Catalytic composition for dehydration of alkylaromatic hydrocarbons (options), method of preparing the same (options), and a process of dehydration of alkylaromatic hydrocarbons

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention provides catalytic composition for dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprising: carrier consisting of alumina in δ phase or in θ phase, or in mixed δ+θ or θ+α, or δ+θ+α phase, modified with silicon oxide and having surface area less than 150 m2/g as measured by BET method; 0.1-35% gallium in the form of Ca2O3; 0.01-5% manganese in the form of Mn2O3; 0-100 ppm platinum; and 0.05-4% alkali or alkali-earth metal oxide, all percentages being based on the total weight of composition. Other variants of composition are also covered by invention. Methods of preparing such catalytic composition (options) envisage use of alumina-based carrier in the form of particles corresponding to group A of the Geldart Classification. Process of dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprises: (i) dehydration of hydrocarbon stream optionally mixed with inert gas in fluidized-bed reactor in presence of catalytic composition consisted of alumina-supported and silica-modified gallium and manganese at temperature within a range of 400 to 700°C, total pressure within a range of 0.1 to 3 atmospheres, and gas hourly space velocity from 50 to 10000 h-1; and (ii) regeneration and heating of catalyst caused by catalytic oxidation of fuel in fluidized-bed reactor at temperature above 400°C.

EFFECT: increased activity of catalytic composition and prolonged lifetime thereof.

22 cl, 2 tbl, 16 ex

 

The present invention relates to a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons.

More specifically, the present invention relates to a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly in the presence of an inert hydrocarbon diluent.

More specifically, the present invention relates to a catalytic composition for the dehydrogenation of ethylbenzene, possibly diluted with an inert product or ethane.

How dehydrogenation of alkylaromatic hydrocarbons is known. For example, in U.S. patent 6031143 described method for the simultaneous dehydrogenation of ethylbenzene and ethane in the presence of a catalytic system consisting of an inorganic carrier such as alumina, impregnated with various metals for the activation of chemical reactions taking place during the implementation of this method.

In the European patent 885654 and international patent application PCT 00/09196 offered other examples of ways dehydrogenation of alkylaromatic hydrocarbons.

Described in these documents, the dehydrogenation of alkylaromatic hydrocarbons, in particular of ethylbenzene to styrene is carried out in the installation, consisting of a system of the reactor/regenerator, both work in the conditions of the fluidized bed. In the system tacos what about the type of installation for dehydrogenation includes a first dehydrogenation reactor in the fluidized bed and the second reactor for regeneration containing coke catalyst. Last continuously extracted from the bottom of the first reactor and sent to the upper part of the second reactor, where the specified Cox support in a fluidized state by means of a mixture of fuel gas, for example methane, and heated air. Thus, the solid is slowly settling in countercurrent to the gas stream, which rises, and during this slow deposition of the catalyst recovered as burn carbonaceous residues. Transporting catalyst from one reactor to another exercise using a carrier gas, such as air or nitrogen.

Optimal temperature conditions in the regenerator is in the range from 500 to 700°With; they are supported by a catalytic oxidation of the fuel gas (such as methane). Thus, the catalytic system includes metals, active in the dehydrogenation reaction, such as gallium or chromium, in combination with the alkaline metal such as potassium, and in the reaction of catalytic oxidation of methane, such as platinum.

As is often the case in heterogeneous catalytic systems containing multiple active ingredients, reduced activity of the individual components may differ several times. In the case of dehydrogenation, while the system is running the reactor/regenerator, catalyst AK is Yunosti platinum is significantly lower catalytic activity of other metals, such as gallium or chrome. It has a certain effect on the economy of the ways dehydrogenation, because replacing the platinum catalyst involves the replacement and all other still active metal catalysts, since they are all printed on the same media.

To date, the applicant found that the impregnation of the inorganic carrier, such as is known in the present technical field, one of only manganese or in combination with platinum together with other dehydrogenation catalysts receive the catalyst, not only active in the catalytic oxidation of methane, but also has validity comparable with validity of other metal catalysts active in the catalytic dehydrogenation.

Thus, the present invention is a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, in the system of the reactor/regenerator, including:

a) a carrier consisting of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g determined using the method of the BET (BET);

b) 0.1 to 35 wt%. gallium represented as Ga2About3;

C) 0.01 to 5 wt%. manganese, presented in the form of Mn2About3;

g) 0-00 masses. parts per million of platinum;

d) 0.05 to 4% of the mass. oxide of an alkaline or alkaline earth metal; and the percentages specified in terms of the total weight of the composition.

In accordance with the preferred implementation of the present invention is a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, in the system of the reactor/regenerator includes:

a) a carrier consisting of alumina in Delta-phase or theta phase or in a mixed Delta + theta, theta + alpha or Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g defined by way BET;

b) 0.2 to 3.8% of the mass. Ga2O3;

in) 0,15-1,5% of the mass. manganese, presented in the form of Mn2About3;

g) 5-90 wt. parts per million of platinum;

d) 0.1 to 3 wt%. oxide of an alkaline or alkaline-earth metal;

moreover, the percentages specified in terms of the total weight of the composition.

The method of preparation described above, the catalytic system can essentially be carried out using the following operations:

- preparation of one or more solution components that must be applied to media;

- dispersion solution on a carrier of alumina-modified silica;

- the loops impregnated carrier; and

- calcining the dried carrier at a temperature in the range from 500 to 900°C;

- you can repeat the previous operations once or twice.

In the preparation of catalysts, which are the subject of the present invention, the carrier of the modified alumina is in the form of particles belonging to the group And Geldart classification (D.Geldart, Gas Fluidization Technology, ed. by D.Geldart, John Wiley & Sons, New York, 1986).

The dispersion of the catalyst components on the carrier can be carried out using traditional techniques, such as impregnation, ion exchange, "steam precipitation or surface adsorption. Preferably use the methods of impregnation with an initial moisture content.

Also unexpectedly found that the catalyst which is the subject of the present invention, effective and mechanical mixtures of components corresponding active metals supported on a carrier. Thus, the present invention is a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, in the system of the reactor/regenerator comprising a mechanical mixture of:

i) 70-99,5 wt. -%, preferably from 80 to 95%, the first active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha is AZE, the modified silicon oxide and having a surface area less than 150 m2/g determined using the method BET, gallium, presented in the form of Ga2About3and oxide of an alkaline or alkaline earth metal supported on a carrier of alumina, in amounts from 0.1 to 35 wt%. and from 0.05 to 4 wt%. accordingly, calculated on the total weight of the composition;

ii) 0.5 to 30 wt. -%, preferably from 5 to 20%, the second active phase essentially consisting of a solid carrier based on alumina in Delta-phase, or theta phase or in a mixed Delta + theta, theta + alpha or Delta + theta + alpha phase, modified silicon oxide and having a surface area defined by way BET, less than 150 m2/g, modified manganese, presented in the form of Mn2O3, platinum and oxides of alkali or alkaline earth metal supported on a carrier of alumina, in amounts from 0.1 to 10 wt%, from 0 to 1000 mass. parts per million, and from 0.025 to 3,95% of the mass. accordingly, calculated on the total weight of the composition.

The preferred catalytic mechanical mixture is a mixture in which the amount of gallium is in the range from 0.2 to 3.8 wt. -%, the amount of manganese is in the range from 0.15 to 1.5 wt. -%, the amount of platinum is in the range from 5 to 50 mass. parts per Milli is h, and the total number of alkaline oxide or alkaline earth metal is in the range from 0.1 to 3% of the mass.

In addition, the present invention is a catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, in the system of the reactor/regenerator comprising a mechanical mixture of:

i) 70-99,5 wt. -%, preferably from 80 to 95%, the first active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area defined by way BET, less than 150 m2/g, gallium, presented in the form of Ga2O3and oxide of an alkaline or alkaline earth metal supported on a carrier of alumina, in amounts from 0.1 to 35 wt%. and from 0.025 to 2% of the mass. accordingly, calculated on the total weight of the composition;

ii) 0-30 wt. -%, preferably from 5 to 20%, the second active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area defined by way BET, less than 150 m2/g of manganese, presented in the form of Mn2O3and oxide of an alkaline or alkaline earth metal supported on a carrier oxide is of luminia, in quantities of from 0.1 to 10 wt%. and from 0.025 to 3,95% of the mass. accordingly, calculated on the total weight of the composition;

(iii) 0-30 wt. -%, preferably from 5 to 20%, the third active phase essentially consisting of a solid carrier based on alumina in Delta-phase, or theta phase or in a mixed Delta + theta, theta + alpha or Delta + theta + alpha phase, modified silicon oxide and having a surface area defined by way BET, less than 150 m2/g of platinum and an oxide of an alkaline or alkaline earth metal supported on a carrier of alumina, in amounts from 0 to 1000 mass. parts per million, and from 0.025 to 3,95% of the mass. accordingly, calculated on the total weight of the composition.

In this second catalytic mechanical mixture, the amount of gallium may be in the range from 0.2 to 3.8 wt. -%, the amount of manganese may be in the range from 0.15 to 1.5 wt. -%, the amount of platinum may be in the range from 5 to 50 mass. parts per million, and the total number of alkaline oxide or alkaline earth metal may be in the range from 0.1 to 3% of the mass.

In the catalytic composition which is the subject of the present invention, regardless of whether it is from a single carrier, impregnated with active metals, or from a variety of media, impregnated separately and then the mechanical the ski mixed, media aluminum oxide modified 0.08 to 5% of the mass. silicon oxide and the preferred alkali or alkaline earth metal is potassium or magnesium.

Also if the catalytic composition consists of a mechanical mixture of media, impregnated separately active metals, the aluminum oxide used in the form of particles belonging to the group a classification Geldart (Gas Fluidization Technology, D.Geldart, John Wiley & Sons).

Catalytic system, which is the subject of the present invention, in the form of a single active phase or mechanical mixtures of different active phases can be used in the method for catalytic dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, in the system of the reactor/regenerator, including:

A) dehydrogenating the flow of hydrocarbons, possibly mixed with an inert gas in the fluidized bed reactor in the presence of catalytic compositions prepared in accordance with any of claims at a temperature in the range from 400 to 650°Since, when the total pressure in the range from 0.1 to 3 ATA (0.01 to 3 MPa) and at a flow rate of gas per hour (GHSV)in the range from 50 to 10000 normal liters/hour·lcat.; and

B) regeneration and heating of the catalyst by means of catalytic combustion in the regenerator pseudowire the aqueous layer at temperatures exceeding 500°C.

Preferred alkylaromatic hydrocarbon is usually ethylbenzene.

As the inert gas can be nitrogen, methane, hydrogen, carbon dioxide and noble gases, preferably nitrogen and methane, with a volumetric ratio of inert gas/flux of hydrocarbons in the range from 1 to 10, preferably from 2 to 6.

In the system of the reactor/regenerator the catalyst in the fluidized state, is continuously circulated between the two devices, which allows the method continuously.

The heat required for dehydrogenation, comes with regenerated catalyst enters the reactor at a temperature higher than the reaction temperature. The catalyst support in the reactor in a fluidized state by means of a mixture of reagents, including, possibly, the inert gas.

The reacted gas after passing system cyclone or other separation system for powdered substances leaves the reactor through its upper part. Then the gas can be directed into the heat exchanger to heat the feed material, and then in section separation, in which the dehydrogenation products separated from unreacted boot material to be applied in recycling. The reaction by-products can be used as fuel and the Aza in the regenerator.

In the dehydrogenation reactor, the catalyst in the fluidized state is moving in countercurrent with respect to the gas phase. He arrives in the upper part of the reactor and out of the lower part of the reactor, passing under the action of gravity in the desorption zone, so that the desorbed gas with a changed ratio of components (shifted) was again admitted to the reactor, thus avoiding the loss of reactants or products.

In the reactor fluidized bed reaction dehydrogenation operation (a) is carried out at a temperature in the range from 450 to 650°C, at atmospheric pressure or a pressure slightly above atmospheric, at flow rate of gas per hour (GHSV) in the range from 100 to 1000 normal liters/hour·lcat.preferably from 150 to 400 N./h·lcat.and when the residence time of the catalyst in the reactor in the range from 5 to 30 minutes, preferably from 10 to 15 minutes.

Within the dehydrogenation reactor may be placed horizontally appropriate internal device capable of preventing re-mixing of gas and catalyst, such as lattice or cylindrical rods, so that the flow of the gas inside the reactor was nearing pressure. The use of such internal devices allows for maximum conversion and selectivity to hydrocarbons.

The catalyst is p which enters the regenerator under the action of gravity or pneumatic conveying system, consisting of:

- conveying line, in which there is at least one area where the catalyst moves downward, it is possible, simultaneously with the filing of a gas (nitrogen or methane); and

- plot, where the catalyst flows upward through the introduction of gas until then, until it reaches the layer of the regenerator.

Regeneration of the catalyst is carried out by burning the carbonaceous residue with air or oxygen, while heating the catalyst to a temperature exceeding the maximum temperature of the reaction, carried out using a catalytic combustion with methane, fuel gas or by-products of the dehydrogenation reaction.

In the regenerator the gas movement and solid substances also occurs in the counter. Air, oxygen or diluted with nitrogen, the air supplied to the catalytic layer, while the fuel gas is fed to the other levels throughout the layer.

The gas leaving the regenerator, essentially consisting of nitrogen and combustion products passes through the cyclone system or another system, located in the upper part of the apparatus, for separating the captured powder.

Regeneration of the catalyst during the operation (C) is carried out at a higher temperature than the temperature of the dehydrogenation, at atmospheric pressure or pressure, nemn the th above atmospheric, when the flow rate of gas per hour (GHSV)in the range from 100 to 1000 norms. l/h·lcat.and when the residence time of the catalyst in the reactor in the range from 5 to 120 minutes. In particular, the regeneration temperature is in the range from 500 to 700°S, and the residence time of particles in the apparatus is in the range from 20 to 40 minutes.

The regenerated and heated catalyst is transported into the reactor by means of a pneumatic system similar to the system described for the transport from the reactor to the regenerator.

The method of dehydrogenation, which is the subject of the present invention is particularly suitable for the simultaneous dehydrogenation of ethane and ethylbenzene. In this case, when the operation of the dehydrogenation of (A) a mixture of ethylbenzene and ethane is sent to the reactor, conducting simultaneous dehydration with the formation of styrene and ethylene. Styrene is then separated and the ethylene together with a stream of benzene enters the setting for alkylation to obtain ethylbenzene.

For a better understanding of the present invention and its implementation are given below some explanatory but not limiting examples.

Tests on catalytic combustion in the following examples were performed in a quartz fluidized bed reactor with porous walls (membranes), also made of quartz heated by an external electrical resistance.

Fuel (methane) and the substance that supports combustion (air)supplied from two different distributors received in the catalytic layer in its lower part, so that they did not engage in any contact before reach the catalytic layer. The overall composition of the load at 3% vol. consisted of methane, and the rest was air.

The exhaust from the reactor gas cooled to room temperature and condensed water separated from the gas component, which was collected in a multilayer bag for sampling.

Finally, the contents of the bag were analyzed using gas chromatography to determine the content of CO, CO2CH4About2and N2.

Finally, the degree of conversion of methane was calculated as follows:

Conv. CH4= 1-(% CH4/(% CH4+ %+% CO2)),

where % CH4= methane concentration (% vol.) in the selected sample;

% = Concentration of carbon monoxide (% vol.) in the selected sample;

% CO2= concentration of carbon dioxide (% vol.) in the selected sample.

Tests on catalytic dehydrogenation was carried out in the equipment and techniques similar to the equipment and techniques described in the European patent 905112.

EXAMPLE 1 (comparative) - inactivated media

Resulting pseudoboehmite with the addition of silicon oxide (1,% mass.) with particle diameters, in the range from 5 to 300 μm, was prepared using a spray drying Hydrosol of alumina and silica trademark Ludox.

Sample pseudoboehmite was progulivali in the stream of air saturated with steam at 450°C for 1 hour and then at 1140°C for 4 hours. The resulting product had a specific surface area of 74 m2/g, porosity of 0.23 ml/g and consisted of the Delta-, theta - and alpha-modifications of aluminum oxide.

An aliquot of this material was investigated in the test for catalytic combustion. The results are listed in table 1, from which it can be understood that the catalytic activity of the sample is unsatisfactory.

EXAMPLE 2 (comparative) catalyst made on the basis of a single gallium without promoters

150 g microspherical alumina, prepared as described in example 1 was impregnated using methods initial humidity of 35 ml of an aqueous solution containing 24.5 g of a solution of Ga(NO3)3(10,71% of the mass. Ga) and 14.3 g of the solution KNO3(6,445% of the mass. K); the remaining part was deionized water.

The impregnated product was kept for 4 hours at room temperature, and then dried at 120°C for 24 hours. The dried product was then progulivali in a stream of dry air at 750°C and kept at this temperature for 4 hours.

Bulk composition of the catalyst was trace the criterion: 2.3% of CA 2O3at 0.7% K2O, 1.6% of SiO2; the remainder to 100% was Al2About3.

The catalytic action of the catalytic combustion of methane was investigated, as described above, are shown in table 1, from which it can be understood that the addition of gallium to the media improves the catalytic activity of the sample with catalytic combustion.

EXAMPLE 2B

The catalyst of example 2 after exposure during the week in the cycles of dehydrogenation was again tested in the catalytic combustion of methane in the above-described operating conditions.

From the results shown in table 1, it is seen that the catalytic activity is reduced to a very small value.

EXAMPLE 3A - catalyst, made on the basis of gallium activated platinum

150 g microspherical alumina, prepared as described in example 1 was impregnated using methods initial humidity of 35 ml of an aqueous solution containing 24.5 g of a solution of Ga(NO3)3(10,71% of the mass. Ga), 14.3 g of a solution KNO3(6,445% of the mass. K) and 1.07 g of a solution of Pt(NO3)2when the Pt content of 1.45%; the remaining part was deionized water.

The impregnated product was dried and progulivali, as described in the previous example.

Bulk composition of the catalyst was as follows: 2,3% Ga2About3, 0.7%2About 100 parts per million Pt, 1.6% Of SiO2; the remainder to 100% of the part with what was Al 2O3.

The catalytic action of the catalytic combustion of methane was investigated, as described above, are shown in table 1.

You can see that the presence of platinum substantially improves the catalytic characteristics of the sample.

EXAMPLE 3B

The same formulation as in example 3A, after tests on catalytic combustion was tested in the reaction of dehydrogenation stream of ethylbenzene and ethane with obtaining styrene and ethylene. Table 2 shows the values of the catalytic characteristics.

EXAMPLE 3C

The catalyst of example 3B after endurance in cycles of dehydrogenation during the week was again tested in the catalytic combustion of methane in the above-described operating conditions.

From the results shown in table 1, we can see that over time the platinum component loses its ability to activate the burning.

EXAMPLE 4A (manganese)

150 g microspherical alumina, prepared as described in example 1 was impregnated as described above, using a solution containing 24.5 g of a solution of CA(NO3)3(10,71% of the mass. Ga), 14.3 g of a solution KNO3(6,445% of the mass. K) and 1.61 g of a solution of Mn(NO3)3when the content of Mn accounted for 14.45%; the remaining part was deionized water.

The impregnated product was dried and progulivali, as described in the previous example.

The mass composition of catalysis of the ora was as follows: 2.3% of CA 2O3, 0.7%2O, 0.2% of Mn (Mn2O3), 1.6% of SiO2; the remainder to 100% was Al2About3.

Catalytic performance in catalytic combustion of methane was investigated, as described above, are shown in table 1. The results show that manganese, and platinum, acts as an activator (promoter) burning.

EXAMPLE 4B

The same formulation as in example 4A, after tests on catalytic combustion was tested in the reaction of dehydrogenation stream of ethylbenzene and ethane with obtaining styrene and ethylene. Table 2 shows the values of the catalytic characteristics.

EXAMPLE 4C

The catalyst of example 4B after endurance in cycles of dehydrogenation during the week was again tested in the catalytic combustion of methane in the above-described working conditions as in example 4.

From the results shown in table 1, shows that the manganese component as a promoter of combustion has higher resistance over time.

EXAMPLE 5 (manganese and platinum)

150 g microspherical alumina, prepared as described in example 1 was impregnated with a solution consisting of 24,09 g of a solution of CA(NO3)3(10.93% per mass. Ga), 14.4 g of a solution KNO3(6,445% of the mass. K)5,33 g of a solution of Mn(NO3)3when the content of Mn 4,37% and 1.07 g of a solution of Pt(NO3)2when the Pt content of 1.45%.

robotany product was dried and progulivali, as described in the previous example.

Bulk composition of the catalyst was as follows: 2,3% Ga2O3, 0.7%2O, 100 ppm Pt, 0.2% Of Mn (Mn2About3), 1.6% of SiO2; the remainder to 100% was Al2O3.

The formulation was tested in the reaction of catalytic combustion and got the results shown in table 1. The results show that a combination of manganese/platinum also active during catalytic combustion.

EXAMPLE 6 (composite mix)

100 g microspherical alumina, prepared as described in example 1 was soaked for 24 CC of an aqueous solution containing 10 and 11 g of the solution KNO3(6,445% of the mass. K) and 25,57 g Mn(NO3)3·4H2O. the Impregnated product is then processed as described in example 2.

Bulk composition of the catalyst was as follows: 0.8%2O, and 7.8% Mn (Mn2O3), 1.5% of SiO2; the remainder to 100% was Al2About3.

3.5 g of this formulation was added to 122 g of the formulation of example 2. The obtained composite mixture had a composition similar to the composition of example 4, i.e. by 2.2% CA2About3, 0.2% of Mn (Mn2O3), 0,72% Off2O; the remaining part was the media.

This mixture was tested in the catalytic combustion of methane, and the results are listed in table 1.

The results show that the addition of manganese in the form with the local impregnated product, and composition of the mixture improves the catalytic combustion.

EXAMPLE 7 (comparative) sample with a high content of platinum

150 g microspherical alumina, prepared as described in example 1 was impregnated PfP using a solution consisting of 24,09 g of the solution Ga(NO3)3(10.93% per mass. Ga), 14.3 g of a solution KNO3(6,445% of the mass. K), 10.7 g of a solution of Pt(NO3)2when the Pt content of 1.45% and 1.6 g of a solution of Mn(NO3)3when the content of Mn accounted for 14.45%.

The impregnated product was dried and progulivali, as described in the previous example.

Bulk composition of the catalyst was as follows: 2,3% Ga2O3, 0.7%2O, 1000 ppm Pt, 0.2% Of Mn (Mn2About3), 1.6% of SiO2; the remainder to 100% was Al2O3.

The formulation was tested in the reaction of dehydrogenation of a mixture of benzene/ethane and got the results shown in table 2. The results show that the high content of platinum, on the one hand, more promotiom catalytic combustion, but, on the other hand, reduces the characteristics of the catalyst during the dehydrogenation.

EXAMPLE 8 (test at varying composition)

150 g microspherical alumina, prepared as described in example 1 was impregnated as described above, a solution consisting of 10,228 g CA(NO3)3·N2O (25.8% of the mass. Ga), from 2.445 g KNO3 , 2,123 g Mn(NO3)3·4H2O 0,031 g Pt(NBO3)2(NH3)4the remainder was deionized water.

The impregnated product was dried and progulivali, as described in the previous example.

Bulk composition of the catalyst was as follows: 2,3% Ga2O3at 0.7% K2O, 70 parts per million Pt, 0.4% Of Mn (Mn2O3), 1.6% of SiO2; the remainder to 100% was Al2About3.

The formulation was tested in the reaction of catalytic combustion and got the results shown in table 1. The results show that high concentrations of manganese improves the catalytic properties of the sample during catalytic combustion.

EXAMPLE 8B

The same formulation as in example 8A, was tested in the reaction of dehydrogenation of ethylbenzene in the presence of ethane. The results are shown in table 2.

EXAMPLE 8C

The same formulation as in example 8A, was tested in the reaction of dehydrogenation of ethylbenzene in the presence of nitrogen. The results are shown in table 2.

EXAMPLE 8D

The same formulation as in example 8A, after the total duration of the test in the dehydrogenation reaction over 450 hours again tested in the reaction of catalytic combustion of methane under the same operating conditions as in example 8A. The results, listed in table 1, confirm the stability of the formulation during some of the CSOs period of time.

TABLE 1
ExampleThe reaction temperature (°)The volumetric rate of gas per hour (GHSV) (norm. liters/cat/l/h)
200400600
162069,748,539,7
64084,561,850,9
650and 88.897,357,0
2A62091,976,065,6
64095,884,274,8
65097,987,979,7
2B62090,873,462,7
64095,483,674,0
65097,297,278,7
FOR640the 98.991,781,5
67099,997,590,4
LC 62091,271,959,3
64095,784,373,9
65097,2of 87.377,9
4A62098,587,178,4
64099,392,585,5
65099,594,688,9
4C62097,483,172,9
64099,290,482,7
65099,093,586,6
67099,9
562098,790,281,9
65099,797,2of 92.7
662093,680,370,0
64097,988,081,3
65099,091,784,7
8 is 60097,6of 89.190,8
62099,495,6
8D600of 97.889,281,5
62099,794,890,1
65099,0

TABLE 2
Etc.Download (% vol.)Press. (ATA)T reaction (°)The volumetric rate of gas /h (N. l/cat/h)The residence time in the stream (h)The degree of Pribram. (%)Select. the styrene (M%)
DLN2C2H6DLC2H6
3B15-851,0259050011045,57,2to 91.1
4B15-851,02 59040011949,16,992,6
720-801,025904002239,54,193,3
715-851,025904004541,14,393,5
8B15-851,025904005348,56,888,3
8S1585-1,0259040022253,8-90,6

1. Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, including

a) a carrier consisting of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g defined by way BET;

b) 0.1 to 35 wt.% gallium represented as Ga2O3;

C) 0.01 to 5 wt.% manganese, presented in the form of Mn2About3;

g) 0-100 the speakers. hours per million of platinum;

d) 0.05 to 4% wt.% oxide of an alkaline or alkaline-earth metal,

moreover, the magnitude of percentage are based on the total weight of the composition.

2. The catalytic composition according to claim 1, including

a) a carrier consisting of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g defined by way BET;

b) 0.2 to 3.8 wt.% Ga2About3;

in) of 0.15-1.5 wt.% manganese, presented in the form of Mn2About3;

g) 5-90 wt. hours per million of platinum;

d) 0.1 to 3 wt.% oxide of an alkaline or alkaline-earth metal,

moreover, the magnitude of percentage are based on the total weight of the composition.

3. Catalyticthe composition offordehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, comprising a mechanical mixture

i) 70-99,5 wt.%, preferably from 80 to 95%, the first active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g determined using the method BET, gallium, presented in the form of Ga2About3and oxide of alkaline or Melo rosemaling metal, deposited on alumina, in amounts from 0.1 to 35 wt.% and from 0.05 to 4 wt.%, respectively;

ii) 0.5 to 30 wt.%, preferably, from 5 to 20%, the second active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g determined using the method BET, modified manganese, presented in the form of Mn2O3, platinum and oxides of alkali or alkaline earth metal supported on alumina, in amounts from 0.1 to 10 wt.%, from 0 to 1000 wt. h-a-million, and from 0.025 to 3,95 wt.%, respectively.

4. The catalytic composition according to claim 3, in which the amount of gallium is in the range from 0.2 to 3.8 wt.%, the amount of manganese is in the range from 0.15 to 1.5 wt.%, the amount of platinum is in the range from 5 to 50 wt. h-a-million, and the total number of alkaline oxide or alkaline earth metal is in the range from 0.1 to 3 wt.%.

5. Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, comprising a mechanical mixture

i) 70-99,5 wt.%, preferably from 80 to 95%, the first active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase,modified silicon oxide and having a surface area less than 150 m 2/g determined using the method BET, gallium, presented in the form of Ga2About3and oxide of an alkaline or alkaline earth metal supported on alumina, in amounts from 0.1 to 35 wt.% and from 0.025 to 2 wt.%, respectively;

ii) 0-30 wt.%, preferably from 5 to 20%, the second active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g determined using the method BET, manganese, presented in the form of Mn2About3and oxide of an alkaline or alkaline earth metal supported on alumina, in amounts from 0.1 to 10 wt.%, and from 0.025 to 3,95 wt.%, respectively;

(iii) 0-30 wt.%, preferably from 5 to 20%, the third active phase essentially consisting of a solid carrier on the basis of aluminum oxide in a mixed Delta + theta + alpha phase, modified silicon oxide and having a surface area less than 150 m2/g determined using the method BET, platinum and oxides of alkali or alkaline earth metal supported on alumina, in amounts of from 5 to 1000 wt. hours per million and from 0.025 to 3,95 wt.%, respectively.

6. The catalytic composition according to claim 5, in which the amount of gallium may be in the range from 0.2 to 3.8 m is from.%, the amount of manganese may be in the range from 0.15 to 1.5 wt.%, the amount of platinum in the range from 5 to 50 wt. h-a-million, and the total number of alkaline oxide or alkaline earth metal is in the range from 0.1 to 3 wt.%.

7. The catalytic composition according to any one of items 1 to 6, in which the carrier is alumina modified 0.08 to 5 wt.% silicon oxide.

8. The catalytic composition according to any one of claims 1 to 6, in which the alkali or alkaline earth metal is potassium or magnesium.

9. The method of preparation of the catalytic compositions according to claim 1 or 2, which includes

the preparation of one or more solution components that must be applied to media;

the dispersion solution on a carrier of alumina-modified silica;

drying the impregnated carrier, and

calcining the dried carrier at a temperature in the range from 500 to 900°C;

perhaps the repetition of previous operations once or twice.

10. The method according to claim 9, in which the carrier of the modified alumina is in the form of particles corresponding to the group classification of Geldart.

11. The method of preparation of the catalytic composition according to any one of p-6, including the mixing of these active phases of the composition, wherein said solid n is Khabibullina on the basis of aluminum oxide is in the form of particles, the relevant group And classification Geldart.

12. Method for catalytic dehydrogenation of alkylaromatic hydrocarbons, possibly mixed with ethane, which includes

A) dehydrogenating the flow of hydrocarbons, possibly mixed with an inert gas in the fluidized bed reactor in the presence of a catalytic composition according to any of the preceding paragraphs, at a temperature in the range from 400 to 650°when the total pressure in the range from 0.1 to 3 ATA (0.01 to 0.3 MPa) and at a flow rate of gas per hour (GHSV)in the range from 50 to 10000 normal liters/h·lcat.and

C) regeneration and heating of the catalyst by means of catalytic combustion in the regenerator fluidized bed at a temperature exceeding 500°C.

13. The method according to item 12, in which the alkylaromatic hydrocarbon is ethylbenzene.

14. The method according to item 12 or 13, in which the inert gas is selected from nitrogen, methane, hydrogen, carbon dioxide and noble gases.

15. The method according to 14, in which the inert gas is selected from nitrogen and methane.

16. The method according to item 12, in which the volumetric ratio of inert gas/the flow of hydrocarbons is in the range from 1 to 10.

17. The method according to clause 16, in which the aforementioned ratio is in the range from 2 to 6.

18. The method according to item 12, in which the reaction of dehydrogenation operations (A) syshestvyut at a temperature of from 450 to 650° C, at atmospheric pressure or a pressure slightly above atmospheric, at flow rate of gas per hour (GHSV) in the range from 100 to 1000 normal liters/h·lcat.and when the residence time of the catalyst in the reactor in the range from 5 to 30 minutes

19. The method according to p, in which the volumetric rate of gas per hour (GHSV) is in the range from 150 to 400 normal liters/h·lcat., and the residence time of the catalyst in the reactor is in the range from 10 to 15 minutes

20. The method according to item 12, in which regeneration of the catalyst is carried out using air, oxygen or air diluted with nitrogen, while the heating is carried out with the aid of methane, fuel gas or by-products of the dehydrogenation reaction at a temperature higher than the temperature of the reaction dehydrogenation, at atmospheric pressure or a pressure slightly above atmospheric, at flow rate of gas per hour (GHSV)in the range from 100 to 1000 normal liters/h·lcat.and when the residence time of the catalyst in the reactor in the range from 5 to 120 minutes

21. The method according to claim 20, in which the regeneration temperature is in the range from 500 to 700°S, and the residence time of particles in the apparatus is in the range from 20 to 40 minutes

22. The method according to item 12, in which during operation Degi who compete (A) a mixture of ethylbenzene and ethane is sent to the reactor, conducting simultaneous dehydrogenation and using ethane in a mixture with benzene to obtain the corresponding alkylaromatic hydrocarbons.



 

Same patents:

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting the parent raw flow in the flow-type reactor with oxygen-free gas flow at increased temperature with a catalyst comprising a precious metal of VII group of the periodic system of elements. The industrial isomerization platinum-containing catalyst SI-1 or industrial hydrogenation catalyst "palladium on active aluminum oxide in sulfured form" is used as a catalyst. Contact of the parent raw with catalyst is carried out by its feeding in inert gas flow, for example, nitrogen at the volume rate 1-2 h-1 at temperature 320-370°C in the presence of the additive representing a solution of hydroquinone or p-benzoquinone in isopropyl alcohol and taken in the concentration 0.01-0.5 mole/l wherein the additive is fed to the parent raw flow in the amount 5-30 vol.%. Invention provides carrying out the highly selective isomerization and cyclization of light petroleum fractions in on industrial Pt- and/or Pd-containing catalysts with the high yield of the end products no containing aromatic compounds and not requiring the presence of hydrogen or hydrogen-containing gas for its realization and regeneration of the catalyst.

EFFECT: improved method for isomerization.

4 cl, 2 tbl, 2 ex

FIELD: chemistry of aromatic compounds, chemical technology.

SUBSTANCE: process involves the following stages: feeding (C2-C5)-alkane, for example, ethane and (C2-C5)-alkyl-substituted aromatic compound, for example, ethylbenzene into dehydrogenation reactor for the simultaneous dehydrogenation to (C2-C5)-alkene, for example, to ethylene, and (C2-C5)-alkenyl-substituted aromatic compound, for example, styrene; separation of the outlet dehydrogenation flow for extraction of gaseous flow containing alkene, hydrogen and alkane, and for extraction of aromatic compounds with the high effectiveness by cooling and compression; feeding a gaseous flow and (C6-C12)-aromatic compound into the alkylation reactor for preparing the corresponding (C2-C5)-alkyl-substituted aromatic compound that is recirculated into the dehydrogenation reactor; feeding the blowing flow from the alkylation unit containing alkane and hydrogen for the separation stage by using cryogenic separator for extraction of alkane that is recirculated into the dehydrogenation reactor, and hydrogen that is extracted with the purity value 99%. Invention provides the development of economic and highly effective process for preparing alkenyl-substituted aromatic compounds.

EFFECT: improved preparing method.

61 cl, 2 tbl, 2 dwg, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: invention relates to dehydrogenation of isoamylenes to isoprene on iron oxide self-regenerating catalysts. Method involves addition of piperylenes in the concentration up to 4 wt.-% representing a by-side product in manufacturing process of isoprene by the indicated method to the parent isoamylenes before their dehydrogenation. Method provides enhancing selectivity of method for isoamylenes dehydrogenation to isoprene in the presence of iron oxide self-regenerating catalysts.

EFFECT: improved preparing method.

1 tbl, 6 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention concerns catalysts for dehydrogenation of C2-C5-alkanes into corresponding olefin hydrocarbons. Alumina-supported catalyst of invention contains 10-20% chromium oxide, 1-2% alkali metal compound, 0.5-2% zirconium oxide, and 0.03-2% promoter oxide selected from zinc, copper, and iron. Precursor of alumina support is aluminum oxide hydrate of formula Al2O3·nH2O, where n varies from 0.3 to 1.5.

EFFECT: increased mechanical strength and stability in paraffin dehydrogenation process.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: 1,3-butadiene is obtained via catalytic dehydrogenation of n-butylenes at 580-640°C and essentially atmospheric pressure while diluting butylenes with water steam at molar ratio 1:(10-12) and supplying butylenes at space velocity 500-750 h-1. Catalyst is composed of, wt %: K2O 10-20, rare-earth elements (on conversion to CeO2) 2-6, CaO and/or MgO 5-10. MoO3 0.5-5, Co2O3 0.01-0.1, V2O5 0.01-0.1, and F2O3 the balance. Once steady condition is attained, dehydrogenation is carried out continuously during all service period of catalyst.

EFFECT: increased yield of 1,3-butadiene and process efficiency.

2 ex

FIELD: petrochemical processes.

SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.

EFFECT: increased process flexibility and extended choice of catalysts.

36 cl

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to production of olefin or diolefin hydrocarbons via dehydrogenation of corresponding paraffinic C3-C5-hydrocarbons carried out in presence of catalyst comprising chromium oxide and alkali metal deposited on composite material including alumina and aluminum wherein percentage of pores larger than 0.1 μm is 10.0-88.5% based on the total volume of open pores equal to 0.10-0.88 cm3/g. Preparation of catalyst involves treatment of carrier with chromium compound solution and solution of modifying metal, preferably sodium or sodium and cerium. Carrier is prepared by from product resulting from thermochemical activation of amorphous hydrargillite depicted by formula Al2O3·nH2O, where 0.25<n<2.0, added to homogenous mass in amount 1.0 to 99.0% using, as additional material, powdered aluminum metal, which is partly oxidized in hydrothermal treatment and calcination stages. Hydrocarbon dehydrogenation process in presence of the above-defined catalyst is also described.

EFFECT: increased activity and selectivity of catalyst.

3 cl, 2 dwg, 4 tbl, 7 ex

The invention relates to catalysts used in the dehydrogenation of hydrocarbons, and to methods of using catalysts

FIELD: inorganic synthesis catalysts.

SUBSTANCE: ammonia synthesis catalyst includes, as catalytically active metal, ruthenium deposited on magnesium oxide having specific surface area at least 40 m2/g, while concentration of ruthenium ranges between 3 and 20 wt % and content of promoter between 0.2 and 0.5 mole per 1 mole ruthenium, said promoter being selected from alkali metals, alkali-earth metals, lanthanides, and mixtures thereof. Regeneration of catalytic components from catalyst comprises following steps: (i) washing-out of promoters from catalyst thereby forming promoter-depleted catalyst and obtaining solution enriched with dissolved promoter hydroxides; (ii) dissolution of magnesium oxide from promoter-depleted catalyst in acidic solvent wherein ruthenium is insoluble and thereby obtaining residual ruthenium metal in solution enriched with dissolved magnesium compound; and (iii) regeneration of residual ruthenium metal from solution enriched with dissolved magnesium compound via liquid-solids separation to form indicated solution enriched with dissolved magnesium compound and ruthenium metal.

EFFECT: increased catalyst activity.

6 cl, 6 ex

FIELD: extraction of platinum and rhenium from decontaminated used platinum-rhenium catalysts; reworking of secondary raw materials of petrochemical industry.

SUBSTANCE: proposed method includes high-temperature oxidizing roasting at temperature of 1200-1300°C, wet trapping of rhenium by alkaline solution, leaching-out of cinder in hydrochloric acid solution at concentration of 100-150 g/dm3 in presence of oxidizing agent for setting the oxidizing-reducing potential of platinum electrode in pulp relative to saturated silver-chloride electrode equal to 850-1000 mV. Used as oxidizing agent is sodium hypochlorite or elementary chlorine or hydrogen peroxide.

EFFECT: enhanced efficiency of process.

1 tbl, 13 ex

FIELD: separation of palladium from waste mangani-palladium catalyst and cleaning of palladium.

SUBSTANCE: palladium-containing concentrate is treated with aqua regia solution and palladium is deposited in form of chloropalladate by means of treatment with aqua regia solution with solid ammonium chloride, pulp thus obtained is settled, cooled and filtered; sediment is treated with saturated hydrochloric acid solution of ammonium chloride. Then sediment thus treated is dissolved in water and solution is filtered and neutralized; pallarium is restored to metal by means of hydrochloric acid hydrazine at pH≥2 or formic acid solution at pH≥6; solution is filtered and metallic palladium is washed and dried at 90-100°C. Prior to treatment, mangani-palladium catalyst with aqua regia, it is dissolved in concentrated hydrochloric acid; solution is neutralized by asmmonia to pH=6-7 and treated with formic acid at flow rate no less than 1 l of HCOOH per kg of mangani-palladium catalyst; then mangani-palladium concentrate is filtered, washed and dried at 90-100ºC.

EFFECT: enhanced purity of metallic palladium at minimum losses of catalyst at all stages of chemical treatment.

4 ex

FIELD: noble metal hydrometallurgy.

SUBSTANCE: invention relates to method for acid leaching of platinum method from secondary raw materials, in particular from ceramic support coated with platinum metal film. Target metals are leached with mixture of hydrochloric acid and alkali hypochlorite at mass ratio of OCl-/HCL = 0.22-0.25 and redox potential of 1350-1420 mV.

EFFECT: decreased leaching temperature, reduced cost, improved platinum metal yield.

2 ex

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