Method for plasmochemical hydrocracking of heavy hydrocarbon fractions and device for its realisation

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

 

The invention relates to a plasma hydrocracking of hydrocarbons, particularly heavy oil feedstock, and is designed to produce light fractions: diesel fuel, kerosene, gasoline, gas, and may be used in the refining industry in the field of deep processing of oil, as well as power generating plants, where rational replacement of liquid fuel to gas.

The prior art method of processing high molecular weight hydrocarbons comprising the hydrogenation of the feedstock at elevated temperature and pressure in the presence of a catalyst produced in the reaction zone interaction dispersed in the volume of the raw material aqueous solution of salts of molybdenum or a mixture of salts of molybdenum and the metals of group VIII of the Periodic system with a sulfiding agent, subsequent separation of the gaseous products of hydrogenation and separation of low-boiling and high-boiling hydrocarbons by vacuum distillation. The hydrogenation is carried out at dispersion in the raw water and the salts of molybdenum in the ratio of water, molybdenum and raw materials(0,005-0,05): (0,0002-0,002):1 respectively, and the amount of hydrogen 500-900 l/kg of raw material (EN 2241020, 27.11.2004).

The disadvantages of this method are the complexity of the process of recycling, and the use of expensive equipment.

Famous square is Sonny pyrolysis decomposition of waste products, in which the input waste is crushed using a plasma arc, thereby ionized, then released discharged they do in the reaction space, which is cooled, and reunited in the gas product and particulate matter. Recombinases products hardened. Alkaline crushed the spray produced by the spray ring, neutralizes recombinases products and moisturizes the particulate matter. The gas product is removed from the family of products using a scrubber, and the gas product is then burned or used for fuel (US 4644877, 24.02.1987).

The disadvantage of this method is the complexity of the raw processing.

The closest analogue of the claimed method of plasma chemical hydrocracking of heavy hydrocarbon fractions is a method for the production of liquid hydrocarbons, in which the heavy hydrocarbon fraction is heated to a temperature of more than 350°thus their cracking. The cracking products in the form of hot gas stream saturated with water vapor, which represents the hydroxide ions and monatomic hydrogen to produce a saturated gas stream. Saturated gas stream komprimerede, and then cooled to normal temperature and pressure. Thus obtained liquid light hydrocarbons and razoobrazny the e-waste. The waste gases passing through the microwave generator form ionized gas stream, or plasma, which is returned in the above-mentioned hot cracking gas stream. Carbon and other residues contained in the waste gas, are oxidized to enter them in the cracking gas. Alternative original gaseous plasma of the microwave generator is mixed with a hot cracking gas stream, forming an ionized gas stream, which is then saturated with water vapor (WO 9842803, 01.10.1998).

The disadvantages of this method, and any known method of hydrocracking, is that a technological regime have to be divided into two stages: first, due to the high temperature heating heavy hydrocarbon fraction, produce cracking, and then filling the resulting cracking of free carbon bonds with hydrogen.

The closest analogue of the claimed device for plasma-chemical hydrocracking of heavy hydrocarbon fractions is a reactor for combustion, pyrolysis and melting gaseous waste materials containing a closed hollow shell, comprising a rotatable drum having an inner surface and having a third opening to receive the gaseous exhaust material entering the casing via the first is twistie; means establishing a drum shell for rotation relative to the shell; a motor for rotating the drum and the drum of the centrifugal force; the plasmatron set so that the jet plasma is included in raw materials (US 4770109, 13.09.1988).

However, this reactor does not eliminate the above disadvantages and in this design cannot be used for the proposed method of hydrocracking.

The objective of the invention is to provide such a method of plasma-chemical hydrocracking of heavy hydrocarbon fractions and device for its implementation, which would rule out the disadvantages indicated above.

Technical result achieved in the implementation of this invention is to simplify the technology of plasma-chemical hydrocracking of heavy hydrocarbons, the Association of cracking of heavy hydrocarbon fractions and the saturation of free carbon bonds with hydrogen (hydrogenation) in one process, and to enable operation of the device in several technological regimes, from one gas to obtain a full set of light hydrocarbons (gas, gasoline, kerosene, diesel fuel).

This technical result is achieved in the plasma-chemical method of hydrocracking heavy hydrocarbon fractions, in which pre beneath ryuu to 60-350° With the heavy hydrocarbon fraction is exposed to plasma for splitting in the zone of high temperature hydrocarbon molecules into atoms, followed by "bombing" them other hydrocarbon chains, crushing them and hydrogenation in the reaction zone without oxygen for the formation of molecules of light hydrocarbon fractions, while the plasma is a high temperature ionized gas.

The size of the molecules of light hydrocarbon fractions regulate the temperature in the reactor materials.

The degree of fragmentation of hydrocarbon molecules regulate the time of the "bombing" of their atoms, changing the kinetic energy of these atoms, the initial temperature of the heavy hydrocarbon fraction (raw).

To get from heavy hydrocarbon fractions of gas in the reactor serves heavy hydrocarbon fraction with a temperature of 60-80°C.

To get from heavy hydrocarbon fractions of liquid and gaseous light fractions in the reactor serves heavy hydrocarbon fraction with temperature up to 350°C.

This technical result is also achieved by a device for plasma-chemical hydrocracking of heavy hydrocarbon fractions containing reactor having a level sensor, a temperature sensor, the outlet nozzle of the reacted part of the hydrocarbon fractions in the vapor SOS is the right and tube feeding raw materials, while inside the reactor is rotating with longitudinal slots of the drum for education in the reactor rotating layer of heavy hydrocarbon fractions, adjacent to the inner walls of the reactor, and in the upper part of the reactor has a plasma torch with a nozzle for the occurrence of plasma jets in heavy hydrocarbon fraction, filed in the reactor.

The drawing shows a device for hydrocracking of heavy hydrocarbon fractions.

Device for plasma-chemical hydrocracking of heavy hydrocarbon fractions contain the reactor 1, which includes the level sensor 2 temperature sensor 3, the outlet nozzle 4 of the reacted part of the hydrocarbon fractions in the vapor state. In the upper part of the reactor 1 is installed plasmatron 5 nozzle 6, in the middle part of the reactor has a feed pipe heavy hydrocarbon fractions (raw) 7. Inside the reactor is set rotating drum 8 with longitudinal slots, driven in rotation by an electric motor 9.

Unreacted portion of the hydrocarbon fractions in the vapor state, which is forced by centrifugal forces through the longitudinal slit of the rotating drum 8, out through the outlet nozzle 4 in a distillation column.

A jet of plasma from the nozzle 6 of the plasma torch 5 is included in the heavy hydrocarbon fraction, filed in the reactor.

Before you begin, and the reactor 1 is evacuated of air by blowing its hydrocarbon gas, the inert gas or nitrogen, include the rotation of the drum.

Pre-warmed to 60-350°With the heavy hydrocarbon fraction is fed via a feed pipe 7 heavy hydrocarbon fractions (raw materials) into the reactor 1. Pressure feed set up so that the supply of raw materials was stopped when reaching the rotating layer of a given level (thickness) due to the counteracting centrifugal forces and resumed again at its reduction. The thickness of the rotating layer of heavy hydrocarbon fractions is monitored by the level sensor 2. After reaching the preset level rotating layer of heavy hydrocarbon fraction into the reactor 1 through the plasma torch 5 and the nozzle 6 serves gas.

In the plane of contact of plasma ions with heavy hydrocarbon fractions (high temperature range), under the influence of high temperature (in excess of 4000 degrees Celsius) hydrocarbon molecules break down into atoms of hydrogen and carbon. Carbon atoms, in the presence in plasma of oxygen, oxidized with heat, thereby expanding the zone of high temperature. In the absence of oxygen in the plasma gas carbon atoms, losing kinetic energy in the reaction zone, may be joined together to form molecules or with the hydrocarbon chain in the place of rupture, leading to recombination of hydrocarbon relations within it, similar to the process for thermal cracking. The formed hydrogen atoms with high kinetic energy, bombard neighboring hydrocarbon chain - reaction zone.

In the collision of atoms with hydrocarbon molecules in the chain, in the scene of the accident, local increase of the kinetic energy transferred from atoms. Where this energy will be equivalent to the temperature at which begins spontaneous rupture of hydrocarbon relations, hydrocarbon molecule is broken. Atoms, losing kinetic energy, become reactive and fill loose ties with carbon.

NOTE. Under the local increase of the kinetic energy refers to the energy increase of only those atoms of hydrocarbon molecules, which were under the influence of atoms with high kinetic energy.

Thus, a hydrocarbon molecule with a shorter chain, there is formed a light hydrocarbon fraction.

The resulting molecule with a short chain, initial boiling point which is below the temperature supplied to the camera heavy hydrocarbon fraction will evaporate from the reaction zone, to be forced out of the rotating layer of raw material under the influence of centrifugal forces and through slots in the drum and the outlet removed from the reactor. Thus there is a selection of light fractions from raw materials, and through the feed pipe 7, in connection with the reduction of thickness of the rotating layer, will receive a new portion of the raw material.

If the temperature in the chamber heavy hydrocarbon fraction does not exceed 150°With, it will be emitted hydrocarbons are gases. If the temperature of the heavy hydrocarbon fraction is 350°With, it will select all the light fraction components of diesel fuel, kerosene, gasoline and gas.

The degree of fragmentation of the hydrocarbon molecules can be adjusted by "bombing" their atoms, changing the kinetic energy of the atoms, the initial temperature in the reactor of raw materials, and thus you can convert heavy hydrocarbon fraction into the lungs.

The device can operate in multiple operating modes:

1 - mode processing of heavy hydrocarbon fractions in the gas (fraction4and below)

2 - mode processing of the heavy hydrocarbon fraction in gaseous and liquid light fractions (C18and below).

3 - intermediate mode of processing, limiting the receipt of light hydrocarbons with the desired boiling point.

1. Technological mode.

In the reactor 1 are served heavy hydrocarbon fraction with a temperature of 60-150°C. Under the influence of "bombing" of the hydrocarbon chains of atoms with high kinetic energy of the reaction zone could the t to leave only the hydrocarbon chain, boiling point below 150°i.e. gases.

The process in the reactor 1 is controlled by the level sensor 2 and temperature 3.

Creating excessive pressure in the reactor 1 is undesirable.

2. Technological mode.

In the reactor 1 is heavy hydrocarbon fraction, pre-heated to 350°C. enabling plasmatron output will receive a mixture of oil vapor state initial boiling point which is below 350 degrees: components of diesel fuel, kerosene, gasoline and gas.

3. Intermediate mode.

At intermediate temperatures fed to the reactor heavy hydrocarbon fraction is set at the boiling point of the longest hydrocarbon chain of light fractions, you want to get. This mode, for example, can be obtained from highly paraffinic feedstock, without any additional processing, liquid light diesel fraction, its characteristics corresponding to "winter" diesel fuel, or to process all the raw materials in the gasoline and gas.

Example

In the reactor 1 is oil heated to 60 to 150°to give it fluidity. In the upper part of the reactor 1 is installed plasmatron 5 (plasma jet - indirect actions.)

When the feed to the reactor 1 heavy hydrocarbon fractions and included nom the plasmatron 5 decomposition of hydrocarbon molecules in a zone of high temperature on atoms and "bombing" their raw material in the reaction zone, resulting chain hydrocarbon molecules are broken. Generated free communication of carbon are filled with atoms of hydrogen and carbon molecules with a short chain that is light hydrocarbon fraction that evaporates from the reaction zone through the exit 4, go to the next stage of processing.

To obtain the quality of the finished product, along with gas, liquid light fractions was carried out by the operation of the device when applying heavy hydrocarbon fractions with different temperatures, i.e conducted the operation on the third and second modes.

option 1: the temperature of the heavy hydrocarbon fraction (raw materials) in the reactor was 190°C.

option 2: the temperature of the substrate was 250°C.

option 3: the temperature of the feedstock in the reactor was 350°C.

As a heavy hydrocarbon fraction used oil obtained after primary processing of oil, the content of light fractions which were missing.

As the plasma source was used plasma device for cutting metal with a capacity of 60 kW. The plasma torch was reconstructed in several modifications with the aim of creating a plasma jet indirect action and its stable operation on a plasma-forming gases: argon, nitrogen, propane, and air.

Thus we obtained the following results:

Table 1The temperature in the reactor heavy hydrocarbon fraction, °Heavy hydrocarbon fractionReceived the product in a weight %GasGasoline, keroseneDiesel fuel190The oil obtained after primary refining3466no25021423735051283

Used as the plasma-forming medium gases with reducing properties (nitrogen, propane), and inert argon gas does not adversely affect the lifetime of the cathode of the plasma torch.

Significant changes in the ratio of received light fractions at different temperatures was not observed. This is probably due to the fact that for each gas had to use various modifications of the plasma torches, allowing functioning plasma installation in accordance with its technical characteristics. So, when working with nitrogen normal plasma installation was provided by the and by increased consumption. when working on the argon in the plasma torch was additionally installed interelectrode insert; when running on propane for the stable operation of the plasma torch was mounted solenoid, limited gas supply. Obviously these changes eliminated the ability of gases to affect the process of hydrocracking due to their different energy consumption and, in General, energy supply in the zone of contact of the plasma with heavy hydrocarbons remained the same.

1. The plasma-chemical method of hydrocracking heavy hydrocarbon fractions, in which the pre-warmed to 60-350°With the heavy hydrocarbon fraction is exposed to plasma for splitting in the zone of high temperature hydrocarbon molecules into atoms without oxygen, followed by "bombing" them other hydrocarbon chains, crushing them and hydrogenation in the reaction zone, leading to the formation of light hydrocarbon fractions, while the plasma is a high temperature ionized gas.

2. The method according to claim 1, characterized in that the size of the molecules of light hydrocarbon fractions regulate the temperature in the reactor materials.

3. Device for plasma-chemical hydrocracking of heavy hydrocarbon fractions containing reactor having a level sensor, a temperature sensor, the outlet nozzle of the reacted part uglev the portly fractions in the vapor state and tube feeding raw materials, while inside the reactor is rotating with longitudinal slots of the drum for education in the reactor rotating layer of heavy hydrocarbon fractions, adjacent to the inner walls of the reactor, and in the upper part of the reactor has a plasma torch with a nozzle for the occurrence of plasma jets in heavy hydrocarbon fraction, filed in the reactor.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

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23 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

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23 cl, 3 ex

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42 cl, 1 ex, 8 tbl, 11 dwg

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10 cl, 5 tbl, 3 ex

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14 cl, 1 tbl, 2 dwg, 4 ex

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14 cl, 1 ex

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4 cl, 1 tbl, 9 ex

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

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4 cl, 1 dwg

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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

The invention relates to the processing of heavy oil residues and oily waste and can be used in the oil and petrochemical industry, namely for plazmokataliticheskoy of oil sludge

The invention relates to the field of gasification of solid carbonaceous materials, including plastic waste, and can be used in the chemical industry, in the processing of solid domestic waste

The invention relates to processes for gases by plasma-chemical method by pyrolysis of hydrocarbons, such as electroretinogram

The invention relates to the refining, petrochemical, gas and chemical industries and can be used for the disposal of gaseous hydrocarbons (petroleum gas, gas condensate and other hydrocarbons) through its processing in solid-phase products

The invention relates to the field of chemical engineering ethylene

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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

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