WO2013114150A1 - Plant for converting hydrocarbon reactants into gaseous and liquid fuel, including a plasma chemotron for said plant - Google Patents

Description

 Plant for the conversion of hydrocarbon educts into gaseous and liquid fuels including plasma memotron to this plant

 Affected area of technology

 The proposed group of inventions belongs to the field of petroleum chemistry, more specifically to the plants for the catalytic processing of hydrocarbon materials.

 Previous state of the art

 Known is a plant for the production of liquid hydrocarbons with a catalytic reactor, which is connected to a carbon monoxide and a hydrogen source (see, for example, Loktev, SM "Sostojanie i perspektivy zydkix uglevodorodov iz oksida ugleroda i vodoroda (= Current state and perspectives of the synthesis of Liquid hydrocarbons from carbon monoxide and hydrogen) ", Moscow, IGI, 1977, p.14).

 The shortcomings of the known plant include the considerable consumption of raw materials and the strong formation of carbon dioxide and various admixtures which escape into the atmosphere.

 There is known a plant for the production of liquid hydrocarbons with a block for the reduction of carbon dioxide to carbon monoxide, which is connected to the input of a catalytic reforming block (Fischer-Tropsch reactor), which in turn is connected to the block for the deposition of liquid hydrocarbons (Patent RU 2198156).

 Among the shortcomings of the plant described is its dependence on the presence of the raw material for obtaining the starting materials for the synthesis, which limits the autonomy of the production processes.

A plant for the synthesis of liquid fuel is known with a reforming reactor, which transforms the hydrocarbon raw material into a synthesis gas containing gaseous carbon monoxide and gaseous hydrogen as the basic constituents, with a reactor which contained in the synthesis gas liquid hydrocarbons synthesized with gaseous carbon monoxide and gaseous hydrogen, with a rectification column which rectifies the liquid hydrocarbons for the separation of the liquid hydrocarbons with the desired hydrogen number or higher, and with a cooler which cools and simultaneously liquefies the gas discharged from the reactor or from the rectification column ( Patent RU 2415904).

 With the aid of the known plant, it is possible to extract the gaseous liquid hydrocarbons having the desired hydrogen number or higher from the overhead product.

 The main disadvantage of this solution, however, is the presence of admixtures (sulfur oxides, phosphorus, silicon, iron, etc.) in the recovered product, while a ten times higher degree of purity is needed to recover useful hydrocarbons. For example, sulfur accounts for 0.5% of hydrocarbons, while reuse requires no more than 0.05%.

 Known are a process for the conversion of solid fuel and a plasma system for its production (Patent RU 56008).

 As a solid fuel different coals are used, including

Brown coals. Known is a plasma system for the conversion of solid fuel with a plasma reactor, a gas generator, a desulfurizer and a

Compressor.

 In the system, an arc plasma is generated, and water vapor is used as the plasma-forming gas.

 The most important weaknesses of the known construction are:

 the low efficiency of the reactor, d. H. Due to the short residence time of the coal particles in the arc (0.1 - 1 s), the process of the transformation of the charcoal, which takes place in it, is incomplete,

- The low life of the electrodes in the hydrogen-containing plasma, because of the irreversible consumption production of the electrodes from the expensive Hafnium is not justified

 - The unnecessary heat consumption due to the liquefaction or reduction of the mineral admixtures, the proportion of which reaches 30 - 40% in brown coal, which simply drives up only the energy consumption of the gasification process.

 Also known is a process for the electrolytic dissociation of water for the production of synthesis gas (Patent 23964).

 In the known method, the high solubility of carbon dioxide in water and its reduction to carbon monoxide is utilized by the hydrogen which is precipitated in the electrolysis of the carbon dioxide-enriched water.

 However, the energy consumption for the hydrogenation of the hydrogen gas from the water amounts to 4.5-5.3 KWh / 1, and the reduction of the carbon by the hydrogen at 600-800 ° C causes the consumption to almost double.

In addition, the ratio of hydrogen and carbon monoxide in the recovered synthesis gas is at least H ₂ / CO = 2 - 2, while for a reaction by the Fischer-Tropsch method, a ratio of H ₂ / CO ~ 1.5 is desirable, otherwise the pressure of the synthesis gas and the temperature must be increased, which in turn increases the energy consumption.

 The proposed method is technologically the closest to a plant for the conversion of hydrocarbons into gaseous and liquid fuel, which consists of the following assemblies: a reactor chamber with attached at its bottom heater and catalyst, a compressor, a reactor for the synthesis of a mixture of gasoline and diesel and a rectification column connected to this reactor (Patent RU 2291350).

The plant allows a more complete utilization of the fuel capacity of the product gas by synthesizing gaseous and liquid fuel as well as continuous operation without interruption to reload the feedstock. However, the known solution has a significant disadvantage, namely the presence of admixtures (sulfur oxides, phosphorus, silicon, iron, etc.) in the product obtained,

 the process of synthesis gas recovery for the synthesis of dimethyl ether, gasoline and diesel proceeds at low pressures and temperatures, which prevents an increase in the conversion rate and the degree of conversion,

 - The comparatively high energy consumption of the plant especially for the operation of the reaction chamber in which the components of the synthesis gas (hydrogen, oxygen and carbon monoxide) are to be generated.

 It is known that the most energy-intensive individual process is the extraction of the basic components of the synthesis gas, the carbon monoxide and hydrogen gas.

 Known are plasma emotron constructions (e.g., WO06 / 055999A1), and especially those which permit separation of the plasma-forming medium (water) into water and oxygen with very little energy expenditure.

The proposed plasma emitron comes from the technical point of view a Plasmachemotron next, which has a vertical transparent body with conical neck, via a neck mounted hydrogen receiver, nozzle for introducing the plasma-forming medium (water H ₂ O) and for discharging the product gases a hermetic chamber in the housing between the anode and cathode electrodes, the base of the interelectrode chamber being delimited by the bottom of the anode consisting of hydrogen and oxygen over inert material, and the cathode being hermetically attached to the hydrogen receiver; and via the power supply lines of the voltage source, which are connected to the upper channel of the hydrogen receiver and the housing wall (see Patent RU 107161).

 The known construction of the plasma memotron allows the cleavage of the

Water in hydrogen and oxygen by igniting a plasma in the water with reduced energy consumption thanks to the high-tech surface of the electrodes. However, the known construction has several disadvantages, namely: - It is difficult to manufacture, since the cathode consists of capillaries, their production

 Composite is very complicated,

 - The cathode is difficult to clean, since for their purification, the entire plasma memotron must be decomposed at regular intervals.

 Explanation of the essence of the proposed group of inventions

The technical solution achieved by the proposed group of inventions consists in the production of such a construction of a plant for the conversion of hydrocarbon educts into gaseous and liquid fuels, which makes it possible to produce water and coal with low energy consumption gaseous and liquid hydrocarbons, which in terms of Admixtures are sufficiently pure.

The technical solution is achieved in the proposed invention, characterized in that one prepares a plant for the conversion of hydrocarbon educts in gaseous and liquid fuel, which consists of: a reactor chamber with attached at its bottom heater and catalyst, a compressor, a reactor for the synthesis of a mixture from gasoline and diesel and a rectification column connected to this reactor, which is equipped according to the invention with a plasma memotron, a mixer for the components of the recovered synthesis gas, a water collector, a separator and a reactor for dimethyl ether synthesis, wherein the plasma memotron a water inlet and two exits one of which is connected for the purpose of discharging the recovered oxygen and water from the plasma memotron via the water collector to the reactor chamber, which is connected via the separator to the mixer connected to the second, the discharge of water connected to the output of the plasma motor, and via the compressor to the dimethyl ether synthesis reactor connected to the reactor for synthesis of gasoline and diesel, the heater of the reactor chamber is made of the composites Ni ₃ Al and NiAl, the catalyst of the chamber, which has the form of a network of MgO-based porous ceramic, is mounted over the heater, the synthesis reactors for the dimethyl ether and the gasoline-diesel mixture are made barothermic with the heaters mounted on their housings and their interiors for accommodating the catalysts of nanoporous copper, platinum and zeolite.

 In the proposed plant, nanoporous catalysts of copper, platinum and zeolite are used at significantly higher pressures and temperatures for the treatment of the synthesis gas produced to obtain dimethyl ether, gasoline and diesel, thereby increasing speed and degree of conversion and high purity products without those for products from crude oil cracking so typical admixtures arise.

The technical solution is also achieved in the proposed invention by producing a plasma memotron, which consists of a vertical and transparent housing with a conical neck, a neck mounted hydrogen receiver, nozzles for introducing the plasma-forming medium (water H ₂ O) and for discharging the product gases, an in-housing hermetic chamber between the anode and cathode electrodes, wherein the base of the interelectrode chamber is bounded by the lower end of the anode made of hydrogen and oxygen over inert material and the cathode is hermetically attached to the hydrogen receiver, and the power supply lines of the voltage source, which are connected to the upper channel of the hydrogen receiver and the wall of the housing, in which according to the invention, the cathode is designed as a palladium-coated bellows made of porous nickel and the anode as a base, on the coaxially arranged and between de n folds of bellows attached to the cylinder are attached.

The proposed invention enables the implementation of the method for splitting the water into hydrogen and oxygen (plasma generation by Capacitive discharge in the water, ie 1.1 - 1.3 kWh / 1).

 The proposed construction of a "transparent" only for the hydrogen cathode allows the immediate separation of products from the dissociation of water into hydrogen and oxygen.

 In the proposed invention, the oxygen obtained from the water can be used for the synthesis of carbon monoxide z. Example, by the carbon, even in lignite, is oxidized or the carbon dioxide is reduced over the heated coal to carbon monoxide.

 In any case, only the carbon is involved in the reaction, and the mineral admixtures remain finely dispersed in the solid phase and can be used in the building materials industry.

 DISCLOSURE OF DIGITAL DOCUMENTATION The proposed group of inventions will be explained with the following description and drawing, in which a diagram shows the plant for the conversion of hydrocarbons into gaseous and liquid fuel with the plasma memotron in profile.

Best Mode for the Group of Inventions The plant for the conversion of hydrocarbon educts into gaseous and liquid fuel consists of the reactor chamber 1 with the heater 2 and the catalyst the compressor 4, the reactor for the synthesis of the mixture of gasoline and diesel 5 connected to them Rectification column the plasma memotron, the mixer for the components of the recovered synthesis gas 7, the water collector 8, the separator 9 and the reactor for dimethyl ether synthesis.

In the container 10 of the reactor chamber 1 are mounted on the ground: consisting of the composites Ni ₃ Al and NiAl heater 2 and the attached above him reticulated catalyst which consists of MgO-based porous ceramic. The container 10 is for loading with the processed carbon, z. B. hard coal or lignite, thought.

 For ordinary coal pieces are to be used, which require no further processing (grinding).

 The reactor for the dimethyl ether synthesis and the reactor for the gasoline and diesel synthesis are carried out barothermally.

 The reactor for the dimethyl ether synthesis consists of the housing 11 to which the heater 12 is attached to the voltage source 13, and the interior 14 is to be filled with the catalyst z. As nanoporous copper, thought.

 The reactor for the dimethyl ether synthesis consists of the housing 5, to which the heater 16 is attached to the voltage source, and the interior is to be filled with the catalyst 19, z. As platinum and zeolite thought.

 The rectification column 6 is to be filled before start of operation with a mixture of diesel and gasoline. The construction of the rectification column is known.

The plasma memotron consists of the vertical conical neck transparent housing 21, the hydrogen receiver housed in this neck 21, the plasma forming medium introduction port 23 (water H ₂ O), and the gaseous product evacuation 24, the hermetic housing Interelectrode chamber 26 with anode and cathode and the power supply lines 27 of the voltage source 28, which are connected to the upper channel of the hydrogen receiver and with the housing wall.

 The cathode is designed as a bellows consisting of porous palladium-coated nickel and is hermetically attached to the hydrogen receiver 21.

 The anode consists of the base on which the cones 31 arranged coaxially and located between the folds of the bellows are fastened.

In this case, the lower base of the Interelektrodenkammer 26 through the base of Anode limited, which consists of a hydrogen and oxygen over inert material, eg. As nickel exists.

 Depending on the technical possibilities and to simplify the installation of the plasma memotron, the housing of the plasma memotron can be mounted and consist of two parts to be joined together.

 The transparent design of the neck 21 of the housing, z. B. organic glass, allows an observation of the process flow of plasma dissociation of water.

 The use of hydrogen and oxygen over inert nickel as the material makes it possible for the impurities accumulated during the "firing" process of the plasma to be collected, above all, in the form of heavy metal compounds (salt, basic hydrides, mechanical impurities).

 The operation of the plant for the conversion of hydrocarbon educts into gaseous and liquid fuels is as follows:

Water is introduced into the housing of the plasma memotron via the Einrullstutzen 23 for the plasma-forming medium (water H ₂ 0) and kept at the specified maximum level of Wasserdissoziation.

 The voltage source 28 is turned on, voltage is applied to the power supply lines 27 and controlled by observation of the plasma, so that it does not come to a violent boiling of the water. The electrolytic dissociation of the water begins. At the moment of starting the plasma memotron, the water level is not filled up, as this destabilizes the plasma.

 Depending on the dissociation and the evaporation of the water, it is continuously filled up, depending on the volume of hydrogen and oxygen required.

 The recovered oxygen is passed through the water collector 8 together with small water vapor residues, the oxygen, for. B. by condensation using a normal water-cooled zeolite capacitor is released.

The released oxygen is through the reactor chamber 1 to the partial Oxidation of the coal passed through the oxygen. The formation of the carbon monoxide from the coal is carried out at a temperature below the dissociation temperature, e.g. B. at 450 - 500 ° C, carried out.

In order to obtain a synthesis gas free of admixtures, the carbon monoxide is purified before the preparation of the mixture CO + H ₂ with 60% H ₂ and 40% CO as constituents in the separator 9 with the aid of liquid Reaktionsssorbenten. This device and these liquid reaction sorbents are known (http://www.turbinist.ru).

 The recovered hydrogen and purified carbon monoxide are further fed to the mixer 7 of the syngas components where the mixture is made.

 The synthesis gas mixture is compressed to a pressure of 100 - 1 atm and processed in the barothermic reactor for dimethyl ether synthesis at a temperature of 260 - 300 ° C with a copper catalyst and dimethyl ether is formed.

 To obtain the mixture of gasoline and 10% diesel, the dimethyl ether is compressed to a pressure of 100 - 1 atm and heated in the presence of the catalyst of nanoporous platinum and zeolite at a temperature of 3 - 360 ° C.

 Thereafter, the mixture of gasoline and 10% diesel is passed through the rectification column, thus producing the final separation of the final products.

Industrial applicability

The presence of coal reserves in some parts of the world, which have no gas or petroleum resources, and the social issues raised with the closure of coal shafts means that the proposed equipment, which allows gas and water to form coal and gas produce liquid fuel without harmful admixtures, highly topical appears. The low energy consumption of the processes for the dissociation of water, the partial oxidation of coal, the synthesis of methane, dimethyl ether and not least gasoline and diesel open up perspectives for the revival of the regions "dead" together with the shafts, for the creation of new jobs and production branches, for example. As the production of synthetic fibers from gaseous hydrocarbons, textile companies, the production of sulfate-containing fertilizer from the separated sulfur and building materials from the added silicon dioxide. The ability to make these processes environmentally friendly on the proposed equipment makes this development a key technology.

 An experimental plant for the conversion of carbon raw material into gaseous and liquid fuel was produced.

 Hard coal in the amount of 1 ton was used as the carbon starting material.

 Water was used as a material for producing hydrogen and oxygen.

 After the conversion process 500 1 gas was won.

Claims

claims 1. Plant for the conversion of hydrocarbon educts in gaseous and liquid fuel, which consists of: a reactor chamber with attached at its bottom heater and catalyst, a compressor, a reactor for the synthesis of a mixture of gasoline and diesel and a rectification column connected to this reactor, characterized in that the system is equipped with a plasma memotron (eg WO2006 / 055999 A1), a mixer for the components of the synthesis gas obtained, a water collector, a separator and a reactor for dimethyl ether synthesis, the plasma memotron being connected via ports (23) for a water inlet and has two outputs (24), one of which outlet is connected to the output of the recovered oxygen and water from the plasma memotron via the water collector to the reactor chamber, which is connected via the separator to the mixer, connected to the second, the discharge of hydrogen (2H) from Pl connected to the reactor for dimethyl ether synthesis, which is connected to the reactor for the synthesis of gasoline and diesel, wherein the heater of the reactor chamber made of the composites Ni ₃ Al and NiAl is prepared, the catalyst of the chamber, which has the form of a network of MgO-based porous ceramic over which heater is mounted, the synthesis reactors for the dimethyl ether and the gasoline-diesel mixture are made barothermic with heaters mounted on their housings and their interiors for accommodating the nanoporous copper catalysts , Platinum and zeolite are determined. 2. A plasma memotron according to claim 1, comprising a vertical housing with conical neck, with a mounted at this neck hydrogen receiver, nozzle for introducing the plasma-forming medium (water H ₂ O) and for discharging the gaseous products, with a hermetically located in the housing Interelectrode chamber between the electrodes, each with it connected anode and cathode, wherein the base of the interelectrode chamber is bounded by the lower end of the anode, which consists of a hydrogen and oxygen inert material, and comprising a hermetically attached to the hydrogen receiver cathode and the power supply lines of the voltage source connected to the upper nozzle the hydrogen receiver and the housing wall are connected, characterized in that the cathode is made of porous palladium-coated nickel and the anode is designed as the base on which cones are mounted. 3. Plasmachemotron according to claim 1 or 2, characterized in that the housing is mountable and consists of two joinable parts. 4. plasma commotron according to claim 1, 2 or 3, characterized in that is used as the hydrogen and oxygen inert material to nickel. 5. Plasmachemotron according to one of claims 1 to 4, characterized in that the cathode is formed rotationally symmetrical with a central cone on the base and with an adjoining, emanating from the base circumferential jacket. 6. A plasma memotron according to claim 5, characterized in that the anode is arranged as a distance from the cone of the cathode, spaced therefrom further cone and that on the basis of a spaced from the circumferential jacket of the cathode extending further jacket of the anode to form the hermetic Interelektrodenkammer is provided.