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Method of producing acetylene from methane

Method of producing acetylene from methane
IPC classes for russian patent Method of producing acetylene from methane (RU 2409542):
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FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylene through oxidative pyrolysis of methane in the presence of oxygen and a catalyst, characterised by that the catalyst is heated to 700-1200°C by passing electrical current through it. The catalyst used is a fechral alloy which is thermally treated on air at temperature 900-1100°C. The ratio of methane to oxygen is varied in the range of 5:1-15:1.

EFFECT: high output and selectivity of the process.

2 cl, 17 ex, 1 tbl, 1 dwg

 

The invention relates to the field of oil refining, petrochemical and gas processing, namely the method of producing acetylene from methane.

As you know, still there is no acceptable technology use and associated oil gases that tens of millions of tons per year are burned in flares. There are several directions for the development of technologies for utilization of this hydrocarbon, which conducted the study. This is, for example, the decomposition of C1-C3paraffins to produce hydrogen as the main target of the product. The other way is the transformation of natural gas in chemical products, which is based on a complex energy - and capital-intensive process prior conversion to synthesis gas.

Recently, interest single-stage process for conversion of methane in chemical products, such as high temperature (≥900°C) oxidative pyrolysis of C1-C3gas to acetylene. The fact of formation of acetylene by incomplete combustion of hydrocarbons known for a long time (Evlanov SF, Lavrov NV // Scientific basis for the catalytic conversion of hydrocarbons, 1977, s-232). When optimizing the yield of acetylene emphasis on the construction of the different types of burners and selection of different conditions of combustion of hydrocarbons. The process of oxidizing pyrolysate several features: a very short duration of initial substances in the reactor (a few milliseconds), the high reaction temperature (1200-1400°C), pressure is atmospheric or slightly increased, quenching the reaction products to a temperature below 300°C using as a cooling medium of water or oil quenching prevents the decomposition of the produced acetylene carbon and hydrogen).

In the patent EP No. 0178853 is a technology according to which part of the methane is partially burned, and high temperature gas mixture (T>1000°C) is passed through a fluidized bed or flowing layer of particles of inert material: fireclay, quartz, corundum, Zirconia, silicon carbide, etc. to reduce the temperature gradient in the gas stream. The maximum selectivity and yield With2+-hydrocarbons equal to 30% conversion of methane 62.8% at 1151°C.

The disadvantage of this method is that part of the methane consumed as fuel to heat the entire mass of gas to 1200-1400°C. in Addition, to save less strong than methane molecules With2+hydrocarbons used hardening of the whole mixture of water, i.e. rapid cooling of the mixture to ~300°C, which complicates the technology.

The study of the oxidative condensation of methane, in which the focus was on finding catalysts and study of the reaction mechanism occurring at 650-850°C (Usanational, the.Acrylol. Oxidative conversion of methane. M.: Nauka, 1998). It is at these temperatures (650-850°C) it is possible to obtain significant yields of ethane and ethylene in the oxidation of methane.

Closest to the present invention is a method of producing hydrocarbons From2-C4where was first used the term "catalytic oxidative pyrolysis of methane" (As the USSR №1216937, prototype). This method is carried out at between 800 and 950°C, contact time of 0.1-2.5 sec, the content in the initial mixture 10-20 vol.% oxygen and 90-80% vol. methane in the presence of a catalyst composition, mol.%: Bi2O30,95-to 7.59 and MeO 92,41-99,05, where Me is Mg, Ca, Sr, BA. The catalyst was allowed to increase the yield of hydrocarbons From2+up to 10 mol.% on missed methane selectivity was 78.5%. Nevertheless, the main products are ethane and ethylene. Acetylene in the resulting mixture and the conversion of methane is very small - up to 20%, which gives low outputs by product.

The purpose of this invention is to increase the yield and selectivity of the process for acetylene through the use of the catalyst of a new type and changes in technology oxidative pyrolysis.

The proposed method of producing acetylene, oxidizing pyrolysis of methane in the presence of oxygen comprises using as the catalyst heat-treated in air at 900-1100°C terralavoro alloy in the form of spirals, ribbons, art is Rina and other forms. Heating of the catalyst is carried out by passing through it an electric current to a temperature of 700-1200°C., and the ratio of methane: oxygen change in the range 5:1 to 15:1.

Contact oxygen-containing mixtures on the basis of methane in certain proportions of CH4/About2(air) with wire working fehrle, heated and electric current to temperatures from 750°C to >1200°C gives the catalytic effect of the change in selectivity With2the hydrocarbon compared with the gas, oxidizing pyrolysis of methane. The gas mixture is served cold, and only contact with the heated ferralium alloy leads to the catalytic effect. As the gas mixture is served cold, the overshoot part of the cold gas leads to a dramatic cooling of the reaction products formed upon contact with high temperature wire, i.e. hardening of the products of oxidative pyrolysis and increase the output of C2hydrocarbons (primarily ethane.

As the catalyst used alloy "wire" in the form of various shapes, mostly in the form of a wire diameter of 0.25 mm

Grade: X 23 W T, composition: up to 0.05%; Si - 0.5%; Mn - 0.3%; Ni - 0.6%; S - up to 0.015%; P to 0.03%; Cr - 22-24% CE - 0.1%; Ti - 0,2-0,5%; Al - 5-5,8%; Ca - up to 0.1%; the rest of the iron. Manufacturer - JSC metallurgical plant Electrostal, GOST 12766 1-90.

is the preparing of fehrle included several operations: wire or tape weight of 0.26-0.28 g twisted into a spiral with an outer diameter of 5 mm, was degreased by washing in acetone and progulivali in air in a muffle furnace at 1000°C for 21 h In the result of this oxidative heat treatment on the alloy surface oxide layer consisting mainly of aluminum oxide.

Prepared in this way the coil was placed on a ceramic tube with a diameter of 2 mm and were placed in a flow reactor.

Installation scheme for the oxidative pyrolysis of methane is represented in the drawing: a - front view, b - lateral view. The scheme includes a quartz reactor 1, perlevel spiral 2 on the ceramic tube 3, laboratory autotransformer (Lattre) 4, the window of the optical quartz 5 and the optical pyrometer 6 laser pointing at the spiral.

The reactor operates in the following way. The spiral 1 using LTR and 3 serves voltage, which heats it to the desired temperature from 700 to 1200°C., the Fixing temperature is performed using an optical pyrometer 6 (PD-7, manufacturer JSC "Etalon", Omsk) with laser guidance on the spiral. For this purpose, the reactor is equipped with a window of optical quartz 5. On the hot wire serves the source of the reaction gas. The gas is in contact with the heated spiral in and out. The sample mixture after the reactor is directed to a chromatographic analysis carried out on the chromatograph brand COLOR-500M. Content ostate the aqueous methane, and formed ethane, ethylene and acetylene is fixed with the help of the detector ionization in the flame. Chromatograph conditions were as follows: capillary column with a stationary phase SiO2length 15 m, the pressure of the carrier gas - nitrogen (1 kgf/cm2, air flow 300 ml/min, the flow rate of hydrogen 30 ml/min, column temperature 50°C.

The proposed method is illustrated with examples.

Example 1.

The reaction mixture composition: 15% vol. methane and 85 vol.% nitrogen (without oxygen, the ratio of methane/oxygen 1/0) is passed through the reactor at a temperature of spiral 1100°C with a bulk velocity of 76 ml/min Spiral made of wire with a diameter of 0.25 mm, the methane Conversion and selectivity to products listed in the table.

Example 2-3.

Similar to example 1, but the reaction mixture passed through the reactor at a temperature of spiral 760°C and 890°C, respectively. The spiral is made of a tape width of 1 mm and thickness of 0.4 mm, the methane Conversion and selectivity to products listed in the table.

Example 4.

Similar to example 1, but the reaction mixture passed through the reactor at a temperature of spiral 970°C. the methane Conversion and selectivity to products listed in the table.

Example 5.

Similar to example 1, but the reaction mixture composition: 15% vol. methane, 1% vol. oxygen (ratio of methane/oxygen 15/1) and 84% vol. nitrogen was passed through the reactor at the temperature of the spiral 1170°C.

Example 6 and 7.

Analogous to example 5, but the reaction mixture passed through the reactor at a temperature of spiral 1000°C and 960°C.

Example 8.

Analogous to example 5, but the reaction mixture passed through the reactor at a temperature of spiral 830°C. the Spiral is made of a tape width of 1 mm and a thickness of 0.2 mm

Example 9.

Analogous to example 5, but the reaction mixture passed through the reactor at a temperature of wire 750°C.

Example 10.

The reaction mixture composition: 15% vol. methane, 1% vol. oxygen (ratio of methane/oxygen 15/1) and 84% vol. nitrogen is passed through the reactor at a temperature of spiral 1160°C and the flow rate through the reactor 80 ml/min

Example 11.

Similar to example 10, but the reaction mixture composition: 20% vol. methane, 1,33% oxygen (ratio of methane/oxygen 15/1) and 78,67% vol. nitrogen is passed through the reactor at a temperature of spiral 1150°C.

Example 12.

The reaction mixture composition: 15% vol. methane, 1,67% vol. oxygen (ratio of methane/oxygen 9/1) and 83,33% vol. nitrogen is passed through the reactor at a temperature of wire 760°C. the flow Rate of 75 ml/min Spiral made of wire with a diameter of 0.25 mm

Example 13 and 14.

Similar to example 12, but the reaction mixture passed through the reactor at a temperature of wire 850°C and 930°C, respectively. The spiral is made of a tape width of 1 mm and thickness of 0.4 mm

Example 15, 16 and 17.

And the illogical example 12, but the reaction mixture passed through the reactor at a temperature of wire 1040°C 1110°C and 1230°C, respectively.

The methane conversion and selectivity to products listed in the table. As can be seen from the table, the invention allows to obtain acetylene with selectivity to 41.8% and an ethylene selectivity of 3.3%, the methane conversion is 56.4%.

Significantly increased total yield for2- hydrocarbons - 25,5% (maximum prototype 9.7%).

1. A method of producing acetylene, oxidizing pyrolysis of methane in the presence of oxygen and a catalyst, wherein the catalyst is heated by passing through it an electric current to a temperature of 700-1200°C as catalyst using heat-treated in air at temperatures of 900-1100°C, fecraly alloy, and the ratio of methane:oxygen change in the range 5:1 to 15:1.

2. The method according to claim 1, characterized in that the heat-treated fecraly alloy used in the form of spirals, ribbons, rods.

 

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