The method of obtaining containing antimony catalysts for the (amm) oxidation of alkanes and alkenes

 

(57) Abstract:

The invention relates to a method for producing a catalyst for the (AMM)oxidation of propane or propylene to Acrylonitrile. The described method of preparation of the catalyst VaSbbMmNnOxuseful when (AMM)oxidation (C2-C5) - hydrocarbon to its corresponding , -unsaturated nitrile comprising heating the aqueous mixture containing V2O5and Sb2O3at a temperature of more than about 100oWith up to 250oC, preferably at 110oC-175oC, most preferably at 120oC - 160oWith, at autogenous pressure, with stirring, to form a catalyst precursor, drying the catalyst precursor and calcination of the catalyst precursor, with formation of the final catalyst. Technical result: the catalyst with higher activity and selectivity to Acrylonitrile. 2 C. and 15 C.p. f-crystals, 3 tables.

The invention relates to the catalytic (AMM) oxidation of paraffins and olefins containing from two to five carbon atoms to the corresponding alpha, beta-unsaturated NITRILES. In particular, the present invention relates to SS="ptx2">

Because of the differences in cost between propylene and propane, there is economic incentive for the development of viable catalyst suitable for the conversion of propane to Acrylonitrile. Development method (AMM)oxidation of propane to Acrylonitrile has become quite complex. U.S. patents 5124016, 5008427, 5258543, 4788317, 4746641, 3860534, 3681421 and patents great Britain 1136135 and 1336136 belong to different containing vanadium and antimony catalysts, useful for (AMM)oxidation of propane to Acrylonitrile, and offer different ways of making such catalysts. The present invention relates to a simple procedure for obtaining sumanabandara catalyst useful in the oxidation reaction and/or (AMM)oxidation, such as the oxidation of o-xylene to phthalic anhydride or (AMM)oxidation of propylene and propane to Acrylonitrile. In particular, the method of the present invention relates to the production of a catalyst that is useful for (AMM)oxidation of propane. The advantage of the method of the present invention is that it is a very simple procedure, essentially precluding the use of rare materials used in the previously developed methods, as well as eliminating many of the stages inherent in radiochemie catalyst, useful when (AMM)oxidation of propane and propylene.

The main purpose of the present invention is a method of producing a catalyst useful in the (AMM)oxidation of olefins and/or paraffins to the corresponding unsaturated NITRILES.

Another objective of the present invention is a method of producing a catalyst useful in the (AMM)oxidation of propane or propylene to Acrylonitrile.

Another objective of the present invention is a method of producing Acrylonitrile from propane or propylene using sumanabandara promoted catalyst obtained in a specific way.

Other objectives, advantages and new features of the present invention may be formulated in part in the description following hereinafter, and in part will be obvious to a person skilled in this technical field when checking the following or may be clarified in the practical application of the invention. Objectives and advantages of the present invention can also be achieved using means and combinations particularly described in the enclosed claims.

To achieve the above objectives, in accordance with the purposes of the present invention, as is pricheski formula:

VaSbbMmNnOx,

where a=0,01-2,00;

b=0,5-4,00;

m=0.01 to 3.0 and

n=0-1,

M=Sn, Ti, Fe, Cu, Mn, Ga, or mixtures thereof,

N=Li, Mg, Sr, Ca, BA, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cr, Te, TA, Se, Bi, Ce, In, As, In, or mixtures thereof,

comprising heating the aqueous mixture containing a water-soluble Vanadate and Sb2ABOUT3and, optionally, at least one M-promoter, at a temperature from temperature phlegmy water mixture (i.e., above about 100o(C) to 250oC, preferably from about 110oWith up to 250oWith, at autogenous pressure, with stirring for a time sufficient to interact, at least slightly soluble in water Vanadate and Sb2ABOUT3with the formation of the catalyst precursor, drying the catalyst precursor removal of water and calcination of the catalyst precursor to obtain the final catalyst.

In another aspect the present invention relates to a method for producing a modified VaSbbOx-catalyst of the formula

VaSbbMmNnOx,

where a=0,01-2,00;

b=0,5-4,0;

m=0.01 to 3.0 and

n=0-1,

M=Sn, Ti, Fe, Cu, Mn, Ga, or mixtures thereof,

N=Li, Mg, Sr, Ca, BA, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cr, Te, TA, Se, Bi, Ce, In, and optionally, at least one M-promoter, 125-250oWith, at autogenous pressure, with stirring for a time sufficient, at least for interaction2O5and Sb2ABOUT3with the formation of the catalyst precursor, drying the catalyst precursor removal of water and calcination of the catalyst precursor to obtain a catalyst.

In a preferred embodiment of the method of the present invention for the formation of the catalyst precursor to the aqueous mixture prior to heating, add at least one promoter is N, which is defined above.

In another preferred embodiment of the method of the present invention, at least one promoter element M is added to the water mixture for the formation of the catalyst precursor after heating.

In another preferred embodiment of the method of the present invention as M-promoter pick tin and tin-promoter is added to the aqueous mixture in the form of a colloidal solution of tin oxide.

In another preferred embodiment of the method of the present invention support the pH of the aqueous mixture of less than 7 so

In another preferred embodiment of the method of the present invention support the pH of the aqueous mixture above 7 by adding a base. The base is preferably an organic or inorganic amine (for example, alkanolamine, the hydroxide of tetraethylammonium).

Now the method of the present invention will be described in detail.

The present invention relates to a method of preparation of the catalyst on the basis of VaSbbOxfor (AMM)oxidation of hydrocarbons, especially (C3-C5)-alkanes and olefins to the corresponding alpha, beta-unsaturated NITRILES. In particular, the present invention relates to the production of catalysts on the basis of antimonate vanadium (AMM)oxidation of propane and propylene to Acrylonitrile. The method of the present invention includes obtaining a catalyst of the empirical formula

VaSbbMmNnOx,

where a=0,01-2,00;

b=0,5-4,0;

m=0.01 to 3.0 and

n=0-1,

M=Sn, Ti, Fe, Cu, Mn, Ga, or mixtures thereof,

N=Li, Mg, Sr, Ca, BA, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cr, Te, TA, Se, Bi, Ce, In, As, In, or mixtures thereof,

comprising heating the aqueous mixture containing a water-soluble Vanadate (e.g., VO4-3, VO3round above the temperature of phlegmy water mixture and up to 250oWith, at autogenous pressure, with stirring for a time sufficient to interact, at least slightly soluble in water Vanadate and Sb2ABOUT3with the formation of the catalyst precursor, drying the catalyst precursor removal of water and calcination of the catalyst precursor to obtain the final catalyst.

In another embodiment, the method of the present invention M-promoter added to the aqueous mixture after mixing and interaction vodorastvorimyh Vanadate and Sb2ABOUT3.

In another aspect the present.the invention is a method of obtaining catalyst VaSbbMmNnOxthe above formula includes heating the aqueous mixture containing V2O5and Sb2ABOUT3at 110-250VoWith, at autogenous pressure, with stirring for a time sufficient for the interaction of metal oxides with the formation of the catalyst precursor, adding at least one M-promoter to the water mixture, drying the catalyst precursor removal of water and calcination of the catalyst precursor to obtain a catalyst.

Hydrothermal reaction of oxidaiton metals with obrazovaniem catalyst precursor. The required reaction time is determined ultimately by the catalytic and physical properties of the final material obtained after calcination. Generally, the reaction proceeds of 0.5 100,0 hours, preferably 1-50 hours, and particularly preferably a time of 1-10 hours Noted that a shorter reaction time is required if you increase the temperature in the process of formation of the catalyst precursor.

An aqueous mixture containing vanadium and antimony components may also contain acid or base, preferably a base that is present in a colloidal solution of tin oxide.

To bring the pH to below 7, you can use any inorganic or organic acid. It is advisable to use an acid that can decompose during calcination, so that they do not remain after this in the form of non-volatile components, such as chlorides or sulfates, which can modify the composition except for the case when this is desirable. It is possible to use inorganic acids such as nitric acid, but this acid can release into the environment of unwanted gases such as NOx. It seems that the preferred acid is ri annealing decompose with the formation of COxand water. The amount of acid that is used in these syntheses, significantly lower than the amount required to dissolve all of the inorganic components (e.g., V2O5before reaction.

To achieve a pH above 7, you can use any inorganic base (for example, ammonium hydroxide or organic amine (including detoxification, the hydroxide of tetramethylbutylamine, alkanolamine, hydroxide tert-butylamine). However, it is advisable to use a base that can decompose during calcination, after which no remains of non-volatile components, such as alkali or alkaline earth metal, unless their presence is undesirable in the final composition of the catalyst. Suitable bases that can be used are ammonium hydroxide and organic bases such as alkylamines followed and alkanolamine. Most preferably, if the base may already be present in the aqueous mixture as a stabilizer/dispersant for hydrated inorganic metal oxide (for example, a colloidal solution of tin oxide), which is used as a raw material source for the M-promoter in the process of education predisease of the invention may include interaction in appropriate quantities V2O5and Sb2ABOUT3(as well as optional oxides of other metals, known for promotion of catalysis (AMM)oksidirovaniya, for example (but not limited to these examples), tin oxide (colloidal solution), oxides of titanium, tellurium, rhenium, silicon, aluminum, iron, niobium, chromium, cobalt, copper, bismuth, tungsten, etc.,), in the presence of water and optionally an acid or base to adjust pH, at 100 (temperature phlegmy) - 250oWith under autogenous pressure and vigorous stirring. In cases where you can't get himself oxide promotor metal for hydrothermal reactions (or not readily available in a suitable form), you do not have to use other sources of metals promoters (for example, nitrates, acetates, hydroxides, complexes with ammonium ion, CARBONYLS, etc). Hydrothermal reactions of these metal oxides continues over time (usually 0,5-100,0 h), sufficient for a suitable dispersion of the metal oxide with the formation of the catalyst precursor. Some metal oxides or other sources can be added after stage hydrothermal reaction, and they can be in the form of fine metal powders, colloidally solution of silica and colloidal solution of alumina. After cooling, the resulting material (usually quite homogeneous suspension, although it may occur some stratification, if the mixture is no mixing) can be mixed/enter further reaction with additional metal oxides (or other sources of metals, such as nitrates, acetates, etc.,), was evaporated to dryness (or spray drying) and ignited in one or more stages to obtain a catalyst. The pH value obtained hydrothermally suspension can be customized before adding other reagents for optimal preparation of the catalyst.

The desired reaction time, temperature, solids content and order of addition of other reactive metal oxides are determined ultimately catalytic and physical properties of the final material. Additional stages of washing and annealing applied to the obtained catalyst when other ways to obtain it, can also be used to improve the performance of these catalysts. For example, to improve the performance of the catalyst can be used under washing and calcination as described in U.S. patent 5214016, 5008427 and 5258543 included in the present Cacela also acceptable for suspensions, obtained in this way.

Found that advantageously the presence of promoter-tin in the form of a colloidal solution of tin oxide/stabilizers during the hydrothermal synthesis of the precursor of the promoted catalyst, especially at a temperature above the temperature of phlegmy (100oC) and up to 250o(For example, from 110oC to 250oC), preferably at 110-175oWith, with the most preferred temperature of 120-160oWith under autogenous pressure.

In addition, the obtaining of aqueous suspensions with high solids content is particularly favorable for the practical implementation of the present invention. The use of stable hydroxide of Tetramethylammonium colloidal solution SnO2can be used to obtain aqueous suspensions with a solids content of about 70%, suitable for the practical implementation of the present invention.

The stage hydrothermal reaction at elevated temperatures reduces the time required to obtain suspensions, which ultimately yield catalysts, which are also good or better catalysts, obtained at a temperature of phlegmy (priblizitel atory phlegmy, i.e. above 100o(C) enhanced by the inclusion of other promoter elements in the basic composition to improve the overall performance. Furthermore, the method of the present invention is easily scalable to commercial production of the catalyst, since it is not necessary that all the raw materials were in solution at any point in time. Therefore, it is possible to achieve a higher content of solids in suspensions without cost on their concentration, for example, by evaporation before spray drying. This increases the efficiency of the reactors and other equipment used in the preparation of the catalyst. The method of the present invention also reduces the amount of water that must evaporate from the slurry to achieve the appropriate content of solids for spray drying, which result in saved time and energy.

It is also noted that the reaction rate of metal oxides at higher temperatures and under autogenous pressure is substantially increased by the presence of promoter-tin in the form of a colloidal solution of tin oxide. In particular, significantly increases the interaction of metal oxides in the presence of colloids Alacati catalysts (predecessors) at a lower reaction times and lower reaction temperatures, than the time and temperature used previously.

There are qualitative factors that indicate that the presence of a colloidal solution of tin oxide increases the speed of reaction of the oxides of vanadium and antimony. In the absence of a colloidal solution of tin oxide coloring phlegmy mixture does not significantly darker (and see yellow streaks, when a drop of the suspension is applied to the sheet of filter paper, showing components containing free and soluble vanadium) after 3-6 h of reaction. In the presence of a colloidal solution of tin oxide color turns black within ~1/2 h, indicating significant interaction. X-ray analysis of the calcined intermediate materials (650o(C) shows that the tin oxide and titanium oxide is better dispersed, if at the stage of the hydrothermal reaction is a colloidal solution of tin oxide. The presence of organic stabilizers in a colloidal solution of tin oxide may be detrimental to the properties of the final catalyst, if you do not take special precautions to remove the stabilizer before the final annealing. Respectively will be some benefit of using low concentrations of STABILO time synthesis using the method of the present invention, which uses a sealed system under autogenous pressure.

In the most simple and convenient way to use the procedures of the present invention in alkaline conditions at a stage hydrothermal reaction of oxides of vanadium and antimony should be colloidal tin-containing solution and the associated stabilizers/dispersers. It may be advantageous for minimizing the migration of particles of tin to the surface of the particles formed during spray drying, to obtain a catalyst in the form of a fluidized bed.

The following examples are provided for illustrative purposes only.

(AMM)oxidation of propylene with a fixed catalyst bed.

EXAMPLE 1.

The catalyst composition of 60% VSb1,2Fe0,08Sn0,5Ti1Ox- 40% SiO2obtained as follows. In a Teflon sleeve corresponding to a 125 ml Parr autoclave equipped with a magnetic stirrer rod, placed 4,55 g V2O5(Stratcore), the rate of 8.75 g Sb2ABOUT3, 0.32 g F2ABOUT3(Baker) and 40 g of water. After stirring for approximately 15 min add 1,58 g of oxalic acid (Baker) and an additional 20 g of water, continuing the stirring. For the second through 93 h, transferred into 800 ml of chemical beaker equipped with a mixing rod, and dilute with water to approximately 150 ml Added to a suspension of 4 g of TiO2(Degussa P25) and stirred for approximately 1 h the mixture is Then heated to boiling. Then add 18,84 g of a colloidal solution Sn2(20% solids) and 47,50 g of a colloidal solution of SiO2(30% solids) and evaporated water up until the gel thickens so that the rod will stop. The resulting material is then dried in an oven at 120oWith during the night. The obtained solid is then calcined in air at 290oC for 3 h, at 425oC for 3 h and at 650oWith over 8 hours the material is Then crushed and sieved, and some portion constituting 20-40 mesh, calcined at 900oC for 3 h, washed with hot methanol, and then calcined at 650oC for 3 h and then washed with hot methanol.

EXAMPLE 2.

Get the catalyst composition of 60% VSb1,2Fe0,08Sn0,5Ti1Ox- 40% SiO2as described above, except that the TiO2present on stage 93-hour hydrothermal reaction at 175oC.

EXAMPLE 3.

To the same way as in example 1, but with 0.10 g Fe2ABOUT3and 0.17 g of Nb2O5(Alfa) present on stage hydrothermal reaction (175oWith, 138 h), and without oxalic acid.

EXAMPLE 4.

The catalyst composition of 60% VSb1,2Cu0,04Sn0,5Ti1Ox- 40% SiO2get a manner similar to the method of example 1, but with 0.14 g of Cu2O (Alfa) present on stage hydrothermal reaction (175oC 91 h).

EXAMPLE 5.

The catalyst composition of 60% VSb1,2Cu0,04Sn0,5Ti1Ox- 40% SiO2get a manner similar to the method of example 4, but with 0.16 g SIO (Alfa), present at the stage of hydrothermal reactions.

EXAMPLE 6.

The catalyst composition of 60% VSb1,2Cu0,04Sn0,5Ti1Ox- 40% SiO2get a manner similar to the method of example 4, but with 0.16 g CuO (Alfa), present at the stage of hydrothermal reactions.

EXAMPLE 7.

The catalyst composition of 60% VSb1,2Cu0,06Sn0,5Ti1Ox- 40% SiO2get a manner similar to the method of example 4, but with 0.24 g CuO (Alfa), and at the stage of hydrothermal reactions are only 0,79 g of oxalic acid.

EXAMPLE 8. 60% VSb1,2Fe0,08Sn0,5Ti12) and 125 ml of water reacts with boiling under reflux for ~24 hours After cooling, add 4,00 g Tio2and 47,50 g of a colloidal solution of silica (30% solids) and suspension concentrate on the hot plate until such time as the rod agitator will not stop. High temperature annealing is carried out at 885oC for 3 h

THE EXAMPLE FOR COMPARISON 9. 60% VSb1,3Feof 0.2Sn0,5Ti1Ox- 40% SiO2< / BR>
The catalyst of the empirical formula 60% VSb1,3Feof 0.2Sn0,5Ti1-Ox- 40% SiO2obtained as follows. To a mixture consisting of 900 cm3H2O and 100 grams of 30% H2ABOUT2in a 2-liter beaker add 12,08 g V2ABOUT5and stirred at room temperature for about 15 minutes until it forms a dark red peroxide complex. Then add 25,17 g Sb2ABOUT3, 2,12 g Fe2ABOUT3(Nano) and 10,61 g TiO2(Degussa, P-25), set the temperature control on hot plates "high" and enjoy a glass of the watch glass. When heated, the color of the suspension changed from yellow to green, and then Crawley 50,05 g of 20% colloidal solution SnO2(Naico 88SN123), then 133,33 g of 30% colloidal solution of silica (Nissan). The suspension of catalyst evaporated on a hot plate with continuous stirring until it thickens. The rest of the procedure is the same as in example 8.

EXAMPLE 10. 60% VSb1,2Fe0,025Ni0,025Sn0,5Ti1Ox- 40% SiO2< / BR>
Get the catalyst composition of 60% VSb1,2Fe0,025Ni0,025Sn0,5-Ti10x- 40% SiO2with 0,093 g NiO and 0.01 g Fe2O3and 0.79 g of oxalic acid present at the stage of hydrothermal reactions (175oC, 16 h), by the method similar to the method of example 4.

EXAMPLE 11. 60% VSb1,2Mn0,025Sn0,5Ti1Ox- 40% SiO2< / BR>
The catalyst composition of 60% VSb1,2Mn0,025Sn0,5Ti1Ox- 40% SiO2receive the same manner as in example 10, except that there 0.11 g Mno2.

EXAMPLE 12. 60% VSb1,2Fe0,025Mn0,025Sn0,5Ti1Ox- 40% SiO2< / BR>
The catalyst composition of 60% VSb1,2Fe0,025Mn0,025Sn0,5Ti1Ox- 40% SiO2receive the same manner as in example 10, except that there are 0.12 g Fe2O3(Baker) and 0.11 g of Mno2.

EXAMPLE 14. 60% VSb1,2Fe0,12Sn0,5Ti1Ox- 40% SiO2< / BR>
The catalyst composition of 60% VSb1,2Fe0,12Sn0,5Ti1Ox- 40% SiO2obtained by reaction of a mixture of V2O5(4,55 g), Sb2O3(8,75 g), Fe2O3(Nano, 0,479 g), 18,84 g of a colloidal solution of tin oxide (3.77 g SnO2) and 120 ml of water at 150oWith under autogenous pressure in an autoclave with stirring for 21 hours, After cooling, add 4,00 g TiO2and 47,86 g of a colloidal solution of silica (30% solids) and suspension concentrate on the hotplate until then, while stirring rod will not stop. HighSn0,5Ti1Ox- 40% SiO2< / BR>
The catalyst composition of 60% VSb1,2Fe0,12Sn0,5Ti1Ox- 40% SiO2obtained by reaction of a mixture of V2O5(7,00 g), Sb2O3(13,46 g), Fe2ABOUT3(Nano, 0.74 g), 28,98 g of a colloidal solution of tin oxide (5,80 g SnO2and 112 ml of water at 150oWith under autogenous pressure in an autoclave with a stirrer for 3 hours After cooling, add 6,15 g TiO2and 73,62 g of a colloidal solution of silica (30% solids) and suspension concentrate on the hotplate until then, while stirring rod will not stop. High-temperature annealing is performed at 900oC for 2.5 h

The catalysts of the above examples 1-15 was tested under the following conditions. Startup value3=/NH3/-O2/N2/H2O in each example is 1,8/2,2/3,9/2,4/6,0 respectively. The results are shown below in table. I.

(AMM)oxidation of propylene in the fluidized bed

EXAMPLE 1.

Get a large batch fluidized catalyst composition 60% V1Sb1,2Fe0,12Sn0,5Ti1Ox- 40% SiO2by following the procedure used to obtain it is added to the suspension, obtained from the stage hydrothermal reaction. Then before spray drying the suspension is concentrated to about 32-33% solids by evaporation of water.

EXAMPLE 2.

Get a large batch fluidized catalyst composition 60% V1Sb1,2Fe0,12Sn0,5Ti1Ox- 40% SiO2by following the procedure used above, except that the suspension obtained from step hydrothermal reaction, concentrate up to 18-20% solids prior to the addition of titanium oxide and silicon oxide. Then, the suspension is concentrated to about ~35% solids before spray drying through the evaporation of water.

Testing of the catalysts of examples 1 and 2 at 40 cm3the reactor with a fluidized bed. Boot the ratio of CH3=/NH3/O2/N2/H2O in the case of the catalysts of examples 1 and 2 is 1,8/2,2/3,9/2,4/16, respectively. The results are shown below in table.II.

(AMM)oxidation of propane

THE EXAMPLE FOR COMPARISON 1.

The catalyst composition VSb1,4Snof 0.2Tia 0.1Oxget a manner similar to the method described above in example 9, except that the e 3 h, calcined at 650oC for 3 h and washed with Isobutanol.

EXAMPLE 2.

The catalyst composition VSb1,4Snof 0.2Tia 0.1Oxobtained as follows. In a 250 ml round-bottom flask, equipped with reflux condenser, placed 7,58 g V2O5, 17,01 g Sb2ABOUT3and 25,57 g of a colloidal solution SnO2stabilized NH4OH containing of 2.51 g of SnO2and approximately 125 g of water. This mixture is boiled with reverse holodilniki with stirring for 22 hours, After cooling the resulting suspension with stirring in chemical beaker containing 0,67 g highly dispersed TiO2. After 1 h, the suspension is concentrated by evaporation until the mixture thickens and placed overnight in an oven at 125oFor drying. The dried solid is warm in air at 290oC for 3 h, then at 425oC for 3 h and then for 8 h at 650oC. the material is Then crushed and sieved, and the fraction 20-35 mesh calcined at 820oC for 3 h, then at 650oC for 3 hours and then washed with Isobutanol.

EXAMPLE 3.

Receive the same composition, which is listed in example 2, except that vascoda is 4.

The catalyst composition VSb1,4Snof 0.2Tia 0.1Oxobtained as follows. In a quartz sleeve is placed 7,58 g V2O5, 17,01 g Sb2ABOUT3, of 0.67 g of highly dispersed TiO2and 27,57 g of a colloidal solution SnO2stabilized NH4OH containing of 2.51 g of SnO2and approximately 125 g of water. This sleeve is then placed and tightly closed 300 cm3autoclave, equipped with overhead stirrer. The mixture is then heated to 125oC and incubated for 6 h with stirring. Then the heater is removed from the autoclave and leave the mixture to cool with stirring overnight. The rest of the procedure is carried out as in examples 2 and 3.

EXAMPLE 5.

To obtain a suspension containing components to obtain a catalyst composition VSb1,4Snof 0.2Tia 0.1Oxuse the same procedure as in example 4. After extraction of the cooled autoclave suspension concentrate in the beaker on the hot plate until the solids content of 29-30%. Add lithium hydroxide in water to reduce the viscosity of the suspension. Continue to evaporate the water and before the rod stirrer will stop receiving the solids content nailed in a stream of air at 810 and 650oWith before the single stage washing, isobutyl alcohol, after annealing at 650oC. the Composition of the resulting catalyst Li0,05VSb1,4Snof 0.2-Tia 0.1Ox.

EXAMPLE 6. (6 hours)

Perform the same procedure as in example 4, except that the final two stages of annealing is conducted as in example 5.

EXAMPLE 7. (4 hours)

Perform the same procedure as in example 6, except that the hydrothermal stage is carried out only for 4 hours

EXAMPLE 8.

Perform the same procedure as in example 4, except that the stage of the hydrothermal reaction is carried out for 4 h at 150oC.

The results of the tests in the reactor with a fixed bed in case (AMM)oxidation of propane are given below in table.III.

The above description is not intended to provide a comprehensive implementation and combination of the method of the present invention. Although the song received to date, is scheduled for catalyst (AMM)oxidation in the case of propane and propylene, it seems that the method is suitable for preparation of catalysts for the oxidation of another type. Have in mind that the way sposob receipt containing antimony catalysts for the (AMM)oxidation of alkanes and alkenes empirical formula

VaSbbMmNnOx,

where a= 0,01-2,00;

b= 0,5-4,0;

m= 0,01-3,00;

n= 0-1;

x is the number of oxygen atoms, which is determined by the oxidation state of other elements,

M= Sn, Ti, Fe, si, Mn, Ga or mixtures thereof;

N= Li, Mg, Sr, Ca, BA, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cr, Te, TA, Se, Bi, Ce, In, As, or mixtures thereof,

comprising heating the aqueous mixture containing a water-soluble Vanadate and Sb2ABOUT3and at least one M-promoter, at 100 - 250oWith the formation of the catalyst precursor, drying the specified catalyst precursor removal of water and calcination of the catalyst precursor, wherein the interaction between vanadium and antimony occurs at autogenous pressure and stirring for a time sufficient to react at least a water-soluble Vanadate and Sb2ABOUT3with the formation of the catalyst precursor.

2. The method according to p. 1, characterized in that add at least one N-promoter to the aqueous mixture prior to heating water mixture for the formation of the catalyst precursor.

3. The method according to p. 1, characterized in that use Sn as M-promoter.

4. The method according to p. 3, characterized in that , trichosis the fact that the pH of the aqueous mixture is supported above 7 by adding a base.

6. The method according to p. 1, characterized in that the pH of the aqueous mixture of support below 7 by the addition of acid.

7. The method according to p. 2, characterized in that the N-promoter is added to the catalyst after the water-soluble Vanadate and Sb2ABOUT3dispersed and reacted with the formation of the catalyst precursor.

8. The method according to p. 5, characterized in that the substrate is selected from the group consisting of inorganic or organic amine.

9. The method according to p. 8, wherein the base is an organic amine selected from the group consisting of alkylamines followed, alkanolamines or mixtures thereof.

10. The method according to p. 6, wherein the acid is an organic acid.

11. The method according to p. 10, wherein the organic acid is chosen from the group consisting of acetic, oxalic acid or mixtures thereof.

12. The method according to p. 6, wherein the acid is an inorganic acid.

13. The method of obtaining containing antimony catalysts for the (AMM) oxidation of alkanes and alkenes empirical formula

VaSbbMmNn is allocated by the degree of oxidation of the other elements;

M= Sn, Ti, Fe, si, Mn, Ga or mixtures thereof;

N= Li, Mg, Sr, Ca, BA, Co, Ni, Zn, Ge, Nb, Zr, Mo, W, Cr, Te, TA, Se, Bi, Ce, In, As, or mixtures thereof,

comprising heating the aqueous mixture containing V2O5and Sb2ABOUT3and at least one M-promoter, 110-250VoC C the formation of the catalyst precursor, drying the catalyst precursor removal of water and calcination of the catalyst precursor, wherein the interaction between vanadium and antimony occurs at autogenous pressure and stirring for a time sufficient to react at least V2O5and Sb2ABOUT3with the formation of the catalyst precursor.

14. The method according to p. 13, characterized in that M-promoter is Sn.

15. The method according to p. 13, wherein Sn is added to the aqueous mixture in the form of a colloidal solution of tin oxide.

16. The method according to p. 13, characterized in that at least one M-promoter is added to the aqueous mixture prior to the formation of the catalyst precursor.

17. The method according to p. 13, characterized in that the N-promoter is added to the aqueous mixture after the formation of the catalyst precursor.

 

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The invention relates to a method for the catalytic vapor-phase ammoxidation3-C5olefins to obtain,- unsaturated mononitriles and HCN, and more precisely, the invention relates to a method for the catalytic vapor-phase ammoxidation (1) of propylene to obtain Acrylonitrile and HCN and (2) of isobutylene to obtain Methacrylonitrile and HCN
The invention relates to an improved method of extraction of Acrylonitrile or Methacrylonitrile, which is used in the production of Acrylonitrile or Methacrylonitrile
The invention relates to a method for producing a tin-containing vanadium-antimony catalysts suitable for the catalytic ammoxidation3-C5-paraffins or olefins, more specifically, to obtain catalysts for the ammoxidation of propane or isobutane, or propylene, or isobutylene with obtaining the appropriate,-unsaturated mononitriles, Acrylonitrile or Methacrylonitrile

The invention relates to a method for producing a cyclic anhydride or a nitride of hydrocarbon and oxygen-containing gas in the presence of an appropriate catalyst, in particular to a method of reducing or eliminating the risk of explosion or fire in the headspace of the reactor system, in which there is a formation of the anhydride, or nitrile of hydrocarbon and oxygen

The invention relates to catalysts and methods of producing the oxide catalysis

The invention relates to catalysts and methods of producing oxide catalysts used in the processes of deep oxidation of organic compounds and carbon monoxide in the gas emissions from industrial productions
The invention relates to a method for producing a tin-containing vanadium-antimony catalysts suitable for the catalytic ammoxidation3-C5-paraffins or olefins, more specifically, to obtain catalysts for the ammoxidation of propane or isobutane, or propylene, or isobutylene with obtaining the appropriate,-unsaturated mononitriles, Acrylonitrile or Methacrylonitrile

The invention relates to the field of inorganic chemistry and can be used in particular for the preparation of the catalyst used for the decomposition of ozone in production with his participation, for the purification of gas mixtures of carbon monoxide, as well as for other industrial and environmental purposes

The invention relates to chromium catalysts and methods for their preparation used for oxidation of organic compounds, hydrogen and carbon monoxide in the gas emissions from industrial productions

The invention relates to the field of catalysts

The invention relates to a solid molded the catalysts are easily separated from the reactants and re-used in the reactions of alkylation, esterification and isomerization

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating of various petroleum fractions, and can be used in the refining industry

The invention relates to catalysts and methods of producing oxide catalysts used in the processes of deep oxidation of organic compounds and carbon monoxide in the gas emissions from industrial productions

The invention relates to methods for nicolacopoulos catalyst used in industry for hydrogenation, for example, organic compounds, for mahanirvana co and CO2and other processes
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