How oxidative amination of alkanes

 

(57) Abstract:

Usage: in the chemical industry. The essence: gaining unsaturated NITRILES. Reagent 1: alkane. Reagent 2: ammonia. Reagent 3: oxygen. Reaction conditions: 350 - 550oC, pressure 1 - 6 bar, gas diluent, possibly water vapor, the catalyst MoaVbMcOxwhere M is Mn, Zn, CO. 7 C. p. F.-ly, 2 ill., table 4.

The invention relates to a method for oxidation of saturated hydrocarbons in the presence of ammonia, i.e., the conversion of alkanes in the mixture containing, unsaturated NITRILES.

There are many ways oxidation of olefins in the presence of ammonia and, in particular propylene. However, while saturated hydrocarbons are more interesting raw materials in economic terms, they do not have comparable reactivity in reactions of this type, to form, in particular, unsaturated NITRILES.

One of the difficulties encountered in the oxidation of saturated hydrocarbons in the presence of ammonia is necessary to have a catalyst capable of degidrirovanii saturated hydrocarbon under conditions that minimize or eliminate the combustion of ammonia and/or combustion of hydrocarbons, providing simultaneously the C propane, or valuable products (the above nitrile and olefin) such as Acrylonitrile and propylene, based on propane.

In U.S. patent N 3365482 proposed to oxidize in the presence of ammonia, in particular, the isobutane to Methacrylonitrile on the catalyst based on molybdenum deposited on ETA-alumina, activated by antimony at a temperature of 508aboutWith on the basis of a gaseous mixture containing isobutane, air, ammonia and water vapor(1:4,5:1:12,5), moreover, the selectivity for Methacrylonitrile reaches 49% for degree of conversion of isobutane value 22%

On the basis of a gaseous mixture of propane and air-ammonia-water vapor (1:4,7: 0,67:12,8) with the same catalyst and at a temperature of 550aboutWith, the selectivity for Acrylonitrile drops to 15 for the degree of conversion of propane value 29%

In the French patent N 2027238 (corresponding partially to the American patent N 3670009) proposes a method of oxidation in the presence of ammonia saturated hydrocarbons in the vapor phase at a temperature exceeding 500aboutWith the solid catalyst, which can in particular be composed of tin oxide, boron oxide, molybdenum oxide and silicon oxide. So, in the table, the selectivity for Acrylonitrile domian-air (1: 1,2:12) in hazardous area.

In the French patent N 2072334 (corresponding to British patent N 1336135) protected way catalytic oxidation in the presence of ammonia, alkanes in the vapor phase at a temperature below 500aboutWith a large concentration of alkane in the input gas mixture on a solid catalyst, which can in particular be composed of tin oxide and molybdenum oxide (90:10 by weight). However, the best results are obtained with catalysts consisting of antimony oxide and vanadium oxide.

In the French patent N 2072399 also offers a way catalytic oxidation in the presence of ammonia alkane in the vapor phase with a large alkane concentration in the source gas mixture on a solid catalyst, which may, in particular, to represent a binary mixture of oxides containing molybdenum oxide.

It should, in particular, to note the following pairs: Mo, Sb; Mo, Sn, Mo, Y; Mo, Ti; Mo, Bi. However, none of these pairs does not give better results than the results obtained with pairs that do not contain molybdenum. The resulting outputs for Acrylonitrile are very small, in the best case 1.7 propane is converted to Acrylonitrile at a temperature of 570aboutWith the catalyst based on oxides of tin and titanium.

In Franz is to use binary composition based on oxides of molybdenum and cerium. However, the effectiveness of the pairs of Mo, CE is insufficient in the absence of halogen or halogen-containing compounds.

In addition, it is known addition to this binary composition (Mo, CE) of the third element selected among tellurium and bismuth (see also U.S. patent N 3833638). Here again, the efficiency of the catalytic system is insufficient in the absence of halogen or halogen-containing compounds. In addition, note that in the presence of CH3Br selectivity for Acrylonitrile reaches 67 in 98-Noah conversion of propane, but under experimental conditions, the resulting reaction mixture propane-ammonia-air (1:1,2:12) in hazardous area.

In the French patent N 2119493 proposed to carry out the oxidation in the presence of ammonia, alkanes in the vapor phase on a solid catalyst containing the oxides of bismuth and molybdenum, and optionally phosphorus and silicon. In this case again the efficiency of the catalytic system is insufficient in the absence of halogen or halogen-containing compounds, and the reaction mixture is in a hazardous area.

To eliminate these disadvantages it is proposed to use solid catalysts on the basis of OPANA in the vapor phase multicomponent metal oxides, containing molybdenum and bismuth and having a structure of structure type zeolite. It turns out that, despite the relatively moderate temperatures, the share of products of combustion (CO, CO2) is very high in all cases (at least 15%), and some catalytic composition has been very little activity in relation to the desired reaction, despite their use in conditions that are in a hazardous area or very close to the specified area. The presence of halogenated compounds can cause corrosion of equipment and, therefore, is not desirable in an industrial way. In addition, the simultaneous production of large quantities of co and CO2is undesirable in an industrial scale. Moreover, the use of reaction mixtures, located in hazardous area, it is undesirable in an industrial scale, if you implement the method in a stationary layer.

Thus, the purpose of the invention increase the selectivity of the method in respect of products containing, unsaturated NITRILES, particularly Acrylonitrile, reducing the cost of raw materials by reducing the formation of oxides of carbon.

The goal is achieved, we offer sposobniji molybdenum, vanadium and oxygen, which consists in the fact that the active phase also contains at least one element selected from among manganese, zinc, cobalt.

In accordance with the invention, saturated acyclic hydrocarbons having from 3 to 12 carbon atoms in the molecule are introduced into the reaction in the vapor phase with ammonia and oxygen in the presence of a catalyst, the active phase of which is specified above.

In this way it is possible to use gaseous diluents are inert in the reaction conditions, such as helium, nitrogen and argon. Similarly, water vapor may be added to the gaseous reaction mixture in a wide range. Thus, the reactive gas (saturated hydrocarbons, ammonia, oxygen may be diluted with an inert diluent and/or water vapor. In this system, the water vapor content can vary within wide limits, in particular from 0 to 50 and preferably between 3 and 30 For a good implementation of the method according to the invention the content of the reactive gas is at least 3 and preferably at least 20

In the reactive gas in the relative content of saturated hydrocarbon, ammonia and oxygen can vary Siroki and 48 For ammonia, this value preferably lies between 5 and 25 and for oxygen it preferably lies between 4 and 25%

For good implementation of the method according to the invention the composition of the reactive mixture should be located outside the hazardous area. If we are talking about the oxidation in the presence of ammonia propane in the absence of an inert diluent, the composition (propane, oxygen, ammonia) mainly selected inside the quadrilateral ABDE depicted inside the triple ABC chart shown in Fig.1. This ternary diagram, the line segment AB represents the content of ammonia from 100 to 0, the line segment BC represents the content of the propane from 100 to 0, the segment SA represents the oxygen content of from 100 to 0. Point D located on the segment BC corresponds to the content of propane 45 in the binary mixture propane-O2point E, located on the segment AC, corresponds to the ammonia 79 in binary mixtures of NH3-O2. Segment DE delimits the triple a chart into two parts: the triangle CDE, which is located inside the hazardous area (defined at a pressure of 1 bar and a temperature of 25aboutC), and the quadrilateral ABDE, in which the composition of the reactive gas mixture predominantly selected.

If we are talking about the oxidation of propane in the presence of ammonia and an inert gas diluent and/or the Mme when the gas-solvent and/or water vapor is present with a fraction.

If we are talking about the oxidation in the presence of ammonia propane through the air as the oxygen source, the composition (propane, air and ammonia) mainly selected inside the rectangle ABFG shown inside the chart ABC shown in Fig.2. In this diagram, the line segment AB represents the content of ammonia from 100 to 0, the line segment BC represents the content of the propane from 100 to 0, the segment SA is an air content of from 100 to 0. Point F located on the segment BC corresponds to the content of propane 16 in a binary mixture of propane and air, the G-spot is located on the segment AC, corresponds to the ammonia 35 in a binary mixture of ammonia and air. Segment FG delimits the triple a chart into two parts: a triangle CFG, which is located inside the hazardous area (defined at a pressure of 1 bar and a temperature of 550aboutC), and the rectangle ABFG, in which mainly, is selected composition of the reactive gas mixture.

Use this chart in the case where the mixture of the oxygen-gas-solvent corresponds to the oxygen content equivalent to the content of air ( 21 odya of propane receive the mixture, containing mainly propylene and Acrylonitrile. Acrylonitrile is an intermediate product obtained in industry on a large scale. Propylene is the raw material traditionally used to obtain Acrylonitrile and other intermediate products, are well known. On the basis of isobutane get the mixture containing Methacrylonitrile and isobutene or n-butenes.

The method according to the invention is particularly suitable for the oxidation in the presence of ammonia propane. If you use a saturated hydrocarbon technical quality, it does not contain significant quantities of compounds with ethylene unsaturation. In particular, used propane contains propylene only in trace amounts.

The method according to the invention is carried out in a reaction in the vapor phase. Therefore, there may be used any device that is suitable for the implementation of the oxidation reactions in the presence of ammonia or oxidation in the vapor phase. The method can be carried out continuously or intermittently, and may include the use of fixed or fluidized bed. The reaction temperature is between 350 and 550aboutWith, and preferably between 415 and 510aboutC. the Total pressure of the reaction mixture can exceed the speed of the gases is set to to hourly space velocity was concluded between 100 and 36000 h-1and preferably 1000 h-1.

You can find a compromise between the temperature of the gas flow, the exact nature of the used catalyst and various other parameters of the reaction, given their production goals.

The catalyst used in the invention correspond to the empirical formula

MoaVbMcOxwhere M represents one or more elements selected from among manganese, zinc, cobalt;

and 0,2 0,4;

b 0,05 0,8;

from 0.4 to 0.9;

x is determined by the oxidation state of other elements is between about 1.75 and 6.

Consider the active phase can be applied in the form of a solid mass or as separate particles. These phases can be used in the form of powder or pellets, for example, extruded or granular (powdered). They can also be applied to an inert carrier or cover it in the form of a shell. The nature of the medium should be chemically inert towards the reactants in the selected reaction conditions. As examples of media that may be suitable for the production of catalysts, it is possible to specify silica, alumina, krympreducerande is non-porous and can be in particular, based on refractory oxide in the form of separate particles, with the most commonly used media is based clay. This medium may, for example, consist of clay balls, inert, Nepali, hard and rough, diameter, concluded between 0.5 and 6 mm, the Exact value of the diameter of the balls can be selected depending on the permissible pressure loss in the reactor. The carrier can also be made non-porous by enameling (glazing).

The media can also be a ceramic substrate, and the specified substrate is preferably in the form of inert and rigid structure type monolith containing channels or passageways. Such carriers are well known and widely described in the literature. Used substrates made of ceramic material are, in particular, substrates containing as the main substance of cordierite, alumina, mullite, porcelain, carbides of boron or silicon.

In the case of catalyst coated amount of the active phase were made in practice between 5 and 35 and preferably between 8 and 20 wt. relative to the entire system (media + active phase).

Preparation of catalysts used in the method according to the invention, mepolizumab by evaporation until dry or with subsequent deposition in the result of addition of the base, such as ammonia, or acids, such as chloromethane acid, or spraying the suspension obtained after mixing of suitable salts.

The most commonly used suitable salts are soluble in water and contain anions and cations, which can decompose when heated during subsequent stages. This is, for example, heptamolybdate of ammonia to molybdenum, ammonium Vanadate for vanadium, nitrates or chlorides of manganese, zinc and cobalt.

Prepare a mixture of salt, can be obtained precursor evaporation. Water from the resulting suspension is evaporated by heating between 20 and 100aboutWith stirring in a period of time necessary to obtain non-current mass. The stirring and heating is then terminated.

Thus obtained mass is smeared to a layer thickness of about 2 cm, dried in air at a temperature of approximately 120aboutC for about 15 h of the thus Obtained precursor is then ground and made red-hot at a temperature between 200 and 1000aboutWith, preferably between 400 and 600aboutWith, for at least 30 min, preferably at least 1 h May be useful to perform several operations is at a rate of 100 to 200aboutWith in the hour, in particular, because of the risk associated with exothermic decomposition of ammonium nitrate at 230aboutC. thus Obtained after cooling, the active phase may then be reduced to a particle size not exceeding about 400 microns.

The precursor may also be obtained by variant, including deposition with the addition of, for example, ammonia or chloroethanol acid after mixing salts to stabilize the pH is approximately 7. It is preferable to heat the suspension at a temperature of between 20 and 100aboutC for approximately 1 h to complete the precipitation of the components.

Then the suspension is filtered and washed. The residue after filtration smeared a thin layer, then dried, crushed and made red-hot in accordance with the conditions described above within the method of evaporation to obtain the active phase. Multiple active phases can be mixed for the formation of a new active phase, for example, in a mortar.

Some catalysts suitable for implementing the method in a stationary layer can be obtained by coating according to the known method from the crushed active phases, intermediate or final. This t is Oh, or end.

After covering balls of the desired number of active phases they are dried with hot air at a temperature of between 70 and 150aboutC for at least 30 minutes, and then introduced into a furnace for annealing at temperatures between 300 and 600aboutWith, preferably between 450 and 500aboutWith, for at least 3 hours

Some catalysts suitable for implementing the method according to the invention in the movable layer or fluidized bed can be obtained by a known method of drying by spraying in the atmosphere, preferably non. As a result of such operations, if necessary, followed by calcination at a temperature of about from 400 to 1100aboutTo obtain powders with spherical particles with a diameter of 5 to 700 μm. Powders comprising at least 80 wt. of particles enclosed between 5 and 100 μm, are preferred in the context of the use of the method in a fluidized bed.

The reaction products can be removed in the outgoing gases using any suitable method. For example, exhaust gas can pass through the condenser, containing diluted sulfuric acid to neutralize the unreacted ammonia. Then the gases can pass through on the and non-condensable vapors containing mainly unreacted propane, propylene, light hydrocarbons, and possibly CO2. You can then separate the Acrylonitrile and hydrocyanic acid from acetonitrile by distillation, and then surpass, in turn, the extracted mixture of Acrylonitrile and hydrocyanic acid to separate the Acrylonitrile from hydrocyanic acid.

The examples illustrate the invention.

P R I m e R 1. Preparation of catalyst (A), the active phase of which corresponds to the formula Mn0,8V1,6Mofor 0.4O6.

Get active phase composition Mn0,8V1,6Mofor 0.4O6according to the following procedure. Prepare a solution (a) of manganese nitrate by dissolving 204,91 g Mn(NO3)2.4H2O purity 98 (included in the trading firm of Prolabo) 300 cm3permuteran water solution (b) heptamolybdate ammonium by dissolving 70,64 g (NH4)6Mo7O24.4H2O (included in trade from Merck) 200 cm3permuteran water and the suspension (s) containing 400 cm3permuteran water 187,17 g NH4VO3(included in the trading firm of Prolabo). Poured a solution to the suspension in the reactor with stirring. Then enter all the time when AC is ACCA dried at 120aboutC for about 15 hours, the Obtained product is then ground, made red-hot in 600aboutC for 6 h, ground again and again made red-hot in 600aboutC for 42 h of the thus Obtained product (1) has a specific surface area measured by BET method, a value of 0.1 m2g-1.

Slowly sprayed 20 g of the product 1 in 123 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously had been placed in rotation installation for the production of pills and moistened with 10% aqueous glucose solution. After the balls are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst And corresponding to the invention, consists of 11.6 wt. Mn0,8V1,6Mofor 0.4O6printed on a clay balls.

P R I m m e R 2. The preparation of the catalyst (C), the active phase of which corresponds to the formula Mn0,8V1,6Mofor 0.4O6.

Get active phase composition of Mn is Westley as follows. The product is ground, made red-hot at 450aboutC for 8 h, ground again, again made red-hot at 450aboutC for 8 h, again ground, made red-hot at 550aboutC for 4 h, ground again and again made red-hot at 550aboutC for 4 h thus Obtained product (1) has a specific surface area measured by BET method, a value of 1.7 m2g-1.

Slowly sprayed 20 g of the product 1 in 123 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. After the balls are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried feast 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst, corresponding to the invention, consists of a 10 wt. Mn0,8V1,6Mofor 0.4O6printed on a clay balls.

P R I m e R 3. The preparation of the catalyst (C), the active phase which is responsible f the ofor 0.3O6in the following way. Prepare a solution of zinc nitrate by dissolving 252,8 g Zn(NO3)2.6H2O (included in the trading firm of Prolabo) 250 cm3permuteran water solution (b) heptamolybdate ammonium by dissolving 52,95 g (NH4)6Mo7O24.4H2O (included in the top-trade firm Merck) 150 cm3permuteran water and the suspension (s) containing 210 cm3permuteran water 165,75 g NH4VO3(included in the trading firm of Prolabo). Mix solutions a and b and poured this mixture to the suspension in the reactor with stirring. Left under stirring for 20 h and gradually increase the temperature to 100-110aboutC. Leave under irrigation by phlegm for 1 h and evaporated. The resulting mass is dried at 120aboutC for about 15 hours and Then the resulting product is ground, made red-hot at 250aboutC for 4 h, again zamylivaetsja and made red-hot at 450aboutC for 8 h, ground again and again made red-hot at 450aboutC for 8 h, ground again and made red-hot at 550aboutC for 4 h, ground again and again made red-hot at 550aboutC for 4 h Obtained in this clicks the

Slowly sprayed 20 g of the product 1 in 123 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. After the balls are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst, corresponding to the invention, consists of a 12 wt. Znof 0.85V1,7Mofor 0.3O6printed on a clay balls.

P R I m e R 4. The preparation of the catalyst (D), the active phase of which corresponds to the formula Cofor 0.9Va 1.8Moof 0.2O6.

Get active phase composition of Cofor 0.9Va 1.8Moof 0.2O6in the following way. Transferred to a suspension of 84 g of NH4VO3100 cm3permuteran water, prepare a solution of heptamolybdate ammonium by dissolving 14 g of (NH4)6Mo7O24.4H2O 100 cm3permuteran water and a solution of nitrate of cobalt p the thief heptamolybdate ammonium to suspension metavanadate ammonium in the reactor with stirring. Then enter all the time with stirring, a solution of nitrate of cobalt. After stirring for 20 h at ambient temperature is evaporated to dryness, dried at 120aboutC, then calcined at 250aboutC for 4 h the resulting product is ground and subjected to the next cycle of prokalivanii-razmalyvanie:

450aboutC for 4 h grinding,

450aboutC for 4 h grinding,

450aboutC for 8 h grinding,

550aboutC for 4 h grinding,

550aboutC for 4 h grinding.

Thus obtained product (1) has a specific surface area measured by BET method, a value of 2 m2g-1.

Slowly sprayed 15 g of the product 1 to 100 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. After the balls are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h pierce the 12 wt. Cofor 0.9Va 1.8Moof 0.2O6,applied clay balls.

P R I m e R 5. The preparation of the catalyst (E), the active phase of which corresponds to the formula Mn0,8V1,6Mofor 0.4O6.

Get the product of (1) composition Mnfor 0.6V1,2Mo0,8O6in the following way. Prepare a solution (a) of manganese nitrate by dissolving 153,7 g Mn(NO3)2.4H2O 225 cm3permuteran water solution (b) heptamolybdate ammonium by dissolving 141,28 g (NH4)6Mo7O24.4H2O 400 cm3permuteran water and the suspension (s) containing 140 g of NH4VO3150 cm3permuteran water. Poured a mixture of solutions a and b to the suspension in the reactor with stirring. Stirred for about 20 h and gradually increase the temperature to 100 110aboutC. the resulting mass is dried at 120aboutC for about 15 hours, the Product is made red-hot air at 250aboutC for 4 h, ground, made red-hot at 450aboutC for 8 h, ground again, again made red-hot at 450aboutC for 8 h, again ground, made red-hot at 550aboutC for 4 h, ground again and again made red-hot at 550about3)2.4H2O 300 cm3permuteran water. Transferred to suspension 116,98 g NH4VO3200 cm3permuteran water. Poured an aqueous solution of manganese nitrate to suspension metavanadate ammonium in the reactor with stirring. After stirring for 10 to 15 minutes at ambient temperature filtered on fittowindow glaze and washed with 2 l permuteran water. The resulting product is then dried at 120aboutC for about 15 h, then calcined in air for 5 h at 500aboutC. Mixed in a mortar 15 g of the product 1 and 15 g of the product 2 obtained in this way. Thus prepared product (3) with the General composition Mn0,8V1,6Mofor 0.4O6has a specific surface area measured by BET method, a value of 3 m2g-1.

Slowly sprayed 10 g of the product 3 67 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. Once the beads are dry on the outside, raspily the operation to the application in the form of a coating of the product 3. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst E, corresponding to the invention, consists of 12.4 wt. Mn0,8V1,6Mofor 0.4O6printed on a clay balls.

P R I m e R 6. Preparation of catalyst (F), the active phase of which corresponds to the formula Mnfor 0.4V0,05Mofor 0.4O1,75.

Get the product of (1) composition Mnfor 0.4V0,05Mofor 0.4O1,75in the following way. Prepare a solution (a) of manganese chloride by dissolving 79,16 g MnCl2.4H2O 300 cm3permuteran water and solution (b) heptamolybdate ammonium by dissolving 70,6 g (NH4)6Mo7O24.4H2O 300 cm3permuteran water. Add to 4.52 g V2O5then the solution b to the solution in the reactor with stirring. Then add 40 cm3NH4OH (20 NH3) and heated at a temperature of education phlegmy within 3 hours Filtered to fittowindow glaze, washed with 1 l permuteran water. The resulting product is then dried at 120aboutC for about 15 h, then made red-hot in air at 500aboutC for 4 h

Slowly sprayed 10 g of the obtained t is m, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. Once the beads are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst F, corresponding to the invention, consists of 9.1 wt. Mnfor 0.4V0,05Mofor 0.4O1,75,applied clay balls.

Comparative experience. Preparation of catalyst (a), which is not included in the scope of the invention and the active phase of which corresponds to the formula MnV2O6.< / BR>
Product 2 obtained in example 5 has a specific surface area measured by BET method, a value of 5 m2g-1. This product is called product 1 in this example.

Slowly sprayed 20 g of the product 1 in 123 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. After Takt 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then sust at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst and not relevant to the invention, consists of 13 wt. alpha MnV2O6printed on a clay balls.

Comparative experience (b). The preparation of the catalyst (b), which is not included in the scope of the invention and the active phase of which corresponds to the formula ZnV2O6.

Get the nitrate solution by dissolving zinc 148, 7mm g Zn(NO3)2.6H2O (included in the trading firm of Prolabo) 200 cm3permuteran water. Transferred to a suspension of 117 g of NH4VO3(included in the trading firm of Prolabo) 200 cm3permuteran water. Poured a solution of zinc nitrate to the suspension of metavanadate ammonium in the reactor with stirring. After stirring for 23 hours at ambient temperature filtered on fittowindow glaze and washed by 400 cm3permuteran water. The resulting product is then dried at 120aboutC for about 15 h, then made red-hot air for 5 h at 500aboutC. the thus Obtained product is sprayed 20 g of the product 1 in 123 g of inert carrier, educated clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. Once the beads are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst b, is not relevant to the invention, consists of 16 wt. ZnV2O6printed on a clay balls.

Comparative experience (s). The preparation of the catalyst (C), which is not included in the scope of the invention and the active phase of which corresponds to the formula CoV2O6.

Get active phase composition CoV2O6in the following way. Transferred to a suspension of 117 g of NH4VO3200 cm3permuteran water and prepare a solution of cobalt nitrate by dissolving 145,5 g With(No3)2.6H2O 200 cm3permuteran water. Poured a solution of nitrate of cobalt to the suspension of metavanadate ammonium in the reactor with stirring. After paramesh vannoy water 3 times 200 cm3. The resulting product is then dried at 120aboutC for about 15 h, then made red-hot air for 5 h at 500aboutC. the resulting product (1) has a specific surface area measured by BET method, a magnitude 3.6 m2g-1.

Slowly sprayed 15 g of the product 1 to 100 g of inert carrier formed clay beads with a mean diameter of 4.8 mm, which previously were placed in a rotary device for cooking beans and moistened with 10% aqueous glucose solution. Once the beads are dry on the outside, spray a small amount of glucose solution. Then again sprayed product 1 on the balls. Alternately continue these operations until the application in the form of a coating of the product 1. Then dried at 120aboutC for 2 h and calcined at 480aboutC for 6 h thus Obtained catalyst, is not relevant to the invention, consists of a 12 wt. V2O6printed on a clay balls.

General research methodology oxidation in the presence of ammonia.

A sample of catalyst is pre-recorded on the measuring stand at 150aboutWith blowing helium for 10 minutes, then it is subjected to treatment which, tanoy vapor and helium. The total pressure of the reaction mixture is 1.3 bar absolute pressure. The gas flow is set such as to have hourly space velocity (Czos) value 1000 h-1except in opposite directions.

Principle studies of the oxidation in the presence of ammonia propane.

Bring the catalyst to a temperature T1for example 300aboutWith, and after stabilization for 30 min at a temperature T1determine by the method of gas-phase chromatography, the composition of the mixture at the outlet of the reactor. Calculate the degree of conversion in percent and the selectivity obtained in the studied catalyst at input temperature T1, on the ratios of type

conversion of propane proreagirovavshego propane/ entered propane;

the selectivity for Acrylonitrile propane turned Acrylonitrile,/ unreacted propane.

Then bring the temperature of the catalyst from 300 to 550aboutWith by increments of 20 30aboutTo determine every 40 min percent conversion and selectivity.

In the examples below, the following symbols are used: TTC3H8conversion of propane, SACN selectivity for Acrylonitrile, SACN + Cis.

P R I m e R 7 comparative (d). Determine the effectiveness of catalysts a and a at different temperatures and under the following conditions: amount of catalyst (active phase + clay balls) 20 cm3total consumption is made up of a mixture of 20 l.h-1the composition of this mixture, about. WITH3H819,0 NH37,5 ABOUT210.0 N2About 25,0 Not 38,5

Results and special conditions listed in the table.1.

P R I m e R 8. comparative (e). Determine the effectiveness of catalysts a and b at a temperature of 480aboutWith and under the following General conditions: amount of catalyst (active phase + clay balls) 25 cm3total consumption is made up of a mixture of 25 l.h-1the composition of this mixture, about. WITH3H820 NH35 O215 N2About 20 Not 40.

Results and special conditions listed in the table.2.

P R I m e R 9 comparative (f). Determine the effectiveness of catalysts D and C at different temperatures and under the following General conditions: amount of catalyst (active phase + clay balls) 25 cm3total consumption is made up of a mixture of 25 l.h-1the composition of this mixture, about. WITH3H87,5 NH315,0 ABOUT215,0 H2About 20,0 Not 42,5

Results and special conditions vetsa the subject of examples 1 to 6, under different conditions with CIOs 1000 h-1.

The link to the used catalyst used, special conditions, and the results are shown in table.4.

1. How oxidative amination of alkanes in the vapor phase in the presence of a solid catalyst active phase which contains molybdenum, vanadium and oxygen, at 350 550oC at a pressure of 1 to 6 atmospheres and in the presence of an inert gas diluent, characterized in that the active phase corresponds to the empirical formula

MoaVbMcOx,

where M is one or more elements selected from manganese, zinc, cobalt;

a 0,2 0,4;

b 0,05 1,8;

c 0,4 0,9;

x 1.75 6.

2. The method according to p. 1, characterized in that alkanol is propane.

3. The method according to p. 1 or 2, characterized in that the process is conducted in the presence of water vapor.

4. The method according to one of paragraphs. 1 to 3, characterized in that the process is conducted at 415 510oC.

5. The method according to one of paragraphs. 1 to 4, characterized in that the process is conducted at a total pressure of 1.3 ATM.

6. The method according to one of paragraphs. 1 to 5, characterized in that the process is carried out at flow rate of 1000 h-1.

7. The method according to p. 1, characterized in that ispoll and water vapor.

8. The method according to PP.1 to 7, characterized in that the use of catalyst containing in addition to the active phase substrate.

 

Same patents:

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 a method of obtaining a mixture of enantiomers (mirror isomers)-cyan-3-phenoxybenzyl-3-(2,2-dichlorovinyl)-2,2 - dimethylcyclopropanecarboxylate (cypermethrin) of the formula I

Owith this ratio of isomers obtained by asymmetric transformation

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

The invention relates to a method for producing substituted aromatic NITRILES by reacting an aromatic carboxylic acid with gaseous ammonia in the presence of a dehydration catalyst

The invention relates to diphenylethylene derived

-cyano-3-phenoxybenzyl 1r, 3s - 2,2-dimethyl-3-(2 - chloropropene-1-yl)-cyclopropanecarboxylic in the form of a mixture of isomers exhibiting insect-acaricide and larvicidal activity" target="_blank">

The invention relates to new chemical product, particularly to-cyano-3-phenoxybenzyl 1R,3S-2,2-dimethyl-3(2-chlorpro - pen-1 - yl)-cyclopropanecarboxylate formula I

in the form of indivisible mixture of isomers Ia and IB in the ratio from 1:2 to 1:4

The invention relates to the technology of basic organic synthesis, more specifically to the process of hydrogenation of the nitrile of acrylic acid (EAA) in propionitrile (MO)

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

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: the scope of invention covers economically feasible methods of isolation and purification of valuable nitrogen-containing organic compounds obtained by catalytic ammoxidation of at least one original compound selected from the group consisting of propane, propylene, isobutane and isobutylene in the presence of ammonia with production of gaseous product. The methods described in invention include cooling of gas flow leaving reactor with water-containing liquid coolant; production of water solution containing relevant unsaturated mononitrile, hydrocyanic acid and other organic products; and application of integrated sequence of distillations and phase separations to isolate for recycling useful water-containing liquid and production of desired nitrogen-containing products.

EFFECT: maintenance of effective quantity to inhibit polymerisation.

30 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: mixed metal oxide catalyst based on antimonite in a catalytic active oxidation state has the empirical formula: MeaSbbXcQdReOf, where Me is at least one element from the group: Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm, or Nd; X is at least one element from the group: V, Mo, or W; Q is at least one element from the group: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, Ta, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group: Bi, B, P, or Te; and the indices a, b, c, d, e and f denote atomic ratios: a has a value from 0.1 to 15; b has a value from 1 to 100; c has a value from 0 to 20; d has a value from 0 to 20; e has a value from 0 to 10 and f is a number, taken to fulfill the valency requirements of the metals answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3 and with one or more compounds of Me, and voluntarily with one or more compounds from the groups: X, Q or R, for obtaining the first mixture (a). The first mixture is then heated and dried to form a solid product (b). After this the solid product is calcinated forming the catalyst. The particular metal oxide catalyst based on antimonite in the catalytic active oxidation state as per the invention has the empirical formula: Ua'FeaSbbMocBieOf, where the indices a, a', b, c, e and f denote atomic ratios: a has a value from 0.1 to 5; a' has a value from 0.1 to 5; b has a value from 1 to 10; c has a value from 0.001 to 0.2; e has a value from 0.001 to 0.2; and f is a number, taken to fulfill the valency requirements of Sb, U, Fe, Bi, and Mo, answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3, oxides or nitrates of bismuth and oxides or nitrates of uranium to form the first mixture (a). The first mixture is then heated under temperature and in a period of time, enough for the induction of the process for the formation of the antimonic oxide crystals and formation of the second mixture (b). An aqueous solution of a ferric compound iss then added to the second mixture for the formation of a third mixture (c). The pH of the third mixture is regulated in the range of 7 - 8.5, a precipitate of a hydrated mixture of oxides in the aqueous phase is formed (d). The precipitate is separated from the aqueous phase (e). An aqueous suspension of precipitate components of hydrated mixed oxides is obtained (f). Molybdate is added to the suspension component of hydrated mixed oxides (g). A suspension of hydrated mixed oxides of Molybdate component in the form of dy particles is formed (h). Later the calcination of the dry particles with the formation of the catalyst is carried out (i).

EFFECT: increase in the activity and selectivity of the catalyst.

30 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention concerns improved method of obtaining at least one product of partial propylene oxidation and/or ammoxidation, propylene selected out of group including propyleneoxide, acrolein, acrylic acid and acrylnitryl, where source substance is propane. Method involves a) at the first stage, homogeneous and/or heterogeneous catalysed dehydration and/or oxydehydration of raw propane in the presence and/or in the absence of oxygen, to obtain gas mix containing propane and propylene; and b) if required, separation of part gas mix 1 obtained at the first stage and its components other than propane and propylene, such as hydrogen, carbon monoxide, or transformation of this part in the other compounds, such as water, carbon dioxide, so that gas mix 1' containing propane and propylene and compounds other than oxygen, propane and propylene is obtained from gas mix 1; and at least one more stage c) heterogeneous catalysed ammoxidation and/or partial gas phase ammoxidation of propylene containing in gas mix 1 and/or gas mix 1' in gas mix 1 or gas mix 1' containing molecular oxygen of gas mix 2, where total C4-hydrocarbon content in gas mix 2 is < 3 volume %.

EFFECT: reduced process performance due to reduced output of target product and enhanced selectivity of carbon oxide generation at the second process stage.

50 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: described is mass of metal oxides, intended as catalyst for heterogeneously-catalysed partial oxidation and/or ammoxidation of at least one saturated and/or unsaturated hydrocarbon, of general stechiometry I MO1VaM1bM2cM3dOn (I), were M1= stands for Te; M2=stands for Nb; M3= stands for at least one of elements from group, which includes Pb, Ni, Co, Bi and Pd; a = 0.05 to 0.6, b= 0.01 to 0.5, c= 0.01 to 0.5, d = 0.0005 to 0.5 and n= equals the number determined by valence and number of different from oxygen elements in (I), whose X-ray diffractogragm has diffraction reflexes h, i and k , whose peaks are at diffraction angles (2Θ) 22.2±0.5° (h), 27.3±0.5° (i) and 28.2±0.5° (k), and - diffraction reflex h in the range of X-ray diffractogram is the most intensive and has peak half-width maximal value 0.5°, intensity Pi of diffraction reflex i and intensity Pk fulfill ratio 0.65≤R≤0.85, in which R is determined by formula R=Pi/(Pi+Pk) intensity ratio, and - half-width of diffraction reflex i and diffraction reflex k each constitute ≤1°, and at least one mass of metal oxides (I) represents such, X-ray diffractogram of which does not have diffraction reflex with peak position 2Θ=50.0±0.3°. Described is mass of metal oxides, which contains equal or more than 80 wt % of at least one mass of metal oxides, indicated above, and whose X-ray diffractogram has diffraction reflex with peak 2Θ=50.0±0.3°.Also described are methods of heterogeneously catalysed partial gas phase oxidation or ammoxidation of at least one saturated or unsaturated hydrocarbon, using as catalytic active mass at least one mass of metal oxides, described above. Described is method of obtaining metal oxides mass by mixing sources of its elementary components, calcination of dry mixture at 350-700°C and washing by organic and/or inorganic acid solution.

EFFECT: increasing target product selectivity.

17 cl, 1 tbl, 16 ex, 17 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to mixed metal oxide oxidation catalysts and ammonolysis of propane and isobutane, methods of obtaining them and usage. Described is a mixed metal-oxide system, containing molybdenum, vanadium, niobium, antimony, germanium and oxygen or molybdenum, vanadium, tantalum, antimony, germanium and oxygen, with the following stoichiometric ratios of elements: molybdenum to antimony from 1:0.1 to approximately 1:0.5, and molybdenum to germanium from 1:>0.2 to approximately 1:1. Description is given of a catalyst, which is a mixed metal-oxide system, effective in vapour-phase conversion of propane to acrylic acid or acrylonitrile or conversion of isobutane to methacrylic acid or methacrylonitrile. The mixed metal-oxide system has an empirical formula Mo1VaNbbSbcGedOx or Mo1VaTabSbcGedOx, in which a ranges between 0.1 and 0.6, b ranges between 0.02 and 0.12, c ranges between 0.1 and 0.5, d ranges from more than 0.2 to 1, and x depends on the oxidation number of other elements in the mixed metal-oxide system. Described also is a method of obtaining the system described above, involving the following stages: addition into a reaction vessel of precursors Mo, V, Nb or Ta, Ge and Sb in an aqueous solvent to form a reaction medium with initial pH 4 or less, and optional addition of another aqueous solvent into the reaction vessel; sealing the reaction vessel; reaction of the reaction mixture at temperature above 100°C and pressure above atmospheric pressure for a period of time, sufficient for formation of a mixed metal-oxide system; optional cooling of the reaction mixture; and extraction of the mixed metal-oxide system from the reaction mixture. Description is given of a method of converting propane into acrylonitrile and isobutane into methacrylonitrile using the catalyst described above.

EFFECT: simple technology of making catalyst, increased catalyst activity and output of the target product in reactions of oxidative ammonolysis of propane and isobutane.

27 cl, 8 tbl, 50 ex, 1 dwg

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 hydrocarbon oxidation catalysts. Described is a catalyst for oxidising hydrocarbons during gas-phase contact, containing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb), having chemical formula 1: Mo1.0VaTebNbcon, (l) where a, b or c independently denotes atomic molar ratios of vanadium, tellurium or niobium, provided that 0.01≤a≤1, 0.01≤b≤1, 0.01≤c≤1 and n denotes the atomic molar ratio of oxygen, which is determined by valence and atomic molar ratios of vanadium, tellurium and niobium, and tungsten (W) or tungsten oxide bonded to the mixed metal oxide, where the atomic molar ratio of tungsten bonded to the mixed metal oxide and molybdenum contained in the mixed metal oxide ranges from 0.00001:1 to 0.02:1. Described is a method of producing said catalyst involving steps for: preparing a first mixture of molybdenum (Mo) precursor, a vanadium (V) precursor, a tellurium precursor (Te), a niobium precursor (Nb) and acid; obtaining a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb) by calcining the first mixture; preparing a second mixture of mixed metal oxide and the tungsten precursor and calcining the second mixture. Described is a method for gas-phase oxidation of hydrocarbons, involving oxidation of hydrocarbons in the presence of the catalyst described above.

EFFECT: high activity and selectivity of the catalyst.

10 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for oxidising hydrocarbons during gas-phase contact, containing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb), having chemical formula 1: Mo10VaTebNbcOn, (1) where a, b or c independently denotes atomic molar ratios of vanadium, tellurium or niobium, provided that 0.01≤a≤1, 0.01≤b≤1, 0.01≤c≤1 and n denotes the atomic molar ratio of oxygen, which is determined by valence and atomic molar ratios of vanadium, tellurium and niobium, and palladium (Pd) or palladium oxide bonded to the mixed metal oxide, where the atomic molar ratio of palladium bonded to the mixed metal oxide and molybdenum contained in the mixed metal oxide ranges from 0.00001:1 to 0.02:1. Described is a method of producing said catalyst, comprising steps for: preparing a first mixture of a molybdenum (Mo) precursor, a vanadium (V) precursor, a tellurium precursor (Te), a niobium precursor (Nb) and an acid; preparing a mixed oxide of molybdenum (Mo), vanadium (V), tellurium (Te) and niobium (Nb) by calcining the first mixture; preparing a second mixture of mixed metal oxide and a palladium precursor and calcining the second mixture. Described is a method for gas-phase oxidation of hydrocarbons, involving oxidation of hydrocarbons in the presence of the catalyst described above.

EFFECT: high activity and selectivity of the catalyst.

10 cl, 2 tbl, 12 cl

Up!