Fluidised-bed reactor and method of hydrogenation in reactor

FIELD: chemistry.

SUBSTANCE: invention relates to a fluidised-bed reactor and a method of catalytic hydrogenation in the reactor. The fluidised-bed reactor comprises a reactor shell, vertical to the ground, a phase separator located within the top part of the shell, an internal circulation zone, located under the phase separator. The internal circulation zone comprises a cylinder, a tapered diffusion section and a guide support. Both the cylinder and the tapered diffusion section at the bottom of the cylinder are located inside the reactor shell, the guide support is fitted on the shell inner wall at the bottom of the tapered diffusion section. The guide support is an annular protrusion of the reactor inner wall.

EFFECT: invention provides effective hydrogenation resulting in a high quality product, and stable operation of the reactor.

26 cl, 2 dwg, 4 tbl, 5 ex

 

AREA of TECHNOLOGY

The invention relates to a reactor and method in which used this reactor, and, in particular, to a fluidized bed reactor and method of hydrogenation, which includes the use of such a reactor.

PRIOR art

Due to changes in the volume of production of heavy crude oil and changes in the structure of consumption of petroleum products in the world, the market has experienced rapid growth in the demand for light fuel oil and the rapid decline in demand for heavy (boiler) fuel. Technology of processing of heavy oil has been the subject of several scientific studies conducted in the industries of oil refining industry. The technology of heavy oil processing, mainly comprised of decarbonization (decarburization) and hydrogenation.

Decarbonisation mainly includes a solvent de-asphalting, coking and catalytic cracking of heavy oil, etc. Despite the fact that the decarbonisation does not require large investments in the means of labor, the yield and quality of liquid products remain low and, in addition, the methods of decarbonization do not meet currently accepted environmental requirements. At the same time, the extracted oil is gradually becoming heavier and lower in quality, and each year the relative yield of residual oil from crude oil increases�I, already reaching 70% of the mass. or more. The most widely used method of decarbonization of heavy oil or residual oil is gumming, which as a by-product, in General, receive large amounts of coke with low added value.

In accordance with the state of the catalyst in the reactor, methods of hydrogenation are divided into hydrogenation with fixed bed, hydrogenation with a moving layer, the hydrogenation in a suspended layer and hydrogenation in a fluidized bed. Methods including hydrogenation, require large capital expenditures as they apply reactionary high pressure equipment, but they allow you to get high quality products and the high yields of liquid products. Hydrogenation allows to alleviate the heavy or residual oil (residual oil obtained by the distillation of crude oil). Currently relatively well-developed methods of hydrogenation of residual oil is a residual oil hydrogenation in a fixed bed of catalyst, but this technique is limited by the nature of the source material and imposes relatively strict requirements with respect to certain parameters, such as the metal content of the starting material, the content of carbon residue, etc. Processing of heavy oil as in suspended slo�, and in a moving layer has certain advantages, but in recent years the development of these methods is slow. Since the hydrogenation in a suspended layer leads to the concentration of large quantities of heavy metals in tailing uniform oil, processing and recycling of tail chasing oil is difficult. When hydrogenation with a moving catalyst bed of crude oil and catalyst in the General case is passed through the reactor in one direction or counter-flow, and heavy oil is treated in the presence of a catalyst having higher activity. This method gives a good yield of hydrogenation, but requires large amounts of catalyst, and hydrogenating activity of the catalyst is not used sufficiently.

Currently the method of hydrogenation in the fluidized bed may include adding and removing catalyst online (without stopping the operation of the equipment, "online"), can be adapted for a variety of source materials and can guarantee long-term operation of the equipment. This technique is rapidly developing. The fluidized bed reactor includes a three-phase fluidized bed, including air, liquid and solid phase. In such a reactor may be treated heavy crude oil of poor quality, containing large amounts of metals and bi�mind. The characteristics of this reactor include: small pressure drop, uniform temperature distribution, a constant catalyst activity during the working cycle and the possibility of adding fresh catalyst and removal of spent catalyst in the process of equipment operation.

For hardware fluidized bed adding and removing catalyst online necessary to ensure proper product quality, stable operation and long service life. Currently the methods of hydrogenation in a fluidized bed means for adding catalyst online in General include gas-phase transport, liquid transport or direct addition of solid catalyst located in the upper part of the reactor, storage tank, located at high pressure in the fluidized-bed reactor under the action of gravity. To maintain the catalyst in a fluidized bed reactor at a high state of fluidization in the reactor should be maintained constant fluid viscosity, pressure reactions, gas-liquid flow and temperature of reaction. However, direct addition of fresh catalyst to the fluidized bed reactor may cause temporary fluctuations Pere�olenych parameters, causes temporary instability of the fluidized bed environment and operating conditions in the reactor. In addition, because of the high initial activity of the fresh catalyst, adding it directly into the fluidized-bed reactor and the subsequent contact and mixing with the original low-quality heavy residual oil leads to a rapid accumulation of carbon deposits on the catalyst and the rapid decrease in activity, which reduces the effect of hydrogenation and increases the frequency of catalyst replacement.

In patent documents CN 101418222A, CN 1335357A and CN 101360808A related to the background art described processing of low-quality residual oil. In patent document CN 101418222A described combined reaction device comprising the fluidized bed and fluidized bed. In patent document CN 1335357A described combined reaction device including the loosened layer and the moving catalyst bed. In patent document CN I described at least two reactor upflow connected in series. However, none of these prior art documents is not described treatment of the catalyst online, after the activity of the catalyst in the reactor, ceases to meet the specified requirements.

In patent document US4398852 described method of adding the catalyst in the fluidized-bed reactor online, which includes the following steps: adding a catalyst in the container for the catalyst which is resistant to high pressure; the flow into a container of hydrogen until the pressure of the reaction and the opening of the valve on the pipe connecting the container to the catalyst reactor in which the catalyst is transported in a fluidized-bed reactor under the action of gravity. According to this method, the catalyst is added directly to the fluidized-bed reactor under the action of gravity, which leads to a rapid accumulation of carbon deposits at the contact of the fresh active catalyst with low-quality source material, that is, the acceleration of the deactivation and increase the frequency of catalyst replacement. At the same time, as the temperature of the preheated catalyst and hydrogen below the reaction temperature, reaction temperature in the fluidized bed will fluctuate, causing destabilization of the operating mode and the reduced product quality.

In patent documents US Re 25770 and US 4398852 characteristic described processing method in a fluidized bed in the fluidized-bed reactor installed a glass for internal circulation, intended for the separation of gas and liquid, which increases the degree of transformation of liquid substances. Nevertheless, the practical application of this technique has the following disadvantages: in the reactor has a small supply of the catalyst and the space inside the reactor is used inefficiently; the circulation pump repair is costly and in case of breakage or malfunction of the circulation pump, the catalyst settles and forms aggregates, which leads to the stop of the device. In addition, when the liquid product in the reactor too long in the absence of catalytic hydrogenation, it is subjected to the second reaction thermal cracking at high temperature to form coke, which also reduces the quality of the product.

In patent documents CN 02109404.7 and CN A, respectively, described the fluidized-bed reactor of a new type, equipped with three-phase separator with a pilot hole used for the effective separation of gas, liquid and solid phases. Compared with a typical fluidized bed reactor, it has a simple design, easy to manage, and this reactor provides a high degree of utilization. However, since the ratio of height to diameter in the fluidized-bed reactor is rather large, in the range of from 1:6 to 1:8 and most effective of the reaction space, with the exception of a three-phase separator in the upper part �of eector, is a hollow tubular structure, in the reactor, there is no design that provides positive mass transfer, i.e. the existing mass transfer between gas, liquid and solid not too effective. Thus, the liquid hydrogenation product is inefficient, resulting in low quality of the product. In addition, the fluidized bed reactor is a reactor with counter-current mixing, i.e. from the reactor, together with a stream of unreacted material, produced as part of the unreacted starting material, i.e. the degree of conversion of the starting material is low.

Has also been described reactor prior art fluidized bed comprising two or more reaction sections. Such a fluidized bed reactor includes a component for the separation of the three phases, separating the gas, liquid and solids in the reactor can consistently implement hydrodemetallization, hydrodesulfurised and hydrodenitrification, applying in each reaction section one or two of the catalyst. Component for the separation of the three phases consists of element flow element and to lock the thread where the element in the flow direction is a tapering or cone-shaped element having with �Vuh all holes one of which is less than the other; besides, use the top element to the flow direction and the lower element in the flow direction, in which the hole of the upper end of the lower element to direct the flow is on one axis and corresponds to the opening at the lower end of the top element to the flow direction. In fact, such a reactor is a reactor of large size, formed by the combination of two reactors without piping connecting the reactor and other devices such as separators and drain reservoirs. The advantage of this reactor is adequate use of thermal energy; however, it has the following disadvantages: the huge size of the reactor, which hinders its transportation, installation, operation and repair; with increasing reaction sections within the reactor also increases the number of three-phase separators, which complicates the design of the reactor; in addition, the greater the number of three-phase separators, the more space they will occupy in the reactor and the less effective space of a reaction between gas, liquid and solid, which means inefficient use of resources, since the fluidized-bed reactor, operating at high temperature and high pressure, has a very in�high cost; in addition, for operation of a plurality of sections connected in series, need a stable working conditions and proper design of plates for the distribution of gas-liquid flow between the sections, because the temporal fluctuations of the parameters affect the separating action of a three-phase separator, namely, the solid particles are captured by the gas and the liquid distribution block plate and destabilize the normal operation of the device.

Summary of the INVENTION

To overcome the shortcomings of the prior art the present invention proposes a fluidized bed reactor comprising a plurality of internal circulation zones that effectively increase the degree of conversion of the starting material.

For that purpose the invention proposes a fluidized bed reactor comprising a reactor vessel positioned vertically relative to the earth, and the phase separator installed at the top of the casing. Under phase separator is the internal circulation zone, which includes the cylinder, tapering diffusion section and guiding structure; at the same time as the cylinder, and a narrowing of the diffusion section, mounted on the lower end of the cylinder, is installed inside the casing of the reactor and a guide structure mounted on internally� wall of the housing of the reactor at the lower end of the tapering of the diffusion section. The guide structure is a ring-shaped protrusion on the inner wall of the reactor, which, according to the present invention, has the shape of a longitudinal section along the axis of the reactor selected from the group consisting of trapezoidal, arched, triangular, semicircular or any other equivalent or a modified form, and has the function guide. The upper end of the cylinder is expanding design with a small extension.

The specific design of the new fluidized-bed reactor according to the present invention is described below.

In the lower part of the casing of the reactor has an opening for the inlet of the source material and a plate for the distribution of gas-liquid flow. In the upper part of the casing of the reactor is cut to release the gas, and on the top wall of the housing has an opening for discharging liquid, which is located on the wall of the casing of the reactor between the hole at the upper end of the inner cylinder of the phase separator and the hole in the lower end of the outer cylinder of the phase separator. The phase separator is installed in the upper part of the inner space of the casing and includes two concentric cylinders having different inner diameters, i.e. the inner cylinder and the outer cylinder. The upper and lower ends of the inner and outer cylinder�ditch opened; the hole at the upper end of the outer cylinder is located above the holes on the upper end of the inner cylinder and the hole at the lower end of the outer cylinder is located above the openings at the lower end of the inner cylinder. The lower end of the inner cylinder represents a narrowing of the diffusion section; the diameter of this hole diffusion section (i.e. the holes at the lower end of the inner cylinder) less than the internal diameter of the reactor. The lower end of the outer cylinder is also a narrowing of the diffusion section; the diameter of this hole diffusion section (i.e. the holes at the lower end of the outer cylinder) is also smaller than the inner diameter of the reactor.

The inner cylinder of the phase separator is a Central pipe of the separator. The annular space between the inner cylinder and the outer cylinder forms a reflective cylinder separator. The annular space between the outer cylinder and the inner wall of the reactor is a collection of pure liquid product obtained in the phase separator. The hole at the lower end of the inner cylinder is an outlet stream. There is a circular hole formed by the hole at the lower end of the inner cylinder and the inner wall of the reactor, is a resp�rsta for release downstream of the catalyst from the phase separator, through which the separated particles of the solid catalyst is returned to the catalyst bed.

The specific size and relative location of each of the components of the phase separator may be determined by the specialist in the art in accordance with the size of the catalyst, the capacity of the reactor, the reaction conditions and the degree of separation, with calculations or simple tests or through traditional means known in the art, such as the means described in patent documents CN02109404.7 or CN101376092A filed by the Applicant of the present invention.

Internal circulation area includes a cylinder, a narrowing of the diffusion section and located near guiding structure. The cylinder is attached to a narrowing of the diffusion section, and the diameter of the bottom opening tapering diffusion section is less than the internal diameter of the reactor. The guide structure is located next to a narrowing of the diffusion section. Thus, all three components form the internal circulation zone. In accordance with the desired height of the reactor to its diameter and the degree of conversion, the reactor may include one or more, preferably 2-3, internal circulation areas, and different internal diameters of the cylinders of the internal circulation zones can be one�thereof, and different. The guide structure may be a ring-shaped protrusion on the inner wall of the reactor, having, according to the present invention, the shape of the longitudinal section along the axis of the reactor selected from the group consisting of trapezoidal, arched, semicircular, triangular, or any other equivalent or a modified form, and having a guide.

Tangent at the point of intersection of the side rail structure located near the phase separator, with the reactor wall forms an angle with the inner wall of the reactor, called the angle of overlap. The overlapping angle is an acute angle which is preferably less than 60 degrees. Tangent at the point of intersection of the other side of the guide structure, remote from the phase separator, with the reactor wall forms an angle with the inner wall of the reactor, called the angle of friction. Friction angle is also an acute angle which is preferably less than 60 degrees. The value of the diameter of the pilot hole formed by the guide structure is in the range of values of the diameter of the inner cylinder to the outer diameter of the cylinder of the phase separator.

According to the present invention in the hydrogenation reactor fluidized bed n�directly below the phase separator can be further guide the design. Additional guide structure located on the property above the middle part of the reactor, between the phase separator and internal circulation area. Additional guide the design of similar design guide that is installed in the internal circulation zone.

The outlet gas in the General case feature in the top center of the reactor.

To extract from the reactor is separated pure liquid in the upper part of the wall of the casing of the reactor between the hole located at the upper end, and a hole located at the lower end of the outer cylinder of the phase separator, in the General case have a hole for discharging liquid.

In the General case, in the upper part of the phase separator is buffer space, which is enriched gaseous product obtained after phase separation and extracted from the reactor through the hole to release the gas.

In the General case, the ratio of height to diameter of the reactor is from 0.01 to 0.1.

The fluidized-bed reactor according to the present invention in the General case further includes at least one component to extract the catalyst from the reactor and at least one component of the feed to the reactor with fresh catalyst. Component for fresh catalyst in the General case n�located in the upper part of the reactor, while the component to extract the catalyst in the General case is near the bottom of the reactor. For example, in the upper part of the casing of the reactor is a pipe for feeding the catalyst, and in the lower part of the reactor is a pipe for the extraction of the catalyst. The system will replace the catalyst and method of its application can be any suitable devices or methods, such as methods described in patent documents US 3398085 or US 4398852.

To create a uniform initial contact of the reacting material with a catalyst in a reactor, generally in the lower part of the cylindrical housing of the reactor plate installed for the distribution of gas-liquid flow. Plate for the distribution of gas-liquid flow can have any design, allowing even distribution of gas and liquid, for example, a plate may be a cap plate.

The principle of operation of the internal circulation zone of the fluidized-bed reactor is as follows. When the flow of material flow through a section of the reactor, having a different cross-sectional area, the flow rate is changed. Material flow in a fluidized bed reactor consists of three phases: gaseous phase, liquid phase and solid phase, namely: catalyst, nodamage� in the solid state, the reaction stream in the liquid state, gaseous hydrogen and received light gaseous hydrocarbons. When changing the cross-sectional areas of the sections of the reactor, through which flows a stream, flow rate of gas and fluid change as well, and in this case, the captured gas-liquid flow, the catalyst can be suspended in the air or deposited. As the reaction in a fluidized bed reactor from the liquid phase source material forms a portion of the light components, which rises together with hydrogen up through the reactor, while a portion of the resulting reaction liquid phase and unreacted starting material move in the same mode with the catalyst, i.e. quick rise up the reactor in the zone of acceleration of a fluid medium having a smaller cross-sectional area, and fall countercurrent to the main thread on the land on which the cross sectional area increases sharply.

Hydrogenation of low-quality crude oil in the fluidized-bed reactor catalyst comprising internal circulation zone and phase separator, allows to increase the degree of conversion of heavy liquid components. Design of a fluidized bed reactor allows to enhance mass transfer and telomere�the Acha between threads inside the reactor.

Another object of the invention is to provide a method of hydrogenation in the fluidized-bed reactor catalyst for stable operation of the device with a fluid bed catalyst during the adding of the catalyst, and thus ensuring stable operating cycle of the device, and also allows you to get a higher quality product due to the additional processing flow after carrying out the reaction in a fluidized bed.

Technical implementation of the method of hydrogenation in the reactor with a fluidized bed catalyst according to the present invention is as follows.

After heating in the heating furnace a mixture of low-quality crude oil and hydrogen fed to the fluidized-bed reactor in the form of rising flux for the reaction of catalytic hydrogenation, and the output stream is separated into gaseous and liquid phases. Part of the resulting liquid phase is directed into the reactor with a loosened layer connected to the fluidized-bed reactor tubing in the reactor and with loosened conduct additional layer of reaction. When the catalytic activity of the catalyst in the fluidized-bed reactor is reduced to an unacceptable level, which cannot provide the required quality of the product, p�actor send an additional amount of fresh catalyst from the reactor with a loosened layer. The amount of catalyst necessary for the operation of the reactor with the loosened layer is served in the form of fresh catalyst from supply tank containing fresh catalyst.

In the method according to the present invention, the coefficient of loosening of the layer in the reactor with the loosened layer is from 5% by volume. up to 25% vol., preferably from 10% by volume. up to 25% vol., most preferably from 15%. up to 20% on. In the present description, the term "degree of fragmentation" means the ratio of the difference between the level of the layer after loosening of the catalyst and the layer level after the initial download to the catalyst layer level after initial loading of the catalyst. In the reactor with a loosened layer supports the following operating conditions: a reaction pressure is from 6 to 30 MPa, preferably from 10 to 18 MPa; reaction temperature is from 350 to 500°C, preferably from 380 to 430°C; space velocity is from 0.1 to 5 h-1preferably from 1 to 4 h-1; and the volumetric ratio of hydrogen to the amount of oil from 400 to 2000, preferably from 600 to 1500.

The amount of catalyst added to the reactor with a loosened layer at a time, ranging from 2 to 20 amounts of catalyst added at a time online in the fluidized-bed reactor. If the reactor with a loosened layer is the amount of catalyst, comp�blausee from 0 to 5 quantities, add one at a time in the online mode in the fluidized-bed reactor, the catalyst should be added from a supply tank containing fresh catalyst installed in the upper part of the reactor with a loosened layer.

After separation of the gaseous and liquid phases obtained liquid phase fed to the reactor with a loosened layer at a level of from 5% by mass. up to 70% of the mass. all liquid phase obtained in the reaction, preferably from 10 wt%. up to 50% of the mass.

Suitable for machining method according to the present invention of low-quality crude oil includes one or more of the following fractions: atmospheric residue, vacuum residue, deasphalting oil, oil Sands, thick (viscous) crude oil, bitumen and heavy oil obtained in the liquefaction of coal.

In the fluidized-bed reactor support the following operating conditions: a reaction pressure is from 6 to 30 MPa, preferably from 10 to 18 MPa; reaction temperature is from 350 to 500°C, preferably from 400 to 450°C; space velocity is from 0.1 to 5 h-1preferably from 0.5 to 3 h-1; and the volumetric ratio of hydrogen to the amount of oil from 400 to 2000, preferably from 600 to 1500.

In the method of hydrogenation of low-quality crude oil according to the present invention, the catalyst in�asisa in the reactor, can be a traditional catalyst for hydrogenation in a fluidized bed, is known in the art. Typical catalyst has the following parameters: carrier - refractory (refractory) inorganic oxide, the active component is a metal of Group VIB and/or Group VIII of the Periodic Table, the diameter of the catalyst particles is 0.8 mm, the length of the particles is 3 to 5 mm, and basic physical and chemical properties essentially the same as the properties of the catalysts conventionally used for hydrogenation in a fixed bed. It is preferable for the invention, there is used a catalyst having the following properties. The particle diameter of the catalyst is from 0.1 to 0.8 mm, preferably from 0.1 to 0.4 mm., the Catalyst contains active in the reaction of hydrogenation components comprising a metal of Group VIB and/or Group VIII of the Periodic Table. The media is a AI2O3. The catalyst contains at least one auxiliary substance selected from the following elements: In, Sa, F, Mg, P, Si, Ti, etc., the Content of the excipient is from about 0.5 wt%. to 5.0 wt%. Pore volume of the catalyst is from 0.6 to 1.2 ml/g pore Volume, the size of which is less than 8 nm, is less than 0.03 ml/g, in General, from 0.005 to 0.02 ml/g. the Average pore diameter is from 15 to 30 nm. Pore volume, the size of which is�GSI in the range from 15 to 30 nm, is 50% or more of the total pore volume, in General, from 50% to 70%. Specific surface area is from 100 to 300 m2/g, preferably from 120 to 240 m2/year.

The catalyst comprises from 1.0 wt%. to 20.0 wt%. metal oxide of Group VIB (for example, MoO3), preferably from 3.0 mass%. to 15.0 wt.%, and from 0.1 wt%. to 8.0 wt%. oxide of a metal of Group VIII (for example, NiO or COO), preferably from 0.5 wt%. to 5.0 wt%. The deterioration of the catalyst is 0.1 wt%. or less.

The catalyst used in the fluidized-bed reactor consists of microspherical particles whose sizes are in the range from 0.1 to 0.8 mm. currently, the conventional fluidized bed reactors, for example in the reactor described in patent document US Re 25570 and related patents, which includes a glass for internal circulation, mainly providing effective separation of gas and liquid, the particles of the used catalyst essentially have the same size as the particles of the traditional hydrogenation catalyst, i.e. the method according to the present invention is not suitable for implementation in conventional fluidized bed reactors.

The fluidized-bed reactor used in the method according to the present invention, may include a fluidized bed reactor containing such �the indoor components, as a three-phase separator for separation of gases, liquids and solids, pilot hole, etc., for Example, for carrying out the method of hydrogenation according to the present invention are suitable both fluidized-bed reactor described in patent documents CN 1448212A and CN 101376092A. Despite the fact that these reactors can be used for implementing the method according to the present invention, it should be considered that the area most effective reaction in the fluidized bed reactor is a cylindrical structure, in which mass transfer is ineffective, that is, the output of hydrogenation in such small reactors. In addition, the reactor with countercurrent mixing are different in that they remove a portion of the unreacted starting material together with a stream of unreacted material, that is, in such reactors receive a low degree of conversion of the starting material.

In the method of hydrogenation of low-quality crude oil according to the present invention heavy crude oil may be treated with a combination treatment comprising the use of a fluidized bed reactor containing the internal circulation zone, three-phase separator and the reactor loosened layer. This improves not only the quality of products containing light oils, but also providing�th sustainable mode of operation in the main reactor, i.e. the fluidized-bed reactor, at the time of filing of the catalyst. In this combined method of treatment of heavy oil may occur in flexible working mode. First heavy crude oil is subjected to hydrocracking in the hydrogenation reactor with a fluidized bed of catalyst, and then the reaction stream is directed into the separation device, which receives gaseous phase and a liquid phase, and a portion of the resulting liquid phase direct recycle to the reactor at a loosened layer on additional hydrogenation. If you want to feed the catalyst into the fluidized-bed reactor, the flow in which is entrained catalyst, enters the fluidized bed reactor from the bottom of the reactor with a loosened layer. This flexible method allows to overcome the disadvantages of the currently available methods associated with fluctuations of temperature and pressure in the reactor, caused by direct loading of the catalyst in the fluidized-bed reactor, and eliminates the effect of the currently available methods for fluid state of the catalyst and the properties of the reaction streams (for example, overcomes the shortcomings of the methods that cause instability in the operation mode, the unwanted capture of the catalyst or swelling of the catalyst layer, the influence�Ute on the quality of the product and the duty cycle of the equipment, etc.). On the contrary, according to the present invention, the fresh catalyst is first fed to the reactor with a loosened layer, and then in the fluidized-bed reactor, creating, thus, a buffer effect; in this case, in the reactor with a loosened layer of the catalyst is pre-heated in a stream to reaction temperature, and, thus, the temperature of the liquid, the catalyst and the gas coming in the next fluidized-bed reactor, essentially equal to the temperature of the reactants in a fluidized bed, which ensures stable operation of the device containing the fluidized bed. In addition, since first the fresh catalyst comes in contact with the thread ennobled in hydrogenation reactions in a fluidized bed, the initial activity of the catalyst is effectively used, carbon deposits on the catalyst in the initial stage of the reaction is not formed, that is, increases the efficiency of the catalyst.

The USEFUL EFFECT of the PRESENT INVENTION

The method according to the present invention is simple, scientifically justified and appropriate. Compared with the prior art, the fluidized bed reactor and method of hydrogenation with the use of such a reactor according to the present invention have the following advantages:

1) in a fluidized bed reactor �according to the present invention has one or more circulation zones, which can form a variety of working areas fluidization, providing greater flexibility of operation of the fluidized-bed reactor as a whole.

2) the Presence of circulating zones increases the residence time of the liquid component in a fluidized bed reactor, thereby increasing the yield of light oils.

3) as in the fluidized bed reactor is maintained at a fairly high level of countercurrent mixing, the flow extracted from the reactor, in General, contains some unreacted starting material. The creation of many small internal circulation zones provides a cyclic circulation of the source material, which increases the degree of conversion of the starting material.

4) Phase separator fluidized-bed reactor is a simple cylindrical design, which, compared with tapering or conical phase separators of the prior art, characterized by greater simplicity of manufacture, lower manufacturing costs, greater ease of installation and maintenance.

5) compared with the use of a single reactor, using a combination of a reactor with a loosened layer and a fluidized bed reactor increases the path and duration of the reaction, increases the degree of contaminant removal and� reagents and, accordingly, improves the quality of the product.

6) Three working modes, i.e. the hydrogenation of the starting material in the fluidized bed, additional hydrogenation of stream treated in a fluidized bed, is transporting layer and the flow of catalyst in the online mode, can be used in a reasonable combinations with each other. This not only improves the quality of the finished products, but also to ensure long-term sustainable operation of the device when using a starting material suitable for hydrogenation in a fluidized bed.

7) fresh catalyst in the first reactor with a loosened layer, and then in the fluidized-bed reactor has a buffer effect and allows preheating of the catalyst, ensuring the stability of the operating cycle as a whole. In addition, the contact of the fresh catalyst with the refined liquid product obtained after hydrogenation in a fluidized bed, allows efficient use of the initial catalyst activity, providing long maintenance of catalytic activity.

BRIEF DESCRIPTION of GRAPHIC MATERIALS

For a better understanding of the present invention, the description is accompanied by a graphic materials. They constitute part of the description and can be used to create unlimited�ivalsa of embodiments of the present invention together with the description. Graphic materials include the following:

Fig. 1 shows the construction of a fluidized bed reactor according to the present invention (including one circulation zone);

Fig. 2 shows a block diagram of a method of hydrogenation in the fluidized-bed reactor according to the present invention.

Used in images and in the examples of the present invention numeric symbols mean the following:

catalyst 1; tank 2 storage catalyst; reactor 3 with loosened layer; hydrogen 4, 5, 11; source material 6 containing heavy hydrocarbons; reactor 7 fluidized bed; separation device 8 high pressure; a cooling device 9 and purification; distillation device 10; gasoline 12; diesel fuel 13; hydrogenated tail oil shoulder straps 14, conduit 15 for the production of the catalyst; the valve 16, 17, 18;

the fitting 101 for feeding material; a dispenser 102 to gas and liquid; the casing 103 of the reactor; design guide 104; the inner cylinder 105; the outer cylinder 106, a layer 107 of the catalyst; the guide hole 108; hole 109 to the inlet of the catalyst; the hole 110 to release the gas; phase separator 111; hole 112 for discharging liquid; a hole 113 for downstream; the cylinder 114; a narrowing of the diffusion section 115; a hole 116 for the production of the catalyst.

DESCRIPTION of embodiments of the INVENTIONS

Below is a description of preferred embodiments of the present invention, which is accompanied by illustrations graphic materials. Obviously, the preferred examples of the implementation are given to illustrate and facilitate the understanding of the present invention and not limit its scope.

As shown in Fig. 1, in a specific example implementation of the present invention, use of a fluidized bed reactor, which includes internal circulation zone and three-phase separator having the following structural features and operating mechanisms.

The original reaction material after mixing is directed into the reactor through the nozzle 101 for supplying the material, and after passing through the dispenser 102 gas and liquid it is evenly distributed on the layer 107 of the catalyst. The amount of catalyst in the casing 103 of the reactor is at least 35% of the volume of the reactor, in General, from 40% to 70%, preferably 50% to 60%. Under the action of the lifting force of the gas-liquid stream, the catalyst bed inflates to a certain height, and its volume after smoothing, in General, from 20% to 70% greater than its volume in the unweighted condition. Gas-liquid stream entering the reaction zone, in contact with the catalyst�m and enters into a chemical reaction, and the reacted gas-liquid stream and unreacted starting material and hydrogen entrain the solid catalyst and the flow upwards along the axis of the reactor in the circulation zone, formed by the guide structure 104, the cylinder 114 and a narrowing of the diffusion section 115. The flow passes through the guide hole 108 formed by the guide structure 104 and a narrowing of the diffusion section 115 of the cylinder and is collected in the channel to the fluid cylinder 114. However, since the cross sectional area of the channel to the fluid narrows, the velocity of gas-liquid flow increases. After the passage of the fluid through the upper part of the cylinder, a conduit for fluid immediately expands, the rate of gas-liquid flow is temporarily reduced, and its ability to transfer the particles of the solid catalyst is dramatically reduced, resulting in a portion of the unreacted liquid and unreacted starting material and the solid catalyst down through the pilot hole through the channel formed by the outer wall of the cylinder and the inner wall of the reactor, and mixed with the stream, rising up from the bottom of the reactor, forming, thus, a small circulation zone. The gaseous stream, the liquid-phase portion of the stream and captured the catalyst moves�I up from the circulation zone and into the guide hole 108, educated design guide 104 directly near the phase separator 111, and then enters the phase separator 111, where phase separation takes place. First separated gas, which is extracted from the reactor through the opening 110 to release the gas. The separated catalyst is returned to the reaction zone through a hole 113 for downflow. Get pure liquid phase essentially containing no catalyst particles are removed from the reactor through an opening 112 for discharging liquid. To quickly retrieve the deactivated catalyst from the reactor and download fresh catalyst fresh catalyst is directed into the reaction system through a conduit 109 for supplying the catalyst attached to the top of the reactor, and a portion of the deactivated catalyst can be extracted from the reactor through the outlet conduit 116, mounted in the lower part of the reactor.

Longitudinal section of the guide structure 104 along the axis of the reactor has a trapezoidal shape formed by the overlapping angle and friction angle are acute angles, preferably having less than 60 degrees. Of course, the longitudinal section of the guide structure 104 along the axis of the reactor may also be arched or any other appropriate form.

The phase separator 111 consists of an inner cylinder 105 and externally�of cylinder 106, arranged concentrically in relation to each other and having different diameters, in combination with the inner wall of the casing 103 of the reactor. The inner cylinder 105 forms the Central pipe of the phase separator. The annular space between the inner cylinder 105 and the outer cylinder 106 forms a reflective pipe of the phase separator. The annular space between the outer cylinder 106 and the inner wall of the casing 103 of the reactor is an area for collection of clean liquid products. The hole diffusion section, located at the lower end of the Central tube, is an outlet flow, and a ring-shaped opening formed by this diffusion hole section and the inner wall of the casing 103 of the reactor, is an outlet downstream of the catalyst. To increase the flow velocity inside reflective of the pipe and increase the efficiency of separation of the vertex angle of the cone of the diffusion section of the outer cylinder in the range of at least 20 degrees, preferably from 40 to 80 degrees, that is less than the diffusion angle of the section of the inner cylinder.

As shown in Fig. 2, a method of hydrogenation in the fluidized-bed reactor according to the present invention is as follows. The mixture of the starting material 6-membered�future heavy hydrocarbons, and hydrogen 5 after heating in the heating furnace is directed into the reactor 7 fluidized bed in the form of upward flow, where it is in contact with the catalyst and reacts. After hydrogenation in a fluidized bed of the stream removed from the top of the reactor and fed to a separation device 8 high pressure where the separation of gas and liquid. Part get separated liquid phase is mixed with hydrogen 4 and then sent in the form of upward flow in the reactor 3 with loosened layer to provide additional hydrogenation. Get unreacted material is removed from the top of the reactor 3 with loosened layer and fed to a separation device 8 high pressure. The gaseous stream is separated in the separation device 8 high-pressure process in the device 9 cool and clean; the gaseous phase can be used as the recycled hydrogen 11, and the condensed light component is mixed with a part of the liquid phase stream from the separation device, and then sent to a distillation device 10, which receives gasoline 12, diesel fuel 13 and hydrogenated tail oil shoulder straps 14. Hydrogenated tail oil shoulder strap can be used as source material for kata�political cracking or hydrogenation of the residual oil with a fixed bed catalyst or may be sent by recycling to the reactor 7 fluidized bed. By reducing the activity of the catalyst in the fluidized-bed reactor, to levels that do not provide the required quality of the product, the catalyst must be replaced. To do this, perform the following steps: the extraction of a portion of deactivated catalyst from the fluidized bed reactor through a conduit 15 for the production of the catalyst; the opening of the valve 18 on the pipe connecting the reactor 3 with loosened coating, a reactor 7 fluidized bed, while closing the valve 17 in the pipeline to flow out from the reactor with a loosened layer, so that the stream containing the solid catalyst enters the reactor 7 fluidized bed, provided that the duration of flow of the catalyst online is from 10 to 50 minutes. When the dispensing of the catalyst in the reactor 7 fluidized bed system returned to normal operation. The catalyst was charged into the reactor 3 with loosened layer as follows: first, the catalyst 1 is directed into the tank 2 storage catalyst is injected into the reservoir for storage of hydrogen to a pressure exceeding the pressure in the loosened layer on a 1-5 PA; open the valve 16 located between the tank 2 storage catalyst and the reactor 3 with loosened layer; and add the fresh catalyst in reactor with loosened layer.

To illustrate the technical solutions and beneficial effects of the present invention the following Examples in which all percentages are given in percent by weight.

DESCRIPTION of embodiments of the INVENTIONS

Example 1

The properties of residual oil used in the tests are shown in Table 1. Presented in Table 1 data show that the content of carbon residue in the residual oil is 13.6% wt., the metal content is 141,9 µg/g, the content of bitumen - 6,4% wt., the sulfur content of 2.5 wt.%, and the nitrogen content of 0.6 wt%.

The average diameter of the microsphere catalyst particles used in this test was 0.6 mm, pore volume amounted to 0.60 ml/g, and specific surface area was 140 m2/g; as a carrier was used alumina. The volume of pores in the size range of less than 8 nm, reached 2.6% of the total pore volume, and the volume of pores whose sizes are in the range from 15 to 30 nm, amounted to 65% of the total pore volume. The catalyst contained 11.2% of the mass. MoO3, of 3.0 wt%. NiO and 1.4% of the mass. R.

In the test used the traditional method of hydrogenation in a fluidized bed in which the fluidized bed reactor includes one internal circulation zone, as shown in Fig. 1.

In the fluidized-bed reactor has od�and circulation zone; the fluidized-bed reactor had the following dimensions: internal size of the casing of the reactor - 160 mm; the height of the casing of the reactor - 3000 mm; the effective volume of the casing 60 l; separator height - 380 mm; the diameter of the cylindrical part of the Central pipe of the separator 92 mm; the diameter of the lower part of the tapering hole in the bottom of the inner cylinder 144 mm; the height of the tapered portion at the bottom of the inner cylinder is 41 mm; the diameter of the cylindrical part of the outer cylinder 128 mm; the diameter of the bottom of the opening in the tapered portion of the outer cylinder -138 mm; the height of the tapered portion is 64 mm; the upper opening of the outer cylinder is located above the upper opening of the inner cylinder; the lower part of the tapering hole in the lower part of the outer cylinder is located above the lower part of the tapering hole in the bottom of the inner cylinder, and the height difference was 38 mm; the vertical distance between the upper hole of the outer cylinder of the separator and the tangent to the upper part of the casing of the reactor was 200 mm; and the vertical distance between the center of the pipe for liquid product and a tangent to the top of the reactor was 338 mm Angle of overlapping annular guide the design was 20°, and the angle of friction - 28°; the diameter of the pilot hole near the phase separator was 100 mm For the formation�Oia circulation zone diameter pilot hole was 100 mm, the inner diameter of the cylinder was 80 mm, the height of the cylinder is 100 mm, the diameter of the lower part of the tapering of the diffusion section is 150 mm, and the height of the tapering of the diffusion section is 45 mm.

Comparative Example 1

In this Comparative Example 1, the basic design of the reactor is similar to the design of the reactor of Example 1, but in this reactor there is no circulation zone. The reaction conditions and the subject of the source material were the same as those in Example 1. Specific experimental conditions and results are shown in Table 2.

Table 1
The properties of the original material
PropertyValue
Density (20°C), kg/m31007,8
Carbon residue, % mass13,6
Viscosity (100°C), mm2/s576,7
The solidification temperature, °C40
Elemental analysiswt. %
S/N86,1/10,3
S/N2,5/0,6
Metalsug/g
Fe/Ni/V2,9/38,6/100,4
Analysis of the four componentswt. %
Saturated hydrocarbons29,0
Aromatic hydrocarbons33,1
Colloids31,5
Asphaltenes6,4

Table 2
Experimental conditions and results
PropertyExample 1Comparative Example 1
Crude oilGDARGDAR
Reaction temperature, °C445445
The reaction pressure, MPa1515
Volume ratio hydrogen/oil/td> 500500
Hourly space velocity of the liquid, h-122
The amount of catalyst l5050
Test results
The degree of desulfuromonas, % mass7965
The degree of demetallization, % mass8974
The degree of transformation of residual 500°C+oil (%vol.6554

Example 2

This Example relates to a method of hydrogenation in the fluidized-bed reactor according to the present invention. The block diagram of the method shown in Fig.2; in a fluidized bed reactor has one internal circulation zone.

The method includes the following steps. The starting material 6 containing heavy hydrocarbons, after mixing with hydrogen 5 is fed into the reactor 7 fluidized bed in the form of upward flow, where it is in contact with the catalyst and reacts. After hydrogenation in p�authorizenet layer stream is removed from the top of the reactor and fed to a separation device 8 high pressure, where there is a separation of gas and liquid. The amount of liquid phase, constituting 15% of the mass. by weight of the unreacted liquid stream is mixed with hydrogen 4, is sent in the form of upward flow in the reactor 3 with loosened layer to provide additional hydrogenation. Get unreacted material is removed from the top of the reactor and fed to a separation device 8 high pressure. The gaseous stream is separated in the separation device of a high pressure, is treated in the device 9 cool and clean. The gaseous phase can be used as the recycled hydrogen 11, and the condensed light component is mixed with a part of the liquid phase stream from the separation device, and the mixture was fed to a distillation device 10, which receives gasoline 12, diesel fuel 13 and hydrogenated tail oil shoulder straps 14. By reducing the activity of the catalyst in the fluidized-bed reactor, to levels that do not provide the required quality of the product, the catalyst must be replaced. To do this, perform the following steps: the extraction of a portion of deactivated catalyst from the fluidized bed reactor through a conduit 15 for the production of the catalyst; the opening of the valve 18 on the pipe connecting� reactor 3 with loosened coating, a reactor 7 fluidized bed, while closing the valve 17 in the pipeline to flow out from the reactor with a loosened layer, resulting in a stream containing solid catalyst enters the reactor 7 fluidized bed, provided that the duration of flow of the catalyst online is 20 minutes. The catalyst was charged into the reactor with a loosened layer as follows: first, the catalyst 1 is directed into the tank 2 storage catalyst is injected into the reservoir for storage of hydrogen to a pressure exceeding the pressure in the loosened layer 2 PA; open the valve 16 located between the tank 2 storage catalyst and the reactor 3 with loosened layer; and adding fresh catalyst to the reactor at a loosened layer. When performing this method, the height of which increases the catalyst bed in the reactor with the loosened layer is 20% by volume; and the amount of catalyst added one at a time in a reactor with a loosened layer is ten times the amount of catalyst added at a time online in the fluidized-bed reactor. When the reactor with a loosened layer is the amount of catalyst is four times longer than a one-time download of the fresh catalyst online in the fluidized-bed reactor, from the reservoir 2 for storing ka�of Aligator arrives fresh catalyst.

Operating conditions in the fluidized-bed reactor and in the reactor with the loosened layer is presented in Table 3 and the results of reaction are shown in Table 4.

Example 3

The method of Example 3 is similar to the method of Example 2, and the basic design of a fluidized bed reactor of similar design Example 1, except that the fluidized bed reactor of Example 3, there are two circulation zones.

Comparative Example 2

Method of Comparative Example 2 is essentially similar to the method of Example 2 except that the reactor loosened layer is absent. Thus, when reducing the activity of the catalyst in the fluidized-bed reactor, to levels that do not provide the required quality of the product, there is a need of adding fresh catalyst, fresh catalyst is added to the fluidized-bed reactor directly from the storage tank of the catalyst installed in the upper part of the fluidized-bed reactor. The adding procedure is similar to adding fresh catalyst to the reactor at a loosened layer of the storage tank of the catalyst described in Example 1. The catalyst and source of crude oil used in Comparative Example 2, the same as in Example 1, respectively. Operating conditions and test results Compare�professional of Example 2 are presented in Table 3 and Table 4 respectively.

Table 3
Of the reaction conditions
No.Example 2Example 3Comparative Example 2
A reactor with a loosened layer
Reaction temperature, °C425422
The reaction pressure, MPa1515
Space velocity of the reactants, h-11,01,0
Volume ratio hydrogen/oil15001500
The fluidized-bed reactor
Reaction temperature, °C425 422425
The reaction pressure, MPa151515
Volume ratio hydrogen/oil700700700
Space velocity of the reactants, h-11,51,51,5

td align="center"> 2,5
Table 4
The results of the reaction
No.Example 2Example 3Comparative Example 2
Gasoline (180°C)
S, ug/g7045360
N, ug/g6,52,145
Yield, % wt.8,49,5
Diesel fuel (180~350°C)
S, ug/g16098580
N, ug/g81,7for 45.1179
Yield, % wt.30,741,725,4
Hydrogenated tail oil shoulder straps (350°C+)
S, % mass0,220,190,9
N (%vol.0,120,10,2
Carbon residue, % mass0,310,27a 5.4
Metal (Ni+V), mg/g8450
Yield, % wt. 58,2to 43.872,1

From the test results presented in Table 4, it is seen that as compared with Comparative Example 2, the content of polluting S and N in the products of Example 2 and Example 3 is greatly reduced, and the outputs of gasoline and diesel fuel increased significantly. Thus, the application of the methods according to the present invention and a fluidized bed reactor, including internal circulation zone for hydrogenation of low-quality crude oil not only improves the quality of the product and increases the yield of light oils, but also allows to obtain high-quality raw material for catalytic cracking. When tested it was found that the method of adding the catalyst according to the present invention ensures stable working condition main reactor, i.e. the fluidized-bed reactor, which, in turn, provides a stable mode of operation of the device and the stability of product quality.

As can be seen from Table 2, the use of a fluidized bed reactor, comprising circulating the area described in Example 1, can effectively increase the degree of dibenzothiophen were and hydrodenitrification, as well as the degree of conversion of the residual oil.

Finally, we should note�'it, what the examples above are only preferred embodiments of the present invention, not limiting the present invention. Although the present invention was described above using Examples, the specialist in the art may make modifications to the technical solutions described in these examples, or can create equivalent replacement part presents technical solutions. Any modifications, equivalent replacements or improvements relevant to the principles of the present invention, included in the scope of the present invention.

1. A reactor with a fluidized bed of catalyst comprising a reactor vessel positioned vertically relative to the earth, and the phase separator installed at the top of the casing, characterized in that a phase separator is the internal circulation zone, which includes the cylinder, tapering diffusion section and guiding structure; at the same time as the cylinder, and a narrowing of the diffusion section at the lower end of the cylinder is installed inside the casing of the reactor; a guide structure mounted on the inner wall of the casing of the reactor at the lower end tapering diffusion section, and the guide structure is a ring-shaped protrusion on the internal�Rennie the reactor wall.

2. A reactor with a fluidized bed catalyst according to claim 1, characterized in that the reactor comprises from 2 to 3 internal circulation zones.

3. A reactor with a fluidized bed catalyst according to claim 1, characterized in that between the phase separator and internal circulation area includes design guide, which is a ring-shaped protrusion on the inner wall of the reactor.

4. A reactor with a fluidized bed catalyst according to claim 1 or 3, characterized in that the shape of the longitudinal section of the guiding structure along the axis of the reactor selected from the group consisting of trapezoidal, arched, triangular and semi-circular form.

5. A reactor with a fluidized bed catalyst according to claim 1, characterized in that the overlapping angle and friction angle of the guide structures are acute angles.

6. A reactor with a fluidized bed catalyst according to claim 5, characterized in that the overlapping angle and friction angle is less than 60 degrees.

7. A reactor with a fluidized bed catalyst according to claim 1, characterized in that the phase separator includes two concentric cylinders having different inner diameters, i.e. the inner cylinder and the outer cylinder,
the upper and lower ends of the inner and outer cylinders are open, the opening at the upper end of the outer cylinder� is located above the holes on the upper end of the inner cylinder and the hole at the lower end of the outer cylinder is located above the openings at the lower end of the inner cylinder;
the lower end of the inner cylinder represents a narrowing of the diffusion section, the diameter of which is smaller than the inner diameter of the reactor; and
the lower end of the outer cylinder is also a narrowing of the diffusion section, the diameter of the hole which is also smaller than the inner diameter of the reactor.

8. A reactor with a fluidized bed catalyst according to claim 7, characterized in that the vertex angle of the cone of the diffusion section of the outer cylinder is less than the vertex angle of the cone of the diffusion section of the inner cylinder by the amount constituting from about 20 to 80 degrees.

9. A reactor with a fluidized bed catalyst according to claim 7, characterized in that the diameter of the pilot hole formed by the guide structure is in the range of values of the diameter of the inner cylinder to the outer diameter of the cylinder of the phase separator.

10. A reactor with a fluidized bed catalyst according to claim 1, characterized in that in the lower part of the casing of the reactor is installed distribution plate.

11. A reactor with a fluidized bed catalyst according to claim 1, characterized in that the outlet fluid from the fluidized-bed reactor is in the upper part of the casing of the reactor, between the hole at the upper end of the inner cylinder of the phase separator and the hole �and the lower end of the outer cylinder.

12. A reactor with a fluidized bed catalyst according to claim 1, characterized in that the upper end of the cylinder is expanding design with a small extension.

13. Method of hydrogenation in the reactor with a fluidized bed catalyst according to any of claims.1-12, characterized in that the method comprises the following steps:
catalytic hydrogenation of a mixture of low-quality source material and hydrogen in a fluidized bed reactor catalyst;
introduction of the liquid product from the products obtained after separation of the gaseous and liquid phases in the reactor with a loosened layer for additional reaction, the reactor loosened layer is connected to the fluidized-bed reactor catalyst by means of the pipeline; and
adding an additional amount of catalyst from the reactor with a loosened layer in the fluidized-bed reactor after the decrease of the catalytic activity of the catalyst in the fluidized-bed reactor, to an unacceptable level.

14. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, characterized in that the fluidized-bed reactor support the following operating conditions: a reaction pressure is from 6 to 30 MPa, reaction temperature is from 350 to 500°C, space velocity of 0.1-5 h-1 and the volumetric ratio of hydrogen to the amount of oil from 400 to 2000.

15. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, characterized in that the fluidized-bed reactor support the following operating conditions: degree of fragmentation of the layer is from 5% by volume. up to 25% vol., the reaction pressure is from 6 to 30 MPa, reaction temperature is from 350 to 500°C, space velocity of 0.1-5 h-1and the volumetric ratio of hydrogen to the amount of oil from 400 to 2000.

16. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, characterized in that, after the reaction in the fluidized-bed reactor catalyst liquid products obtained after separation of the gaseous and liquid phases is fed into the reactor with a loosened layer at a level of from 5% by mass. up to 70% of the mass. the total mass of liquid products.

17. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 16, characterized in that, after the reaction in the fluidized-bed reactor catalyst liquid products obtained after separation of the gaseous and liquid phases is fed into the reactor with a loosened layer at a level of from 10 wt%. up to 50% of the mass.

18. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, distinguish�ISA, what
the amount of catalyst added to the reactor with a loosened layer at a time, ranging from 2 to 20 amounts of catalyst added at a time online in a reactor with a fluidized bed of catalyst, and
when the amount of catalyst remaining in the reactor with a loosened layer is from 0 to 5 amounts of catalyst added at a time online in a reactor with a fluidized bed of catalyst, the additional catalyst is fed from a supply tank containing fresh catalyst.

19. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, characterized in that the catalyst carrier is a refractory inorganic oxides, and the active components of the catalyst selected from the metals of Group VIB and/or Group VIII of the Periodic table.

20. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 19, characterized in that the catalyst has the following properties:
the particle diameter of the catalyst is from 0.1 to 0.8 mm, the catalyst comprises an active hydrogenating component based on metals of Group VIB and/or Group VIII of the Periodic table and the carrier is an Al2O3;
the catalyst includes at least one auxiliary substance selected from the following elements: In, Sa, F, g, P, Si, Ti, and the content of the excipient is from about 0.5 wt%. to 5.0 wt.%;
pore volume is from 0.6 to 1.2 ml/g and the average pore diameter is from 15 to 30 nm;
the volume of pores whose diameter is from 15 to 30 nm is 50% or more of the total pore volume and pore volume, the diameter of which is less than 8 nm, is less than 0.03 ml/g; and
specific surface area is from 100 to 300 m2/year.

21. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 14, characterized in that the fluidized-bed reactor support the following operating conditions: a reaction pressure of 10 to 18 MPa, reaction temperature from 400 to 450°C., space velocity of 0.5-3 h-1and the volumetric ratio of hydrogen to oil - from 600 to 1500.

22. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 15, characterized in that the fluidized-bed reactor support the following operating conditions: degree of fragmentation of the layer is from 10%. up to 25% vol., the reaction pressure is from 10 to 18 MPa, reaction temperature from 380 to 430°C, the volume rate - of 1-4 h-1and the volumetric ratio of hydrogen to oil - from 600 to 1500.

23. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 20, characterized in that the metal of Group VIB in the active hydraulic�tion component, is a Mo, the content of which ranges from 1.0 wt%. to 20.0 wt%. in terms of weight of metal oxide MoO3;
the metal of Group VIII in an active hydrogenating component represents Ni or Co, the content of which is 0.1% of the mass. to 8.0 wt%. in terms of the mass of NiO or COO.

24. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 23, characterized in that the content of Mo is from 3.0 wt%. to 15.0 wt%. in terms of weight of metal oxide Moo3and the content of Ni or Co is 0.5 wt%. to 5.0 wt%. in terms of the mass of NiO or COO.

25. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 20, characterized in that the pore volume of the catalyst, the diameter of which is less than 8 nm, is from 0.005 to 0.02 ml/g;
the volume of pores whose diameter is from 15 to 30 nm, greater than or equal to 50%, but 70% or less of the total pore volume; and
the specific surface of the catalyst is from 120 to 240 m2/year.

26. Method of hydrogenation in the reactor with a fluidized bed catalyst according to claim 13, characterized in that the low-quality crude oil selected from one or more of the following fractions: atmospheric residue, vacuum residue, deasphalting oil, tar Sands oil, viscous crude oil, liquid bitumen and heavy�Loy oil, obtained by the liquefaction of coal.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: invention is related to hydrocarbon oil hydrotreating method using at least the first and second reactors. The method includes (i) contacting of hydrocarbon oil in the first reactor at high temperature and pressure with hydrotreating catalyst in presence of hydrogen-containing gas wherein hydrogen is consumed; (ii) division of the outgoing flow obtained at the stage (i) into partially hydrotreated hydrocarbon oil and contaminated hydrogen-containing gas by means of a steam stripper, wherein the waste hydrogen-containing gas is used as stripping gas; (iii) contacting of partially hydrotreated hydrocarbon oil obtained at the stage (ii) in the second reactor at high temperature and pressure with hydrotreating catalyst in presence of pure hydrogen-containing gas with consumption of this hydrogen, at that at least 80% of hydrogen consumed at the stages (i) and (iii) are replenished by additional pure hydrogen-containing gas supplied to the second reactor; (iv) separation of the product produced at the stage (iii) in the second reactor into hydrotreated hydrocarbon oil and waste hydrogen-containing gas, at that hydrotreated hydrocarbon oil may be extracted as a product, and (v) transporting of at least a part of hydrogen-containing gas obtained at the stage (iv), which has temperature of at least 200°C to perform the stage (ii) while using this gas as stripping gas.

EFFECT: effective usage of waste hydrogen-containing gas promotes minimisation of the required capacity of the compressor, facilitation of steam stripping, improvement of heat usage.

17 cl, 2 dwg

FIELD: process engineering.

SUBSTANCE: proposed process comprises compression of boost hydrogen in first compressor to get first flow of compressed boost hydrogen. First flow of compressed boost hydrogen is compressed in second compressor to get second flow of compressed boost hydrogen. Said second flow of compressed boost hydrogen is separated as second flow of compressed boost hydrogen for hydraulic treatment. First flow of hydrocarbons is processed over first flow for hydraulic processing including second flow of compressed boost hydrogen and first hydraulic processing catalyst to get first effluent flow of hydroprocessing products. Second flow of hydrocarbons is processed over second flow for hydraulic processing including first flow of compressed boost hydrogen and first hydraulic processing catalyst to get second effluent flow of hydroprocessing products. Said second effluent flow of hydroprocessing products is separated to get vaporous second effluent flow of hydroprocessing products. Said vaporous second flow is added to said boost hydrogen flow upstream of said first compressor.

EFFECT: perfected feed of hydrogen to separate process units.

9 cl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to method of diesel fuel production. Particularly, it pertains to compression of makeup hydrogen flow in compressor to bleed hydrogen flow from said compressed makeup hydrogen flow. Hydrocarbons flow is subjected to hydro cracking in the presence of hydrogen flow and catalyst to get outlet hydro cracking products flow to be separated in liquid flow and vapour flow to be compressed to get hydrogen compressed flow. Liquid outlet flow is fractionated to obtain diesel fuel flow. Hydrogen flow is bled for hydraulic cleaning from said compressed hydrogen flow for hydraulic cleaning of diesel fuel flow in the presence of hydrogen flow and catalyst to get outlet hydro cracking products flow. Invention covers also the diesel fuel production plant.

EFFECT: perfected process.

10 cl, 2 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention is related to hydrocracking processes, under conditions of which large proportion of heavy hydrocarbon stock e.g. Vacuum Gas Oil (VGO) turns to hydrocarbons with lower molecular mass and lower boiling temperature. The invention relates to the method of production of base oil, involving: a) hydrocracking of heavy hydrocarbon stock with hydrocracking catalyst containing the preset amount less than 15 wt % of beta-zeolite with flow coming out of a hydrocracking plant containing at least 40 wt % of hydrocarbons boiling at temperature of 382°C (720°F), and b) separation from flow coming out of a hydrocracking plant of unconverted oil with pour point not above 18°C (65°F) in form of high-boiling fraction containing base oil.

EFFECT: improvement of base oil quality.

11 cl, 1 dwg, 4 tbl, 2 ex

FIELD: oil and gas industry.

SUBSTANCE: invention is related to a combined method of conversion of oil-derived hydrocarbon fractions into high-quality hydrocarbon mixtures as fuel, which includes catalytic cracking of hydrocarbon fraction in catalyst fluidised bed with catalyst containing ERS-10 zeolite, where the specified catalyst contains at least two components, where the specified components represent: (a) a component containing one or more catalytic cracking catalysts in fluidised, and (b) a component containing ERS-10 zeolite for obtaining Light Cycle Gas Oil (LCGO), hydrotreatment of light cycle gas oil, interaction of hydrotreated light cycle gas oil obtained at the previous stage of hydrotreatment in presence of hydrogen with catalytic system. The invention also touches the method of catalytic cracking and a stage of catalytic cracking in fluidised bed.

EFFECT: production of high-quality hydrocarbons, conversion increase.

21 cl, 3 tbl, 1 ex

FIELD: machine building.

SUBSTANCE: invention relates to the hydroconversion method for raw hydrocarbons in the mix with the circulating part of the hydroconversion vacuum residue by a high-aromatic modifier, dispersion of a catalyst precursor and hydrogen-containing gas which is supplied in the amount of maximum 800 nm3 per 1 m3 of raw material in terms of hydrogen and of minimum the value of chemical hydrogen demand. The above is carried out in a reactor with an internal circular baffle plate which adjoins the reactor top in a pressure tight way and forms axial and circular cavities, and with separation space at the top of the circular cavity. Hydroconversion gas is removed from the separation space, liquid hydroconversion product is removed from the top of the axial cavity, circulating reaction mass is removed from the bottom of the reactor's circular cavity, cooled and delivered for mixing with heated raw liquid-vapour mixture, the temperature of the liquid hydroconversion product is kept close to the upper limit of the hydroconversion temperature range, the temperature of the heated raw mixture and the temperature of the circulating reaction mass are kept close to the lower limit of the hydroconversion temperature range. Hydroconversion products are separated and rectified to isolate light fractions, heavy gas oil and vacuum residue, part of the latter is recirculated, and the balance part is recovered to produce regenerated catalyst precursor.

EFFECT: reduction of power inputs and metal consumption of equipment along with the provision for high yield of light fractions.

1 dwg, 1 ex

FIELD: engines and pumps.

SUBSTANCE: invention relates to production of fuel for jet engines from kerosene stock. Proposed method comprises hydrofining of kerosene stock with freezing point interval of 163-302°C (325-575°F) over hydrofining catalyst under conditions of hydrofining. This allows getting hydrofined kerosene stock. Besides, it includes dewaxing of, in fact, all hydrofined kerosene stock over catalyst including 1-D molecular sieve with ten rings under conditions of dewaxing to get water-dewaxed kerosene stock. Also, it includes fractionating of water-dewaxed kerosene stock to get fuel for jet engines.

EFFECT: higher yield, better properties.

10 cl, 1 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: initial hydrocarbon raw material is initially separated and first part of initial raw material is introduced into first zone of dehydration reaction, which functions without oxidation re-heating, and obtained as a result output flow is introduced into second zone of dehydration reaction, which functions without oxidation re-heating. Obtained as a result output flow from second zone of dehydration reaction, together with second part of initial raw material is introduced into third zone of dehydration reaction, which functions with oxidation re-heating.

EFFECT: increased method productivity.

10 cl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention is referred to method of production of high-octane petrol and includes fractionation of hydrotreated naphtha into light and heave fractions; light naphtha isomerisation and heavy naphtha reforming in presence of platinum-containing catalyst with delivery of excessive hydrogen from reforming to isomerisation. Isomerisation is carried out with sulfate-zirconia catalyst with subsequent separation of isomerisate into three fractions: low-boiling fraction, medium fraction containing n-hexane and methylpenthanes and high-boiling fraction; medium fraction is recirculated to isomerisation raw material. By rectification from reformate light and heavy reforming fractions are obtained; heavy fraction is mixed with low- and high-boiling fractions of isomerisate with production of the target product while light fraction of reforming boiling away up to 85-95°C is subjected to hydroisomerisation at 250-300°C in presence of platinum-containing catalyst and obtained hydroisomerisate is delivered to be mixed with isomerisate.

EFFECT: reduction of benzole and aromatic hydrocarbons content in compliance with requirements to modern types of petrol with preservation of integration for reforming and isomerisation processes.

2 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for hydrocracking a hydrocarbon stream involving the following operations: providing hydrocarbon starting material (12); feeding the hydrocarbon starting material (12) into a hydrofining zone (14) to obtain an output stream (30) of the hydrofining zone; feeding the output stream (30) of the hydrofining zone into a separation zone (16) in order to separate one or more streams of hydrocarbons with a lower boiling point (34, 58, 62, 66) from a stream of liquid hydrocarbons with a higher boiling point (68); inlet of at least a portion of the stream of liquid hydrocarbons with a higher boiling point as material (68) for hydrotreatment without using a considerable amount of hydrocarbons coming from the hydrotreatment zone with an essentially continuous liquid phase; adding hydrogen (70) to the material (68) for hydrotreatment in an amount which is sufficient to maintain essentially liquid-phase conditions; feeding the material (68), mixed with hydrogen, for hydrotreatment into the hydrocracking zone (24) with an essentially continuous liquid phase; and carrying out a reaction for hydrocracking the material (68) for hydrotreatment in the hydrocracking zone (24) with an essentially continuous liquid phase with a hyrocracking catalyst in hydrocracking conditions to obtain an output stream (72) of the hydrocracking zone having a lower boiling point compared to the stream (68) of liquid hydrocarbons with a higher boiling point. The invention also relates to another method for hydrocracking a hydrocarbon stream.

EFFECT: improved characteristics of products, higher conversion.

16 cl, 5 dwg, 4 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining engine fuel in interval of petrol boiling by benzole alkylation. Invention deals with method of obtaining hydrocarbon product in interval of petrol boiling, which has concentration of benzole not more than 1 vol.% and regulated temperature of evaporation, from raw material, which consists of reforming product, with concentration of benzole at least 20 wt %, which includes reforming product alkylation in reactor of alkylation in presence of zeolite catalyst MWW at least in two immobile catalytic layers in mode of single passing in liquid phase by alkylation agent.

EFFECT: high level of benzole and olefin conversion.

10 cl, 10 dwg, 15 tbl, 14 ex

FIELD: oil and gas industry.

SUBSTANCE: as an additive to increase the processing depth of hydrocarbon-containing raw materials, in thermocatalytic processes there used is organic salt having the following formula: M(OOC-R)n, or M(SOC-R)n, or M(SSC-R)n, where R means alkyl, aryl, isoalkyl, tert-alkyl, alkylaryl, possibly containing hydroxylic, keto-, amino-, carboxylic, thiocarbamic groups, n 1-3, and M means transition metal from the elements of the Mendeleyev's Classification Table. Also, invention refers to the method for increasing the processing depth of hydrocarbon-containing raw materials, in which the above additive is used.

EFFECT: use of the described invention allows increasing the processing depth of hydrocarbon-containing raw materials in thermocatalytic processes.

14 cl, 8 ex, 12 tbl

FIELD: oil and gas industry.

SUBSTANCE: catalytic reforming system described below includes the following: raw material stream including naphtha and at least one compound containing manganese, which is chosen from the group consisting of manganese cyclopentadienyl tricarbonyl, manganese methylcyclopentadienyl tricarbonyl, manganese dimethylcyclopentadienyl tricarbonyl, manganese trimethylcyclopentadienyl tricarbonyl, manganese tetramethylcyclopentadienyl tricarbonyl, manganese pentamethylcyclopentadienyl tricarbonyl, manganese ethylcyclopentadienyl tricarbonyl, manganese diethylcyclopentadienyl tricarbonyl, manganese propylcyclopentadienyl tricarbonyl, manganese isopropylcyclopentadienyl tricarbonyl, manganese tert- butylcyclopentadienyl tricarbonyl, manganese octylcyclopentadienyl tricarbonyl, manganese dodecyclopentadienyl tricarbonyl, manganese ethylmethylcyclopentadienyl tricarbonyl and manganese indenyl tricarbonyl; and catalyst; at that, catalyst of reforming plant includes the following: substrate; precious metal on substrate; and deposit of free particles of manganese on catalyst, which are formed during decomposition at least of one manganese containing compound which is described above. Method for increasing octane number of mixture of reforming product produced with catalytic reforming plant at oil refinery having the stream of raw product of reforming plant is described; the above method includes the following: addition of catalyst to raw product stream of reforming plant; the above catalyst contains oxidised manganese; as a result, octane number of mixture of the produced reforming product increases relative to octane number of mixture of produced reforming product obtained at oil refinery without any addition of catalyst containing the oxidised manganese; at that, oxidised manganese catalyst is obtained from group of manganese tricarbonyls which are specified above.

EFFECT: increasing catalyst service life or increasing octane number of reforming product stream.

19 cl

The invention relates to systems for producing high-octane gasoline low-octane reforming of gasoline fractions

FIELD: chemistry.

SUBSTANCE: reactor contains reactor case, and device of air input of distribution type and device of air input of cyclone type are located in lower parts of reactor case, device of air input of distribution type contains a series of tubes of air distribution, and device of air input of cyclone type consists of several tubes of cyclone air input, located below tubes of air distribution, with segment of air output of said tubes of cyclone air input being inclined at 45-60° relative to reservoir case radius. Application of combined device of air input can make liquid at the bottom of reactor rotate under pressure of proper amount of air, in addition reactor has good air dispersion, in such way, preserving materials in suspended state.

EFFECT: reactor improvement.

9 cl, 2 dwg

FIELD: oil and gas industry.

SUBSTANCE: at least one reactor with fluidised bed is used in hydroconversion method; besides, raw material is added to gas space above the specified reactor. The above method involves separation of the above raw material in reactor into steam-like fraction and liquid fraction. The invention also refers to the reactor design allowing to implement the above method.

EFFECT: improvement of use efficiency of hydroconversion and performance characteristics of the process.

21 cl, 4 dwg, 3 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method (10) includes supply of gaseous reagents (18) into layer of suspension (14) in container (12), catalytic reaction of gaseous reagents with formation of liquid and gaseous hydrocarbons and filtration of mixture of products, containing liquid product and enzyme particles. Filtration is performed by passing liquid product through filtering means (30) to separate catalyst particles from liquid products. Gaseous products are withdrawn (23) and cooled with formation of multiphase product, which is separated to obtain at least hydrocarbon condensate flow (88) and flow of residual gas (84). At least part of hydrocarbon condensate flow (88) is processed (96) to remove oxygen-containing components obtaining condensate for blowback method. From time to time filtering means (30) from formation stage is subjected to blowback, passing condensate for blowback through filtering means (30).

EFFECT: increased efficiency of filtering means.

9 cl, 4 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing a composition of aromatic dicarboxylic acid, involving (a) oxidation of a multiphase reaction medium in a primary oxidation reactor to obtain a first suspension; (b) further oxidation of at least a portion of said first suspension in a secondary oxidation reactor which is of the bubble column type, wherein the method further involves feeding an aromatic compound into said primary oxidation reactor, where at least about 80 wt % of said aromatic compound fed into said primary oxidation reactor is oxidised therein, wherein head gases are moved from the top of the secondary oxidation reactor into the primary oxidation reactor. Disclosed are an optimised process and equipment for more efficient and cheaper liquid-phase oxidation. Such liquid-phase oxidation is carried out in a bubble column type reactor which ensures a highly efficient reaction at relatively low temperatures. When the oxidised compound is para-xylene and the oxidation reaction product is crude terephthalic acid (TPA), such a product, TPA, can e purified and extracted using cheaper methods than when TPA is obtained using the conventional high-temperature oxidation process.

EFFECT: improved method of producing a composition of aromatic dicarboxylic acid.

30 cl, 4 tbl, 31 dwg

FIELD: chemistry.

SUBSTANCE: present inventions relate to a method of producing precipitated calcium carbonate (PCC) and the design of a low-power reactor system for realising the method such that, the amount of dry residues in the PCC product can be increased to 35% or more without a dehydration step. The disclosed method involves steps for bringing calcium hydroxide into contact with a carbon dioxide-containing gas in parallel or two or more separate reaction vessels in order to form calcium carbonate. Calcium oxide, lime or dry calcium hydroxide or a combination of any of the three components are also added to a portion of the obtained mixture of calcium hydroxide and calcium carbonate. When used in the production of PCC, the reactor system has at least one reactor vessel with an optional water inlet and gas inlet and at least one recirculation reservoir for inlet of components and optional water inlet.

EFFECT: use of the disclosed method and device ensure efficient and economical production of PCC with a given structure and high content of dry residues.

21 cl, 8 dwg, 9 ex

Up!