The method of chemical processing of methane

 

(57) Abstract:

The invention relates to the technology of basic organic synthesis, in particular the methods of chemical processing of natural gas to produce hydrocarbons and their derivatives, such as ethylene, acetylene, benzene, naphthalene, perchloroethylene, carbon tetrachloride and other Way is to oxidative condensation of methane and other natural gas components in the external zone of the diffusion flame fuel taken in excess with continuous removal of products of transformation. Fuel and/or oxidant is preheated to 500-1100C. For process control in the reaction of introducing non-flammable catalytically inactive substances. The process is simple apparatus, is carried out at atmospheric pressure at a comparative low temperature and environmentally safe. 2 C.p. f-crystals, 1 Il.

The invention relates to the technology of basic organic synthesis, in particular to methods of chemical processing of natural gas to produce hydrocarbons and their derivatives, such as ethylene, acetylene, benzene, naphthalene, perchlorethylene, carbon tetrachloride, etc.

The composition of natural gas, depending on the field is changed as obrienidae connection helium.

The known method of chemical processing of methane (U.S. Pat. 4205194, publ. 1980) by oxidative condensation. In the known method the methane is fed to a solid catalyst containing from 0.01 to 0.2% of a metal of group VIII of the media as MgO, TiO2, ZrO2, Al2O3. The reaction proceeds at temperatures above 700oC., In particular at start-up of methane on Pt - Al2O with the addition of MgO, BaO and Cr2O3.

The main disadvantage of this method is the use of a catalyst, which is economically disadvantageous, and it is not always possible to stop the process of oxidative condensation on the necessary steps.

A method of refining liquefied natural gas (Soros educational journal, No. 9, 1999, S. 42-43. the source S. N. Vereshchagin Gupalov V. K. Ansimov L. N. et al. // Book Abstr. III Workshop C1-C3 Hydrocarbon Conversion. Krasnoyarsk, 1997. P. A23) by combining the exothermic oxidative condensation of methane with an endothermic dehydrogenation reaction of ethane using as raw material liquefied natural gas. In the known method is recirculated methane and ethane, the heat of reaction of oxidative condensation of methane and liquefied natural gny method is only feasible with the use of catalysts, in addition, the effectiveness of this method is small due to the use of liquefied methane.

A method of refining methane (Clarige J. B., Green, M. L. H., Tsang, S. C. , York A. P. Appl. Catal. 1992, A Vol 89, No. 1 p. 103-106), selected by the authors as a prototype, as the closest to the technical essence and the achieved positive effects. In the specified way processing of methane is carried out by oxidative condensation of methane to aromatics in the empty reactor at 950oC in the mix: CH4-O2- N2= 10-1-4. At 1 MPa yield of aromatics reaches of 2.6%, methane to aromatics in the empty reactor at 950oC in the mix: CH2-O2-N2= 10-1-4. At 1 MPa yield of aromatics reaches of 2.6%, the conversion of CH4-12,28%; 0.1 MPa methane reforming 12,25, the yield of aromatics is 0.3%.

The disadvantage of the prototype is that the process takes place in static conditions and it is not possible to use it for practical purposes. With a fairly high degree of conversion of methane to benzene and toluene is reached only at a pressure of 10 ATM.

The task of the invention to provide an industrial method for processing natural gas for the purpose more complex than methane hydrocarbons and their derivatives, for example utilizada is solved by that oxidative condensation is conducted at the surface, in the outer area of the diffusion flame of methane or natural gas, and methane or natural gas taken in excess, add to it 5 to 80% by volume of non-combustible gas and, if necessary, for example, if not enough high activity of the oxidant is heated to a temperature near the point of thermal dissociation of methane. The combustion products are removed by condensation or pumping. Target products, along with the rest of the hydrocarbons extracted and separated in a known manner, the latter being returned to the process or sent to the furnace. If necessary to control the process in the flame injected flame-retardant substances.

The invention consists in the transformation of the combustion of hydrocarbon from the exhaustive process of oxidation and education only CO2and H2O, in the process of primary education intermediate products of oxidative condensation, which allows to obtain from any hydrocarbon whole range of hydrocarbons, as well as oxo-, chlorine - and other derivatives, i.e., to manage the process fiery synthesis. To this end, the methane or other hydrocarbon is burned in such a way that part of it burns, forming extensive diffusion is what the flame occurs in the combustion of methane between the two streams of oxidizer, for example, air heated somewhat above the temperature of dissociation of methane at one heat exchanger, the heat of combustion of the methane, and then in another heat exchanger, or heat of combustion residues methane contained in the gas after removing from it the valuable conversion products, or other fuel.

The proposed method is carried out on the installation, reactor which is shown on the drawing. Methane or natural gas, particularly gas, are taken in a certain excess against the amount of oxidant required for complete combustion, is supplied to the burner tube 2 And inserted into the tube 3 is heated by the heater B-800oC. If the oxidant is air, then half of it is introduced into the tube 1, and the other half in the tube 3. Passing through the tube 3, the air heats up and through the wall of the tube 2 heats up to 600 - 700oC flowing through it combustible gas, which in turn also through the wall of the tube, heats the remainder of the air flowing through the tube 1 to 500 - 600oC. Gas fire and it burns diffusion flame. In the outer zone diffuses from the outside air and the inside of the intermediate zone b - radicals, "hot molecules, nitrogen, CO, COis it from the inner zone and, with methane. Thanks to this process the path of short-lived particles in this area so close that they get into it without losing activity and colliding with molecules of methane, initiate effective oxidative condensation coming from outside oxygen.

Formed in the reactor, the mixture of products of synthesis and direct combustion in the heat exchanger, from which it enters the separator, then the collection of liquid products or the gas tank. Unreacted methane from the separator is sent to a re-conversion in the same way, or use one of the above methods. Methane or natural gas and oxidizer enter the reactor in ratios that depend on the nature of the oxidant and the desired target products. For example, when using as the oxidant oxygen of the air, the volumetric ratio of methane - oxygen can be close to the stoichiometric ratio to 20 to 1. When used as an oxidizer chlorine ratio of methane to chlorine from close to stoichiometric to 100 to 1.

The reactor may be made of metal, ceramics or heat-resistant glass. Can be used any oxidant, a burning flame in the environment of methane. Improving the population it from 1 to 90% non-flammable gas. The reactor and the furnace can be one - Autonomous or stationary thermochemical generator (THG) chemical products and heat energy as any big power.

The essence of the proposed method is illustrated by examples.

Example 1. In a laboratory reactor heat-resistant glass with a length of 100 mm and a diameter of 70 mm serves methane and oxygen in a volume ratio of 89:11. Methane is here heated to 500oC, in a known manner is ignited and burns diffusion flame with oxygen diffusion from the inside of the flame. As a result of reactions with this in the outer zone of the flame at the outlet of the reactor gain in volume %: H2- 9,6%, CO - 5,9% (synthesis gas), CO2BY 1.3%, C2H4- 12%, C2H2BY 1.3%, C2H6- 0,8%, C2H6TO 1.4%, C10H8for 1.1%. Else H2O and disperse the carbon and unreacted methane.

The methane conversion was reached 37%, the selectivity for H2, CO, C2H2C2H4C2H6C6H6and C10H8was 64%.

Example 2. The conversion is carried out analogously to example 1, but in the reactor, made of metal, a length of 200 mm and a diameter of 14 mm Methane and Kilgore in the outer zone of the flame, where and converted. As a result, have volume %: H2- 50%, CO - 27% (synthesis gas), CO2of 4.2%. C2H4- 0,7%, C2H2- 2,9%, C6H6- 0,24%, C10H8to 0.15%, the Rest of H2O, particulate carbon and unreacted methane. The methane conversion was 87%, the selectivity for H2, CO, C2H4C2H2C6H6C10H8was 76%.

Example 3. In a reactor made of heat-resistant glass, length 200 mm, diameter 14 mm serves methane and air in a volume ratio of 67:33. Here they are heated up to 750oC and lit a known manner. As a result of reactions similar to the previous examples in the outer zone at the surface are in% by volume: N2- 15%, CO - 2,5% (synthesis gas), CO2- 0.9%, C2H2- 3%, C2H6- 0.6%, C6H6- 1.1%. C10H8to 0.8%. The rest of the nitrogen from the air, H2O, particulate carbon and unreacted methane. The methane conversion was 48%, the selectivity for H2, CO, C2H2C2H6C6H6C10H8- 78%.

Example 4. In a reactor made of heat-resistant glass with a length of 100 mm and a diameter of 80 mm is served without preheating MIA, flowing in the external zone of the latter, at the exit of the reactor are volume percent: CH2Cl2- 0,56%, CHCl3- 1,35%, CCl4- 5,6%, C2HCl3TO 1.0%, C2Cl4is 1.2%. The rest HCl, dispersed chlorinated carbon, unreacted methane and chlorine, hydrocarbons from C10to C30and their chlorinated. The methane conversion was 75%, the selectivity for CH2Cl2, CHCl3, CCl4C2HCl3C2Cl4amounted to 27%.

Example 5. In a reactor made of heat-resistant glass with a length of 100 mm and a diameter of 70 mm serves preheated to a temperature of 600oC nitrogen, methane and chlorine in the ratio of 50-30-20% and a known manner organize diffusion flame. In the reaction in the outer area of the latter at the exit of the reactor have volume %: CH2Cl2- 0,5%, CHCl3of 0.77%, CCl4- 1.7%, C2HCl3- 0,58%, C2Cl4to 1.0%. The rest of HCl and unreacted methane and chlorine. The methane conversion was 50%, the selectivity for CH2Cl2, CHCl3, CCl4C2HCl3C2Cl4- 56%. The formation of carbon was not observed.

Example 6. In a reactor made of heat-resistant glass with a length of 200 mm and a diameter of 20 mm is served heated to a temperature which rsiu in the external zone of the diffusion flame data of hydrocarbons. In response to the output from the reactor are% by volume:2- 9%, CO - 3,2%, CO2TO 3.0%, - 8%, C2H4and C2H2- 10%, C6H6- 0,5%, C10H80.4%, and the nitrogen - 39%, CH4- 24%, the rest of H2O, particulate carbon, unreacted propane and butane. The diffusion flame combustion occurs in the reactor with water cooling of the outer walls. The conversion of methane to hydrocarbons amounted to 52%, the selectivity of transformation in H2, CO, C2H2C2H4C6H6C10H8amounted to 68%.

Methane, all of the examples were taken from the household mains natural gas.

1. The method of chemical processing of methane or natural gas by oxidative condensation, characterized in that the oxidative condensation is conducted in the outer zone of the diffusion flame fuel taken in excess with continuous removal of products of transformation.

2. The method according to p. 1 wherein the fuel and/or oxidant is preheated to 500-1100C.

3. The method according to PP.1 and 2, characterized in that to control the process in the reaction of introducing non-flammable catalytically inactive substances.

 

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