Transport process unit of partial oxidation and method for low temperature conversion neskazannyh hydrocarbon streams

 

(57) Abstract:

The invention relates to a transport process unit partial oxidation and method of low-temperature conversion neskazannyh hydrocarbon streams. The installation includes aerial installation for the formation of oxygen-enriched stream, a line for supplying an oxygen stream and the source of the hydrocarbon stream in the transport reactor for partial oxidation zone containing a partial oxidation for substochiometric oxidation of carbon deposited on the circulating particles, riser for making a mixture of the original hydrocarbon stream and products from the zone of partial oxidation, creating a flowing stream containing hydrogen, light hydrocarbons, carbon monoxide and carbon dioxide, and deposition of carbon on the particles of the stream flowing out of the riser, and the separation zone to extract particles for recirculation zone of the partial oxidation and formation of gas product, essentially not containing particles, steam boiler for heat extraction and cooling of the gaseous product from the transport reactor, a filter for extracting particles from the cooled gas and gas product,, the e containing particles, the installation of separate hydrogen to highlight the tempered gas product enriched in hydrogen stream and a stream of light hydrocarbons, a regulator for regulating the flow rate of the oxygen stream into the zone of partial oxidation and maintaining the temperature of the stream flowing out of the riser, essentially between about 870 and about 1090C in response to speed changes and carbon composition of initial hydrocarbon stream to maintain the amount of carbon deposited on the particles is between about 0.5 and about 40% by weight relative to the circulating particles. This invention allows to process neskazanny hydrocarbon stream into usable products (hydrogen and/or synthesis gas). 2 C. and 20 C.p. f-crystals, 3 ill., table 1.

The present invention relates to a transport process unit partial oxidation, in which the applied transport reactor operating at a relatively low temperature and substochiometric oxidizing conditions to convert neskazannyh hydrocarbon streams to hydrogen or synthesis gas, and to a method of low-temperature conversion neskazannyh hydrocarbon streams.

Waste and/or residual flows, which Malinovka, typically associated with their reuse or disposal. The usual proposal for resolution of the problem is the use of the heating capability of waste flows in combustion processes. Examples include exhaust gas containing hydrocarbons, carbon dioxide, carbon monoxide and water vapor; metal-containing sludge and resin; emulsion flows of hydrocarbons in water (for example, obtained by separation and dehydration of the emulsion); streams containing aromatic solvent; spent caustic streams; suspension of coal dust; exhaust gases toxodontia, solid particles of coke, etc., However, such flows are usually classified as hazardous waste. Removing the thus classified streams often requires great care and skill while minimizing adverse impacts on the environment. Benefits obtained by the combustion of such flows are usually limited to costs associated with the requirements of prudence.

To obtain a clean, acceptable from the point of view of environmental protection heat from exhaust streams, the removal of which otherwise is difficult and expensive, well-known bisokotuwa with approximately the stoichiometric amount of oxygen and Inuktitut in the combustion zone, in which the hydrocarbon feedstock is burned up with the formation of mainly carbon dioxide and water at a temperature of 3000oF (1648,9oC). The resulting heat is then removed for production purposes.

The above process in practice has several drawbacks. For example, the receipt of the waste stream at the facility are usually largely depends on the speed and composition. When the ratio of hydrocarbon to oxygen is changing rapidly, too many hydrocarbons leads to the formation of soot, while a very small number of hydrocarbons causes the output of the flame.

To smooth these changes in raw materials is usually necessary to take complex measures, usually carefully designed system of mixing the various components and systems of excessive power.

The transformation of hydrocarbons into synthesis gas containing carbon monoxide for the production of methanol or hydrogen for ammonia production, hydrogenation and other applications, is well known in this field. The hydrocarbon stream is usually transform in the presence of water vapor at an elevated temperature in the carbon monoxide and hydrogen. It is also known that monoosnoc temperature shift reaction.

To avoid waste streams, it is desirable to transform differently composed nescience hydrocarbon streams in one or more valuable product streams, such as hydrogen and/or synthesis gas (H2+ CO). In addition, it is preferable that the conversion process was a versatile when working with raw materials of different composition in a continuous process without violations. In addition, it is preferable that the transport reactor conversion worked at a relatively low temperature, reduced oxygen consumption and increased efficiency.

Nescience hydrocarbon streams efficiently processed in a process plant with a closed circuit containing a transport reactor conversion, working at low temperature, substochiometric oxidative conditions to obtain valuable synthesis gas and/or hydrogen which can be recycled in the process, from which were obtained nescience flows. When used in the process neskazannyh threads the number of waste streams that require removal from the process can be dramatically reduced.

When using the transport reactor conversion, in which the carbon is seated on circular the a and shift CO, the reactor has a light fitting in a continuous process without interruption of the partial oxidation reaction, you get a raw AC hydrocarbon composition and with different water content. In addition, the reactor can operate at a lower temperature, reduced oxygen supply and a higher efficiency in comparison with the methods of the combustion exhaust stream, used in the preceding field.

Benefit when using petrochemical installation includes, in particular, a significant reduction of the pollution source installation and reduction of exhaust gas and liquid flows, obtained, for example, in the processes of toxodontia. In this way perform the transformation nizkozhirnogo hydrocarbon stream into usable products, such as hydrogen and/or synthesis gas that can be recovered and used in the method, from which were obtained nescience flows. As a result, the amount of carbon dioxide decreases. In addition, see a significant decrease in the evaporation of heavy metals (due to much lower operating temperature of the reactor).

According to one aspect of the present invention provided the shackles in the hydrogen or synthesis gas. The installation includes air equipment for education stream enriched in oxygen.

For the feed line of flow of the oxygen source and a hydrocarbon stream in a transport reactor for partial oxidation, containing: 1) a zone of partial oxidation for substochiometric oxidation of carbon deposited on the circulating particles. 2) riser for making a mixture of the original hydrocarbon stream and products from the zone of partial oxidation, creating a flowing stream containing hydrogen, light hydrocarbons, carbon monoxide and carbon dioxide, and deposition of carbon on the particles from the stream flowing out of the riser, and 3) the separation zone to extract particles for recirculation zone of the partial oxidation and formation of gas product, essentially not containing particles, provided the line (for example, pipes or pipelines). To extract the heat and cooling of the gaseous product from the transport reactor is provided with a steam boiler.

To extract the particles from the cooled gas and gas product, essentially no particle filter. For circulating water in the tower for quenching the gaseous product containing no particles, obook light hydrocarbons provides the installation for the separation of hydrogen.

In response to the speed change and the carbon composition of source of hydrocarbon flow and deposition of carbon on the circulating particles in the quantity being between about 0.5 and about 40% by weight relative to the circulating particles includes a regulator for regulating the feed rate of the oxygen stream into the zone of partial oxidation and maintaining the temperature of the stream flowing out of the riser, essentially between about 870oC (about 1600oF) and about 1090oC (about 2000oF).

The source of the hydrocarbon stream is fed in, can be subjected to fluctuations in the water content essentially between 0 and about 40% by weight from the initial hydrocarbon stream, when the carbon content is essentially between 75% and about 95% by weight relative to the source of the hydrocarbon stream in terms of dry weight and the atomic ratio of H:C essentially between about 0.5 and about 4.0. The original hydrocarbon stream preferably includes waste hydrocarbon gases, residual liquid hydrocarbon streams, solid particles from the oil refinery or a combination thereof, having a total atomic ratio H:C of about 1 to 2 in terms of dry weight. In the preferred embodiment, this device includes a first line for Ogorodov and any solid components. The line preferably provide in the supply of water vapor in the riser with such speed, that the weight ratio of total water to water vapour and the source of the hydrocarbon stream to the hydrocarbon in the original hydrocarbon stream ranged from 0.3 to 0.5.

The oxidized zone of the transport reactor for partial oxidation is preferably tailored to the oxidation of carbon deposited on the circulating particles substochiometric the flow of the oxygen stream to form a stream of products of partial oxidation, essentially do not contain chemically active oxygen. Feed injection zone is preferably tailored to the continuous introduction of the original hydrocarbon stream into a stream of products of partial oxidation for education and mixtures thereof riser adopted for the mixture of the feed injection zone. The reactor preferably includes a delay zone particles for making the extracted particles having deposited on their carbon line transfer for transporting particles from the zone of the delay zone of the partial oxidation and the loading of the particles, including the besieged them carbon zone delays particles and recirculation through the riser, the separation zone and a line transfer in kolichestva blowing part of the particles, extracted from the separation zone transport reactor for partial oxidation to provide the pipeline. For processing purged particles and obtain a solid product or associated metal product can be used leaching of metal or the binding system.

According to another aspect of the present invention provides a method of low-temperature conversion neskazannyh hydrocarbon streams to hydrogen or synthesis gas.

As a stage (a) initial hydrocarbon stream is injected into a continuous stream of products of partial oxidation, containing fine particles. As a stage (b) the mixture obtained from stage (a) is passed through essentially adiabatic the pyrolysis zone during transportation to obtain a flowing stream comprising hydrogen, light hydrocarbons, carbon monoxide and carbon dioxide and for the deposition of carbon on the particles. At the stage (C) remove particles covered with carbon from the product of stage (b) to obtain a synthesis gas essentially containing no particles. At stage (d) the main part of the extracted particles and substochiometric the amount of chemically active oxygen is continuously fed to the partial oxidation for the significant fluctuations of the initial hydrocarbon stream, selected from the rate of mass flow, water content, carbon content of the hydrocarbon, the atomic ratio H:C hydrocarbons and combinations thereof, the amount of chemically active oxygen supplied to the partial oxidation regulate at the stage (b) to maintain the temperature at the exit of the pyrolysis zone is essentially between about 870oC (about 1600oF) and about 1090oC (about 2000oF) and for receiving particles from the stage of extraction (C), with average content of deposited carbon on the merits between 0.5 and 40% by weight.

As an example of the method of the invention the source of the hydrocarbon stream may contain an emulsion of malovodnoje separator or tank to flotation. The original hydrocarbon stream may contain metal, which adsorb on the particles at the stage (b), and the synthesis gas from stage (C) essentially does not contain metal.

The particles are preferably fed to the partial oxidation stage (d) with a speed of 10 to 250 times greater than the flow rate at the stage (a). Oxygen, essentially not containing nitrogen, preferably fed to the partial oxidation stage (d) in an amount of less than about 5% of the stoichiometric relative to the carbon particles, padave the gasification part of the carbon in the pyrolysis zone serves water vapor. The source of the hydrocarbon stream has a water content of from 0 to 40% by weight, of carbon from 75 to 95% in terms of dry weight and the atomic ratio H:C in terms of dry weight from 0.5 to 4, but preferably from 1 to 2.

Steam can be fed into the inlet of the pyrolysis zone in an amount necessary to ensure the weight ratio of water from water vapor and the source of the hydrocarbon stream to the hydrocarbon in the original hydrocarbon stream is from about 0.3 to about 0.5. A hydrocarbon is introduced at the stage (C) may contain an aromatic ring, and the synthesis gas and carbon deposited on the inorganic particles from step (C), does not inherently contain compounds with aromatic rings.

Particles at the stage (a) can contain exhaust fluidized catalyst catalytic cracking or other appropriate capable of fluidization of the particles. The mixture of stage (b) may include a small amount of caustic soda. As another stage of the synthesis gas from step (C) is preferably quenched to a significant inhibition of the formation of tar.

Fig. 1 is a schematic representation of the low-temperature transport reactor for partial oxidation of this from the torus used in the reactor of Fig. 1.

Fig. 3 represents schematically a picture of a small transport reactor of the present invention used to evaluate this method of converting hydrocarbons.

Nescience hydrocarbon streams, or solid, or liquid, or gaseous, or a combination of them in turn flows produce synthesis gas and/or hydrogen by introducing hydrocarbons in a continuous manner in the transport riser reactor of the present invention, where the hydrocarbons are destroyed and pyrolized, you get a solid carbon, which is deposited on the carrier of the solid particles circulating in the reactor. The energy required for the endothermic cracking and pyrolysis reactions produced by substochiometric partial oxidation of deposited carbon. This reactor conversion can work together with installations of absorption resulting reaction gas flow for the formation of a closed circulation circuit to produce synthesis gas and/or hydrogen, are suitable, for example, for use in the same industrial setting (e.g., oil), which was received neskazanny hydrocarbon stream. Thus, nescience Ugledar is their source of contamination installation using the method of conversion with a closed circulation loop.

In Fig. 1 shows a reactor 10 of the present invention operating in the hydrodynamic transport mode, which contains the riser 12 above the mixing zone 14. The mixing zone 14 includes a lower zone of a partial oxidation 16, in which at least part of the carbon deposited on the carrier of the circulating particles are oxidized to the formation of the high-speed flow of products substochiometric combustion (mainly of carbon monoxide and fine particles.

Oxygen in the partial oxidation of 16 passes through line 18. Oxygen is usually carried out at a speed suitable for regulating the temperature of the partial oxidation zone 16 and the riser 12, and it may include air, oxygen-enriched air, mixtures of oxygen and inert gas, for example nitrogen or argon, pure oxygen, or etc., For facilitating the formation of carbon monoxide in excess of the formation of carbon dioxide in the zone of the partial oxidation of 16 molar ratio of oxygen to carbon, is mounted on the circulating particles, support substochiometric proportions. Supplied oxygen is preferred is Yes, submitted in the partial oxidation of 16, to carbon dioxide for formed products substochiometric combustion essentially did not contain unreacted oxidant.

Feed injection zone 20 is preferably placed in the mixing zone 14 above the zone of partial oxidation of 16.

The original hydrocarbon stream Inuktitut through the line 22 to the feed injection zone 20 and is mixed with a high-speed flow of waste water and particles from the partial oxidation zone 16. The heat generated in the partial oxidation of 16, used in the mixing zone 14 and the riser 12 for splitting any hydrocarbons with high molecular weight in raw materials into products with a lower molecular weight, including a lower hydrocarbon and carbon. In addition, the products of pyrolysis include hydrogen, carbon monoxide, carbon dioxide and carbon, which are also produced by interaction with water vapor. In accordance with a feature of the present invention the main part of carbon, obtained by reactions of cracking and pyrolysis precipitated on an inert particles from the partial oxidation zone 16. The flow of incoming material 22 may contain hydrocarbon exhaust gas residual coal the invention the flow of incoming material 22 can vary according to the water content, the carbon content and the ratio of hydrogen to carbon, depending on the type and availability (suitability) of residual and/or low flow, subject to transformation. The flow of incoming material 22 may include water at a concentration of from 0 to about 40% by weight and carbon at a concentration of from about 75% by weight to about 95% by weight. The flow of incoming material 22 may have an atomic weight ratio of carbon to hydrogen (in terms of dry weight) from about 0.5 to about 4:1, preferably from 1 to 2:1.

Examples of suitable source of hydrocarbon streams, which can be converted in the present invention include emulsions of oil in water obtained by dewatering installations of equipment for processing oil, aromatic solvents, settling liquid and solid particles of resin with petrochemical equipment, and flue gases, exhaust gases of toxodontia, sludge and settling liquid, and solid particles of coal received at the refinery installations. Additional examples of residual or neskazannyh hydrocarbon streams, which can be used include bituminous shale, tar, bitumen, dust from coal and from installations for the production of plastics, OTP is, ulpi, emulsions, suspensions, etc. solids, liquids and gases depending on the state of the subject (them) to transform the stream (s). Usually solid and gas components to facilitate handling and pumping should be dissolved and/or suspended in the liquid hydrocarbon media.

Alternative gaseous components can be entered separately through a separate line for raw material supply (not shown). To ensure quiet operation of the reactor the flow of incoming material 22 can be introduced into the mixing zone of the reactor 14 at a desired speed, depending in part upon the composition of the feedstock, the composition of the reaction of the resulting gas stream and process parameters occurring in reactor 10.

Water vapor is preferably Inuktitut in the mixing zone 14 through line 26 above the feed injection zone 20. Water vapor is mixed with a rising high-flow partial oxidation and partially destroyed by products near the entrance to essentially adiabatic the pyrolysis zone 30 in the riser 12. Alternative and/or additional water vapor can inject with hydrocarbons, in particular, when the feedstock comprises volatile and/or gaseous hydrocarbon compaccio water vapor 26 and the incoming hydrocarbon stream 22 to hydrocarbons in the incoming hydrocarbon stream 22 is between 0.3 and 0.5.

Flows arising from the mixing zone 14, is passed under the reduction conditions through the riser 12, in which there are several endothermic reaction processes. Volatile hydrocarbons present in the raw materials evaporate. Hydrocarbons with high molecular weight craterous into hydrocarbons of lower molecular weight, such as methane and ethane, and fixed carbon is deposited on the circulating particles. Water vapor react with the carbon and hydrocarbons with the formation of hydrogen and carbon monoxide and carbon monoxide to form additional hydrogen and carbon dioxide in accordance with the well-known shift reaction conversion. Since the source gas is not exposed to combustion processes, the formation of light hydrocarbons increases.

Products high-speed partial oxidation encourage rapid internal recycle stream of carrier particles in the riser 12, which acts like a thermal centrifugal wheel, effectively transferring heat from the partial oxidation zone 16, in which the particles are heated by the exothermic oxidation reaction in the adiabatic pyrolysis zone 30 for supplying heat to andote particles of the carrier, recirculating zone of a partial oxidation 16, preferably greater than from about 10 to about 250 times the rate of mass flow of feedstock into the mixing zone 14 entering through line 22. Materials suitable for use as carrier particles circulating in the reactor 10 are fine refractory materials, which have a large surface area and are generally inert under the reaction conditions of the present method.

Examples are aluminum dioxide and silicon dioxide and the spent catalyst from the reactor fluidized catalytic cracking (FCC).

Since the reaction of partial oxidation of the fuel supply through the oxidation of carbon deposited on the particles of the medium, instead kreiranih hydrocarbon products (volatile components), the concentration of light hydrocarbons and carbon monoxide in the resulting reaction stream in comparison with the methods of the preceding region increase. In addition, the reactor 10 has a high adaptability to continuous adoption of a wide range of source materials and compositions of the raw materials without interrupting the process. The carbon deposited on the circulating particles, is between the AI and shear reactions comes from the riser 12 in the separation zone 32, in which particles covered with carbon, remove from the reaction product to obtain a stream of hydrogen and/or synthesis gas essentially containing no particles. The separating zone 32 preferably includes one or more high-efficiency cyclone separator plates. Loaded with particles of the gas from the riser 12 is fed through line 36 into the cyclone 34. If necessary, can be used incremental secondary cyclone separators (not shown).

The cyclone 34 includes diplex 38 having a delay zone particles 40, to increase the residence time of particles loaded with carbon, and the line transfer 42 for transporting particles in a zone of partial oxidation 16 at a rate sufficient to maintain continuous operation of the partial oxidation zone 16 and the feed injection zone 20. The separating zone 32 contains, in addition, the purge line 44, through which a portion of the solids from the zone delay 40 can be purged from the reactor 10 to maintain the desired maximum concentration of metals in the solid particles. To meet the hydraulic working conditions through line 48 first load layer with an inert carrier. During the process to maintain the desired concentration of metals in noisy low content of particles extract from the cyclone 34 through line 46.

Depending on the operating pressure of the reactor 10 of the present invention operates at a temperature suitable to facilitate pyrolysis, gasification and shear reactions without the need for catalytic activity of circulating media. These reactions can usually be started at such a low temperature as 788oC (1450oF). Preferably the reactor 10 operates in a temperature range from about 870oC (about 1600oF) to about 1090oC (about 2000oF), measured at the exit of the riser 12. Compared with the methods of the preceding region reduced operating temperature of the present invention reduces the amount of volatilized metal and instead absorbs the metal particle media. (This helps to prevent the deposition and accumulation of metal on the walls of the production equipment and the piping system and facilitates the obtaining of metal by removal from the circulating solids).

Operating temperature range usually adjusted by accurately determining the feed rate of the oxidizer in the zone of partial oxidation 16 and the rate of recirculation of the media. In addition, optional heat can be Udal response to changes in the feed rate of the source material and the carbon composition of the hydrocarbon stream 22, to maintain the operating temperature of the riser 12 in a desirable range and ensure appropriate carbon content in the reactor 10 for regulating the feed rate of the oxygen stream 18 in the zone of the partial oxidation of 16 may be used by the controller (not shown).

Transport reactor can be designed so that it operates at an elevated pressure up to about 4 MPa (600 lb-ft2) (42,186 kg/cm2to increase productivity per unit cross-sectional area of the reactor.

The crude gas obtained on line 36, preferably clean installation of the gas absorption (see Fig. 2) located downstream, before use, for example, oil refining installation or before passing to the installation of the production of methanol or ammonia. Located downstream of the installation of the gas absorption may include removing the heat, remove traces of particles, suppressing the formation of tar, desulphurisation and distillation of the component.

In Fig. 2 shows a method of converting hydrocarbon 100 of the present invention in a closed circuit. When performing the method 100 using A for accumulation of technological transport temperature reactor 102 of the present invention, which is described above. The oxidizer to the reactor 102 provide via an air separation installation B, and the gas emanating from the reactor, will desulfurized and purified using the install gas absorption C to receive the stream of synthesis gas and/or hydrogen.

Installing the accumulation of source material A contains one or more pairs of collections 104a and 104b that are many neskazannyh liquid and/or solid hydrocarbon streams 106, 108, 110, respectively containing oily process effluent streams, residual oil streams and other solid particles from the oil refineries. Incoming hydrocarbon streams 106, 108, 110 is pumped by a pump 112 through line 114 into the reactor 102, operating in accordance with the present invention in partial oxidation. To maintain appropriate viscosity of the raw material collections 104a, 104b, the pump 112 and line 114 is preferably heated. Nescience hydrocarbon streams, which are gaseous, such as flue gas, preferably injected into the reactor 102 directly through the line 116. When necessary, through line 117 to the reactor 102 loads the inert particles of the medium.

Air separating unit B is divided into the TV, known in this field. For submission to a variety of refining processes nitrogen can be removed through line 120. Essentially pure oxygen stream is removed through line 122 as oxidative raw material for the reactor 102. Water vapor required for pyrolysis gasification and shift reactions in the reactor 102, is fed through a line 124. Optionally, steam may be combined with oxygen to supply through the line 122.

The stream flowing from the reactor 102, miss upstairs in the cell allocation particles (not shown) for separating particles of the carrier for recycling. Hot gaseous stream essentially containing no particles pass from cell allocation of cell extract waste heat 126. In the cell extract heat 126 heat fed to the reactor 102, can be partially removed for a variety of useful purposes, including supplying water from the heating boiler to produce steam. The cooled reaction effluent stream is passed through line 128 in high-efficiency filtration cell 130 for further separation of the particles captured from the gaseous stream 128. Examples of suitable filtration devices include cyclones, ceramic filters, centrifugal separator is further processing, as will be described below. The flow of solid particles 132 includes various non-volatile inorganic compounds present in crude oil, which is usually extracted from streams located in the installation base for refining in the form of non-combustible residue (ash). Streams of solid particles 132 may also contain particles of spent fluidized catalytic cracking catalyst, alumina or other suitable particles used as the substrate for the development of carbon.

Gas filtrate from the filter 130 through contour hardening 133 for further cooling the resulting flow and inhibition significantly the formation of tar. Contour hardening 133 includes a quenching tower 134 containing aqueous hardening liquid. For cooling the stream of solid particles 132 by exchanging heat with the hardening liquid is removed through line 136 from the quenching tower 134, it is preferable to provide a heat exchanger (not shown). The heated stream of water for quenching of the heat exchanger of solid particles (not shown) is passed through line 138 in cooling the collector 140 to dissipate the absorbed heat. Chilled water flow for quenching 142 extending from the cooling collector 140, connect, cogency stream, resulting from the quenching tower 134 through line 148, can pass through an optional setting for conversion, containing hydrogen sulfide or reactive sulfur, 150. Installation for conversion, containing hydrogen sulfide or reactive sulfur, 150 contains a catalyst suitable for the interaction of carbon monoxide and water with additional hydrogen in the presence of sulfides. The resulting stream enriched in hydrogen, is passed through line 152 to a cell in the removal of acid gas 153 in which to absorb the carbon dioxide and hydrogen sulfide using conventional means. Separated sulfides are removed through line 154 to supply in regenerative cell (not shown), in which sulfides are reduced to elemental sulfur. Carbon dioxide separated from the crude flowing stream removed through line 156 for further use or ventilation.

Purified effluent stream removed from the cell for separating acid gas 153, is passed through line 156, in the cell for separating hydrogen 158 in which to separate the hydrogen product from the other components in the output stream, mainly from carbon monoxide, using a conventional absorption at peremeny to separate hydrogen 158 through line 160 in the form of a purified stream, suitable, for example, for use in installations hydrogenation refinery, or in the production of several chemicals. The byproduct stream containing primarily carbon monoxide and/or light hydrocarbons are removed through line 162 to use, for example, with methanol or as a fuel gas for the production of useful products.

Solid residues after the implementation of the method 100, including particles metallized carrier, ash, inorganic substances etc. that are drawn from the reactor 102 through the purge line 164, and the solid particles are separated from the resulting crude gas flow in the high-performance filter 130, connected to line 166. Then thread the United solids is cooled by heat exchange with water for quenching, mentioned above, and need not be unloaded in the installation of metal leaching and/or binding solid particles 168.

In the installation of 168 metals in particles metallized carrier, ash and inorganic substances can be extracted through the line 170 in the form of a metallic product through traditional methods of leaching. Among the common metals present in the oil bottom pot is ing solids, which is extracted through a line 122 to remove.

Examples

To illustrate the applicability and performance of the transport reactor in the method of the present invention, including the transformation of neskazannyh hydrocarbon streams into hydrogen and/or synthesis gas, in the following examples used the test set containing the transport reactor laboratory scale fluidized bed. Target sectors include: the rate of deposition of carbon, the amount of carbon required to sustain the endothermic pyrolysis reactions, analysis of the products obtained and the rate of flow of compounds containing aromatic rings where used aromatic raw materials.

The particles of the medium, including the spent catalyst is aluminum oxide/silicon dioxide-type fluidized catalyst catalytic cracking, had a hard durable solid form at temperatures mainly between about 870oC and about 1090oC.

Generalized diagram of the test set, containing the transport reactor shown in Fig. 3. Transport reactor of the present invention 200, designed for carrying out the process in the laboratory is the UCA 202 was closed casing through the riser 206, forming a zone of accumulation of the carrier 208 in the annular space. The separation zone of the carrier 210 output from the Central vertical pipe 202 was used for release of the fluid medium from the resulting gas. The separation zone of the carrier 210 contained centrifugal plate 212. The resulting gas is removed from the zone in the separation of the carrier 210 via line 214 to analyze.

Zone of fluidization media 218 input vertical pipe 202 has created a fluidized bed of particles. Particles pseudological through pseudoviruses gas, which was barbotirovany in the zone of fluidization 218 through the bubbler 220 at the end of the line sparging gas 224. Fluidized particles were injectively into the inlet of the vertical pipe 202 through the ejector 226. The inlet tube 228 having a conical valve 230 at its input, filed hydrocarbons in the reactor 200 in the form of steam. Source pairs also served as injection gas for the ejector 226. The ejector 226 was established to regulate the gas velocity through the vertical pipe 202. The reactor contained electric heating elements 238 used for plating of the riser 206, and the jacket water cooling (not shown) for vertical pipe 202.

The reactor 200 was (0,0452 ft2). The reactor 200 contained a spare pipe (not shown), but without the annular closing valve.

The heating jacket 238 included six sections of the heating elements. Blowing and pseudoviruses gases contained compressed nitrogen.

The incoming steam flow contained aromatic solvent rubber, diluted with nitrogen. Solvent rubber was pumped using pump 240 from the container 242. Then the flow of solvent 244 mixed with steam introduced through line 246, and mixed flow pass through the heater 248 for evaporation of the solvent. Vapor diluted with nitrogen, introduced through line 250, and diluted couples filed in the reactor 200 through the line 252.

To determine the products of pyrolysis of aromatic hydrocarbons from the reactor 200 has removed the leaking gas. For separating particles from gas used dust filter 216. The obtained filtered gas to prevent the formation of tar tempered in a hot separator 252. Then tempered steam cooled by heat exchange with cooling water in a closed casing line 254 and missed in the cold separator 256 for condensation of water components in the received stream. Gaseous vihodiashiy chromatograph (CC) (not shown). Following the above reaction of the pyrolysis vapor, the reactor 200 cooled and to determine the weight percent of carbon from hydrocarbons deposited on the media, removed a media environment.

Example 1

Solvent rubber was subjected to pyrolysis vapor in the reactor 200 at a temperature of 900oC (1650oF) and a pressure of 0.34 MPa (g) (50 pounds/inch2) (3,5155 kg/cm2). Heat reactions were served through the heating jacket 238. The particles of the medium containing the precipitated carbon, and then collected for analysis. The time of contact in a vertical tube was less than two seconds. Equilibrium fluidized catalyst catalytic cracking, steam deactivated, was used as the circulating medium at the operating temperature of 900oC. the diluent nitrogen contained about 75% of the non-condensable products. Analysis by gas chromatography gaseous products, the weight percent of carbon, consecrated on the media, and calculated the carbon material is presented in the table.

Example 2

The reactor 200 worked at 900oC (1650oF) and a pressure of 0.34 MPa (g) (50 pounds/inch2) (3,5155 kg/cm2) (without heating jacket 238) partial to the actor 200 through the line 246 instead of water vapor was applied to the air. Then the reaction products of partial oxidation were analyzed by a gas chromatograph as in example 1. The results of the reaction of partial oxidation can be seen in the table.

Example 3

The reactor 200 worked in accordance with the methodology, such as that described in example 1, except that the solvent of the rubber was added with 20 wt.% mixed xylenes, the pyrolysis reaction with water vapor was carried out at 950 - 980oC (1750 - 1800oF) and a pressure of 0.34 MPa (g) (50 pounds/inch2) (3,5155 kg/cm2and as the carrier medium used fluidized catalyst catalytic cracking, deactivated with water vapor, from example 2, is essentially not containing carbon. The results are presented in the table. In conclusion, essentially all of the carbon obtained in the reactions of pyrolysis of hydrocarbons with water vapor (examples 1 and 3), was deposited on the circulating medium. In addition, destroyed aromatic rings and carbon oxidation in order to provide sufficient heat to replenish the heat required for endothermic reactions. Therefore, it was shown that the adiabatic process at 870 - 1100oC. (1600 - 2000oF) is feasible.

This method of converting hydrocarbons and submit the above description as restrictive illustration, as specialists in this field from their point of view will be obvious many have been modified. Have in mind that all such modifications are within the scope and essence of the appended claims, which consequently affected.

1. Transport technological installation for conversion neskazannyh hydrocarbon streams to hydrogen or synthesis gas, characterized in that it contains air installation for the formation of enriched oxygen stream, the line for supplying the oxygen stream and the source of the hydrocarbon stream in Transportny the partial oxidation reactor containing a partial oxidation for substochiometric oxidation of carbon deposited on the circulating particles, riser for making a mixture of the original hydrocarbon stream and products from the zone of partial oxidation, creating a flowing stream containing hydrogen, light hydrocarbons, carbon monoxide and carbon dioxide, and deposition of carbon on the particles from the stream flowing out of the riser, and the separation zone to extract particles for recirculation zone of the partial oxidation and formation of gas product, essentially, not containing particles, steam boiler for heat and Oh the product and obtaining the gas product, essentially, not containing particle, a recirculation line for circulating water in the tower for quenching the gaseous product containing no particles, the installation of separate hydrogen to highlight the tempered gas product enriched in hydrogen stream and a stream of light hydrocarbons, a regulator for regulating the flow rate of the oxygen stream into the zone of partial oxidation and maintaining the temperature of the stream flowing out of the riser, essentially, between about and about 870 1090oC, in response to speed changes and carbon composition of initial hydrocarbon stream to maintain the amount of carbon deposited on the particles is between about 0.5 and about 40% by weight relative to the circulating particles.

2. Technological transport installation according to p. 1, wherein the liquid source of the hydrocarbon stream contains the waste hydrocarbon gases, residual liquid hydrocarbon streams, solid particles from the oil refinery or a combination thereof.

3. Technological transport installation according to p. 1, characterized in that it contains the first line for supplying into the reactor for partial oxidation of exhaust hydrocarbon gases and a second line for supplying liquid hydrocarbons and any solid components.

5. Technological transport installation according to p. 1, characterized in that the partial oxidation reactor further comprises a feed injection zone for continuous introduction of the original hydrocarbon stream into a stream of products of partial oxidation for the formation of a mixture thereof, delay zone of solid particles for making the extracted particles, including the besieged them carbon line transfer for transporting particles from the zone of the delay zone of the partial oxidation.

6. Technological transport installation according to p. 5, characterized in that the source of the hydrocarbon stream contains liquid hydrocarbons having a total atomic ratio: H : C, calculated on the dry weight of about 1 to 2.

7. Technological installation under item 1, characterized in that it contains a line for purging part of the particles extracted from the separation zone transport reactor for partial oxidation.

8. Technological installation according to p. 7, characterized in that it contains a system of leaching of metal or svyazyvaniem low temperature conversion neskazannyh hydrocarbon streams to hydrogen or synthesis gas, wherein the stage includes the introduction of the original hydrocarbon stream in a continuous flow of products substochiometric oxidation containing fine particles, the bandwidth in terms of the transportation of the mixture obtained from the previous stage through essentially adiabatic zone of pyrolysis to obtain a flowing stream of hydrogen, light hydrocarbons, carbon monoxide and carbon dioxide and for the deposition of carbon on the particles, extracting particles covered with carbon, resulting from stream to obtain a synthesis gas essentially containing no particles, the continuous feed of the main part izvlechennykh particles and substochiometric amount of reactive oxygen in the partial oxidation for the formation of a product stream partial oxidation stage for the introduction of the original hydrocarbon stream in a continuous flow, throttling reactive oxygen supplied to the partial oxidation, in response to significant fluctuations of the initial hydrocarbon stream selected from the rate of mass flow, water content, carbon content of the hydrocarbon, the atomic ratio H : C hydrocarbon, and combinations thereof, to maintain the temperature Nadia extraction with average content of deposited carbon, essentially, between 0.5 and 40% by weight.

10. The method according to p. 9, characterized in that the source of the hydrocarbon stream contains an emulsion of the oil-water separator or tank flotation.

11. The method according to p. 9, characterized in that the source of the hydrocarbon stream contains metal, which adsorb on the particles at the stage of passing through the pyrolysis zone, and the synthesis gas from the extraction stages particles essentially do not contain metal.

12. The method according to p. 9, characterized in that the particles are served at the stage of controlling the amount of reactive oxygen in the partial oxidation with a speed of from about 10 to about 250 times higher than the rate of mass flow of the source of the hydrocarbon stream at the stage of introduction of the initial hydrocarbon stream.

13. The method according to p. 9, characterized in that in the zone of the partial oxidation stage throttling reactive oxygen serves oxygen, essentially, does not contain nitrogen.

14. The method according to p. 9, wherein the chemically active oxygen is fed to the partial oxidation stage throttling chemically active oxygen in amounts less than about 5% of the stoichiometric relative to operanation involves feeding water vapor into the pyrolysis zone for shear conversion into hydrogen at the stage of pyrolysis.

16. The method according to p. 9, characterized in that the source of the hydrocarbon stream has a water content of from 0 to 40% by weight, hydrocarbons contain carbon in an amount of from 75 to 95% by weight in terms of dry weight, and hydrocarbons have an atomic ratio of H : C from 0.5 to 4 in terms of dry weight.

17. The method according to p. 16, characterized in that it further includes a supply of water vapor at the inlet of the pyrolysis zone in a quantity providing weight ratio of water from water vapor and the source of the hydrocarbon stream to the hydrocarbon in the original hydrocarbon stream is from about 0.3 to 0.5.

18. The method according to p. 15, characterized in that the hydrocarbon in the original hydrocarbon stream has an atomic ratio H : C in terms of dry weight between 1 and 2.

19. The method according to p. 9, characterized in that the hydrocarbon is introduced at the stage of extraction of the particles contain aromatic rings, and the synthesis gas and carbon deposited on the inorganic particles from the stage of extraction of the particles essentially do not contain aromatic ring compounds.

20. The method according to p. 9, characterized in that the particles at the stage of introduction of the initial hydrocarbon stream containing exhaust fluidized catalyst catalytic cracking.

22. The method according to p. 9, additionally comprising a stage of quenching the synthesis gas from the stage of extraction of the particles to a significant inhibition of the formation of tar.

 

Same patents:

The invention relates to the processing of hydrocarbon raw materials, in particular the production of synthesis gas from hydrocarbons

The invention relates to the processing of hydrocarbon raw materials, in particular the production of synthesis gas from hydrocarbons

The invention relates to a method of stimulating metal systems for the uptake (absorption) of hydrogen and its isotopes (deuterium and tritium) in large quantities

The invention relates to techniques for high pressure, creating a pressure of hydrogen in a volume of1000 MPa with further study of hydrogen-strength material

The invention relates to a method of steam reforming of carbon monoxide in the converted gas, widely used for the production of ammonia from natural gas

The invention relates to a process of selective catalytic oxidation of methane with oxygen in the synthesis gas and the catalyst for this process and may find wide application in chemical industry

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: power engineering.

SUBSTANCE: method includes searching for continental or oceanic rift generation zones, supported by abnormal mantle with output of substance branches to earth crust. Drilling of wells by turbodrills into mantle substance. After well enters mantle substance a reaction hollow is formed in it by putting together force and product wells or by expanding force and/or product wells. Water is pumped into force well and gas-like hydrogen is outputted to surface through product well forming during reaction of inter-metallic substances fro mantle substance to water. Water is fed in amount, adjusting output of hydrogen, while reaction surface of reaction hollow is periodically regenerated, for example, by high pressure water flow, supplied through jets in reaction hollow, on remotely controlled manipulators. Expansion of well may be performed via explosions of explosive substances charges, and it is possible to separate forming gaseous hydrogen and water steam by separator mounted therein.

EFFECT: higher effectiveness of hydrogen production.

9 cl

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: autothermal catalytic reforming of hydrocarbon feed stream.

SUBSTANCE: method relates to method for reforming of hydrocarbon feed stream with water steam at elevated temperature to produce gas enriched with hydrogen and/or carbon oxide. Hydrocarbon stream is passed through water steam reforming catalyst bed wherein oxygen is fed through oxygen-permeable membrane followed by removing of finished product from this bed. Said catalyst bed contains in input region catalyst with reduced or without water steam reforming activity, but having hydrocarbon feed oxidation activity.

EFFECT: process with improved characteristics due to temperature controlling in reactor.

3 cl, 1 dwg

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

FIELD: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.

SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.

EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.

2 cl, 2 dwg

FIELD: petrochemical industry.

SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.

EFFECT: the invention allows to decrease a carbon share on the catalyst.

3 cl, 2 tbl, 2 ex

FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

FIELD: methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the process of production of hydrogen and carbon oxide, which mixture is used to be called a synthesis gas, by a selective catalytic oxidation of the hydrocarbonaceous (organic) raw material in presence of the oxygen-containing gases. The method of production of the synthesis gas includes a contacting with a catalyst at a gas hourly volumetric speed equal to 10000-10000000 h-1, a mixture containing organic raw material and oxygen or an oxygen-containing gas in amounts ensuring the ratio of oxygen and carbon of no less than 0.3. At that the process is conducted at a linear speed of the gas mixture of no less than 2.2 · 10-11 · (T1 + 273)4 / (500-T2) nanometer / s, where: T1 - a maximum temperature of the catalyst, T2 - a temperature of the gas mixture fed to the contacting. The linear speed of the gas mixture is, preferably, in the interval of 0.2-7 m\s. The temperature of the gas mixture fed to the contacting is within the interval of 100-450°C. The maximum temperature of the catalyst is within the interval of 650-1500°C. The technical effect is a safe realization of the process.

EFFECT: the invention ensures a safe realization of the process.

10 cl, 5 ex

FIELD: chemical industry; petrochemical industry; oil refining industry and other industries; methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the field of the methods of production of a synthesis of gas and may be used in chemical, petrochemical, oil refining and other industries. The method of production of synthesis gas using a vapor or a vapor-carbon dioxide conversion of a hydrocarbonaceous raw material provides for purification of the hydrocarbonaceous raw material from sulfuric compounds, its commixing with steam or with steam and carbon dioxide with formation of a steam-gas mixture. The catalytic conversion of the steam-gas mixture is conducted in a reactor of a radially-spiral type, in which in the ring-shaped space filled with a nickel catalyst with a size of granules of 0.2-7 mm there are the hollow spiral-shaped walls forming the spiral-shaped channels having a constant cross section for conveyance of a stream of the steam-gaseous blend in an axial or in a radially-spiral direction. At that into the cavities of the walls feed a heat-transfer agent to supply a heat into the zone of reaction. The invention ensures intensification the process.

EFFECT: invention ensures intensification the process.

4 cl, 4 dwg, 2 tbl, 3 ex

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