Catalytic system and method for the oxidative dehydrogenation of alkylaromatic hydrocarbons or paraffins to the corresponding alkanolamines hydrocarbons or to the corresponding olefins

 

The invention relates to a catalytic system and to a corresponding method for oxidative dehydrogenation of alkylaromatic hydrocarbons, in particular benzene, or paraffins to the corresponding alkanolamines hydrocarbons, in particular styrene, or to the corresponding olefins. Described catalytic system for the oxidative dehydrogenation of alkylaromatic hydrocarbons, in particular benzene, or paraffins to the corresponding alkanolamines hydrocarbons, in particular styrene, or to the corresponding olefins, comprising, by wt.%: the vanadium oxide, in terms of V2O5from 1 to 15; the oxide of bismuth, in terms of Bi2O3from 2 to 30; carrier-based magnesium - rest. There is also described a method of dehydrogenation of alkylaromatic hydrocarbons at 400-750oWith pressure from 0,69 kPa to 207 kPa in the presence of the catalytic system described above, providing for its regeneration at temperatures above 400oC. Technical effect is an increase in the activity of the catalyst. 2 C. and 8 C.p. f-crystals, 2 tab., 20 Il.

The invention relates to a catalytic system and to a corresponding method for oxidative dehydrogenation of alkylaromatics, in particular styrene, or to the corresponding olefins.

Styrene, which is an important intermediate compound in the production of plastics, mainly used in the production of polystyrene (crystal polystyrene, General purpose, GPPS, shockproof hips and foaming UPU), copolymers of Acrylonitrile, styrene and butadiene (ABS) and copolymers of styrene and Acrylonitrile (SAN), styrene-butadiene rubbers (BSC).

Currently, styrene basically get through two processes: by dehydrogenation of ethylbenzene (EB) and as a by-product when epoxydecane propylene with ethylbenzene hydroperoxide with a catalyst based on molybdenum complexes.

An alternative way of obtaining the monomer is the dehydrogenation of ethylbenzene with simultaneous oxidation of hydrogen that can be carried out in the presence or in the absence of oxygen.

Oxidative dehydrogenation in the absence of oxygen is to use one or more metal oxides, which in addition to the catalysis of the reaction of dehydrogenation of ethylbenzene is capable of oxidation of hydrogen produced by the oxygen present in the oxide, to facilitate the shift of the equilibrium towards the formation of styrene (STY) moreeee reaction, speaking as a reactant: at the beginning of the reaction it is in the oxidation state (catoxand able to give up some of its oxygen and turn into restored (catred). To make the catalytic reaction, it is necessary that the recovered catalyst was able to easily restore the oxygen to become the initial oxidized particles suitable for the new cycle, oxidative dehydrogenation, by reactionThis special way of carrying out the dehydrogenation has the same advantages as traditional oxidative dehydrogenation, i.e. in the presence of oxygen, and allows to generate heat required for dehydrogenation, as well as to shift the equilibrium of the dehydrogenation reaction in the direction of products without defects such as the formation of oxidized compounds as by-products produced by the oxidizing gas.

The idea of the oxidative dehydrogenation of hydrocarbons without oxidizing gas was known already in the first half of the 60's thanks to US 3118007 (Voeg). This patent pending method of dehydrogenation of hydrocarbons without oxidizing gases and catalysts based on iron oxides, which are also daeryung removal of the catalyst, which should be subjected to the subsequent oxidation and subsequent recycling to the reaction stage.

Various patents for oxidative dehydrogenation without oxidizing gases come out over the last few years, of which the most relevant are the following.

In EP-482276 (FINA) described the way in which complete conversion of the ethylbenzene is achieved at 505oWith a catalyst, which acts as a carrier of oxygen and which, once spent, can be regenerated in the second reactor processing air. The catalyst containing the oxides of transition metals, preferably on the basis of vanadium deposited on the magnesium has a high dehydrogenation activity as well as a significant trend to ensure structural oxygen for the combustion of hydrogen. The results described in this patent show that burning is the most critical phase reactions: in fact, at the beginning of the catalytic activity styrene is obtained with low selectivity together with a large number of carbon oxides produced during the combustion of ethylbenzene and/or styrene. This patent shows that preliminary partial recovery of catalyst handling monoxide from the e in the first stages of activity. In this case, however, the conversion decreases rapidly and soon stabilizes at values of around 50%.

In GB-2297043 (BASF) claimed the use of a catalyst comprising a mixed oxide based on bismuth, titanium, lanthanum, potassium and treated noble metal, for oxidative dehydrogenation of ethylbenzene without oxygen. These results do not allow to accurately estimate time-catalytic characteristics. In the text of the patent alleges that the catalyst initially very active, but not very selective in the formation of compounds generated by combustion of hydrocarbons. As already discussed in the case of patent FINA, as the process the catalyst becomes less active and more selective, until it reaches the maximum value.

The authors found that the use of catalysts based on vanadium and bismuth deposited on a suitable carrier, in comparison with the known above-described catalysts not only increases their selective characteristics, mainly in the beginning of the reaction, and overall efficiency and lifetime of the catalyst also increases.

The catalytic system according to this invention to the corresponding alkanolamines hydrocarbons (in particular, styrene) or to the corresponding olefins includes: - vanadium oxide; bismuth oxide; and the media on the basis of magnesium, where the amount of vanadium in terms of V2O5is in the range from 1 to 15 wt.%, preferably from 2 to 10%, the amount of bismuth, in terms of Bi2About3is in the range from 2 to 30 wt.%, preferably from 5 to 20 wt.%, and the rest to 100 km / media.

The media on the basis of magnesium is preferably selected from: - carriers, comprising magnesium oxide;
vehicles, including magnesium oxide and zirconium oxide, where the amount of magnesium in terms of MgO is preferably in the range from 20 to 40 wt. % with respect to the catalytic system, and the amount of zirconium in terms of ZrO2is in the range from 30 to 50 wt.% with respect to the catalytic system;
- carriers, comprising the hydrotalcite magnesium and aluminum, where the atomic ratio of magnesium/aluminum is preferably in the range of from 70/30 to 30/70.

The method of preparation of the catalytic system described above can essentially be done by the following operations:
- preparation of solutions or suspensions based on the derivatives of the components of the catalytic system;
- mixing the W of the dried solids at a temperature in the range from 550 to 780oC.

The inventive catalyst system can be applied to any dehydrogenation of ethylbenzene in a fixed, fluidized or moving bed.

When the catalytic system consists of a vanadium oxide or bismuth oxide on a carrier, comprising magnesium oxide or zirconium oxide, in its calcined at 750oWith the form (see example 1), it has x-ray diffraction spectrum obtained by a vertical goniometer equipped with an electronic pulse counting using CuKradiationcontaining the main reflexes listed in table. 1 (where d represents the interplanar distance), and Fig.1.

We can see the presence of unknown phase (not structurally characterized), designated as phase (x) and phase ZrO2and Mao.

We also found that again in the case of a catalyst system comprising a vanadium oxide, bismuth oxide on a carrier containing magnesium oxide and zirconium oxide, when carrying out the last stage of cooking, i.e. annealing, within a very specific range of temperatures, obtained by catalytic system, which unexpectedly has the best catalytic activity, the Skye system with improved catalytic activity, which is also a task of the present invention includes:
the vanadium oxide;
oxide of bismuth;
and a carrier consisting of magnesium oxide and zirconium oxide,
where the amount of vanadium in terms of V2O5is in the range from 1 to 15 wt.%, preferably from 2 to 10%, more preferably from 2 to 5%,
the amount of bismuth, in terms of Bi2About3is in the range from 2 to 30 wt.%, preferably from 5 to 25 wt.%,
amount of magnesium in terms of MgO is in the range from 20 to 40 wt.%,
the amount of zirconium in terms of ZrO2is in the range from 30 to 50 wt.% and is characterized by having in its calcined form, an x-ray diffraction spectrum obtained by a vertical goniometer equipped with an electronic pulse counting using CuKradiationcontains basic reflexes listed in table. 2 (where d represents the interplanar distance), and Fig.2.

Compared with the catalytic system described above, calcined at 750oWith, you will notice that this system has no diffraction peaks related to the phase (x).

As mentioned above, the method Edna operation preparation, carried out at a temperature in the range from 585 to 615oC.

The method of preparation of the catalytic system described above, therefore, essentially involves the following steps:
- preparation of solutions or suspensions based on the derivatives of the components of the catalytic system;
- mixing the prepared solutions or suspensions before gelation of the mixture;
- drying the obtained gel;
- the calcination of the dried solids at a temperature in the range from 585 to 615oC.

The way the oxidative dehydrogenation of alkylaromatic hydrocarbons, in particular benzene, or paraffins in the appropriate alkenylamine hydrocarbons, in particular styrene, or into the corresponding olefins, who is also an objective of the present invention essentially involves the reaction of alkylaromatic hydrocarbons or paraffins in the reactor at a temperature in the range from 400 to 750oC, at a pressure in the range from 0.1 to 30 psia (abs. pound/square inch) (from 0.69 to 207 kPa) and hourly average volumetric gas flow rate from 0.01 to 10-1preferably from 0.1 to 1-1(STD. L. hydrocarbons /liter of catalyst), possibly in the presence of a diluent, as described above catalytically reaction stage, at temperatures above 400oC.

Oxidative environment used in this method may be oxygen and/or air.

A possible diluent may be, for example, N2CH4N2Ocouples, CO, CO2and other

For better illustration of the present invention shows some examples, which, however, should not be construed as limiting the scope of invention.

EXAMPLES
Described 9 syntheses of catalysts (including 5 comparative) with subsequent relevant catalytic tests.

EXAMPLE 1. The synthesis of the catalyst, deposited on the MgO and ZrO2.

Prepared with the following mixture:
suspension: 4,30 Mr. VOSO45H2O in 20 g of ethanol (molecular mass (M M)= 253 g-mol-1, 0,0085 mol V2O5),
solution: 59,46 g Zr(OS3H7)4at a concentration of 70% (M M=327 g-mol-1, to 0.127 mol ZrO2),
solution D: 3,79 g TRA-HE (the hydroxide of tetrapropylammonium) (40%) in 12 g of N2O (M M=203 g-mol-1, 0,0075 mol).

The solution is added to the suspension And when heated (60oC) and stirring with a magnetic stirrer and get brown suspension (suspension). 8,24 g Bi(NO3)35H2O (M M=485 g-mol-1, 0,0085 mol Bi2OoWith overnight and finally calcined at 750oWith 4 hours in air flow. The composition of the catalyst: 4.7 wt.% V2O5, to 12.1 wt.% Bi2O3, 35.5 wt.% Mao and 47.7 wt.% ZrO2.

EXAMPLE 2. The synthesis of the catalyst, applied to MD-Al hydrotalcite.

0.97 g NH4VO3(M M=117 g-mol-1, 0,0041 mol V2O5) dissolved in 40 g of water; 7,28 g hydrotalcite (MLA/Al2O3=1 by mass) is added to thus obtained solution. 3,98 g Bi(NO3)35H2O (M M=485 g-mol-1, 0,0041 mol Bi2O3) add in the thus obtained yellow-white suspension. Yellow-orange suspension is stirred for 5 hours, then dried, and calcined solid at 650oC for 4 hours in air. The composition of the catalyst: 7.5 wt.% V2O5and 19.2 wt.% Bi2O3and 73.3 wt.% hydrotalcite.

EXAMPLE 3. The synthesis of the catalyst, deposited on Mao.

2,80 g NH4VO3(M M=117 g-mol-1, 0.012 mol V2O5) was dispersed in 100 g of water at a temperature of 90oC. This su is O (M M= 40,3 g-mol-1, the 0.375 mol Mao) and 11,64 g Bi(NO3)35H2O (M M=485 g-mol-1, 0.012 mol Bi2O3to 100 g of water. The mixture, thus obtained, leave to boil for 90oC for 2 hours, then dried in a current of N2. It is then calcined in a stream of air for 4 hours at a temperature of 600oC. the Composition of the catalyst to 9.6 wt.% V2O5, 24.6 wt.% Bi2About3and 65.8 wt.% Mao.

EXAMPLE 4. The synthesis of the catalyst, deposited on the MgO and ZrO2, calcined at 600oC.

The catalyst prepared on the basis of V2O5and Bi2About3deposited on the MgO and ZrO2obtained analogously to example 1, except for the annealing, which is performed for 4 hours in a stream of air at 600oWith instead of the 750oC. the Composition of the catalyst: 4.7 wt.% V2O5, to 12.1 wt.% Bi2About3, 35.5 wt.% Mao and 47.7 wt.% ZrO2.

EXAMPLE 5. Comparative: vanadium oxide deposited on the MgO and ZrO2.

Prepare the following mixture:
suspension: 2.15 g VOSO45H2O in 20 g of ethanol (M M=253 g-mol-1, 0,0042 mol V2O5),
solution: 59,46 g Zr(OS3H7)4at a concentration of 70% (M M=327 g-mol-1, to 0.127 mol ZrO2),
solution D: 3,79 g TRA-HE (40%) in 12 g of N2O (is eshiwani magnetic stirrer; get brown suspension (suspension). 11,65 g MLA (M M=40,3 g-mol-1, 0.29 mol Mao) is added while heating and stirring with a magnetic stir bar to the suspension thus obtained; receive a suspension, which is added to the solution D. Adding a hydroxide of alkylamine causes the formation of gel, which is subjected to aging for 24 hours; the gel is then dried at 120oWith overnight and finally calcined at 750oWith 4 hours in air flow.

EXAMPLE 6. Comparative: bismuth oxide, deposited on the MgO and ZrO2.

Prepare the following solutions:
solution: 59,46 g Zr(OS3H7)4at a concentration of 70% (M M=327 g-mol-1, to 0.127 mol ZrO2),
solution: 3,79 g TRA-HE (40%) in 12 g of N2O (M M=203 g-mol-1, 0,0075 mol).

50 g of ethanol are added to a solution A, and add under stirring with a magnetic stirrer 4.12 g Bi(NO3)35H2O (M M=485 g-mol-1, 0,0042 mol Bi2O3and 11,65 g MLA (M M=403 g-mol-1, 0.29 mol Mao); get the suspension, which is added to solution C. the Addition of the hydroxide of alkylamine causes the formation of gel, which is subjected to aging for 24 hours; the gel is then dried at 120oWith overnight and finally calcined p/p> 1,93 g NH4VO3(M M=117 g-mol-1, 0,0082 mol V2O5) is dissolved by heating in 40 g of water; the solution, thus obtained, is used for impregnation of 8.50 g of hydrotalcite (MLA/Al2O3=1 by mass). After impregnation pressed on the filter, the solid is dried in an oven at 80oC overnight and then calcined at 650oWith 4 hours in the air.

EXAMPLE 8. Comparative: the vanadium oxide - aluminum oxide - magnesium oxide.

Prepare the following mixture:
solution: 1,82 g NH4VO3(M M=117 g-mol-1, 0,0156 mol V) dissolved in 20 g of water, padmalochan of 7.90 g TRA-HE (40% in water) (M M=203 g-mol-1, 0,0156 mol),
solution: 20,54 g Al (dt-OS4H9)3(M M=246 g-mol-1, 0,0835 mol Al) in 50 g of ethanol.

The solution is added to the suspension; 4,25 g MLA (M M=40,3 g-mol-1, 0,105 mol Mao) is added under stirring with a magnetic stir bar to the suspension obtained in this way. The suspension is stirred for 5 hours, and then dried, and calcined solid at 650oWith 4 hours in the air.

EXAMPLE 9. Comparative: the vanadium oxide is magnesium oxide.

The catalyst prepared in accordance with example 1 of EP-0403462 (FINA).

Prepare the following mixture:
the comfort in 100 g of N2O.

The suspension is then heated to a temperature of 90oC.

The solution And add when heated to the suspension, and the resulting slurry for mixing with a magnetic stirrer for 2 hours. Then it is heated to 120oWith, and remove the solvent in a stream of N2.

The dried product is calcined at 600oC for 4 hours.

Catalytic testing of the catalysts of examples 1-9.

All catalytic tests were carried out in the microreactor with a pulsed supply of ethylbenzene. In all trials was downloaded about 500 mg of catalyst that has been activated in air at 500oC for 2 hours. After this pre-treatment reaction was performed at 500o(Except one, where the used catalyst from example 4, conducted at 480o(C) with a pulsed supply of ethylbenzene approximately 3 mg, contact time of about 1.1 with.

The conversion of ethylbenzene and selectivity for styrene indicated in the graphs of Fig. 3.1-3.9 and 3.1 b 3.9 b, respectively (where the number following the 3 refers to the example of the synthesis of the catalyst utilized).


Claims

1. Catalytic system for oxidation of digimortal or to the corresponding olefins, including vanadium oxide, bismuth oxide and a carrier, characterized in that as the carrier media used on the basis of magnesium, the amount of vanadium in terms of V2O5is in the range from 1 to 15 wt.%, the amount of bismuth, are very rare in Bi2O3is in the range from 2 to 30 wt.%, and the rest up to 100 wt.% is the media.

2. The catalytic system under item 1, characterized in that the carrier on the basis of magnesium selected from carriers, including magnesium oxide, magnesium oxide and zirconium oxide, hydrotalcite, magnesium and aluminum.

3. The catalytic system under item 2, characterized in that the magnesium in terms of MgO is in the range from 20 to 40 wt.%, and zirconium, in terms of ZrO2is the interval from 30 to 50 wt.%.

4. The catalytic system under item 2, characterized in that the atomic ratio of magnesium/aluminum hydrotalcite is in the range from 70/30 to 30/70.

5. The catalytic system under item 1, characterized in that the amount of vanadium in terms of V2O5is in the range from 2 to 10 wt.%, and the amount of bismuth, in terms of Bi2O3is in the range from 5 to 25 wt.%.

6. The catalytic system under item 1, characterized in that the vanadium in terms of V2
is in the range from 30 to 50 wt.% and has x-ray diffraction spectrum as shown in the table.2.

7. The catalytic system under item 6, characterized in that the vanadium in terms of V2O5is in the range from 2 to 10 wt.%, and bismuth, in terms of Bi2O3is in the range from 5 to 25 wt.%.

8. The catalytic system under item 7, characterized in that the vanadium in terms of V2O5is in the range from 2 to 5 wt.%.

9. The catalytic system according to any one of paragraphs.6-8, characterized in that it is derived through the following operations: preparation of solutions or suspensions based on the derivatives of the components of the catalytic system; mixing the prepared solutions or suspensions before gelation of the mixture; drying the obtained gel; calcining the dried solids at a temperature in the range from 585 to 615C.

10. The method of dehydrogenation of alkylaromatic hydrocarbons, in particular benzene, or paraffins to the corresponding alkanolamines hydrocarbons, in particular styrene, or to the corresponding olefins, essentially VK is the interval from 400 to 750C, at a pressure in the range from 0.1 to 30 psia (abs. pound/square inch) (from 0.69 to 207 kPa) and hourly average volumetric gas flow rate from 0.01 to 10-1(STD. L. hydrocarbons/liter of catalyst), with a catalytic system, and the regeneration of the specified catalyst system in a regenerator by burning coke, otlichayushchegosya during the reaction stage at a temperature above 400, Characterized in that the catalytic system used catalytic system according to one or more paragraphs.1-9.

 

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