WO2015140058A1 - Device and method for producing organic compounds having a boiling point of 15°c or higher from a methane-containing gas - Google Patents

Abstract

The invention relates to a device and method for producing one or more organic compounds having a boiling point of 15°C or higher from a methane-containing gas by plasma reaction.

Description

 Apparatus and method for producing organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas

The present application relates to an apparatus and a method for producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas. The term "boiling point" refers to the boiling point at standard pressure (101325 Pa).

The exploitation of natural gas deposits, which are very far from potential consumers (so-called stranded gas fields) is currently economically not useful because of the high cost of transporting the gas through specially constructed lines or tankers or tankers. The same applies to natural gas deposits with limited capacity or low pressure of natural gas (for example, in the final stage of exploitation of a natural gas deposit) as well as other sources of fossil or synthetically produced methane-containing gases for whose material or energy use there is no local market. Fossil or synthetically produced methane-containing gases from sources other than natural gas deposits include, for example, crude oil associated with crude oil production, biogas, coal bed gas, mine gas, landfill gas and methane produced by methanation of carbon dioxide.

Of a material or energetic use of such methane-containing gases often conflicting additional effort for the removal of the gas can be reduced by conversion into liquids. By converting from the gaseous to the liquid state, a volume reduction by several orders of magnitude can be achieved. Is the liquefaction of the purified methane-containing gas by cooling ment and compression, the product is CNG (Compressed Natural Gas) or LNG (Liquefied Natural Gas). In order to keep it in the liquid state, compression and cooling must be maintained during transport. Alternatively, the production under normal conditions (ie at the standard pressure of 101325 Pa) of liquid substances from the purified methane-containing gas by chemical conversion processes comes into consideration ("gas to liquid" process). However, this requires the establishment of the necessary for the chemical processes including required upstream purification stages (eg desulfurization) devices in close proximity to the source of methane-containing gas, for example in the vicinity of a conveyor system for the exploitation of a stranded gas occurrence.

Anderson et al. describe in a journal article (Fuel 81 (2002) 909-925) a process for the conversion of natural gas via acetylene as an intermediate to liquid fuels. The process comprises, as a first step, the conversion of methane to acetylene by means of a thermal plasma quenched by contact with the reactor walls or aerodynamically by expansion by means of a supersonic nozzle and, as a second step, the conversion of acetylene into liquid products in a catalytic process , The method is particularly suitable for use on remote natural gas production sites, e.g. on the north coast of Alaska, for which the construction of a gas pipeline for the removal of the gas is unprofitable. The publication does not indicate how the necessary for the plasma electrical energy to be provided. The catalytic process downstream of the catalytic process requires purification of the natural gas, in particular desulfurization, and the formation of soot must be avoided.

Tonkovich et al. describe in the publication "Gas-to-Liquids Conversion of Associated Gas Enabled by Microchannel Technology" (White paper, Velocys © 2009, http://www.velocys.com/ocgf06.php) the conversion of associated petroleum gas or in the vicinity of the petroleum production plant by a combination of catalytic steam reforming of the methane and Fischer-Tropsch synthesis in a microchannel reactor to "synthetic crude oil", which can be fed into the extracted crude oil stream. Both the steam reforming of the methane and the Fischer-Tropsch synthesis are carried out in the presence of catalysts. There is the risk of deactivation of the catalysts, for example by deposition of soot or impurities contained in the associated petroleum gas. The catalysts for the Fischer-Tropsch synthesis are particularly sensitive to poisoning by sulfur-containing compounds. Therefore, it is essential to remove all sulfur compounds from the gas stream prior to the Fischer-Tropsch synthesis (see also Steve LeViness et al., "Improved Fischer-Tropsch Economics Enabled by Microchannel Technology", White paper, Velocys © 201 1 http://www.velocys.com/ocgf06.php). The desulfurization is usually carried out at 350 ° C to 400 ° C in a catalytic process. The temperature level required for steam reforming (700 ° C to 1100 ° C) is generated by catalytic combustion of hydrogen in the microchannel reactor. Thus, the process comprises a total of up to four catalysed process steps, each associated with the risk of deactivation of the catalysts involved. In order to set an optimum CO: H ₂ ratio of 1: 2 for the Fischer-Tropsch synthesis stage, it is necessary to separate hydrogen from the process gas in an intermediate step after the steam reforming stage. In the micro-channel reactors used, there is a risk of blocking individual cells or channels. For an overall process management in terms of optimal energy integration, it is disadvantageous that the process has a stepped temperature level (350 ° C to 400 ° C for the catalytic desulfurization, 700 ° C to 1 100 ° C for the steam reforming, 210 ° C. for the Fischer-Tropsch synthesis). The method and the apparatus required for it are therefore relatively complex and have numerous weak points, which makes it difficult to use in the immediate vicinity of the source of fossil or synthetically produced methane-containing gas, for example in the vicinity of a conveyor system for the exploitation of a stranded gas occurrence.

WO 2012/175279 A1 proposes a method for modifying a methane-containing gas volume flow, e.g. a natural gas stream comprising the steps: i) taking at least a partial volume flow from a methane-containing gas flow, ii) treating the partial flow with an electrically generated plasma to produce a modified gas composition comprising a lower proportion of methane than the methane-containing gas flow used and iii) recycling of modified gas composition in the methane-containing gas flow. By means of this method, part of the methane from the methane-containing gas volume flow is converted to hydrogen and higher hydrocarbons, and the treated partial volume flow receives a higher calorific value than the methane-containing gas volume flow. This method should make it possible to convert electrical energy, in particular excess energy produced from renewable sources into a storable form. The conversion of methane into compounds which are liquid under normal conditions is not described.

US 201 1/0054231 A1 discloses a process wherein natural gas with external hydrogen sources is converted to reactive hydrocarbons comprising acetylene and the reactive hydrocarbons are reacted to form liquid hydrocarbons. A plasma is not used in this procedure. WO 2012/135515 A2 discloses a method for producing a hybrid fuel, the method comprising: feeding a first reactant to a reactor, wherein the first reactant comprises one or more light gases sufficient to expose the first reactant to a non-thermal plasma under conditions sufficient for generating syngas and free radicals, supplying a first liquid fuel feed to the reactor, and bringing the syngas generated from the first reactant and the free radicals into intimate contact with the first liquid fuel feed in the reactor to produce a modified liquid fuel.

EP 0 289 391 A1 discloses a process for the thermal conversion of methane to higher molecular weight hydrocarbons in a ceramic reaction zone having a set of adjacent channels grouped in rows and extending at least over part of the entire reaction zone parallel to its axis, the Rows of channels are not adjacent to each other, and the reaction zone further comprises, on the one hand, a heating zone substantially surrounding the channel rows, either on said portion of the reaction zone or on a portion of the length of the reaction zone, if the channels are full length on the other hand a cooling zone, which is an extension of the heating zone, characterized in that a methane-containing gas circulates in the channels of the rows, the heating zone is heated by means of elektret energy supply by successive, independent transverse sections substantially and perpendicular to the axis of the reaction zone and substantially parallel to the plane of the rows and close to the channels of the reaction zone, a cooling liquid is introduced into the cooling zone and the higher molecular weight hydrocarbons are collected at the end of the reaction zone. The primary object of the present invention is to provide an apparatus for producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas. In developing a solution to the above problem, consideration must be given to the typically limited space available at the site of the device near a source of methane as described above, as well as the fact that the supply of available co-reactants and chemical process supplies is typically limited there , and electrical energy not readily available in any amount from the outside, eg via the mains, is available.

This object is achieved by a device according to the invention and a method according to the invention for producing one or more organic compounds a boiling point of 15 ° C (at standard pressure) or higher from a methane-containing gas.

An apparatus according to the invention for producing one or more organic compounds having a boiling point of 15 ° C or higher from a gas containing methane

 a device for providing a methane-containing gas

 at least one reactor for plasma assisted production of one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas, said reactor comprising:

 a first reactor section, in which

 Means for supplying at least one plasma gas,

Means for generating a plasma with a temperature greater than 5000 K with the supplied plasma gas,

 and means for cooling the plasma gas to a temperature in the range of 2500K to 5000K

 are arranged;

 a second reactor section following in the flow direction of the plasma gas to the first reactor section, in which

 Means for supplying a methane-containing educt gas taken from the device for providing a methane-containing gas are arranged to the plasma gas cooled to a temperature in the range from 2500 K to 5000 K., wherein this reactor section is set up so that a product gas containing one or both compounds is formed from the group consisting of ethylene and acetylene;

 a third reactor section following in the flow direction of the product gas to the second reactor section, in which

 Means are arranged to contact the product gas formed in the second reactor section with a methane-containing quench fluid so that a quenched product gas having a temperature in the range of 750 K to 1100 K is formed;

wherein the means for supplying a methane-containing educt gas and the means for contacting the product gas with a quench fluid containing methane are set up to set a ratio of methane in the educt gas to methane in the quench fluid in the range of 3: 1 to 1: 3

 in which

 (i) the reactor is adapted to form a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C or higher

 or

 (ii) the reactor comprises one or more further reactor sections for further treating the quenched product gas to form one or more organic compounds having a boiling point of 15 ° C or higher.

A method according to the invention for producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas comprises the steps

 Providing a methane-containing gas

 plasma enhanced production of one or more organic compounds having a boiling point of 15 ° C or higher from a methane containing gas, comprising:

 Supplying at least one plasma gas, generating a plasma having a temperature greater than 5000 K with the supplied plasma gas, and then cooling the plasma gas to a temperature in the range of 2500 K to 5000 K;

 Supplying a methane-containing feed gas withdrawn from the supplied methane-containing gas to the plasma gas cooled to a temperature in the range of 2500K to 5000K and forming a product gas containing one or both of ethylene and acetylene;

 contacting the product gas with a methane-containing quench fluid to form a quenched product gas having a temperature in the range of 750 K to 1100 K;

 wherein a ratio of methane in the reactant gas to methane in the quench fluid in the range of 3: 1 to 1: 3 is set

in which (i) forming a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C or higher, or

 (ii) the quenched product gas is further treated to form one or more organic compounds having a boiling point of 15 ° C or higher.

The reactor contained in the device according to the invention for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas comprises at least three sequentially in the flow direction reactor sections, wherein the temperature drops from the first to the third reactor section. The individual reactor sections differ from each other in terms of temperature and gas composition. The first reactor section is the plasma generation section of the reactor. The following second reactor section is the plasma near zone, and the subsequent third reactor section is the plasma remote section. The terms "plasmanah" and "plasma-core" refer both to the spatial distance to the plasma generation region and to the difference between the temperature in the second or third reactor section and the temperature of the plasma in the plasma generation region.

In the first reactor section of the reactor (the plasma generation region of the reactor) contained in the device according to the invention, a plasma gas - preferably a gas available or producible at the point of use of the apparatus or method according to the invention - is partially ionized by the action of an arc formed between two electrodes. The above-mentioned means for generating a plasma accordingly comprise the electrodes for generating the arc together with the power supply. The plasma formed (DC plasma) has a temperature greater than 5000 ° C to a maximum of 30,000 ° C, preferably 7000 ° C to 27000 ° C, more preferably 10000 ° C to 25000 ° C. The plasma contains ions, electrons and atoms in equilibrium. The recombination of ions and electrons releases thermal energy. Suitable ways of producing a plasma by means of operating materials and energy carriers available or producible at the site of the device or the method according to the invention are shown below in detail. The first reactor section is actively cooled, so that the temperature of the plasma gas as it flows through the first reactor section to a value in the range of 2500 K to 5000 K decreases. In the second reactor section of the reactor contained in the apparatus according to the invention (the plasma-near region of the reactor), means are preferred for supplying a methane-containing educt gas taken from the device for supplying a methane-containing gas to a temperature in the range from 2500 K to 5000 K. 3000 K to 4000 K cooled plasma gas arranged.

The means for supplying the methane-containing educt gas usually comprise means for preheating the methane-containing educt gas to a temperature in the range of 100 ° C to 1200 ° C, preferably from 200 ° C to 1000 ° C, more preferably from 400 ° C to 700 ° C. As a result of the action of the thermal energy released in the first reactor section, gaseous low molecular weight hydrocarbons, in particular methane, contained in the feed gas introduced are pyrolyzed and dissociate into free-radical species, in particular methyl radicals and hydrogen radicals. The methyl radicals form unsaturated C ₂ hydrocarbons (predominantly acetylene, but also ethylene by dimerization and hydrogen abstraction), whereby the molar ratio between acetylene and ethylene is influenced by the choice of the process parameters pressure, temperature, average residence time and quench rate). Thus, in the second reactor section, a product gas containing one or both compounds is formed from the group consisting of ethylene and acetylene. The conversion of methane to acetylene and hydrogen is an endothermic reaction, so that in the second reactor section after supplying the methane-containing educt gas, the temperature further decreases.

From the compounds formed in the second reactor section from the group consisting of ethylene and acetylene higher molecular weight organic compounds are formed in subsequent reactor sections or subsequent process steps by oligomerization, which in turn act under suitable conditions as starting material for the formation of carbon black.

Means are arranged in the third reactor section of the reactor (the plasma remote region of the reactor) included in the apparatus according to the invention for contacting the product gas with a methane-containing quench fluid such that a quenched product gas having a temperature in the range of 750 K to 1100 K is formed. The quenching aborts the reactions taking place in the second reactor section, but in the form of the quench fluid a new reaction partner is introduced which can undergo subsequent reactions with the constituents of the product gas formed in the second reactor section. According to the invention, a methane-containing gas is used as the quench fluid in the third reactor section. Without the present invention is bound to a theory, it is currently believed that the methane contained in the quench fluid causes chain extension of the C ₂ hydrocarbons already formed in the second reactor section by providing additional carbon atoms. The methane content of the quench fluid is preferably 50% by volume or more, more preferably 75% by volume or more.

The methane-containing quench fluid is preferably withdrawn from the methane-containing gas provided for the process according to the invention. In the apparatus of the invention, the means for contacting the product gas with a quench fluid containing methane preferably comprises means for contacting the product gas with a quench fluid containing methane withdrawn from the methane-containing gas supply means. In this preferred embodiment of the device according to the invention, therefore, both the methane-containing educt gas and the methane-containing quench fluid are taken from the device for providing a methane-containing gas. According to the invention, a ratio of methane in the educt gas to methane in the quench fluid is set in the range from 3: 1 to 1: 3. Our own investigations have shown that this results in a particularly high yield of organic compounds having a boiling point of 15 ° C or higher. Preference is given to a ratio of methane in the educt gas to methane in the quench fluid in the range from 1: 1.5 to 1: 2.5, more preferably 1: 2.

Since the processes of radical formation, dimerization, oligomerization, hydrogen splitting and soot formation have different reaction enthalpies and reaction rates, the composition of the reaction products formed can be influenced by the choice of the process parameters pressure, temperature, mean residence time and quench rate. By appropriate choice of these process parameters and appropriate design of the reactor, the reaction is controlled either to form a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C or higher, or alternatively such that by further treating the quenched product gas or more organic compounds are formed with a boiling point of 15 ° C or higher. Both embodiments are encompassed by the present invention and are each characterized by specific advantages, which are described below.

In addition to the components described above, the device according to the invention preferably comprises means for bringing the quenched product gas into contact with one or more further quench fluids. Preferably, the inventive Method in addition to the method steps described above, contacting the quenched product gas with one or more other quench fluids. In one variant, the quench fluid quenched with a methane product gas is brought into contact with quench fluid containing further methane. Other variants use air or water as another quench fluid. Also preferred is the use of a partial volume flow of the organic compounds produced having a boiling point of 15 ° C or higher as another quench fluid.

The organic compounds having a boiling point of 15 ° C. or higher and produced by the device or the process according to the invention are typically prepared for further recycling in the same manner as crude oil, preferably together with crude oil in a petroleum refinery. Due to the achieved by the conversion of the gaseous into the liquid state volume reduction by several orders of magnitude, the removal of inventively produced at standard pressure liquid products for material processing in a - if necessary far away from the site of the device or the inventive method - oil refinery much more profitable as a removal of the methane-containing gas in the gaseous state to a suitable for material or energetic use of the gas location.

According to the invention available organic compounds having a boiling point of 15 ° C or higher (under normal pressure as defined above) are compounds selected from the group consisting of benzene, alkyl-substituted benzenes (eg methylbenzene (toluene), dimethylbenzenes (xylenes), vinylbenzene (styrene), Isopropylbenzene (cumene), methylethylbenzene, butylbenzene), further substituted aromatic compounds (eg cresol, biphenyl, indanone), polycyclic aromatic hydrocarbons (PAH, eg indane (cyclopentenobenzene), naphthalene, acenaphthene, phenyltoluene, anthracene, fluoranthene, pyrene and higher polycyclic aromatic hydrocarbons) and saturated aliphatic hydrocarbons having more than 5 carbon atoms in the molecule (eg decalin).

The device according to the invention comprises a device for providing a methane-containing gas, from which a methane-containing educt gas can be removed. Accordingly, the method according to the invention comprises a step of providing a methane-containing gas, and from the provided methane-containing gas, a methane-containing educt gas is taken. Usually, the methane content of the methane-containing gas provided and the methane-containing starting gas taken therefrom is 50% by volume or more, more preferably 75% by volume or more, the methane content being from the source of the methane provided containing gas depends. Preferably, the methane-containing gas provided contains less than 5 vol%, more preferably less than 4% carbon dioxide.

The device according to the invention and the method according to the invention are particularly suitable for processing methane-containing gases from the group consisting of:

 oil associated with oil production

 natural gas

 biogas

 Coal bed gas

- mine gas

 methane formed by methanizing carbon dioxide

 Landfill gas.

The means for providing the methane-containing gas is thus preferably selected from the group consisting of:

- Facilities for the provision of associated petroleum gas during crude oil production

 Facilities for providing natural gas

 Facilities for providing biogas

 Means for providing seaming gas

- Facilities for the provision of mine gas

 Means for providing methane formed by methanation of carbon dioxide

 Facilities for providing landfill gas.

In order to keep the transport routes for the methane-containing gas short, the device according to the invention is typically arranged in close proximity to a source of a suitable methane-containing gas, ie in close proximity to a natural gas production facility, a petroleum production facility with means for collecting associated petroleum gas , a coal deposit or mine with devices for catching coalmine or mine gas, a biogas plant or a methanation plant for carbon dioxide. The means for providing the methane-containing gas thus regularly comprises means for obtaining from a suitable source. To transfer methane-containing gas into the inventive device, for example, a connection to a corresponding gas line, which connects the source of methane-containing gas with the device according to the invention.

For the process according to the invention, the methane-containing gas provided is preferably selected from the group consisting of:

 oil associated with oil production

 natural gas

 biogas

 coalbed methane

- mine gas

 methane formed by methanizing carbon dioxide

 Landfill gas.

Associated Petroleum Gas (APG) is a mixture of gaseous chemical compounds, similar in composition to natural gas, released from oil wells during oil production.

Coal gas or mine gas is naturally produced from coal deposits. Coalbed gas or coalbed gas is coal gas released through a well in the uncracked mountain range, while mine gas refers to the coal gas obtained in mines.

Methods and devices for recovering biogas or landfill gas or for methanating carbon dioxide are known in the art.

In addition to methane, the methane-containing gas contains depending on the origin typical further constituents of natural gas, associated gas, biogas, coalbed gas or mine gas, for example hydrocarbons selected from the group consisting of ethane, propane and butane, and constituents from the group consisting of water vapor, Hydrogen sulfide, carbon monoxide, carbon dioxide, nitrogen and noble gases. If the methane is formed by methanation of carbon dioxide, the gas containing methane used according to the invention optionally contains by-products formed during the methanation of the carbon dioxide. Natural gas and crude oil associated with the production of crude oil usually have a methane content of 75 vol .-% to 99 vol .-% and can therefore be used without further treatment for the inventive device and the inventive method. The same applies to seaming and mine gas, whose methane content is typically 80 vol .-% to 95 vol .-%. Some However, the above sources provide a gas with a methane content of less than 50% and / or a carbon dioxide content of more than 5 vol .-%. This applies in particular to landfill gas and partly also to biogas. In these cases, it is provided that the device for providing the methane-containing gas comprises means for increasing the methane concentration, for example in the form of a membrane system for separating unwanted gas constituents.

If the required methane content of 50% by volume or more is present or has been adjusted, further purification of the methane-containing gas, e.g. by desulfurization, for the device according to the invention or the method according to the invention is not absolutely necessary, since the device according to the invention or the inventive method can be operated without catalysts. Sulfur-containing constituents of the methane-containing educt gas (for example, in the case of natural gas or associated petroleum gas, primarily hydrogen sulfide and low molecular weight thiols) are converted in the plasma to more complex organosulfur compounds, hydrogen and / or elemental sulfur. This is not a problem, since during the treatment in a petroleum refinery desulfurization takes place anyway. The elimination of desulfurization of the educt gas is a significant advantage of the device or the method according to the invention, as this simplifies the method and apparatus and the space requirements and the demand for supplies are reduced, and the use of highly acidic natural gas sources or APG gas sources is facilitated ,

Only for a specific variant of the device according to the invention, in which a further reactor section is provided, in which one or more catalysts for forming one or more organic compounds having a boiling point of 15 ° C or higher from contained in the quenched product gas contained acetylene and / or ethylene are (see below), and the process according to the invention, wherein formed from the quenched product gas acetylene and / or ethylene in the presence of one or more catalysts, one or more organic compounds having a boiling point of 15 ° C or higher (see below), deacidification of the methane-containing educt gas (washing out of hydrogen sulfide) is necessary.

In a first preferred embodiment of the process according to the invention, a quenched product gas comprising one or more organic compounds having a boiling point of 15 ° C. or higher is formed. In a first preferred embodiment of the device according to the invention, the reactor is set up so that a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C. or higher is formed.

In this first preferred embodiment of the invention, the reactor is preferably set up such that the average residence time in the second reactor section is 0.1 ms to 20 ms, preferably 0.1 ms to 10 ms, particularly preferably 0.1 ms to 5 ms at a volume flow of methane from 1 standard m ³ / h to 10000 standard m ³ / h, preferably from 1 standard m ³ / h to 4000 standard m ³ / h, and an energy input through the plasma per kg of methane of 1 kWh to 40 kWh, preferably from 1 kWh to 20 kWh and more preferably from 6 to 14 kWh (based on pure methane).

The quench rate in the first preferred embodiment of the invention is 10 ² K / s to 10 ⁷ K / s, preferably 10 ³ K / s to 10 ⁶ K / s, more preferably 10 ⁵ K / s to 10 ⁶ K / s. The pressure is 50 kPa to 5000 kPa, preferably 80 kPa to 1500 kPa, more preferably 100 kPa to 500 kPa. In order to avoid uncontrolled subsequent reactions in the quenched product gas, in the first preferred embodiment of the device according to the invention the third reactor section preferably comprises means for keeping the quenched product gas within a certain temperature range over a defined mean residence time. For this purpose, an immediately after the means for bringing the product gas with a methane-containing quench fluid in contact, the following outlet section is provided. The quenched product gas is preferably maintained in the outlet section over a mean residence time of 100 ms to 1000 ms, more preferably from 300 ms to 500 ms, at a temperature in the range of 400 ° C to 1000 ° C. Means are preferably arranged at one or more positions in the outlet section in order to bring the quenched product gas flowing through the outlet section, which has already been brought into contact with a quench fluid containing methane, into contact with one or more further quench fluids, that is, in the outlet section ongoing processes and thus to control the composition of the quenched product gas.

Our own investigations have shown that the mean residence time in the first third of the outlet section has a decisive influence on the composition of the quenched product gas. In order to achieve that the quenched product gas contains one or more hydrocarbons with a boiling point of 15 ° C or higher, the average residence time in the first third of the discharge path is preferably 5 ms to 100 ms, preferably 10 ms to 80 ms, particularly preferred set to 25 ms to 60 ms. The average residence time in the first third of the outlet section is adjustable by appropriate choice of the volume flows of the plasma gas, the methane-containing educt gas and the quench fluids. Means are preferably arranged in the first third of the outlet section in order to bring the quenched product gas, which has already been brought into contact with a quench fluid containing methane, into contact with one or more further quench fluids. In one variant, the quench fluid quenched with a methane product gas is brought into contact with quench fluid containing further methane. Other variants use air or water as another quench fluid. Also preferred is the use of a partial volume flow of the organic compounds produced having a boiling point of 15 ° C or higher as another quench fluid.

In the first preferred embodiment of the invention, a conversion based on the methane contained in the reactant gas of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher is preferably achieved and a carbon yield of organic compounds having a boiling point of 15 ° C. or higher from 2% to 20%, preferably from 2% to 30%, more preferably from 2% to 70%.

The first preferred embodiment of the invention, especially in its variants marked as preferred, is characterized in that the quenched product gas formed in the third reactor section already contains the desired organic compounds having a boiling point of 15 ° C. or higher. As a result, the reactor can be made relatively compact and simple, and a catalyst is not required.

In a specific variant of the first preferred embodiment of the process according to the invention, a quenched product gas comprising one or more organic compounds having a boiling point of 15 ° C. or higher and carbon black is formed.

In a specific variant of the first preferred embodiment of the device according to the invention, the reactor is set up so that a quenched product gas containing one or more hydrocarbons having a boiling point of 15 ° C. or higher and carbon black are formed. The formation of soot can be achieved by appropriate adjustment of the above-mentioned process parameters, for example the choice of a relatively high energy input by the plasma per kg of methane and a relatively long residence time in the outlet section, with a higher residence time is necessary, the smaller the temperature in the outlet section is. Suitable is, for example, an energy input of 14 kWh / kg of methane or more in combination with a mean residence time of 400 ms or more at an average temperature of the outlet line of 500 ° C or more, and an energy input of 20 kWh / kg methane or more in combination with a mean residence time of 300 ms or more at a mean temperature of the outlet line of 200 ° C or more. In this particular variant of the first preferred embodiment of the invention, the hydrocarbons formed having a boiling point of 15 ° C or higher are partially adsorbed by the resulting carbon black. Typically, the proportion of hydrocarbons having a boiling point of 15 ° C or higher adsorbed by carbon black is 10 to 30 mol% based on the total amount of hydrocarbons having a boiling point of 15 ° C or higher. The carbon black adsorbed compounds are predominantly aromatic hydrocarbons (including polycyclic aromatic hydrocarbons). The content of carbon black adsorbed on aromatic hydrocarbons is preferably up to 25 wt .-%, preferably up to 30 wt .-%, particularly preferably up to 50 wt .-%. In the refinery processing, the carbon black adsorbed organic compounds having a boiling point of 15 ° C or higher are desorbed and further processed, leaving the carbon black as a solid residue. The remaining in the petroleum distillation and refining solid residue after calcination is usually processed by known methods to petcoke (Pet-coke), for example, for the production of Soderberg electrodes, especially for aluminum extraction, and as a raw material for the production of synthetic Graphite, in particular as an electrode material for the production of electrical steel, is used. Thus, this particular variant of the first embodiment of the invention opens up access to further value-added chains. In a second preferred embodiment of the process according to the invention, a quenched product gas containing one or both compounds is formed from the group consisting of ethylene and acetylene, and

the quenched product gas is further treated to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher. In a second preferred embodiment of the device according to the invention, the reactor is arranged so that a quenched product gas containing one or both compounds is formed from the group consisting of ethylene and acetylene, and

the reactor in the flow direction of the quenched product gas following the third reactor section comprises a fourth reactor section for further treating the quenched product gas to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher. In this second preferred embodiment of the invention, the reactor is preferably set up so that the mean residence time in the second reactor section of the reactor is 0.1 ms to 20 ms, preferably 0.1 ms to 10 ms, particularly preferably 0.1 ms to 5 ms at a volumetric flow of methane from 1 standard m ³ / h to 10000 standard m ³ / h, preferably from 1 standard m ³ / h to 4000 standard m ³ / h and an energy input through the plasma per kg of methane from 1 kWh to 40 kWh, preferably from 3 kWh to 20 kWh and particularly preferably from 8 to 13 kWh.

The quench rate in the second preferred embodiment of the invention is 10 ² K / s to 10 ⁷ K / s, preferably 10 ³ K / s to 10 ⁶ K / s, particularly preferably 10 ⁵ K / s to 10 ⁶ K / s. The pressure is 50 kPa to 6000 kPa, preferably 80 kPa to 1500 kPa. The level of pressure influences the selectivity for the formation of acetylene or ethylene. If a high proportion of acetylene is desired, the pressure is preferably selected in the range 100 kPa to 1000 kPa, for a high proportion of ethylene, however, in the range of 1000 kPa to 6000 kPa.

In the specific variants of the second preferred embodiment of the invention described below, no catalysts are provided in the fourth reactor section.

In order for one or more organic compounds having a boiling point of 15 ° C. or higher to be formed in the fourth reactor section from acetylene and / or ethylene, this is preferably set up so that the average residence time is 0.1 s to 120 s, preferably 1 s to 60 s, more preferably 2 s to 30 s is at a temperature in the range of 100 ° C to 1500 ° C, preferably from 100 ° C to 1300 ° C, more preferably from 200 ° C to 800 ° C. Preferably, means are arranged at one or more positions in the fourth reactor section to bring the quenched product gas, which has already been contacted with a quench fluid containing methane, into contact with one or more other quench fluids so as to effect the processes occurring in the fourth reactor section and thus to control the composition of the gas stream.

Our own investigations have shown that the average residence time in the first third of the fourth reactor section has a decisive influence on the composition of the gas stream. In order to achieve that one or more organic compounds having a boiling point of 15 ° C. or higher are formed in the fourth reactor section, the average residence time in the first third of the fourth reactor section is preferably 1 ms to 80 ms, preferably 2 ms to 50 ms , more preferably set to 5 ms to 30 ms. The average residence time in the first third of the fourth reactor section can be adjusted by appropriate selection of the volume flows of the plasma gas, the educt gas and the quench fluids. Means are preferably arranged in the first third of the fourth reactor section in order to bring the quenched product gas, which has already been brought into contact with a quench fluid containing methane, into contact with one or more further quench fluids. In one variant, the quench fluid quenched with a methane product gas is brought into contact with quench fluid containing further methane. Other variants use air or water as another quench fluid. Also preferred is the use of a partial volume flow of the organic compounds produced having a boiling point of 15 ° C or higher as another quench fluid.

For the embodiment of the fourth reactor section, in which no catalysts are provided, there are two basic alternatives. In the first alternative, a constant temperature selected from the region defined above, preferably from the area designated as preferred, is impressed on the fourth reactor section by cooling or heating. Particularly preferred is a constant temperature in the range of 400 ° C to 1000 ° C.

In the second alternative, the fourth reactor section is subdivided into individual successive modules each with individually adjustable temperature and with means for bringing the gas flow into contact with a quench fluid, the quench rate being individually adjustable for each module. Preferably, the temperatures are adjusted so that the temperature decreases from module to module in the direction of flow. As a result, the gas flow when passing through the fourth reactor section passes through a temperature profile from higher to lower temperatures, the temperatures of the individual modules being selected from the range defined above, preferably from marked as preferred area. Particularly preferred is a temperature profile which extends from a maximum value of 1000 ° C at the entrance of the fourth reactor section to a minimum value of 100 ° C at the outlet of the fourth reactor section. Size and number of the successive modules are designed so that the desired average residence time, based on the fourth reactor section as a whole, is achieved.

In the second preferred embodiment of the invention, a conversion based on the methane contained in the educt gas of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher is preferably achieved and a carbon yield of organic compounds having a boiling point of 15 ° C. or higher from 5% to 50%, preferably from 10% to 60%, most preferably from 20% to 80%.

The second preferred embodiment of the invention - in particular in their variants marked as preferred - is characterized in that first high selectivity and high carbon yield acetylene and / or ethylene are formed from the methane contained in the reactant gas, and then the acetylene formed and / or Ethylene in a controlled thermal oligomerization (ie with higher selectivity and typically higher carbon yield compared to the first embodiment of the invention described above) to compounds having a boiling point of 15 ° C or higher, for example is converted from the group consisting of benzene, naphthalene and anthracene without the need for a catalyst.

In a specific variant of the second preferred embodiment of the method according to the invention

 a quenched product gas containing one or both compounds selected from the group consisting of ethylene and acetylene, and

 the quenched product gas is further treated to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher and carbon black.

In a special variant of the second preferred embodiment of the device according to the invention

 the reactor is arranged to form a quenched product gas containing one or both compounds selected from the group consisting of ethylene and acetylene, and

the reactor comprises, in the flow direction of the quenched product gas following the third reactor section, a fourth reactor section for further of the quenched product gas to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher and carbon black.

In this particular variant of the second preferred embodiment of the invention, no catalysts are provided in the fourth reactor section. The formation of carbon black can be achieved by appropriate adjustment of the o.g. Process parameters, e.g. Choice of a relatively high energy input per kg of methane by the plasma and a relatively long residence time or high temperature in the fourth reactor section, wherein the higher the residence time, the smaller the temperature in the fourth reactor section.

In the first alternative described above with a constant temperature in the fourth reactor section, soot formation is achieved with mean residence times of more than 20 s at a temperature in the fourth reactor section of at least 1000 ° C., average residence times of more than 10 s at a temperature in the fourth reactor section of at least 1300 ° C, and average residence times greater than 1 s at a temperature in the fourth reactor section of at least 1600 ° C, wherein no catalysts are provided in the fourth reactor section.

If the fourth reactor section according to the second alternative described above consists of successive modules each with individually adjustable temperature, e.g. an energy input of 14 kWh / kg of methane or more by the plasma in combination with a mean residence time of 400 ms or more at a mean temperature in the fourth reactor section of 500 ° C or more, and an energy input of 20 kWh / kg of methane or more the plasma in combination with a mean residence time of 1 s or more at a mean temperature in the fourth reactor section of 300 ° C suitable for soot formation.

In this particular variant of the second preferred embodiment of the invention, the hydrocarbons formed having a boiling point of 15 ° C or higher are partially adsorbed by the resulting carbon black. Typically, the proportion of hydrocarbons having a boiling point of 15 ° C or higher adsorbed by carbon black is 10 to 30 mol% based on the total amount of hydrocarbons having a boiling point of 15 ° C or higher. The carbon black adsorbed compounds are predominantly aromatic hydrocarbons (including polycyclic aromatic hydrocarbons). The content of carbon black adsorbed on aromatic hydrocarbons is preferably up to 25 wt .-%, preferably up to 30 wt .-%, particularly preferably up to 50 wt .-%. In the refinery processing, the organic compounds absorbed by carbon black having a boiling point of 15 ° C or higher are desorbed and processed while the carbon black remains as a solid residue. The remaining in the petroleum distillation and refining solid residue is usually processed after calcination by known methods to petcoke (Pet-coke), for example, for the production of Söderberg electrodes, in particular for the production of aluminum, and as a raw material for the production of synthetic graphite, is used in particular as electrode material for the production of electrical steel. Thus, this particular variant of the second embodiment of the invention provides access to additional value chains.

In a further specific variant of the second preferred embodiment of the method according to the invention described above

 a quenched product gas containing one or both compounds selected from the group consisting of ethylene and acetylene, and

 the quenched product gas is further treated in the presence of one or more catalysts to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher.

In a further specific variant of the second preferred embodiment of the device according to the invention

 the reactor is arranged to form a quenched product gas containing one or both compounds selected from the group consisting of ethylene and acetylene, and

 the reactor comprises, in the flow direction of the quenched product gas following the third reactor section, a fourth reactor section for further treating the quenched product gas to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher, in the fourth reactor section or more catalysts are arranged.

The fourth reactor section for forming one or more organic compounds having a boiling point of 15 ° C or higher, in which one or more catalysts are arranged, is preferably arranged so that the mean residence time of 10 ms to 1000 ms, preferably 100 ms to 1000 ms , more preferably 300 ms to 1000 ms at a temperature in the range of 100 ° C to 1500 ° C, preferably from 200 ° C to 600 ° C, more preferably 200 ° C to 300 ° C. Average residence time and temperature are chosen so that the formation of soot, which could deposit on the catalyst and block it, is avoided.

In this particular variant of the above-described second preferred embodiment of the invention, a conversion based on the methane contained in the educt gas of 5% or higher, preferably 20% or higher and particularly preferably 60% or higher, is preferably achieved. Based on the acetylene formed, a conversion of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher is achieved and a carbon yield of ethylene of 20% or higher, preferably 40% or higher, and up to 80%, preferably up to 90% and more preferably up to 100%, or a carbon yield of acetylene of 10% or higher and up to 50%. The carbon yields of acetylene and ethylene are additive and taken together to a maximum of 100%. Depending on the catalysts to be used in the fourth reactor section, either a gas stream rich in acetylene or in ethylene is advantageous. For the specific variant of the second preferred embodiment of the invention described above, all catalysts are suitable which have Lewis acidic and / or Brönsted acidic catalytically active centers.

Preferred are catalysts (optionally in combination with promoters) based on elements from the 3rd to 14th group of the periodic table (except carbon) on a suitable support material, preferably a support material having Lewis acid and / or Brönsted acid centers. Preferred elements from the 3rd to 14th group of the Periodic Table are molybdenum, manganese, iron, cobalt, nickel, aluminum, boron and silicon.

Preferred support materials are selected from the group consisting of aluminum oxide, silicon dioxide, silica-titanium dioxide mixtures, aluminum-containing clays, silicon-containing clays, synthetic or natural silicate-containing minerals such as phyllosilicates (eg steatite), ring silicates (eg cordierite), isolated silicates (eg mullite , Sillimanite, andalusite); Zeolites, eg ZSM 5 (Zeolite Socony Mobil, developed by Mobil Oil) and mesoporous silicate frameworks of the MCM (= Mobile Crystalline Material or Mobile Composition of Matter) SBA (= Santa Barbara Amorphous type-Silica), MSU (= Michigan State University mesoporous silica), KSW (named after Kimura et al., Angew Chem. Int. Ed. 2000, 21, 3855-3859), FSM (= Folded sheets mesoporous- materials), or HMM type (= Hiroshima mesopourous material) or other mesoporous silicate-containing structures. Particularly preferred catalysts according to the invention are, for example, zeolite H-ZSM5 (a form of the zeolite ZSM 5 in which the metal cations are exchanged by protons), nickel-doped zeolite ZSM 5 and a catalyst comprising molybdenum on a zeolite, in particular zeolite ZSM 5. The special variant of the second preferred embodiment of the invention described above, in which one or more catalysts are arranged in the fourth reactor section to form one or more organic compounds having a boiling point of 15 ° C. or higher from acetylene and / or ethylene, is characterized-in particular in the variants characterized as being preferred - characterized in that the formation of one or more organic compounds having a boiling point of 15 ° C or higher from acetylene and / or ethylene in the presence of one or more catalysts at lower temperatures is feasible than in the absence of catalysts, since the catalysts are the act reduce the energy levels of the reactions involved. Another advantage of this particular variant of the second preferred embodiment of the invention described above is that the selectivity of the process and the bandwidth of the spectrum of the available reaction products can be influenced by appropriate selection of the catalysts. For example, by selecting appropriately suitable catalysts, the proportion of certain compounds, such as, for example, benzene and / or naphthalene, in the formed reaction products can be increased. The quenched and optionally further treated product gas contains, in addition to the desired organic compounds having a boiling point of 15 ° C or higher and components with a boiling point below 15 ° C (in each case based on standard pressure, see above). These constituents having a boiling point below 15 ° C include, in particular, hydrogen which, as described above, is formed by recombination of hydrogen radicals or by hydrogen abstraction from plasma-formed compounds having two or more carbon atoms, unreacted or by recombination of radicals formed methane, optionally Ethylene and / or acetylene and - depending on the composition of the educt gas - gases from the group consisting of hydrogen sulfide, carbon monoxide, carbon dioxide, nitrogen and noble gases. According to a preferred embodiment of the present invention, it is provided to use the constituents of the quenched product gas having a boiling point below 15 ° C., if possible, as operating materials and / or energy sources for the device according to the invention or for the method according to the invention.

Therefore, it is preferred according to the invention that the device according to the invention additionally comprises, with regard to the constituents described above, a device for comprising a gas from the quenched product gas or from the further-treated product gas. send one or more components from the group consisting of hydrogen, methane, acetylene and ethylene separate. Accordingly, it is preferred that the method of the present invention comprises, in addition to the steps described above, separating a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene from the quenched product gas or from the further treated product gas. This applies to all embodiments of the device according to the invention and of the method according to the invention, but in particular to the first and second preferred embodiments described above. For the gas comprising one or more constituents from the group consisting of hydrogen, methane, acetylene and ethylene, which has been separated from the quenched product gas or from the further treated product gas, a use within the apparatus according to the invention or within the method according to the invention is offered as Energy carrier (in particular for providing the necessary for the generation of the plasma electrical energy), as a quench fluid and / or as a plasma gas.

Preferred embodiments of the device according to the invention thus comprise a device for separating from the quenched product gas or from the further-treated product gas a gas comprising one or more constituents from the group consisting of hydrogen, methane, acetylene and ethylene for use for one or more purposes from the group consisting of

 quench

 Fuel for the supply of electrical energy

 Plasma gas.

The gas separated from the quenched product gas or from the further treated product gas comprising one or more constituents from the group consisting of hydrogen, methane, acetylene and ethylene is used in preferred embodiments of the process according to the invention for one or more purposes from the group consisting of

 quench

- Fuel for the provision of electrical energy

 Plasma gas.

Alternatively or additionally, methane-containing gas taken from the methane-containing gas provided is within the device according to the invention or within the method according to the invention as an energy source (in particular for providing the necessary for the generation of the plasma electrical energy), as a quench fluid and / or plasma gas used.

In preferred embodiments of the device according to the invention, therefore, methane-containing gas is taken from the device for providing a methane-containing gas in addition to the methane-containing educt gas for use for one or more purposes from the group consisting of

 quench

 Fuel for the supply of electrical energy

- plasma gas.

From the methane-containing gas which is provided, in preferred embodiments of the process according to the invention, methane-containing gas is thus removed in addition to the methane-containing educt gas for one or more purposes from the group consisting of

- Quench fluid

 Fuel for the supply of electrical energy

 Plasma gas.

A device according to the invention preferably comprises in addition to the components described above

a device for providing electrical energy, comprising a device for burning at least one fuel,

 Means for supplying to the means for providing electrical energy at least one fuel selected from the group consisting of:

 a gas comprising one or more constituents selected from the group consisting of hydrogen, methane, acetylene and ethylene which has been separated from the quenched product gas or from the further-treated product gas,

 and

 a methane-containing gas taken from the means for supplying a methane-containing gas

Means for transmitting the provided electrical energy to the means for generating a plasma. The means for providing electrical energy is preferably a gas turbine or a gas and steam (CCGT) turbine.

A method according to the invention thus preferably comprises the steps in addition to the steps described above

Providing electrical energy comprising combusting at least one fuel selected from the group consisting of:

 a gas comprising one or more constituents selected from the group consisting of hydrogen, methane, acetylene and ethylene which has been separated off from the quenched product gas or from the further-treated product gas,

 and

 a gas containing methane-containing gas extracted from the supplied methane-containing gas

 Generating a plasma by means of the electrical energy provided. In the method according to the invention, the plasma is preferably a noble gas-free plasma, and the means for producing a plasma in the device according to the invention are means for producing a noble gas-free plasma. The use of a noble gas-free plasma takes into account the fact that at the site of the device according to the invention or the process according to the invention operating materials such as noble gases, which must be specially brought from outside, usually only to a very limited extent or not at all available. However, it is not excluded according to the invention that the plasma gas contains traces of noble gases, since these are optionally part of the methane-containing gas provided in the apparatus according to the invention or in the method according to the invention. Thus, it is preferred according to the invention that the plasma gas does not contain a noble gas which originates from sources other than the methane-containing gas provided in the apparatus according to the invention or in the method according to the invention; and the means for generating the plasma no noble gas is supplied, which originates from sources other than in the apparatus according to the invention or in the process according to the invention provided methane-containing gas.

In the device according to the invention, the means for supplying a plasma gas preferably comprise means for supplying at least one plasma gas selected from the group consisting of: a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene separated from the quenched product gas or from the further treated product gas, and

 a methane-containing gas taken from the methane-containing gas supply means.

In the process according to the invention, preference is given to feeding at least one plasma gas, preferably selected from the group consisting of:

 a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene separated from the quenched product gas or from the further treated product gas, and

 a gas containing methane-containing gas extracted from the supplied methane-containing gas.

Preferably, the inventive method is carried out with the device according to the invention, particularly preferably with one of the preferred embodiments of the device according to the invention described above. The device according to the invention is preferably set up to carry out the method according to the invention, particularly preferably one of the preferred embodiments of the method according to the invention described above.

A further aspect of the present invention relates to the use of a device according to the invention for producing one or more organic compounds having a boiling point of 15 ° C. or higher from a gas containing methane, preferably by the process according to the invention. With regard to preferred embodiments of the device and the method, the above statements apply.

Depending on the amount of educt gas containing methane to be processed, a single or a plurality of devices according to the invention connected in parallel (as defined above) are provided at one site.

The device according to the invention and the method according to the invention ensure profitable operation even with relatively small quantities of methane of from 100 kta to 20,000 kta, since the device and the method require very little space. According to the invention can be by means of a thermal plasma, which is very limited locally, enter the energy required for the conversion of methane into organic compounds with a boiling point of 15 ° C or higher targeted and with high efficiency in the process, ie a high proportion of the enlisted energy is actually available for the desired reactions. Thanks to this high energy efficiency, combined with the relatively small space requirement, the apparatus and the method according to the invention to be used characterized by a particularly high productivity based on the available reactor volume and are particularly suitable to be used under the conditions of a limited space become. Since the device according to the invention is relatively compact and easily assembled and disassembled, it allows a profitable use of sources with a temporary supply of methane-containing gas.

The device according to the invention and the method according to the invention are i.a. suitable for use in combination with - possibly already existing - power generation plants, the methane-containing gas - e.g. Biogas, coalbed gas, mine gas or landfill gas - use as fuel. In periods with an oversupply of electricity in the network from other sources (eg by the increasing use of fluctuating regenerative energy sources) then generated by combustion of methane gas stream can be used for the operation of the device according to the invention and so in the form of organic compounds produced with chemically stored at a boiling point of 15 ° C or higher. In this way, the flexibility of the plant for power generation is improved with respect to fluctuations in the absorption capacity of the power grid.

The invention will be explained below with reference to embodiments with reference to the accompanying figures. Hereby show:

FIG. 1 a shows a first embodiment of a reactor for a novel reactor

 contraption

Figure 1 b shows a second embodiment of a reactor for an inventive

 Contraption.

FIG. 1 c shows a reactor for the first preferred embodiment of the device according to the invention

FIG. 1 d shows a reactor for a first variant of the second preferred embodiment of the device according to the invention 1 e a reactor for a second variant of the second preferred embodiment of the device according to the invention

FIG. 1f shows a reactor for a third variant of the second preferred embodiment of the device according to the invention. FIG. 2 shows a flow chart of a method according to the invention in a device according to the invention

The figures are purely schematic representations, not to scale and not the real size proportions.

Figures 1a and 1b show a first and a second embodiment of a reactor for a device according to the invention. The reactor 60a according to FIG. 1a or the reactor 60b according to FIG. 1b comprises three successive flow sections in the flow direction, the temperature decreasing from the first to the third reactor section. In certain embodiments, the reactor contains further reactor sections, not shown in the figures. In FIGS. 1a and 1b, identical components are provided with identical reference symbols.

The reactor 60a according to FIG. 1a or the reactor 60b according to FIG. 1b comprises a first reactor section 1a or 1b, in which

 Means 1 1a for coaxially supplying a plasma gas or means 1 1 b for tangentially supplying the plasma gas

- means for generating a plasma, i. an electrode 12a, 12b and power supply 13 for generating an arc 14a, 14b

 and means 15 for cooling the plasma gas 10 to a temperature in the range of 2500K to 5000K

are arranged. In the reactor section 1a and 1b, respectively

 fed a plasma gas,

 generates a plasma with a temperature greater than 5000 K with the supplied plasma gas,

and then cooling the plasma gas to a temperature in the range of 2500K to 5000K. The coaxial feed 1a of the plasma gas according to FIG. 1a has the advantage that the plasma gas enters the reactor close to the wall and thus contributes to the cooling of the reactor wall. However, the generated arc 14a is fluctuating. The tangential feed 11 b of the plasma gas according to FIG. 1 b has the advantage that a more stable arc 14b builds up.

In the flow direction of the plasma gas 10 following the first reactor section 1a or 1b, the reactor 60a according to FIG. 1a or the reactor 60b according to FIG. 1b comprises a second reactor section 2, in which means 21 are arranged for supplying one from a device for providing The methane-containing reactant gas taken from a methane-containing gas to the cooled to a temperature in the range of 2500 K to 5000 K plasma gas 10. The reactor section 2 is arranged so that a product gas 20 containing one or both compounds selected from the group consisting of ethylene and Acetylene is formed.

In the reactor section 2 is

a feed gas containing methane-containing methane-containing feed gas is fed to the plasma gas cooled to a temperature in the range from 2500 K to 5000 K,

 a product gas containing one or both compounds selected from the group consisting of ethylene and acetylene. Following in the flow direction of the product gas 20 to the reactor section 2, the reactor according to Figure 1a and 1b, a third reactor section 3, in which means 31 are arranged to bring the product gas 20 formed in the reactor section 2 with a quench fluid containing methane in contact in that a quenched product gas 30 having a temperature in the range of 750 K to 1100 K is formed. In the reactor section 3, the product gas 20 formed in the reactor section 2 is contacted with a methane-containing quench fluid so that a quenched product gas 30 having a temperature in the range of 750 K to 1100 K is formed.

The means 21 for supplying a methane-containing educt gas and the means 31 for bringing the product gas 20 into contact with a methane-containing quench fluid and forming a quenched product gas 30 are arranged to have a ratio of methane in the educt gas to methane in the quench fluid in the Range from 3: 1 to 1: 3. According to the invention, a ratio of methane in the educt gas to methane in the quench fluid is set in the range from 3: 1 to 1: 3. In the preferred embodiments of the reactor 60a according to FIG. 1a or of the reactor 60b according to FIG. 1b, means 32 are arranged in the reactor section 3 in order to bring the quenched product gas into contact with one or more further quench fluids, wherein the further quench fluids are selected from Group consisting of quench fluids containing methane, air and water. Also preferred is the use of a partial volume flow of the organic compounds produced with a boiling point of 15 ° C or higher than another quench fluid (see also Figure 2). In the preferred embodiments of the reactor, in the reactor section 3, the quenched product gas is contacted with one or more other quench fluids.

FIG. 1 c shows a reactor 60 c for the above-described first preferred embodiment of the device according to the invention. The reactor 60c is arranged to form a quenched product gas 30a containing one or more organic compounds having a boiling point of 15 ° C or higher and optionally carbon black.

In the embodiment of the reactor 60c shown in FIG. 1c, the first reactor section 1b has the same basic structure as in reactor 60b from FIG. 1b, identical reactor components are therefore designated with identical reference symbols in FIGS. 1b and 1c. In an alternative embodiment of the reactor for this first preferred embodiment of the device according to the invention, the first reactor section has the same basic structure as in reactor 60a of Figure 1a.

In the second reactor section 2c, a feed gas containing methane containing methane-containing gas is supplied via means 21 to the plasma gas 10 cooled to a temperature in the range from 2500 K to 5000 K. The reactor section 2c is set up so that a product gas 20 containing one or both compounds from the group consisting of ethylene and acetylene is formed. The reactor section 2c is preferably designed such that the parameters residence time, volume flow of methane, and energy input by the plasma per kg of methane are in the preferred ranges indicated above. The third reactor section is followed by a discharge line comprising the means 31 for contacting the product gas with a methane quench fluid, comprising a first third 3a, a second third 3b, and a third third thirdc. In the outlet section, the quenched product gas 30a containing one or more organic compounds having a boiling point of 15 ° C. or higher and optionally carbon black is maintained over a defined average residence time in a specific temperature range. In the first third of the outlet section 3a and at the end of the outlet section means 32 and 33 are provided to bring the quenched product gas 30a with one or more other quench fluids in contact, the other quench fluids are selected from the group consisting of methane-containing quench fluids , Air and water. Also preferred is the use of a partial volume flow of the organic compounds produced with a boiling point of 15 ° C or higher than another quench fluid (see also Figure 2). The quenched product gas 30a is preferably maintained in the outlet section for a mean residence time of 100 ms to 1000 ms, more preferably 300 ms to 500 ms, at a temperature in the range of 400 ° C to 1000 ° C.

FIG. 1d shows a reactor 60d for a first variant of the second preferred embodiment of the device according to the invention described above. The reactor 60d is configured to form a quenched product gas 30b containing one or both of ethylene and acetylene in the third reactor section 3d, and includes a fourth reactor section 4d for further treating the quenched product gas to include a further treated product gas 40 to form one or more organic compounds having a boiling point of 15 ° C or higher and optionally carbon black.

In the embodiment of the reactor 60d shown in FIG. 1d, the first reactor section 1b has the same basic structure as in reactor 60b from FIG. 1b, identical reactor components are therefore designated with identical reference symbols in FIGS. 1b and 1d. In an alternative embodiment of the reactor for this variant of the second preferred embodiment of the device according to the invention, the first reactor section has the same basic structure as in reactor 60a of Figure 1a.

In the second reactor section 2d, a reactant gas containing methane-containing methane-containing methane gas is fed via means 21 to the plasma gas 10 cooled to a temperature in the range of 2500 K to 5000 K. The reactor section 2d is set up so that a product gas 20 containing one or both compounds from the group consisting of ethylene and acetylene is formed. The reactor section 2d is preferably designed such that the parameters residence time, volume flow of methane and energy input by the plasma per kg of methane are in the preferred ranges indicated above.

In the third reactor section 3d, the product gas 20 formed in the reactor section 2d is brought into contact with a methane-containing quench fluid by means 31, so that a quenched product gas 30b containing one or both of the group consisting of ethylene and acetylene having a temperature in the range of 750 K to 1100 K is formed.

In this first variant of the second preferred embodiment, the fourth reactor section 4d of the reactor 60d is set up so that a constant temperature selected from the range of 400 to 1000 ° C. is impressed on the quenched product gas 30b by means 43 for cooling or heating. optionally, means 42 are provided to bring the quenched product gas with one or more other quench fluids in contact, the other quench fluids are selected from the group consisting of methane-containing quench fluids, air and water. Also preferred is the use of a partial volume flow of the organic compounds produced with a boiling point of 15 ° C or higher than another quench fluid (see also Figure 2).

FIG. 1 e shows a reactor 60 e for a second variant of the second preferred embodiment of the device according to the invention described above. The reactor 60e is configured such that a quenched product gas 30b containing one or both of the group consisting of ethylene and acetylene is formed in the third reactor section 3e, and includes a fourth reactor section 4e for further treating the quenched product gas to include a further treated product gas 40 - Send one or more organic compounds having a boiling point of 15 ° C or higher and optionally to form carbon black

In the embodiment of the reactor 60e shown in FIG. 1e, the first reactor section 1b has the same basic structure as in reactor 60b from FIG. 1b, identical reactor components are therefore designated in FIGS. 1b and 1e with identical reference numerals. In an alternative embodiment of the reactor for this variant of the second preferred embodiment of the device according to the invention, the first reactor section has the same basic structure as in reactor 60a of Figure 1a.

In the second reactor section 2e, a feed gas containing methane containing methane-containing gas is supplied via means 21 to the plasma gas 10 cooled to a temperature in the range from 2500 K to 5000 K. The reactor section 2e is set up so that a product gas 20 containing one or both compounds is formed from the group consisting of ethylene and acetylene. Preferably, the reactor section 2e is designed so that the Parameters residence time, volume flow of methane, and energy input by the plasma per kg of methane in the preferred ranges given above.

In the third reactor section 3e, by means 31, the product gas 20 formed in the reactor section 2e is contacted with a methane-containing quench fluid so that a quenched product gas 30b containing one or both of the group consisting of ethylene and acetylene having a temperature in the range of 750 K is formed up to 1 100 K.

In this second variant of the second preferred embodiment, the fourth reactor section 4e of the reactor 60e is subdivided into individual successive modules 41 ', 41 ", 41"', 41 "", 41 "'' with respective means 43 ', 43", 43 "', 43" ", 43" "' for individual cooling or heating and with means 42 ', 42", 42 "', 42" ", 42" "'to the quenched product gas 30b with one or more other quench fluids to bring into contact. The quench rate is individually adjustable for each module. Thus, as it flows through the reactor section 4e, the gas stream undergoes a temperature profile from higher to lower temperatures, the temperatures of the individual modules being selected from the range defined above, preferably from the region characterized as being preferred. Particularly preferred is a temperature profile which extends from a maximum value of 1000 ° C at the entrance of the reactor section 4e to a minimum value of 100 ° C at the outlet of the reactor section 4e. FIG. 1f shows a reactor 60f for a third variant of the second preferred embodiment of the device according to the invention described above. The reactor 60f is arranged to form in the third reactor section 3f a quenched product gas 30b containing one or both compounds selected from the group consisting of ethylene and acetylene and a fourth reactor section 4f to continue the quenching product gas in the presence of one or more Catalysts to form a further treated product gas 40 comprising one or more organic compounds having a boiling point of 15 ° C or higher.

The first reactor section 1b has the same basic construction in the embodiment of the reactor 60f shown in FIG. 1f as in the reactor 60b from FIG. 1b, identical reactor components are therefore designated with identical reference symbols in FIGS. 1b and 1f. In an alternative embodiment of the reactor for this variant of the second preferred embodiment of the device according to the invention, the first reactor section has the same basic structure as in reactor 60a of Figure 1a. In the second reactor section 2f, a feedstock gas containing methane-containing methane-containing methane gas is fed via means 21 to the plasma gas 10 cooled to a temperature in the range of 2500 K to 5000 K. The reactor section 2f is set up so that a product gas 20 containing one or both compounds from the group consisting of ethylene and acetylene is formed. The reactor section 2f is preferably designed such that the parameters residence time, volume flow of methane, and energy input by the plasma per kg of methane are in the preferred ranges indicated above.

In the third reactor section 3f, by means 31, the product gas 20 formed in the reactor section 2f is contacted with a methane-containing quench fluid so that a quenched product gas 30b containing one or both of the group consisting of ethylene and acetylene having a temperature in the range of 750 K is formed up to 1 100 K. Optionally, means 32 are provided for contacting the quenched product gas with one or more other quench fluids prior to contact with the catalysts 44, the further quench fluid being selected from the group consisting of methane-containing quench fluid, air, and water. Also preferred is the use of a partial volume flow of the organic compounds produced with a boiling point of 15 ° C or higher than another quench fluid (see also Figure 2). In this third variant of the second preferred embodiment, one or more catalysts 44 are arranged in the fourth reactor section 4f of the reactor 60f. The reactor section 4f preferably has means 43 for cooling or heating. Preferably, the catalyst or catalysts 44 are arranged in the fourth reactor section 4f in the form of a heated or unheated fixed bed. FIG. 2 shows a flow chart of a method according to the invention in a device 100 according to the invention. A methane-containing feed gas 51 is taken from a device 50 for providing a methane-containing gas and fed to a reactor 60. The reactor 60 is preferably one of the preferred embodiments 60a to 60f described above. The reactor 60 comprises, as stated above, at least three successive reactor sections (not shown in Figure 2, but see Figures 1a-1f). In the first reactor section, a plasma gas, for example a gas 54 removed from the apparatus 50, is fed via means 11, producing a plasma having a temperature greater than 5000 K with the supplied plasma gas, and subsequently the plasma gas to a temperature in the range of 2500 K cooled to 5000 K. In the second In the reactor section, a feed gas 51 containing methane containing from the means 50 for providing a methane-containing gas is supplied to the plasma gas cooled to a temperature in the range of 2500 K to 5000 K, and a product gas containing one or both of ethylene and acetylene is formed , In the third reactor section, the product gas formed in the second reactor section is contacted with a methane-containing quench fluid, eg, a methane-containing gas 52 removed from the device 50 so as to form a quenched product gas having a temperature in the range of 750K to 1100K becomes. Depending on the device of the reactor (FIGS. 1 c - 1 f), a quenched product gas 30a containing one or more organic compounds having a boiling point of 15 ° C. or higher and optionally carbon black is formed (see FIG. 1c), or containing a quenched product gas 30b one or both compounds from the group consisting of ethylene and acetylene. In the latter case, the reactor 60 comprises a fourth reactor section following the third reactor section for further treating the quenched product gas to produce a further treated product gas 40 comprising one or more organic compounds having a boiling point of 15 ° C or higher (see FIGS. 1d-1f ) and optionally carbon black (see Figures 1d and 1 e) to form.

In preferred embodiments, the device 100 according to the invention additionally comprises a device 70 for obtaining from the quenched product gas 30a or from the further treated product gas 40 a gas 71 comprising one or more constituents selected from the group consisting of hydrogen, methane, acetylene and ethylene from the organic compounds produced 80 with a boiling point of 15 ° C or higher to separate. In preferred embodiments of the device 100 according to the invention, a partial volume flow 82 is separated from the organic compounds 80 having a boiling point of 15 ° C. or higher for use as further quench fluid in the reactor 60. The fraction 81 of the organic compounds 80 with a boiling point provided for further processing of 15 ° C or higher, the intended further processing is suitably supplied.

The gas 71 separated from the quenched product gas 30a or after further treating the quenched product gas 40 in the apparatus 70, comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene, is in preferred embodiments of the process of the invention for one or more purposes used from the group consisting of

Quench fluid 72 Fuel 73 for the provision of electrical energy for the production of the plasma

 Plasma gas 74.

In preferred embodiments, the device 100 according to the invention additionally comprises a device 90 for providing electrical energy 91 comprising a device for burning at least one fuel with supply of air 92. Via means 93, the device 90 for supplying electrical energy is supplied with at least one fuel selected from the group consisting of:

 a gas 73 comprising one or more components selected from the group consisting of hydrogen, methane, acetylene and ethylene, which has been separated in the device 70 from the quenched product gas 30a or from the further treated product gas 40,

and

 a methane-containing gas 53 taken from the device 50 for providing a methane-containing gas

2, the electrical energy 91 provided is transferred to the means 12a, 12b, 13 (not shown in FIG. 2) for generating a plasma in the reactor 60 via corresponding means, not shown in FIG.

Claims

claims: An apparatus (100) for producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas (51)  means (50) for providing a methane-containing gas to at least one reactor (60, 60a, 60b, 60c, 60d, 60e, 60f), said reactor comprising:  a first reactor section (1a, 1b) in which  Means (11, 11a, 11b) for supplying at least one plasma gas,  Means (12a, 12b, 13) for generating a plasma having a temperature greater than 5000 K with the supplied plasma gas, and means (15) for cooling the plasma gas (10) to a temperature in the range of 2500 K to 5000 K.  are arranged;  a second reactor section (2, 2c, 2d, 2e, 2f) following in the flow direction of the plasma gas (10) to the first reactor section (1a, 1b), in which  Means (21) for supplying a methane-containing starting gas (51) withdrawn from the means (50) for supplying a methane-containing gas to the plasma gas (10) cooled to a temperature in the range of 2500 K to 5000 K,  said reactor section (2, 2c, 2d, 2e, 2f) being arranged to form a product gas (20) containing one or both compounds selected from the group consisting of ethylene and acetylene; a third reactor section (3, 3a, 3b, 3c, 3d, 3e, 3f) following in the flow direction of the product gas (20) onto the second reactor section (2, 2c, 2d, 2e, 2f), in which Means (31) are arranged to bring the product gas (20) formed in the second reactor section (2, 2c, 2d, 2e, 2f) into contact with a methane-containing quench fluid such that a quenched product gas (30, 30a, 30b) is formed at a temperature in the range of 750 K to 1100 K; wherein the means (21) for supplying a methane-containing educt gas (51) and the means (31) for bringing the product gas (20) into contact with a methane-containing quench fluid are adapted to control a ratio of methane in the educt gas (51 ) to methane in the quench fluid in the range of 3: 1 to 1: 3  in which  (i) the reactor (60c) is adapted to form a quenched product gas (30a) containing one or more organic compounds having a boiling point of 15 ° C or higher  or  (ii) the reactor (60d, 60e, 60f) comprises one or more further reactor sections (4d, 4e, 4f) for further treating the quenched product gas (30b) to add one or more organic compounds having a boiling point of 15 ° C or higher form. The apparatus of claim 1, wherein the means (50) for providing the methane-containing gas is selected from the group consisting of:  Facilities for providing crude oil associated with crude oil production  Facilities for providing natural gas  Facilities for providing biogas  Means for providing seaming gas  Means for providing mine gas  Means for providing methane produced by methanation of carbon dioxide,  Facilities for providing landfill gas. Apparatus according to claim 1 or 2, wherein the means (31) for contacting the product gas (20) with a quench fluid containing methane comprises means for supplying the product gas (20) with one of the means (50) for providing a quench fluid Methane-containing gas brought quench fluid (52) containing methane brought into contact. Device according to one of claims 1 to 3, additionally comprising  Means (32, 33, 42, 42 ', 42 ", 42"', 42 "", 42 "" ') for contacting the quenched product gas (30) with one or more other quench fluids (72, 82) , Device according to one of claims 1 to 4, wherein  the reactor (60c) is arranged to form a quenched product gas (30a) containing one or more organic compounds having a boiling point of 15 ° C or higher and optionally carbon black. The apparatus of any one of claims 1 to 4, wherein the reactor (60d, 60e) is arranged to form a quenched product gas (30b) containing one or both compounds selected from the group consisting of ethylene and acetylene, and  in the flow direction of the quenched product gas (30b) following the third reactor section (3d, 3e) comprises a fourth reactor section (4d, 4e) for further treating the quenched product gas to a further treated product gas (40) comprising one or more organic compounds having a boiling point of 15 ° C or higher and optionally to form carbon black. Device according to one of claims 1 to 4, wherein the reactor (60f)  is set up so that a quenched product gas (30b) containing one or both compounds is formed from the group consisting of ethylene and acetylene, and downstream of the third reactor section (3f) in the flow direction of the quenched product gas (30b) comprises a fourth reactor section (4f) for further treating the quenched product gas to a further treated product gas (40) comprising one or more organic compounds having a boiling point of 15 ° C or higher, wherein in the fourth reactor section (4f) one or more catalysts (44) are arranged. Apparatus according to any one of the preceding claims, further comprising: means (70) for recovering from the quenched product gas (30a) or from the further treated product gas (40) a gas (71) comprising one or more of hydrogen, methane To separate acetylene and ethylene. Device according to one of the preceding claims, additionally comprising: means (90) for providing electrical energy (91) comprising means for burning at least one fuel,  Means (93) for supplying to the means for providing electrical energy at least one fuel selected from the group consisting of:  a gas (73) comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene separated from the quenched product gas (30a) or from the further treated product gas (40),  and  a methane-containing gas (53) taken from the device (50) for providing a methane-containing gas Means for transmitting the provided electrical energy to the means (12a, 12b, 13) for generating a plasma. Device according to one of the preceding claims, wherein the means (11, 11a, 11b) for supplying at least one plasma gas (10) comprises means for supplying at least one plasma gas selected from the group consisting of:  a gas (74) comprising one or more of the group consisting of hydrogen, methane, acetylene, and ethylene separated from the quenched product gas (30a) or from the further treated product gas (40), and a methane-containing gas (54) withdrawn from the means (50) for providing a methane-containing gas. A method of producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas comprising the steps  Providing a methane-containing gas  plasma enhanced production of one or more organic compounds having a boiling point of 15 ° C or higher from a methane containing gas, comprising:  Supplying at least one plasma gas, generating a plasma having a temperature greater than 5000 K with the supplied plasma gas, and cooling the plasma gas to a temperature in the range of 2500 K to 5000 K;  Supplying a methane-containing feed gas withdrawn from the supplied methane-containing gas to the plasma gas cooled to a temperature in the range of 2500K to 5000K and forming a product gas containing one or both of ethylene and acetylene;  contacting the product gas with a methane-containing quench fluid to form a quenched product gas having a temperature in the range of 750 K to 1100 K,  wherein a ratio of methane in the reactant gas to methane in the quench fluid in the range of 3: 1 to 1: 3 is set  in which  (i) forming a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C or higher  or (ii) the quenched product gas is further treated to form one or more organic compounds having a boiling point of 15 ° C or higher. 12. The method of claim 11, wherein the provided methane-containing gas is selected from the group consisting of:  oil associated with oil production  natural gas  - biogas  coalbed methane  marsh gas  methane formed by methanizing carbon dioxide,  Landfill gas. 13. The method of claim 1 1 or 12, wherein the methane-containing quench fluid is taken from the provided methane-containing gas. 14. The method of claim 1, further comprising the step of contacting the quenched product gas with one or more other quench fluids. A method according to any one of claims 11 to 14, wherein  a quenched product gas containing one or more organic compounds having a boiling point of 15 ° C or higher and optionally carbon black are formed. The method of claim 1 1 to 14, wherein  forming a quenched product gas containing one or both compounds selected from the group consisting of ethylene and acetylene and further treating the quenched product gas to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher and optionally carbon black. 17. The method of claim 1 1 to 14, wherein a quenched product gas containing one or both compounds from the group consisting of ethylene and acetylene is formed and the quenched product gas is further treated in the presence of one or more catalysts to form a further treated product gas comprising one or more organic compounds having a boiling point of 15 ° C or higher. 18. The method according to any one of claims 1 1 to 17, additionally comprising the step  Separating a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene from the quenched product gas or from the further treated product gas. 19. The method according to any one of claims 1 1 to 18, additionally comprising the steps  Providing electrical energy comprising combusting at least one fuel selected from the group consisting of:  a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene separated from the quenched product gas or from the further treated product gas,  and  a gas containing methane-containing gas extracted from the supplied methane-containing gas  Generating a plasma by means of the electrical energy provided. 20. The method of claim 1, wherein at least one plasma gas supplied is selected from the group consisting of:  a gas comprising one or more of the group consisting of hydrogen, methane, acetylene and ethylene which has been separated from the quenched product gas or after further treating the quenched product gas,  and  a gas containing methane-containing gas extracted from the supplied methane-containing gas. A method according to any one of claims 11 to 20, wherein the method is carried out according to any one of claims 1 to 10. 22. Device according to one of claims 1 to 10, wherein the device is adapted to perform a method according to any one of claims 1 1 to 20. 23. Use of a device according to one of claims 1 to 10 for producing one or more organic compounds having a boiling point of 15 ° C or higher from a methane-containing gas, preferably by a method according to any one of claims 1 1 to 20.