 85% SbV1,2Snof 0.2Ti0,5Ox15% SiO2, were prepared as follows: 23,13 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3water and 100 g of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 44,26 g powder Sb2
(Nalco 1181 D), and then added 10,11 g fuming TiO2(Degussa, P-25) and 50.0 g of 30% Zola SiO2(Nalco). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed by extraction with methanol by Soxhlet and then dried at 120oC.

Example 15. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,5Ox40% SiO2, were prepared as follows: 16,33 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3water and 60 g 30% H2O2was stirred at RT for about 15 min to form a dark red peroxy complex. Then added 31,24 g powder Sb2O3, established a t the m As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 50,31 g 10.7% of Zola SnO2(Nalco 1181 D), and then added 7,14 g fuming TiO2(Degussa, P-25) and 133,3 g 30% Zola SiO2(Nalco). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 150 cm3Isobutanol at RT, and then was dried at 120oC.

Example 16. A catalyst having the empirical formula VSb1,2Snof 0.2Ti0,5Ox, were prepared as follows: 17,41 g NH4VO3was dissolved in 1 liter of hot water. Added 26,03 g powder Sb2O3and the suspension was heated in a flask under reflux for 3 hours Then added 41,92 g 10.7% of Zola SnO2(Nalco 1181D) and 5,95 g fuming TiO2(Degussa, P-25). The suspension is evaporated on hot at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8.0 g of calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 17. Part of the calcined catalyst last example was extracted with methanol by Soxhlet for 1.5 h instead of washing with isobutyl alcohol.

Example 18. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,75Ox40% SiO2, were prepared as follows: 15,41 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3H2O and 60 g 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 29,49 g powder Sb2O3set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 25,40 the Suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 290oC for 3 h, at 425oC for 3 h, at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed 125 cm3Isobutanol at RT, and then was dried at 120oC.

Example 19. A catalyst having the empirical formula VSb1,2Snof 0.2Ti0,5Ox, were prepared as follows: 17,41 g NH4VO3dissolved in 600 cm3hot water was added dropwise over 2 h to 26,03 g powder Sb2O3, raspolojennoe 400 cm3water. The mixture is boiled for one hour. Then added 37,38 g 12% Zola SnO2(Nalco 1188) and 5,95 g fuming TiO2(Degussa, P-25). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved to a force with a cell size power 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 h Before assessment in MIA at 120oC.

Example 20. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,5K0,001Ox40% SiO2, were prepared as follows: 16.3 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3water and 60.0 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 31,24 g powder Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Drop of the suspension was then tested on filter paper, to see whether it will leak if not, then added to 26.9 g of 20% Zola SnO2(Nalco 88SN123), then added 7,13 g fuming TiO2(Degussa, P-25), 0.18 g of 10% aqueous solution of KNO3and 100.0 g of 40% Zola SiO2(Nalco 2327).

The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 290oC for 3 h at 425oC m cell strainers 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8.0 g of calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 21. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,540% SiO2, were prepared as follows: 27,21 g V2O5added to 2 liters of chemical glass to a mixture consisting of 900 cm3water and 100 g of 30% H2O2and stirred at RT for 15 min to form a dark red peroxy complex. Then added 52,07 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; added water to maintain constant volume. Then added 83,85 g 10.7% of Zola SnO2(Nalco 1181 D), and then added 11,89 g fuming TiO2(Degussa, P-25). The suspension is boiled for 0.5 h and then added 222 g of 30% Zola SiO2(Nissan). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried overnight in the Le of this catalyst was grinded and sieved on a sieve with a mesh size of power 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 22. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,5Ox40% SiO2, were prepared as follows: 16,33 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3water and 60.0 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 31,24 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 26,92 g 20% Zola SnO2(Nalco 88SN123), then added 7,14 g of powdered TiO2and 133,33 g 30% Zola SiO2(Nissan). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali in accordance with the Wali and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8.0 g of calcined catalyst was washed with 100 cm3Isobutanol at RT and then was dried at 120oC.

Example 23. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,540% SiO2, were prepared as follows: 16,33 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3water and 60.0 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 31,24 g powder Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 26,92 g 20% Zola SnO2(Nalco 88SN123), then added 7,14 g fuming TiO2) (Degussa, P-25) and 117,65 g 34% Zola SiO2(Nalco H-1034). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali in techwadi and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8.0 g of calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 24. A catalyst having the empirical formula of 60% VSbSnof 0.2Ti0,5Ox40% SiO2prepared as follows: 17,88 g V2O5added to 2 liters of chemical glass to a mixture consisting of 540 cm3water and 60 g 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 28,51 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Then added 29,47 g 20% Zola SnO2(Nalco 88SN123), then added 7,31 g fuming TiO2(Degussa, P-25) and 133,33 g 30% Zola SiO2(Nissan). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali when the Wali and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 25. This catalyst was used as in the first example, except that it was used more. He had the same composition as in the example. However, after the formation of the suspension procedure differed in that the suspension was concentrated to some extent by evaporation, and then subjected to spray drying at a pilot plant size with a spray dryer to obtain a fluidized bed of microspherical catalyst. Then took 4.5 pound of catalyst from the camera and 3.5 pounds from a cyclone.

500 g of the sample chamber product was progulivali at 290oC for 3 h, at 425oC for 3 h at 650oC for 8 hours and at 810oC for 3 h, 100 g of this catalyst was washed 150 cm3Isobutanol and then dried.

Example 26. A catalyst having the empirical formula of 60% VSb1,2Snof 0.2Ti0,5Oxprepared as follows: 16,33 g V2O5added in 2 l of chemical gap resulting dark red peroxy complex. Then added 31,24 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added to 50.3 g of 20% Zola SnO2(Nalco 88SN123), then added 7,14 g fuming TiO2(Degussa, P-25) and 133,3 g 30% Zola SiO2(Nalco). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then was dried at 120oC.

Example 27. A catalyst having the empirical formula of 80% VSb1,2Gaof 0.2Ti0,5Ox20% SiO2, were prepared as follows: 5,63 g V2O5added min, to form a dark red peroxy complex. Then added 10,78 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. After dissolution in a small amount of water added 5,15 g Ga(NO3)39H2O, then added 2,46 g fuming TiO2(Degussa P-25) and 16,67 g 30% Zola SiO2(Nissan). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC from Saturday through Monday and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 75 cm3Isobutanol at room temperature, and then dried at 120oC.

Example 28. The catalyst having EMPI and within 10 min to a stirred mixture of 240 g of H2O and 80 g of concentrated (70%) HNO3when 95-100oC. Then to stir the suspension for 30 min was added 18,94 g metal powder Sn (size 325 mesh) while maintaining the temperature of 95-100oC. Stirring at this temperature was continued for another 15 min, then the suspension was cooled and centrifuged. The solid precipitate resuspendable in 240 g of water at 40oC. the pH of the slurry was increased to 7.0 by the addition of approximately 80 cm3solution of NH4OH, consisting of 1/3 of 28% NH4OH and 2/3 H2O. the Suspension was stirred for another 5 min, re-installed the pH of the suspension is equal to 7.0, and the suspension is again centrifuged. The solid precipitate resuspendable 240 cm3water and again centrifuged. Added to solid draft 14,63 g of the powder and thoroughly mixed. The wet paste was dried in a thin layer all night at the 120oC. the Dry powder was progulivali at 290oC for 2 h at 425oC for 2 h at 650oC for 3 h and at 850oC for 16 h

Example 29. In this example, the portion of the catalyst of the previous example was washed with Isobutanol using for washing 8 g of catalyst 75 cm3water. Again, it was dried overnight at 120oC.

Example 30. Catalizador follows: 8,16 g V2O5added in 2 l of chemical glass to a mixture consisting of 450 cm3water and 50 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 15.62 wide g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for approximately 3 hours; from time to time added to the water to maintain a constant volume. Added 13,46 g 20% Zola SnO2(Nalco 88SN123), then added 3.57 g fuming Ti02(Degussa, P-25) and 33.33 g of 30% Zola SiO2(Nissan) and 10.0 g of fuming SiO2(Acrosil). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 290oC in section 3 h at 425oC for 3 h at 650oC for 8 hours After that, the catalyst was crushed and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at USD>xprepared as follows: of 9.21 g V2O5added in 2 l of chemical glass to a mixture consisting of 450 cm3water and 50 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 17,62 g powder Sb2O3set "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black, the mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 75,89 g 20% Zola SnO2(Nalco 88SN123), then added with 8.05 g of fuming TiO2(Degussa, P-25). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC howling night and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh size of power 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT and se0,5Oxprepared as follows: 27,21 g V2O5added in 2 l of chemical glass to a mixture consisting of 900 cm3water and 100 g of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 52,07 g powder Sb2O3set "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 83,85 g 10.7% of Zola SnO2after which he added 11,89 g fuming TiO2(Degussa, P-25). The suspension is evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 75 cm3Isobutanol at RT, and then was dried at 120oC.

Example 33. The catalyst elusiv> added in 2 l of chemical glass to a mixture consisting of 450 cm3water and 50 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 22, 95mm g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 49,42 g 20% Zola SnO2(Nalco 88SN123), then added of 5.24 g of fuming TiO2(Degussa, P-25). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3methanol at RT, and then was dried at 120oC.

Example 34. Catalyst, himeville in 1 l of chemical glass to the mixture, consisting of 450 ml of water and 50 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 32,18 g powder Sb2O3set "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 17,82 g 25% Zola SnO2(Nyacol), and the suspension was heated for another hour. Then the suspension was cooled and centrifuged to get rid of unreacted Sb2O3and get the black aqueous colloidal solution with solid content 10,02%

123,1 g of the above product was combined with 9,23 g 40% Zola SiO2(Nalco 41D01) and evaporated on a hot plate, and then dried overnight at 120oC to obtain 15,58 g of solid. The solid was further heated 425oC for 3 hours and at 650oC for 8 hours. Then the solid was grinded to obtain to 7.61 g of particles with a size of 20 to 35 mesh. Then the solid was finally heated at 810oC for 3 hours, and then washed with 22 liters of water.

Premiuum follows: 15,02 g V2O5added in 2 l of chemical glass to a mixture consisting of 540 cm3water and SiO2and 60 g 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 33,54 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 24,77 g 20% Zola SnO2(Nalco 88SN123), then added to 6.57 g of fuming TiO2(Degussa, P-25) and 133,33 g 30% Eola SiO2. The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol at RT, and then SUB>Ox, were prepared as follows: 10,19 g V2O5added in chemical beaker to a mixture consisting of 450 cm3water and 50.0 g 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 19,50 g powder Sb2O3, set temperature control on hot plate "to the max", and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 42,01 g 20% Zola SnO2(Nalco 88SN123), then added of 4.45 g of fuming TiO2(Degussa, P-25) and 25.0 g of 30% Zola SiO2(Nissan). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed 125 composition 80% VSb1,2Feof 0.2Ti0,520% SiO2, were prepared as follows: 11,42 g V2O5added in chemical glass to the mixture containing 450 cm3water and 50 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 21,85 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Then added 4.35 g of the acetate of ferrous iron, 4,99 g fuming TiO2(Degussa, P-25) and 33.33 g of 30% Zola SiO2(Nissan). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC within 8 hours After the catalyst was grinded and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of calcined to an empirical formula of 80% VSb1,4Crof 0.2Ti0,5Oxprepared the same way as in the previous example, except that acetate ferrous iron was replaced by CrO3taken in an amount corresponding to the empirical formula.

Example 39. A catalyst having the empirical composition of the VSb1,4Snof 0.2Tifor 0.3Ox, were prepared as follows: 26,10 g V2O5added in 2 l of chemical glass to a mixture consisting of 400 cm3and 100 grams of 30% H2O2and stirred at RT for about 15 min to form a dark red peroxy complex. Then added 58,45 g powder Sb2O3, established the "maximum" temperature control on the hot plate, and chemical glass covered the Supervisory glass. As heat color of the suspension changed from yellow to green to black. The mixture is boiled for about 3 hours; from time to time added to the water to maintain a constant volume. Added 42,12 g 20,58% Zola SnO2after which he added 6,87 g fuming TiO2(Degussa P-25). The suspension of catalyst evaporated on a hot plate with constant stirring until thick. Then it was dried overnight at 120oC and progulivali at 650oC within 8 hours After CAG who was entrusted progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8.0 g of calcined catalyst was washed with 100 cm3Isobutanol, and then dried at 120oC.

Sol SnO2used in the above preparation of this catalyst was prepared as follows: 1800 ml of water and 900 ml of concentrated nitric acid was placed in a 4 l chemical beaker equipped with a magnetic stirrer and thermometer. Added 300 g of metallic tin (-20 mesh) for 2-2 .5 hours to maintain the reaction temperature 55-60oC (not more than 60oC). The white suspension was stirred at room temperature overnight, and then centrifuged. This allowed us to separate the SnO2and drain excess liquid without disturbing the solid. Mixed solid suspended in water (total volume of approximately 2.5 liters). Then, the suspension is brought to pH 7 by addition of 380 ml of concentrated NH4OH. The suspension was diluted up to 3500 ml and was stirred overnight. Then, the suspension is again centrifuged, and the solid was removed and diluted 3500 ml of fresh water (the first water washing), this suspension was stirred overnight and then centrifuged a third time. The water was removed and the solid was washed a second time (second rinse) by restoring the suspension in the vessel is controlled vessel centrifuge and centrifuged fourth time. Clean wash water was removed. Wash water still showed > 0.5 g/l of nitrate ion using IPB indicator paper from Aldrich. Therefore, the 3rd washing was done by re-suspension of solid in water in a vessel for centrifugation. This wash water after centrifugation was diluted muddy Aol. The solid was only 0,113% and pH paper showed approximately 1 g of nitrate on l (when diluted wash 1:10 before use paper). Another washing will lead to greater peptization SnO2so the process at this point stopped. After the last wash was removed 1564,2 g wet sediment SnO2. Prepared 20% Sol by adding to the wet solid 117,8 g of 40% solution of methylamine and grinding into powder with the aim of obtaining a translucent gray paste and dilute paste 2122 g of water. Rubbing the powder was made difficult because of the formation of solid pieces that due to partial penetration of the amine solution. These pieces were sticky, slippery and difficult dispersible. The most disturbing pieces were removed from the chemical glass and soak in a large evaporating the Cup when using the bottom chemical glass breaking KRU who has spent the last centrifugation in treatment 30 minutes This allowed us to separate the metal, but the Sol decantation not clean. Therefore, the Sol was filtered through a glass mikrovolnovuu filter paper on a Buchner funnel to remove suspended metal. The final Sol was bright, gray-green with solid content 20,58%

Example 42. Pre-prepared suspension of the catalyst of the same composition as in example 1, but, unlike example 1, in larger quantities. Then a small portion of the slurry catalyst is evaporated on a hot plate with constant stirring until thick. Then it was dried at 120oC all night and progulivali at 290oC for 3 h, at 425oC for 3 h and at 650oC for 8 hours After that, the catalyst was crushed and sieved on a sieve with a mesh 20-35 mesh. The ground catalyst was finally progulivali at 810oC for 3 hours Before being evaluated in the microreactor 8 g of the calcined catalyst was washed with 100 cm3Isobutanol.

The above-mentioned catalysts tested in the experiments for the ammoxidation table. 1 and 2. In these experiments the catalysts listed in the left column, used in the cylindrical reactor size 3/4 inch, made of stainless steel, with nebody inogo heating, which is immersed in a temperature controlled bath of molten salts. The source material was applied over the catalyst for at least half an hour before collecting the product; the experiences of each sample lasted for 30-60 minutes, during which he collected for analysis of the obtained product.

1. The method of vapor-phase ammoxidation3WITH5-monoolefins to obtain ,-monounsaturated acyclic NITRILES WITH3WITH5and HCN introduction of monoolefins, molecular oxygen and ammonia in a reaction zone containing solid oxide ammoxidation catalyst containing V, Sb and one or more polyvalent metals, obtained by carrying out stages: mixing, drying and calcining, at a molar ratio insertion of molecular oxygen and ammonia to the corresponding monoolefins at least 1.5 and 1, respectively, characterized in that the use of total catalyst of the empirical formula

V1SbaMmNnOx,

where a 0,5 2;

M is one or more metal selected from Sn, Ti, Fe, Ga;

m 0,05 3,

n is not more than 0.5;

N one or more element selected from W, Bi, Mo, Li, Mg, P, Zn, Mn, Te, Ge, Nb, Zr, Cr, Al, Cu, Ce, B,

x takes the value which corresponds the vanadium and antimony compounds provided that vanadium is in solution, when heated, followed by the addition of oxides and/or oxides of polyvalent metal, drying and calcining at a temperature of at least 750oC.

2. The method according to p. 1, characterized in that when the ammoxidation of propylene and isobutylene, respectively, received Acrylonitrile and Methacrylonitrile.

3. The method according to p. 1, wherein m is at least equal to 0.1.

4. The method according to p. 2, wherein m is at least equal to 0.1.

5. The method according to p. 1, characterized in that m is not greater than 1.

6. The method according to p. 2, characterized in that m is not greater than 1.

7. The method according to p. 1, characterized in that m is in the range from 0.1 to 1.

8. The method according to p. 2, characterized in that m is in the range from 0.1 to 1.

9. The method according to p. 2, characterized in that as starting monoolefins use propylene.

10. The method according to p. 9, characterized in that m is in the range of 0.05 to 1.

11. The method according to p. 9, wherein m is between 0.1 and 1.

 

Same patents:

The invention relates to an improved method and catalyst of oxidative ammonolysis of mixtures of olefin ammonia in unsaturated NITRILES and, in particular, relates to an improved method and catalyst of oxidative ammonolysis of mixtures of propylene with ammonia and isobutene ammonia to Acrylonitrile and Methacrylonitrile respectively

FIELD: industrial organic synthesis.

SUBSTANCE: process, in which, in particular, acrylonitrile or methacrylonitrile are obtained, comprises reacting hydrocarbon selected from propane, propylene, and isobutylene with ammonia and oxygen source in presence of catalyst in reaction zone at elevated temperature. Reactor effluent containing unsaturated mononitrile is transferred into first column to be cooled therein with the aid of the first water stream. Cooled effluent containing unsaturated mononitrile is transferred into second column wherein it comes into contact with second water stream to absorb unsaturated mononitrile. Unsaturated mononitrile-containing second column effluent is fed into first distillation column to separate crude unsaturated mononitrile from the second water stream and routed to the second distillation column to remove at least some impurities from crude mononitrile, which is transferred into third distillation column to be further purified. Water in the form of steam and/or distilled water is added in amounts 100 to 2000 ppm to side-cut distillate containing purified mononitrile or to bottom stream coming out of the third distillation column. At least part of the latter is recycled into lower section of third distillation column or directly into column below side-cut distillate withdrawal point.

EFFECT: enhanced process efficiency.

16 cl, 1 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods (variants) for producing acrylonitrile and preparing hydrogen cyanide and acetonitrile as co-products. Methods involve addition of hydrocarbon that is taken among propylene or propane, ammonia and oxygen-containing gas to the reaction zone containing a catalyst for oxidative ammonolysis and reaction is carried out at increased temperature to form acrylonitrile, hydrogen cyanide and acetonitrile, and isolation of acrylonitrile, hydrogen cyanide and acetonitrile from reactor also. According to the first variant reaction is carried out in the presence of alcohols mixture containing methanol and a second alcohol among ethanol, propanol or their mixtures wherein the weight ratio of methanol to the second alcohol in alcohols mixture is maintained depending on necessary amounts of hydrogen cyanide and acetonitrile. According to the second variant reaction is carried out in the presence of alcohols mixture containing methanol and ethanol taken in the weight ratio from about 99:1 to 1::99. According to the third variant reaction is carried out in the presence of one or more alcohols taken among crude methanol, crude ethanol or crude propanol. According to the fourth variant reaction is carried out in the presence of one or more crude (C1-C4)-alcohol. Proposed method provides enhancing yield of one or both co-products, i. e. HCN and acetonitrile, formed in producing acrylonitrile.

EFFECT: improved producing method.

21 cl, 2 tbl, 8 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for reducing breakthrough fraction of ammonia in the process for manufacturing acrylonitrile. Method involves addition of hydrocarbon taken among the group consisting of propane and isobutene, ammonium and oxygen-containing gas to the bottom reactor compartment with fluidized bed and containing a catalyst for ammoxidation followed by interaction in the presence of indicated catalyst to form acrylonitrile. Method involves addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefins that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that allows to carry out the significant reducing the ammonia amount presenting in the reaction flow coming out from the reactor. Except for, invention relates to a method for conversion of acrylonitrile manufacture based on propylene raw wherein propylene, ammonia and oxygen react in reactor in the presence the catalyst used in acrylonitrile manufacturing to the process of acrylonitrile manufacturing based on propane raw wherein propane, ammonia and oxygen reacts in the presence of catalyst used in preparing acrylonitrile. Method involves the following stages: (a) replacing the parent propylene-base raw with the propane-base parent raw; (b) addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefin that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that results to reducing the amount of ammonia presenting in the reaction flow coming out from the reactor, and (c) addition agents for separation, trapping and recycling of unreacted propane to the process.

EFFECT: improved manufacturing method.

13 cl, 19 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention is dealing with catalyst applicable in saturated hydrocarbon ammoxidation process resulting in corresponding unsaturated nitrile. Catalyst composition of invention comprises complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel and magnesium, and at least one of lithium, sodium, potassium, rubidium, and thallium and is described by following empirical formula: AaBbCcFedBieCofCegSbhMomOx, wherein A represents at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, and mixtures thereof; B represents at least one of Li, Na, K, Rb, Cs, Ti, and mixtures thereof; C represents at least one of Ni, Mg, and mixtures thereof; a varies from 0 to 4.0, b from 0.01 to 1.5, c from 1.0 to 10.0, d from 0.1 to 5.0, e from 0.1 to 2.0, f from 0.1 to 10.0, g from 0.1 to 2.0, h from 0.1 to 2.0, m from 12.0 to 18.0, and m is a number determined by requirements of valences of other elements present. Ammoxidation processes for propylene, ethylene, or their mixtures to produce, respectively, acrylonitrile, methacrylonitrile, or their mixtures in presence of above-defined catalytic composition is likewise described.

EFFECT: increased olefin conversion.

9 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: proposed catalyst contains a complex of catalytically active oxides, including oxides of rubidium, cerium, chrome, magnesium, iron, bismuth, molylbdenum and at least, one of nickel or nickel with cobalt. The ratio of components is presented by the following general formula: RbaCebCrcMgdAeFefBigMo12Ox, where A is Ni or a combination of Ni and Co, a approximately ranges from 0.01 to 1, b approximately ranges from 0.01 to 3, c approximately ranges from 0.01 to 2, d approximately ranges from 0.01 to 7, e approximately ranges from 0.01 to 10, f approximately ranges from 0.01 to 4, g approximately ranges from 0.01 to 4, and x is a number, defined by valency of other present elements. "b"+"c" is greater than g. The catalyst does not contain manganese, noble metal or vanadium. The carrier is chosen from a group comprising silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The catalyst is used for oxidative ammonolysis of olefin, chosen from a group containing isobutylene or their mixture, with formation of acrylonitrile, metacrylontrile and their mixture, respectively.

EFFECT: high activity of the catalyst.

19 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process.

EFFECT: increased output of desired products and efficiency of the process.

72 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to versions of catalyst compositions for ammonolysis of an unsaturated hydrocarbon into an unsaturated nitrile and to the method of converting olefin using such a catalyst. In the first version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaKbCscCedCreCOfNigFeiBijMo12Ox. In this formula, A is Rb, Li or their mixture, a assumes values from 0 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In the second version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaLia'KbCscCedCreCofNigFeiBijMo12Ox. A is Rb, a assumes values from 0 to 1, a' assumes values from 0.01 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In these given versions, the catalyst does not contain manganese and zinc and is put onto a carrier, selected from a group containing silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The method of converting olefin into acrylonitrile, methacrylonitrile and their mixture involves reacting olefin with a gas, containing molecular oxygen or ammonia in vapour phase, in the presence of the above mentioned catalyst. The olefin used is propylene, isobutylene or their mixture.

EFFECT: invention allows for obtaining a catalyst with high activity and increases output of nitriles.

14 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to an improved method of producing at least one product of partial oxidation and/or ammoxidation of a hydrocarbon, chosen from a group containing acrolein, acrylic acid, methacrolen, methacrylic acid, acrylonitrile and methacrylonitrile. At least one saturated hydrocarbon is subjected to heterogeneous catalysed dehydrogenation in a gas phase, obtaining a gas mixture, containing at least one partially dehydrogenated hydrocarbon. Components of the gas mixture except saturated hydrocarbon and partially dehydrogenated hydrocarbon are left in the mixture. Alternatively, the extra gas mixture obtained is partially or completely separated, and the gas mixture and/or extra gas mixture are used for obtaining another gas mixture, containing molecular oxygen and/or molecular oxygen and ammonia. This gas mixture is subjected to at least single heterogeneous catalysed partial oxidation and/or ammoxidation of at least one partially dehydrogenated hydrocarbon contained in the gas mixture and/or extra gas mixture. The gas mixture, extra gas mixture and/or the other gas mixture, before at least one partial heterogeneous catalysed oxidation and/or ammoxidation, are subjected to at least a single mechanical separation, aimed at separating particles of solid substance contained in the above mentioned gas mixtures.

EFFECT: reliable and continuous realisation of the process for relatively long periods of time.

6 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for oxidative ammonolysis in the presence of mixed metal oxide catalysts. The method for oxidative ammonolysis to obtain an unsaturated nitrile involves bringing saturated or unsaturated hydrocarbon or a mixture of saturated or unsaturated hydrocarbon with ammonia and an oxygen-containing gas in the presence of a catalyst composition containing molybdenum, vanadium, antimony, niobium, tellurium, at least one element selected from a group consisting of titanium, tin, germanium, zirconium, hafnium and mixtures thereof, at least one lanthanide selected from a group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and mixtures thereof. Disclosed is a version of the method for oxidative ammonolysis, where the catalyst contains, in addition to the listed elements, lithium and an element selected from sodium, caesium, rubidium and mixture thereof.

EFFECT: catalysts are characterised by very low content of tellurium in the composition, catalyst compositions are effective in gas-phase conversion of propane to acrylonitrile and isobutane to methacrylonitrile.

25 cl, 2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acrylonitrile from glycerine. The method involves a first step for gas-phase dehydration of glycerine in the presence of a catalyst having Hammett acidity, denoted by H0, less than +2, at temperature ranging from 150°C to 500°C and at pressure and at pressure ranging from 1 to 5 bar, to obtain acrolein; a second step for ammoxidation of acrolein on an ammoxidation catalyst at temperature ranging from 300°C to 550°C and at pressure ranging from 1 to 5 bar, to obtain acrylonitrile; and an intermediate step for partial condensation of water and heavy byproducts obtained at the dehydration step. The invention also relates to acrylonitrile with 14C content of the order 10-10 wt % with respect to total weight of carbon which can be obtained using the method given above.

EFFECT: method enables to optimise the acrolein ammoxidation step by reducing the amount of water and impurities in a stream rich in acrolein.

3 cl, 2 dwg, 1 tbl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process, in which, in particular, acrylonitrile or methacrylonitrile are obtained, comprises reacting hydrocarbon selected from propane, propylene, and isobutylene with ammonia and oxygen source in presence of catalyst in reaction zone at elevated temperature. Reactor effluent containing unsaturated mononitrile is transferred into first column to be cooled therein with the aid of the first water stream. Cooled effluent containing unsaturated mononitrile is transferred into second column wherein it comes into contact with second water stream to absorb unsaturated mononitrile. Unsaturated mononitrile-containing second column effluent is fed into first distillation column to separate crude unsaturated mononitrile from the second water stream and routed to the second distillation column to remove at least some impurities from crude mononitrile, which is transferred into third distillation column to be further purified. Water in the form of steam and/or distilled water is added in amounts 100 to 2000 ppm to side-cut distillate containing purified mononitrile or to bottom stream coming out of the third distillation column. At least part of the latter is recycled into lower section of third distillation column or directly into column below side-cut distillate withdrawal point.

EFFECT: enhanced process efficiency.

16 cl, 1 dwg

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for extraction of organic material comprising hydrogen cyanide prepared in reactor flow in carrying out the ammoxidation reaction of propylene or isobutylene for preparing acrylonitrile or methacrylonitrile followed by feeding vapor flows from technological devices to the torch head part. At least one part of organic material from torch head part comprising hydrogen cyanide is fed to the extraction stage. Method provides reducing amount of acrylonitile and HCN feeding to combustion.

EFFECT: improved method for extraction.

9 cl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for extraction of acrylonitrile, methacrylonitrile or hydrogen cyanide obtained from the reaction flow in the ammoxidation reaction of propane, propylene or isobutylene that involves passing the reactor flow through absorption column, extraction column and head fraction column. Method involves using such regimen of the process to prevent formation of an aqueous phase above feeding plate in the head fraction column. Method provides reducing unfavorable polymerization of hydrogen cyanide that provides significant decreasing or excluding stoppage of the head fraction column.

EFFECT: improved method for extraction.

12 cl, 1 dwg, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods (variants) for producing acrylonitrile and preparing hydrogen cyanide and acetonitrile as co-products. Methods involve addition of hydrocarbon that is taken among propylene or propane, ammonia and oxygen-containing gas to the reaction zone containing a catalyst for oxidative ammonolysis and reaction is carried out at increased temperature to form acrylonitrile, hydrogen cyanide and acetonitrile, and isolation of acrylonitrile, hydrogen cyanide and acetonitrile from reactor also. According to the first variant reaction is carried out in the presence of alcohols mixture containing methanol and a second alcohol among ethanol, propanol or their mixtures wherein the weight ratio of methanol to the second alcohol in alcohols mixture is maintained depending on necessary amounts of hydrogen cyanide and acetonitrile. According to the second variant reaction is carried out in the presence of alcohols mixture containing methanol and ethanol taken in the weight ratio from about 99:1 to 1::99. According to the third variant reaction is carried out in the presence of one or more alcohols taken among crude methanol, crude ethanol or crude propanol. According to the fourth variant reaction is carried out in the presence of one or more crude (C1-C4)-alcohol. Proposed method provides enhancing yield of one or both co-products, i. e. HCN and acetonitrile, formed in producing acrylonitrile.

EFFECT: improved producing method.

21 cl, 2 tbl, 8 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for reducing breakthrough fraction of ammonia in the process for manufacturing acrylonitrile. Method involves addition of hydrocarbon taken among the group consisting of propane and isobutene, ammonium and oxygen-containing gas to the bottom reactor compartment with fluidized bed and containing a catalyst for ammoxidation followed by interaction in the presence of indicated catalyst to form acrylonitrile. Method involves addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefins that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that allows to carry out the significant reducing the ammonia amount presenting in the reaction flow coming out from the reactor. Except for, invention relates to a method for conversion of acrylonitrile manufacture based on propylene raw wherein propylene, ammonia and oxygen react in reactor in the presence the catalyst used in acrylonitrile manufacturing to the process of acrylonitrile manufacturing based on propane raw wherein propane, ammonia and oxygen reacts in the presence of catalyst used in preparing acrylonitrile. Method involves the following stages: (a) replacing the parent propylene-base raw with the propane-base parent raw; (b) addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefin that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that results to reducing the amount of ammonia presenting in the reaction flow coming out from the reactor, and (c) addition agents for separation, trapping and recycling of unreacted propane to the process.

EFFECT: improved manufacturing method.

13 cl, 19 ex

FIELD: chemical industry; petrochemical industry; methods (versions) of the ammoxidation of the carboxylic acids in the mixture of nitriles.

SUBSTANCE: the invention is pertaining to the methods (versions) of the ammoxidation or to the method of increasing of the yield of the acetonitrile in the form of the by-product produced in the process of manufacture of acrylonitrile, which provide for injection of the reactants, which contain at least one hydrocarbon selected from the group, which includes propylene and the propane, at least one С1-С4 carboxylic acid, ammonia and the gas containing the molecular oxygen, into the reaction zone containing the catalyst of the ammoxidation, and realization of the reaction of the indicated reactants above the indicated catalyst at the heightened temperature with production of the yield, which contains acrylonitrile, hydrogen cyanide and acetonitrile. The method may additionally include the contact of the effluent of the reaction zone with the liquid of extinguishing, which contains the water and at least one С14 carboxylic acid, and the addition of at least a part of the extinguishing liquid into the reaction zone after the extinguishing liquid contacting the liquid of the reaction zone. The invention allows to increase the yield and, predominantly, the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.

EFFECT: the ensures the increased yield and the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.

22 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: proposed catalyst contains a complex of catalytically active oxides, including oxides of rubidium, cerium, chrome, magnesium, iron, bismuth, molylbdenum and at least, one of nickel or nickel with cobalt. The ratio of components is presented by the following general formula: RbaCebCrcMgdAeFefBigMo12Ox, where A is Ni or a combination of Ni and Co, a approximately ranges from 0.01 to 1, b approximately ranges from 0.01 to 3, c approximately ranges from 0.01 to 2, d approximately ranges from 0.01 to 7, e approximately ranges from 0.01 to 10, f approximately ranges from 0.01 to 4, g approximately ranges from 0.01 to 4, and x is a number, defined by valency of other present elements. "b"+"c" is greater than g. The catalyst does not contain manganese, noble metal or vanadium. The carrier is chosen from a group comprising silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The catalyst is used for oxidative ammonolysis of olefin, chosen from a group containing isobutylene or their mixture, with formation of acrylonitrile, metacrylontrile and their mixture, respectively.

EFFECT: high activity of the catalyst.

19 cl, 1 tbl, 16 ex

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