The plasma-chemical method of pyrolysis of hydrocarbons

 

(57) Abstract:

Plasma pyrolysis of hydrocarbons according to the present method is designed primarily to obtain acetylene ensuring high efficiency of the process, including precluded the formation of cyanide compounds, which, in turn, reduces the cost of preconcentration and separation of this product. This process is characterized by the fact that in the plasma-forming gas plasma pyrolysis of hydrocarbons injected water vapor. The mixture includes carbon of carbohydrates and oxygen from water in the following molar ratio 1 : (1 : 1,5), preferably 1 : 1.1 to. As a plasma-forming gas used tail carbon-containing gases. For the formation of water vapor and/or cooling of the reaction products using water-saturated hydrocarbons.

The invention relates to processes for making acetylene by the pyrolysis of hydrocarbons by electroretinogram and chemical methods.

Known methods of plasma chemical pyrolysis of hydrocarbons by mixing raw materials with the coolant heated in an electric environment. The coolant used argon, hydrogen, natural gas, products of pyrolysis (Mastadon when used as a carrier of natural gas or products of pyrolysis is the formation of cyanide compounds, as for natural gas, and therefore in the products of pyrolysis contains nitrogen. As a result, when the selection of lower olefins (acetylene, ethylene, etc.,) from the pyrogas need to be cleaned from cyanide compounds (hydrocyanic acid), which is a very difficult stage in the technological scheme of isolation and purification of the lower olefins.

The aim of the invention is to eliminate the formation of hydrocyanic acid in the pyrolysis of nitrogen-containing hydrocarbon gas mixtures, first and foremost, natural gas, nitrogen content which is 2 8 volume.

This is achieved by the fact that, as the plasma gas, is heated in an electric arc (heat carrier) using a gas mixture of water vapor, hydrocarbons or hydrocarbon mixtures in the ratio of carbon hydrocarbons oxygen water vapor equal to 1 (1 to 1.5), preferably 1 to 1.1.

In addition, as a plasma-forming gas used tail gases of the production of acetylene. Thus for the formation of water vapor and/or cooling of the reaction products used water, saturated hydrocarbons.

The method is as follows.

Example 1. In electric arc heater (plny volume: methane 93,8; Ethan 2,0; propane 0.8; butane 0,4; nitrogen 2,6; carbon dioxide 0,4) in the amount of 1200 m3/h and water vapor in the number 95.4 kg/h (the ratio of carbon to oxygen is 1 1).

The output of the electric arc heater is formed is heated to 3200 K jet of gas mixture composition, percent: carbon monoxide (CO) 33,6; hydrogen 65,6; nitrogen 0,8.

This stream serves 2500 m3natural gas pyrolysis, mix for 10-3with the carrier to obtain a temperature of 1800 1900 K and cooling ("quenching") of water. The result is a sin, containing 1 t/h of acetylene.

Example 2. Condition as in example 1, but serves water vapor 1430 kg (ratio of carbon to oxygen is 1 to 1.5).

In this case, the pyrolysis serves natural gas in the amount of 3000 m3and get 1 t/h of acetylene.

Example 3. In electric arc heater (electric power 11,65 MW offers plasma gas mixture of hydrocarbon gases (tail gases of pyrolysis) composition, interest volume: acetylene 0,6; carbon 6,0; nitrogen 1,1) in the amount of 3200 m3/h and water vapor in the amount of 250 kg/h (the molar ratio of carbon to oxygen is 1 to 1.1).

Heated to a temperature of 3200 K gas mixture composition, procentec. The result is a sin, containing acetylene (up 11.3 percent) in the amount of 1 t/h

The given examples show that water vapor is introduced into a plasma-forming gas for the oxidation of carbon included in the composition of carbohydrates, which eliminates the possibility of formation of cyanide compounds. When this water vapor is injected with an excess, preferably 10-20 compared with the required number of stoichiometry.

However, water vapor is not allowed to drive less than the ratio of carbon to oxygen of 1 to 1, because then there is the probability of formation of cyanide compounds. It is impractical to enter more than the ratio of 1 to 1.5, as in this case will be converted to carbon monoxide and hydrogen to hydrocarbons fed to the pyrolysis, which will lead to increased consumption of raw materials and, consequently, worsen the economic performance of the process.

During quenching energy of pyrogas is used for liquid heating and evaporation. The extended surface of contact liquid-gas created by the dispersion of the water jets. Not evaporated during the quenching water is also used for transporting and washing away the soot from the reactor.

Water for quenching fed into the reactor in two tiers injectors: on top arylidene acetylene. The relationship between the volumes of hot and cold water is on the order of 0.8.

To prevent reverse, parallel or serial adverse reactions leading to a decrease in the concentration of acetylene, use the hardening of pyrogas water dirty working cycle or saturated hydrocarbons. The sin from the reactor is directed to a system, apparatus suacide and cooling. The composition of the pyrogas in terms of dry gas in volume percent, the following: CH44,3; N20,9; H277,4; C2H211,4; C2H40,32; CO 5,0; C3H40,01; C3H40,2; C4H20,44; C4H40,01; C4H60,01; C6H80,01.

The reaction conversion in electric arc plasma torch of the type of ADN aircraft, consisting of electric arc heater reaction chamber and a quenching device, when the temperature of the electric arc described by bruttopreis.

Resulting from the conversion of gas at a temperature of 3500 K in the condition of low temperature plasma has a high enthalpy and serves as a carrier for the endothermic pyrolysis reactions.

After the arc heater plasma-forming gas is mixed with natural gas or Kazuyoshi gas T 3500 K and a cold flow of natural gas T 293 K, as well as the reactions of pyrolysis produces sin, having a temperature of 1700 K. the Amount of pyrogas 1270 nm3/am reactor Pressure of 2.5 kgf/cm2the time of formation of acetylene in the reaction chamber of the order of 0.001 sec.

A set of processes taking place in the reactor, is described by the following equation:

98,52 CH2+ 0,17 C2H6+ 0,11 C3H8+ 0.02 H C4H10+ 0.01 and-C4H10+ 1,12 H2+ 4,98 H2O + 132,29 H2+ 44,17 CO _ 5,32 CH4+ 1,12 H2+ 278,95 H2+ 33,66 C2H2+ 4,16 C2H4+ 49,15 CO + 0,075 p C3H4+ 0,6 OM - C3H4+ 1,35 C4H2+ 0,34 C4H4+ 0,04 C4H6+ 0,11 C6H6+ 3,76 C

The present technical solution differs from the well-known high efficiency, including precluded the formation of cyanide compounds, which reduces the cost for the concentration and isolation of acetylene.

1. The plasma-chemical method of pyrolysis of hydrocarbons mainly to obtain acetylene, comprising heating in an electric arc plasma gas containing hydrocarbons, the flow and mixing of raw materials with the gas and cooling the reaction products, characterized in that plazmoferezle 1 1,1.

2. The method according to p. 1, characterized in that as the plasma gas used tail carbon-containing gases.

3. The method according to p. 1, characterized in that for the formation of water vapor and/or cooling of the reaction products using water-saturated hydrocarbons.

 

Same patents:

FIELD: chemical industry branches, possibly manufacture of calcium carbide, calcium oxide, acetylene, carbonic acid and slaked lime.

SUBSTANCE: coal-carbonate mineral raw material - lime is fired in reactor 1 with use of acetylene as high-temperature energy carrier. Lime produced in reactor 1 is fed to user and(or) to second reactor 2 and adding coke or coal with fraction size 20 -25 mm and with sulfur content less than 1% into reactor 2. Some part of acetylene further produced is also added to reactor 2. Ready calcium carbide is removed out of reactor 2 and it is fed to user and(or) to fourth reactor 4 where after contact with water acetylene and slaked lime are formed. Acetylene is fed through pipeline 15 to user and(or) to reactors 1 and 2. Ready slaked lime is fed to user. Gaseous products such as carbon dioxide from reactor 1 and carbon oxide from reactor 2 are fed to third reactor 3 where after contact with water carbonic acid is formed and fed to user as "dry ice" or in liquefied state.

EFFECT: possibility for producing wide assortment of commercial products in one waste-free cycle, elimination of environment contamination.

2 cl, 1 dwg

FIELD: inorganic compounds technologies.

SUBSTANCE: invention is directed to production of acetylene and lime through hydrolysis of calcium carbide. Hydrolysis solution is prepared from water/ethanol mixture containing at least 68 wt % ethanol. After hydrolysis, ethanol vapors are condensed to give anhydrous ethanol. Acetylene and lime are also obtained in anhydrous form.

EFFECT: enhanced process efficiency due to wastelessness of the process and possibility of using carbide dust and fines, improved safety of process, and improved quality of generated acetylene.

1 dwg, 2 ex

FIELD: production processes.

SUBSTANCE: there proposed is the method of device cleaning from deposits formed as a result of purified N-methylpyrrolidone regeneration by N-methylpyrrolidone distillation from material flow of contaminated N-methylpyrrolidone. Contaminated N-methylpyrrolidone is formed according to the method of extractive separation of acetylene from reaction mixture of partial hydrocarbon oxidation after distillation of gaseous acetylene. Note that hot water is supplied to the device and mixed.

EFFECT: proposed method permits to exclude manual operation with solid substances, but at the same time regenerating significant part of purified contaminated N-methylpyrrolidone.

9 cl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method of processing carbon-carbonate mineral involves burning limestone in a reactor, obtaining calcium oxide, production of calcium carbide by reacting part of calcium oxide obtained from burning limestone with carbon, bringing part of the obtained calcium carbide into contact with water, obtaining acetylene and caustic lime, bringing gaseous wastes from burning limestone into contact with water to obtain carbonic acid. Limestone is burnt using heat obtained from burning part of the volume of acetylene, obtained from part of the volume of calcium carbide. At least part of the obtained acetylene is used in synthesis of ethanol and/or dichloroethane and/or ethyleneglycol and/or acetone. During synthesis of ethanol and/or dichloroethane, acetylene is reacted with hydrogen in the presence of palladium as catalyst, after which at least part of synthesised C2H4 material is reacted with water vapour, obtaining ethanol, and/or reacted with chlorine, obtaining dichloroethane. Also at least part of the obtained acetylene is subjected to hydrolysis, obtaining ethyleneglycol. Also during synthesis of acetone, part of the obtained acetylene is reacted with water vapour, where the hydrogen obtained is used in said synthesis of ethanol and/or dichloroethane and/or burnt in the burning process. Carbon dioxide obtained from synthesis of acetone is used in the process of producing carbonic acid.

EFFECT: wide range of obtained finished products and prevention of formation of industrial wastes.

4 cl, 1 ex, 1 dwg

FIELD: chemistry.

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

EFFECT: high output and selectivity of the process.

2 cl, 17 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for continuous use of apparatus for producing acetylene from hydrocarbons which are alkanes having chain length of up to C10 via partial oxidation to obtain a mixture of reaction gas, which is directed through one or more compressors, wherein the pressure of the mixture of reaction gas on the suction side of the compression zone is regulated using a regulating device in a given range, characterised by that a predicting regulating device is also used, which works at a higher level which supports this model, where the said predicting regulating device is a Feed-Forward regulator, which reacts to sudden change in mass flow of the mixture of reaction gas greater than 5%.

EFFECT: use of the present method ensures continuous operation of apparatus for producing acetylene in case of high processed mass flow.

14 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylene and synthetic gas via thermal partial oxidation of hydrocarbons which are gaseous at temperatures used for preheating, in a reactor which is fitted with a burner with through holes, characterised by that the starting substances to be converted are quickly and completely mixed only directly in front of the flame reaction zone in through holes of the burner, where in the mixing zone within the through holes the average flow rate is higher than the propagation speed of the flame under the existing reaction conditions. The invention also relates to a device for realising the said method.

EFFECT: possibility of avoiding preliminary and reverse inflammations.

9 cl, 3 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylene through partial oxidation, splitting in an electric arc or pyrolysis of hydrocarbons. The reaction stream containing the obtained acetylene and soot is directed into a compressor, characterised by that the compressor used is a screw compressor, where liquid which absorbs a large amount of soot contained in the reaction stream is injected into the compressor. If water is injected, content of soot in the water coming out of the compressor is between 0.05 and 5 wt % and if other liquids are injected, the viscosity of the suspension must be comparable with the viscosity of the soot suspension in water.

EFFECT: use of the method enables to use the screw compressor for long periods without preliminary separation of soot.

15 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of acetylene by plasma chemical pyrolysis of minced solid raw stock with grain size of smaller than 100 mcm by steam in impulse electric discharge plasma generator. Proposed method consists in using shock wave and differs from known methods in that electric discharge in plasma generator is effected in interval smaller than 1 ms while gas product rate is reduced in tubular heat exchange arranged downstream of Laval nozzle. Invention relates also to device intended for implementation of above described method.

EFFECT: high yield of acetylene, power savings.

6 cl, 1 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for partial oxidation of hydrocarbons in a reactor, according to which a stream containing a hydrocarbon and a stream containing oxygen are fed into said reactor. The method is characterised by that both said streams are independently fed into the reactor respectively through one or more spaced apart lines inside of which there are turbulence generators which provide a given change in direction of flow, owing to which downstream beyond the turbulence generators a highly turbulent flow field is formed, wherein the turbulence generators cover the cross-section of the lines by a value ranging from 10% to 70%, wherein during passage of the streams through the turbulence generators, there is an arched change in the direction of flow in an inscribed angle ranging from 45° to 360°, and wherein right after coming out of the lines, the flow velocity includes a tangential component and the streams are mixed in a mixing zone and then react in a reaction zone. The invention also relates to an apparatus realising said method.

EFFECT: use of the present invention enables to achieve fast and quality mixing of reactants during short-term dwell thereof in a small space.

8 cl, 1 ex, 3 dwg

FIELD: chemical industry; other industries; methods and devices for conversion of the methane by the plasma-catalytic oxidation.

SUBSTANCE: the invention is pertaining to the method for conversion of the methane by the plasma-catalytic oxidation and to the and devices fro the method realization. The method of conversion of methane is conducted by the super high frequency (SHF)radiation plasma-catalytic oxidation with production of ethylene. The method includes activation of the catalyst by the SHF radiation and formation of the non-equilibrium "cold" SHF plasma. Simultaneously exercise activation of the catalyst by the super high frequency radiation and by the SHF plasma and create the non-equilibrium "cold" super high frequency plasma simultaneously in the Е010 type resonator or on Е01 with the symmetry of rotation from the SHF generator and on the total wave Н11° with rotation of the polarization plane of the continuous SHF generator. In the device realizing the indicated process the round waveguide is smoothly transforms into the waveguide with the partial dielectric filling-up and contains the aligner used for reduction of the reflections of the super high frequency energy, the encapsulant for provision of vacuum in the SHF plasma-catalytic reactor and the SHF plasma generation on the butt of the quartz rod, with the located on it quartz plates and the catalyst. The batchers of the uniform feeding of the reactants (СН4 + О2 + Аг) are installed with the capability of rotation and movement with respect to the SHF plasma. The system of the reaction products withdrawal is located in symmetry to the axis of the with respect to the plasmatron. The invention stimulates the increase of efficiency of the conversion process of methane into ethylene.

EFFECT: the invention ensures stimulation of the increased efficiency of the conversion process of methane into ethylene.

9 cl, 2 ex, 4 dwg, 1 tbl

FIELD: petrochemical industry; other industries; methods and the devices for hydrocracking of the heavy hydrocarbon fractions.

SUBSTANCE: inventions is pertaining to the method of hydrocracking of the heavy hydrocarbon fractions. The previously heated up to the temperature of 60-370°С heavy hydrocarbon fraction is exposed to "bombardment" by hydrogen ions and ions of the hydroxyl group in the reactor without access of oxygen. At that the ions of hydrogen and the ions of the hydroxyl group are fed into the chamber in the form of plasma. As the object of the invention is the device used for hydrocracking of the heavy hydrocarbon fractions. The device contains the reactor, which has: the level sensor, the temperature detector, the fitting pipe used for withdrawal of the non-reacted part of the heavy fractions in the liquid state, the fitting pipe used for withdrawal of the reacted part of the hydrocarbon fractions in the vaporous state. At that in the upper part of the reactor there is the mounted plasmatron with the nozzle, and in its lower part there is the mounted fitting pipe used for feeding of the heavy hydrocarbon fractions with the spray jet with the capability to adjust the spacing interval from the nozzle of the plasmatron up to its upper part. The method and the device for its implementation are aimed to simplify the production process of hydrocracking of the heavy hydrocarbon raw, to increase efficiency at the expense of capability to adjust the degree of splitting of the hydrocarbon molecules by the duration of the "bombardment" by their ions, by the kinetic energy of the ions, the initial temperature of the hydrocarbon molecules, and also due to the capabilities of the device to operate in two technological modes: production of the gas or the liquid light factions.

EFFECT: invention ensures simplification the technology of hydrocracking of the heavy hydrocarbon raw, the increased efficiency, the device capabilities to operate in two technological modes: production of the gas or the liquid light fractions.

4 cl, 1 dwg

FIELD: technological processes; metallurgy.

SUBSTANCE: heavy hydrocarbon fraction, previously heated up to 60-350°C, is exposed to plasma for hydrocarbon molecules splitting into atoms in high temperature area without oxygen access, further "bombardment" of other hydrocarbon chains with them, their crushing and hydrogenation in reaction zone, which results in creation of light hydrocarbon fractions, at that plasma represents ionised high-temperature gas.

EFFECT: simplification of technology for plasmochemical hydrocracking of heavy hydrocarbon raw material, combination of heavy hydrocarbon fractions cracking and hydrogenation into single process, possibility to adjust extent of hydrocarbon molecules crushing with time of their bombardment with hydrogen and carbon atoms and temperature of raw material supplied into reactor, provision of possibility for device to operate in several technological modes.

3 cl, 1 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: active particles are synthesised on the first stage: in a plasmatron - atomic hydrogen, in a forreactor - methyl radicals, under the effect on natural gas, coming into a pyrolysis reactor, from which ethylene with acetylene impurities is produced, which, without separation from pyrolysis gas, is selectively hydrogenated into ethylene on the next stage in the presence of a catalyst in gaseous phase, with subsequent separation of concentrated ethylene from the hydrogenation products using low temperature rectification method, return of part of methane and hydrogen mixture from the hydrogenation stage to the pyrolysis stage in the forreactor and use of a balance quantity of methane and hydrogen mixture to produce electrical energy or as an end product. Content of methane in the methane and hydrogen mixture, fed into the forreactor, does not exceed 13 wt %.

EFFECT: increased output of ethylene with low energy consumption.

4 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to oil processing and specifically to a method of processing oil and/or gas condensate to obtain engine fuel. The invention relates to a method of processing oil and/or gas condensate, involving a step for fractionating the initial material with extraction of straight-run petrol, diesel and residual fractions or petrol, kerosene and residual fractions, or naphtha and residual fractions, and possibly hydrocarbon gases, subsequent high-temperature processing of the residual fraction, possibly in a mixture with gaseous hydrocarbons, through vapour and/or vapour-oxygen and/or vapour-carbon dioxide gasification to obtain synthetic gas. The obtained synthetic gas is converted to oxygen-containing products, including crude methanol, at high temperature and excess pressure on a copper-containing catalyst. The straight-run naphtha or straight-run petrol fraction, together with the oxygen-containing products, are brought into contact at temperature of 300-480°C and pressure of 2-40 atm with a catalyst which contains ZSM-5 or ZSM-11 zeolite, including that which is modified with group I, II, III, V, VI and VIII elements, separation of the contacting products with extraction of gaseous fractions and the end high-octane petrol fraction. The straight-run kerosene or diesel fraction is obtained as an end product or undergoes hydrofining to obtain an end product.

EFFECT: increased output of light petroleum products to 90 wt %, wide range of products.

13 cl, 6 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to apparatus for pyrolysis of hydrocarbons to obtain carbon nanostructures, acetylene and hydrogen, having a plasma-chemical reactor with a plasmatron, cooler, separator, reaction product lines and a line for feeding the gas to undergo pyrolysis. There is an ejector in the line for feeding the gas to undergo pyrolysis, the inlet of the sucking chamber of which is connected to a 'volatile' catalyst container, and the outlet of the ejector is connected to the inlet cavity of the plasmatron. The invention also relates to a method for pyrolysis of hydrocarbons.

EFFECT: improved technology of carrying out plasma-chemical reactions of hydrocarbons in form of high efficiency of the process and wide range of reaction products.

2 cl, 1 tbl, 2 dwg

FIELD: oil and gas production.

SUBSTANCE: invention refers to installation for plasma-chemical hydro-cracking of hydrocarbon fractions consisting of reactor and plasmatron. The plasmatron consists of a lower and upper vortexes, of a cathode flange inside of which there is located a hollow cathode with an electromagnetic coil and of an anode flange with an expanding nozzle-anode installed in it. Also, a cylinder is arranged in the reactor beneath of the anode flange. The cylinder is used as an anode when the anode flange is disconnected from ground. Additionally, the cylinder has a channel for supply of a counter flow of water gas into a plasma jet and for change of plasma jet direction from axial to radial. The channel for supply of the counter flow of water gas into the plasma jet is tied with a water supplying pipe. The reactor has a branch for supply of hydrocarbon raw material and a branch of reaction products outlet.

EFFECT: simplified design and raised efficiency of hydro-cracking.

5 cl, 1 tbl, 2 dwg

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for cracking heavy fractions of oil. The procedure consists in thermal treatment of source raw stock in an active zone by exposure it to high frequency plasma. In volume of the active zone there is generated high frequency plasma with intensity 0.05÷0.2 Wt·cm2·and value of plasma carrier frequency from 106 Hz to 108 Hz. Raw stock is subjected to preliminary heating before treatment in the active zone. According to another version of the procedure low frequency plasma with intensity 0.05÷0.2 Wt·cm2 and value of plasma carrier frequency from 102 Hz to 105 Hz is generated in volume of the active zone; and raw stock is subjected to preliminary heating before treatment in the active zone. The invention also refers to the plasma reactor for cracking heavy fractions of oil and heavy oil residues.

EFFECT: increased efficiency of processing source raw stock, including heavy hydrocarbons, into motor fuel; increased depth of treatment of source raw stock due to maximal area of plasma contact with vapour-gas phase of raw stock; reduced power consumption per unit of product.

8 cl, 1 tbl, 2 dwg

Up!