Method of catalytic preliminary reforming of hydrocarbon raw materials containing higher hydrocarbons

FIELD: petrochemical industry.

SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.

EFFECT: the invention allows to decrease a carbon share on the catalyst.

3 cl, 2 tbl, 2 ex

 

The present invention relates to a process for the catalytic treatment of hydrocarbons, in particular to a method preliminary catalytic reforming of a hydrocarbon feedstock containing higher hydrocarbons.

The known method preliminary catalytic reforming of a hydrocarbon feedstock containing higher hydrocarbons, provides for the transmission of the specified hydrocarbon material through a zone of a catalyst containing a catalytically effective amount of a monolithic catalyst based on at least one transition metal, in the presence of oxygen, water vapor or carbon dioxide partial oxidation, and the specified transition metal selected from the group consisting of iron (Fe), ruthenium (Ru), osmia (Os), cobalt (Co), rhodium (Rh), iridium (Ir), Nickel (Ni), copper (cu), palladium (Pd) and platinum (Pt) (see international application W0 99/35082, 01 3/38, published. 15.07.1999,).

Pre-reforming process is a process carried out prior to catalytic reforming with water vapor, in the production of a gas rich in hydrogen and/or carbon monoxide. At the stage of preliminary reforming the content of higher hydrocarbons are converted to methane and the reaction (1) reforming of methane and the reaction (2) conversion of water vapor are in equilibrium near operating temperature.

4+H2O ↔ CO+3H2(1)

CO+H2O ↔ CO2+H2(2)

Exothermic reactions (3) and (4) catalytic oxidation

CH4+1/2O2CO+2H2(3)

CH4+O2CO2+2H2(4)

are the prevailing reactions on the input set for the pre-reforming process, in which heat for the subsequent reactions leading to elevated temperature of the process gas regardless of the oxygen content in the original gaseous reaction mixture. If the oxygen content in the process gas is consumed by the above reactions (3) and (4), the endothermic reforming reaction of methane is the main reaction, leading to a decrease in temperature of the process. Due to the heat in the reactions (3) and (4) catalytic combustion gas at the outlet will have a higher temperature and a higher temperature equilibrium of the reforming process of methane than the temperature in the process of catalytic reforming with water vapor at the inlet of the source of the reaction gas mixture. For this reason, the subsequent stage of reforming with water vapor requires less power to obtain the same amount of hydrogen and/or carbon monoxide in the exhaust gas emitted during the overhaul the ha with water vapor.

The oxygen in the original gaseous reaction mixture results in oxidative dehydration of hydrocarbons and olefins. Catalysts pre-reforming process is critical to the concentration of olefin in the gas and will form carbon when its concentration exceeds some critical value.

The present invention is the provision of a method of catalytic pre-reforming a hydrocarbon feedstock containing higher hydrocarbons, essentially without the formation of harmful carbon on the catalyst pre-reformer.

The specified task is solved by means of the proposed method preliminary catalytic reforming of a hydrocarbon feedstock containing higher hydrocarbons, which provides for the transmission of the specified hydrocarbons through the zone catalyst comprising a fixed bed containing a noble metal, in the presence of oxygen and water vapor, due to the fact that the hydrocarbons are passed through a specified area of the catalyst containing the specified noble metal oxide magnesium (MgO) and/or spinel (MgAl2O4).

Catalysts containing a noble metal, intended for use in the method corresponding to the present invention, receive any pic of the BOV, usually used in this technical field involving impregnation of the substrate material with an aqueous solution containing a noble metal, and firing the impregnated material in the air.

As already mentioned, the catalyst containing a noble metal, is a fixed bed in the reactor installation for pre-reformer.

A catalyst containing a noble metal, can be used as the top layer in the reactor installation for pre-reforming process on a conventional catalyst pre-reformer.

See below for more description of the present invention, made with reference to the examples.

Example 1

The substrate materials catalyst comprising a magnesium oxide (MgO) and spinel (MgAl2O4)having a particle size of 4.5 mm were impregnated with about 3 wt.% rhodium (Rh), when using an aqueous solution of rhodium nitrate, followed by calcination at a temperature of 750° by which nitrate was split into oxides.

Thus obtained catalyst was disposed as a fixed layer in the pipe reactor, and the volume of the layer of 74.5 ml corresponded 58,4 g of catalyst.

The tube reactor was placed in pyatitonnoy the furnace to maintain in the course of the experiments essentially isothermal temperature profile.

Oven and input the e sections were heated in a stream of nitrogen. When the desired operating temperature of injected water vapor, and nitrogen was substituted for the previously received by the mixture of natural gas-air and butane in accordance with the composition shown in Table 1.

Table 1
CH4(vol.%)With2H6+ (vol.%)N2(vol.%)CO2(vol.%)O2(vol.%)AG (% vol.)Butane (vol.%)H2O (% vol.)
13,340,69of 5.680,171,110,063,9774,99

The composition of the initial reaction mixture With2H6+ specifies all hydrocarbons containing two or more carbon atoms.

Total consumption was approximately 380 nl/h, which corresponded to the flow rate of the expiration of about 5000 hours-1.

The experiments were performed at a temperature of oven to 450° and 480° C. Both experiments showed a complete conversion of oxygen to the source of the reaction gas mixture and an almost complete conversion of butane methane (0-580 parts per million on the yield of dry product). At the same time, the equilibrium reaction of the reforming of methane and the reaction conversion of water vapor was within 10° With temperature p the Chi.

It was found that in the upper part of the reactor was an area with a higher temperature than the set point adjustable temperature due to the exothermic catalytic oxidation in the presence of oxygen, and this area followed the zone of lower temperature than the set point adjustable temperature gradually increasing to the setpoint adjustable temperature. This was due to the endothermic reforming reaction of methane.

Example 2

The substrate of the catalyst, made of spinel (MgAl2O4containing approximately 10 wt.% α -aluminium oxide and having a particle size of 4.5× 4.5 mm was impregnated with about 2 wt.% rhodium (Rh) using an aqueous solution of rhodium nitrate, followed by calcination at a temperature of 750° by which nitrate was split into oxides.

The catalyst was placed in a fixed bed in a tube reactor, and the volume of the layer of 74.5 g corresponded to 79.8 g of the specified catalyst. To maintain essentially isothermal temperature profile during experiments the tube reactor was placed in pyatitonnoy the oven.

The furnace and the input section was heated in a stream of nitrogen. When the desired operating temperature of injected water vapor, and nitrogen was substituted for the previously obtained mixture is natural gas-air and butane in accordance with the composition, are shown in Table 2.

Table 2
CH4(vol.%)With2H6+ (vol.%)N2

(vol.%)
CO2(vol.%)O2(vol.%)AG (% vol.)Butane (vol.%)H2O (% vol.)
13,340,69of 5.680,171,110,063,9774,99

The composition of the initial reaction mixture. With2H6+ specifies all hydrocarbons containing two or more carbon atoms.

Total consumption was approximately 380 nl/h, which corresponded to the flow rate of the expiration of about 5000 hours-1.

The experiments were performed at a temperature of oven to 450° C. the Experiments showed complete conversion of oxygen and full conversion of butane methane. At the same time, the equilibrium of the reforming reaction of methane was in the range of 15° With the temperature of the furnace, whereas the reaction of the conversion of water vapor had a negative offset of - 20° to 60° C, indicating that the equilibrium temperature of the composition is higher than the temperature of the reactor.

Due to the consumption of oxygen exothermic reactions the temperature profile in the reactor had a more high what kind of temperature, than the set value of the adjustable value of the reactor temperature at the entrance. Due to the endothermic reforming reaction below this zone the temperature was decreased to approximately setpoint variable temperature.

1. Method preliminary catalytic reforming of a hydrocarbon feedstock containing higher hydrocarbons, which provides for the transmission of the specified hydrocarbons through the zone catalyst comprising a fixed bed containing a noble metal, in the presence of oxygen and water vapor, characterized in that the hydrocarbons are passed through a specified area of the catalyst containing the specified noble metal oxide magnesium (MgO) and/or spinel (MgAl2O4).

2. The method according to claim 1, characterized in that the rhodium catalyst used in the magnesium oxide and/or spinel.

3. The method according to claim 1, characterized in that the catalyst containing a noble metal is used as the top layer of the pre-reformer on conventional stationary catalyst.



 

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