Methods of hydrocracking with receiving of hydroisomerised product for base lube oils
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
The technical field to which the invention relates.
The invention relates to a method of transforming the original heavy hydrocarbons (e.g., vacuum gas oil) into hydrocarbons of lower boiling point (for example, within the diesel fuel boiling and below) by hydrocracking the simultaneous achievement in the stream coming from the hydrocracking unit, the high-boiling fraction, which is subjected to hydroisomerization for the purpose of lowering the freezing temperature, increasing its value as a basic component of lubricating oils.
The level of technology
Refineries often produce the required products, such as lubricating base oil (hereinafter intermediate basic components of lubricating oils, hydrocracking source of hydrocarbons obtained, for example, from crude oil. The raw material most often subjected to hydrocracking with the aim of obtaining intermediate basic components of lubricating oils are the oils and heavy oils obtained from crude oil by distillation. A typical gas oil contains a significant proportion of hydrocarbon components, typically 50 wt%. or more, with a boiling point above 382°C. (720°F). The typical temperature range of vacuum gas oil boiling in the range of 316°C (600°F) to 566°C (1050°F).
Hydrocracking, as p is Avila, carried out by contacting the hydrocracking reactor or reaction zone of the gas oil or other feedstock to be processed, in the presence of an appropriate catalyst hydrocracking conditions of high temperature and pressure. The reactions of hydrocracking leads to a decrease in the total molecular weight of the heavy hydrocarbon raw materials to produce products of high quality (i.e., higher values), including mixtures of components of motor fuels, such as diesel fuel and gasoline. These products are of high quality, which are the result of the conversion in the reaction zone hydrocracking, usually separated from the General flow of hydrocracking unit in the form of low-boiling fractions using one or more allocation and/or distillation. The residual fraction with a higher boiling point, often referred to as not transformed the oil return in the hydrocracking reactor or reaction zone to increase the total conversion hydrocracking.
Despite the fact that this recycle material mainly contains hydrocarbons with a higher molecular weight, however, it is generally considered that "not converted" oil is improved as compared with fresh heavy hydrocarbon feedstock due prot is Chania other reactions in the hydrocracking zone. In particular, impurities are removed heteroatomic compounds, and specifically, compounds of sulfur and nitrogen, aromatic compounds hydronauts to the corresponding saturated cyclic compounds, and the viscosity decreases. This transformed the oil is stabilized and, as a rule, is characterized by properties that are preferred for the intermediate base oils lubricants (for example, used in car engines). Not usually into the oil hydrocracking processed in the second stage catalytic conversion, such as or hydroisomerization dewaxing in the presence of a suitable catalyst, often containing a noble metal such as platinum or palladium. As a result of hydroisomerization normal paraffins into ISO, while dewaxing leads to lower molecular weight paraffins, and the result of both of these catalytic processes is a significant lowering of the pour point is not turned oil. After these reactions, leading to the lowering of the freezing temperature, then you can use the stage Hydrotreating for additional hydrogenation of residual unsaturated hydrocarbons and removal of sulfur and nitrogen, thus improving the quality of the intermediate base components lubrication is the Asel with regard to various desired properties, such as thermal stability and oxidation resistance.
A typical way to obtain intermediate basic components of lubricating oils using a hydrocracking described, for example, in U.S. patent 6432297, in which the flow coming from the hydrocracking unit, is subjected to a desorption treatment hot hydrogen followed by hydroisomerization and Hydrotreating fraction coming from the bottom of the Stripping column. Despite the fact that in the industrial production of semi-basic components of lubricating oils used in a large variety of technological schemes, operating conditions and catalysts, there remains a need for new methods, including methods using hydrocracking, which can reduce costs and increase efficiency.
Embodiments of the invention relate to disclosure methods hydrocracking, in which (i) a significant part of the original heavy hydrocarbon feedstocks such as vacuum gas oil (VGO), is converted into hydrocarbons of lower molecular weight and lower boiling points, and (ii) achieved a very significant reduction in pour point of the high-boiling fractions, some of which can be returned to the hydrocracking reactor or reaction zone, and the other part use the VAT as intermediate basic components of lubricating oils optional, after one or more additional stages of processing, such as Hydrotreating. The ability to provide a significant improvement in the quality by reducing the molecular weight, and flow of hydroisomerization (or lowering the pour point) of the high-boiling fraction is implemented based on a combination of hydrocracking catalyst used and the operating conditions, as described in more detail below.
Corresponding to the basic components of lubricating oils obtained by means containing hydrocracking, as described in the invention preferably correspond to the specifications on the base oil lubricants group II and group III from the point of view of the content of saturated hydrocarbons, sulfur content and viscosity index, established by the American petroleum Institute (API). According to the characteristic variations of the invention are not converted oil that is returned in the form of a fraction, boiling at higher temperatures (for example, from the point of view of its initial boiling point) relative to the total flow coming from the hydrocracking unit, can be used as intermediate basic components of lubricating oils, optionally, after Hydrotreating, but without the need for the implementation stage catalytic hydroisomerization or catalytic dewaxing. Perhaps the th exception of this stage of the method allows to obtain intermediate basic components of lubricating oils by hydrocracking at a much lower cost compared to known methods, require, for example, the reactor, the catalyst and associated equipment for the individual stages of hydroisomerization. In particular, the catalysts based on noble metals, for example platinum or palladium), is usually required to hydroisomerization to reduce sufficiently the freezing temperature is not turned oil, represent a significant expense that can be saved when implementing the methods of obtaining intermediate basic components of lubricating oils, which do not include this stage.
Data and other implementation options related to the present invention, follow explicitly from the following detailed description.
Brief description of drawing
The drawing shows a diagram of a typical method comprising hydrocracking followed by Hydrotreating in sequential zones of the reactor, to obtain intermediate basic components of lubricating oils.
The implementation of the invention
Embodiments of the invention relate to a method of hydrocracking to obtain intermediate basic components of lubricating oils. Typical methods include hydrocracking source of heavy hydrocarbon feedstocks to obtain flow coming from the hydrocracking unit, which usually is a common product, output is Asim from the hydrocracking reactor or reaction zone. The source of the heavy hydrocarbons, as a rule, is the fraction obtained by distillation, characterized by the temperature of boiling above the boiling temperature of diesel fuel. A typical source of heavy hydrocarbons for hydrocracking is a mixture of recycle fractions are not converted oil taken from the flow coming from the hydrocracking unit, in the form of a high-boiling fraction and returned to the hydrocracking reactor, with any fresh component raw materials in respect of which the hydrocracking can be effective to reduce the molecular weight of the component materials and/or removal of organic sulfur and nitrogen, and metals.
Suitable fresh components of the heavy hydrocarbon feedstocks include gas oils, such as vacuum gas oil (VGO), which boils in the typical range of temperatures, for example from 288°C (550°F) up to 593°C (1100°F), and often from 343°C (650°F) to 566°C (1050°F). Complementary VGO or other than the specific fresh raw material components, therefore, include a large variety of straight and subjected to transformations hydrocarbon fractions obtained in the processes of oil refining (i.e. derived from crude oil), such as atmospheric gas oils, vacuum residues and neasfaltirovanyj vacuum residues (for example, wikipad the e above 566°C (1050°F)), atmospheric residue (for example, wikipaedia above 343°C (650°F)), distillates coking, straight-run distillates, potenziani and stripped of crude oil, including heavy crude oil, pyrolysis oil, wysokiej synthetic oils, cycle oils and distillates catalytic cracking unit (for example, fluid catalytic cracking or FCC). Fresh components of the heavy hydrocarbon feedstock may also include mineral and synthetic oils (e.g., resins, bitumen, coal oil, shale oil, products from tar sand etc) and their fractions.
Any of the above-mentioned fresh raw components or combinations of components can be subjected to a Hydrotreating prior to the introduction into the hydrocracking reactor or reaction zone to remove, for example, compounds of sulfur and/or nitrogen in such a way that fresh component of raw materials was characterized by a total content of sulfur and nitrogen below, for example, 500 ppm wt. and 100 ppm of the mass. respectively. Hydrotreating can be done in a separate Hydrotreating reactor or in the same reactor that is used for hydrocracking, for example by placing a layer of Hydrotreating catalyst to a catalyst for hydrocracking.
Typical source of heavy hydrocarbons is a combination of fresh component raw materials VGO or mainly VGO (for example, the commonly, at least 50%and often at least 75% of the mass. VGO) and a recycle fraction of the flow coming from the hydrocracking unit. Regardless of the specific components that make up the original heavy hydrocarbons, this stream typically contains at least 50%and often at least 75% of the mass. hydrocarbons boiling at temperatures above the initial boiling point of the required intermediates basic components of lubricating oils. Initial boiling point source of heavy hydrocarbons, typically, is at least 288°C (550°F), and often at least 343°C (650°F). Therefore, demonstration sources of heavy hydrocarbons typically include hydrocarbons boiling above 288°C (550°F), and usually contain at least 25%, usually at least 35%, and often at least 50 wt%. hydrocarbons, wikipaedia in the range of 316°C (600°F) to 538°C (1000°F).
The original heavy hydrocarbon feedstock typically contains organic nitrogen compounds and organic sulfur compounds. The total sulfur content, largely represented by organic sulfur compounds, such as alkylbenzene typically is in the range from 0.1% to 7%, typically from 0.2% to 5%, and often from 0.5% to 3% of the mass. total sulfur. The original heavy hydrocarbon feedstock also contains, as a rule, from 10 ppm to 2%, and usually from 100 ppm to 2000 ppm of the mass. total nitrogen, largely represented by organic nitrogen compounds, such as minority aromatic compounds, including carbazole. The content of metal contaminants (e.g., Nickel, iron and vanadium) heavy hydrocarbons usually ranging from 0.1 ppm to 20 ppm mass. and the carbon balance Conradson is usually from 0.1% to 5% of the mass. The API gravity, as a rule, is in the range from -5° to 35°. In addition, the heavy hydrocarbon feedstock typically contains asphaltenes, which are polycondensation aromatic compounds containing heteroatoms of oxygen, nitrogen and sulfur, and heavy metals such as Nickel and vanadium.
As discussed above, to date, has unexpectedly found that hydrocracking can be carried out in such conditions and in the presence of catalysts, which provide not only a significant decrease in molecular weight components of the flow coming from the hydrocracking unit, but also contribute and hydroisomerization high-boiling fractions of the given output stream, part of which is usually returned to the hydrocracking reactor, and the other part is used optionally after further processing stages, which may include Hydrotreating, as the intermediate base components of lubricating oils. Specifically, depending on the degree of conversion of heavy hydrocarbons into one or more products with lower molecular weight (e.g., naphtha and diesel fuel), which can be distinguished from the flow coming from the hydrocracking unit, separate streams of products using one or more single-stage (evaporation) or multistage (distillation) process selection section selection of products below, in the course of the stream, typically at least 40% (e.g., from 50% to 90%), usually at least 55% (for example, from 60% to 85%), and often at least 70% (e.g., from 70% to 80%) of the hydrocarbons in the stream coming from the hydrocracking unit, referred to the volume of the original heavy hydrocarbons that boil at temperatures below 382°C. (720°F) (boundary temperature or boundary boiling fractions) and, therefore, are transformed into hydrocarbons boiling within the diesel fraction, or more light. Therefore, the overall conversion volume of liquid for passage" (based on flow rate source of heavy hydrocarbons and selected fractions with lower boiling points, high-temperature end of the distillation below this boundary temperature), typically characterized by these values, or is within, above.
Specialists in this is blasti techniques understand the values of conversion hydrocracking for any given heavy hydrocarbons and the catalytic system can be changed by regulation process variables, specifically, the average temperature of the catalyst layer and/or the residence time in the reactor (or flow rate of the liquid, LHSV). Depending on the degree of hydroisomerization dedicated high-boiling fraction with an initial boiling point above this boundary temperature) flow coming from the hydrocracking unit, the pour point of this is not converted oil (in any characteristic values of the conversion mentioned above) is usually not higher than 18°C (65°F), usually not higher than 10°C (50°F), and often no higher than -1°C (30°F).
Compared to traditional ways gidroksicarbonata pour point not converted oil extracted from the exit stream to the hydrocracking unit in the form of a high-boiling fraction is a result of the action of the catalyst and conditions used for hydrocracking, which simultaneously promotirovat largely the hydroisomerization (i.e. conversion premiani paraffins into branched paraffins) in the hydrocracking reactor or reaction zone, along with decreasing molecular weight of the heavy hydrocarbon feedstock, as discussed above. The hydrocracking of heavy coal is dorodnova raw materials, as described above, is usually carried out in the presence of a hydrocracking catalyst and hydrogen.
Typical hydrocracking conditions include an average temperature of a layer of a hydrocracking catalyst comprising from 260°C (500°F) up to 593°C (1100°F), often from 316°C (600°F) to 454°C (850°F); the partial hydrogen pressure of 3.5 MPa (500 psi) up to 21 MPa (3000 psi), often from 8.3 MPa (1200 psi) to 17.2 MPa (2500 psi); LHSV, component from 0.1 h-1up to 30 h-1often from 0.5 h-1up to 3 h-1; and the circulation rate of the hydrogen component of the 2000 standard cubic feet per barrel (337 normal m3/m3) up to 25,000 standard cubic feet per barrel (4200 normal m3/m3), often from 4000 standard cubic feet per barrel (692 normal m3/m3) to 15,000 standard cubic feet per barrel (2530 normal m3/m3).
Suitable catalysts for use in the catalyst bed of hydrocracking or the receiving area of the flow coming from the hydrocracking unit, as described above, include catalysts containing a metal selected from the group consisting of iron, Nickel, cobalt, tungsten, molybdenum, vanadium, ruthenium and mixtures thereof, deposited on the zeolite. Typical zeolites for speakers of hydrocracking catalysts, in which case, as described here,you can get the preferred results, include beta-zeolite, zeolite Y, and zeolite MFI. The structure of zeolite Y and zeolite MFI described and additional references are given in the Atlas Meier, W. M, et al., Atlas of Zeolite Structure Types, 4thEd., Elsevier: Boston (1996).
Beta zeolite is illustrative material for the carrier of hydrocracking catalysts used in the methods described herein. Beta zeolite is well known in the art as a component of catalysts for hydrocracking and described, for example, in U.S. patent 3308069 and document US Re # 28341, which are included here in connection with the description of this material. Beta-zeolite, which is used in the method described here is characterized by a molar ratio of silica: alumina (SiO2:Al2O3) less than 30:1, in one of the embodiments of the invention; less than 25:1, in another embodiment, more than 9:1 and less than 30:1, in another embodiment, more than 9:1 and less than 25:1, in the fourth embodiment; more than 20:1 and less than 30:1, in the fifth embodiment, and more than 15:1, and less than 25:1, in the sixth embodiment of the invention.
Beta zeolite is usually synthesized from the reaction mixture containing template. The use of templates for the synthesis of beta zeolite is well known in the art. For example, in U.S. patent 3308069 and document US Re # 28341 described using hydroxide of tetraethylammonium, and in U.S. patent 5139759 to the categories included here by reference describes the use of ion tetraethylammonium obtained from the corresponding halide of tetraethylammonium. It is believed that the selection of a particular template is not critical for the successful implementation of the method of hydrocracking, unveiled here. In one of the embodiments of the invention beta-zeolite is calcined in air at a temperature of 500°C (932°F) to 700°C (1292°F) for a period of time sufficient to remove a template from a beta-zeolite. The process of calcination in order to remove a template can be done before or after the unification of beta zeolite with a carrier and/or hydrogenating component. Although assume that template can be removed by calcination temperatures above 700°C (1292°F), very high temperature calcination can cause a significant decrease in SF6 adsorption capacity of the beta zeolite. For this reason, I believe that when receiving a beta-zeolite should be avoided calcination temperatures above 750°C (1382°F) to remove the template. Preferably, SF6the adsorption capacity of beta zeolite was at least 28% of the mass.
For use in the composition of hydrocracking catalysts known zeolites subjected to hydrothermal treatment. However, the steam treatment is relatively rough. In the case of any given zeolite steam treatment leads to reduction of kislotno the zeolite. When using zeolite, steamed, as a catalyst for hydrocracking obvious result is that the overall yield of the distillate increases, but the output of the LPG, and the catalyst is reduced. This is an obvious correlation between the output of distillate, on the one hand, and the release of LPG and activity of the catalyst, on the other hand, means that to achieve high activity and high yield of LPG product, the zeolite should not be subjected to the steam treatment, although it reduces the outputs of distillate products. This apparent correlation between total output and activity of the catalyst is necessary to take into account, and it limits the improvement that can be achieved when processing a zeolite with steam.
In ways hydrocracking disclosed here can be applied catalysts containing relatively small amounts of beta-zeolite, characterized by a relatively low molar ratio of silica:alumina and relatively high SF6adsorption capacity. It was discovered that achieved different indicators for the inclusion of such beta-zeolite catalysts in hydrocracking for this method. Increases not only the activity of the hydrocracking catalyst in comparison with the activity of catalysts containing steamed bet the zeolite, but suddenly increases and the yield of the product.
The hydrocracking catalyst is characterized by a size and shape generally similar to those in conventional industrial catalysts. It is preferably produced in the form of a cylindrical extrudate with a diameter of from 0.8 to 3.2 mm (1/32-1/8 inch). However, it is possible to prepare the catalyst of any other desired shape, such as a sphere or pellet. The extrudate can be characterized by forms other than cylindrical, such as the well-known three-petal form or other form, which has advantages from the point of view of either reduced diffusion distances, or differential pressure.
The hydrocracking catalyst may contain a number neoreality materials, which can have a beneficial effect on the strength of the particles, cost, porosity and performance. Therefore, other components of the catalyst are making a positive contribution to the catalyst as a whole, even if not necessary as the components that are active in cracking. These other components are part of a catalyst carrier. Some traditional media components, such as aluminium silicate, usually contribute to craterous the ability of the catalyst. In one of the embodiments of the invention, the catalyst disclosed here provides the specified number, less than 15 percent of the masses. beta-zeolite based on the weight of the beta zeolite and the other components of the medium, combined on a nonvolatile basis. Non-volatile basis refers to the weight of the beta zeolite and the media, particular after heating each of them at 500°C (932°F) to remove all volatiles. Based on the weight of the beta zeolite and the other components of the medium, combined on a nonvolatile basis, the content of zeolite in the catalyst used in the open here the way is a specified amount less than 3% of the mass. in another embodiment of the invention, less than 2% of the mass. in the third embodiment, less than 1.5% of the mass. in the fourth embodiment, less than 1% of the mass. in the fifth embodiment, less than 0.5% of the mass. in the sixth embodiment, and from 0.1 to 2% of the mass. in the seventh embodiment. The remaining portion of the catalyst particles, with the exception of the zeolite component may be filled with mainly traditional media components of the hydrocracking catalyst, such as alumina and/or aluminosilicate. The presence of aluminosilicate helps in achieving the required performance characteristics of the catalyst. In one of the embodiments of the invention, the catalyst contains at least 25% of the mass. aluminum oxide and at least 25% of the mass. the silicate by weight of the catalyst. In another embodiment of the invention, the content of aluminum is silicate in the catalyst is higher than 40 wt. -%, and the content of aluminum oxide is higher than 35 wt. -%, both values are given per mass of catalyst. However, the aluminum oxide is believed, can only act as a binder and is not active craterous component. The catalyst carrier may contain more than 50 wt%. aluminosilicate or more than 50 wt%. aluminum oxide by weight of the total carrier. In a typical embodiment of the invention using approximately equal amounts of silicate and aluminum oxide. Other inorganic refractory materials that can be used as a carrier in addition to the silicate and the aluminum oxide include, for example, silicon dioxide, zirconium dioxide, titanium dioxide, boron oxide and a mixture of zirconium dioxide with aluminum oxide. These media materials mentioned above can be used separately or in any combination.
Apart from beta-zeolite, and other components of the carrier of the hydrocracking catalyst may contain a metal hydrogenation component. Hydrogenating component is preferably provided in the form of one or more base metals, uniformly distributed in the catalyst particle. You can use noble metals such as platinum and palladium, but the best results were obtained with the combination of the two base metals. In particular, either Nickel is, or cobalt combined well with tungsten or molybdenum, respectively. The preferred composition of the metal hydrogenation component comprises Nickel and tungsten, and the massive amount of elemental tungsten 2-3 times more Nickel. The amount of Nickel or cobalt is preferably from 2 to 8 percent of the mass. by weight of the finished catalyst. The amount of tungsten or molybdenum is preferably from 8 to 22 percent of the mass. by weight of the finished catalyst. The total number of base metal hydrogenating component is from 10 to 30 percent of the mass.
The hydrocracking catalyst can be prepared using standard industrial techniques. In very General terms it can be reduced to mix a beta zeolite with other inorganic oxide components and liquids, such as water or a weak acid, to form suitable for extrusion thick mass with subsequent burst through multi-die plate. The extrudate is collected and preferably calcined at high temperature to give it strength. Extruded particles are then sorted according to size by sieving and add hydrogenating components through impregnation by immersion or widely known methods for the impregnation of water capacity. If produce is R consists of hydrogenating component two metals, they can be added sequentially or simultaneously. The catalyst particles can be ignited between stages of adding metals, as well as after they are added. The finished catalyst should have a surface area of from 300 to 550 m2/g and an average bulk density (ABD) from 0.9 to 0.96 g/cm3.
The hydrocracking catalyst may also contain zeolite Y. it is Implied that the term "zeolite Y", as used here, applies to all crystalline zeolite characterized by a typical powder x-ray diffraction, is shown in U.S. patent 3130007, or a modified zeolite Y, which is characterized by a powder x-ray diffraction, similar to that described in U.S. patent 3130007, but offset to some extent by the period d of the grating, because, as I understand the experts in this field of technology, cationic exchanges progulkami etc. that are generally required to convert the zeolite Y in catalytically active and stable form.
In the method described here can be used as a hydrocracking catalyst zeolite Y, which is characterized by either one or both of the two properties mentioned above, such zeolites Y are modified zeolite Y, in contrast to zeolite Y, reported in U.S. patent 3130007. Used here, the size of the unit cell is the size of the unit cell, defined by the powder roentgenol is the Amma. Preferably, the amount of zeolite Y catalyst hydrocracking less than the number of beta-zeolite, and preferably, the catalyst containing zeolite Y, use on stage, which is relatively high conversion per pass, for example above 70% or above 90%, with the formation of hydrocarbons, wikipaedia within the diesel boiling fraction, and lighter. The preferred zeolite Y get chetyrehstennoy procedure reported in U.S. patent 5350501 and which is incorporated here by reference. Zeolite Y obtained chetyrehstennoy procedure in U.S. patent 5350501 is a zeolite UHP-Y, ultrahydrophobic zeolite Y, as defined in U.S. patent 5350501. The preferred zeolite UHP-Y, is described in U.S. patent 5350501 is a zeolite LZ-10, which is suitable for the hydrocracking catalyst zeolite Y. in Addition, a suitable catalyst for hydrocracking the Y zeolites include zeolites obtained by the method described in U.S. patent 5350501, except for changing the conditions of calcination on the fourth stage of processing in U.S. patent 5350501 thus, in order to obtain the zeolite with the size of the unit cell is less than 24,36 angstroms. The fourth stage of processing in U.S. patent 5350501 comprises calcining the zeolite obtained at the third stage of processing, in the presence of a sufficient quantity PA is s water in the atmosphere, consisting mainly of a pair of or consisting of a pair), such that provides the zeolite with the size of the unit cell is less than 24,40, and most preferably, not more than 24,35 angstroms, and relatively low sorption capacity for water vapor. In addition, a suitable catalyst for hydrocracking the Y zeolites include zeolite Y, which are the result of acid leaching of Y zeolites prepared by the method described in U.S. patent 5350501, or in the acid washing of the zeolite Y prepared by the method described in U.S. patent 5350501 and including a modified fourth stage of processing. As a result of this acid washing of the zeolite Y is removed the extra framework aluminum and can be made by methods known to experts in the given field of technology.
Although it is known that the steaming of the zeolite, such as beta-zeolite, causes changes in the existing crystal structure, the possibilities of modern analytical techniques did not allow to precisely control and/or to characterize these changes at the level of important structural elements of the zeolite.
The situation is even more complicated in the case of beta zeolite in comparison with zeolite Y, as in beta zeolite contains nine different types of tetrahedral aluminum centers and only one in zeolite Y. Vestitoo as indicators of the changes, and extent of these changes are used to measure different physical properties of the zeolite, such as surface area. For example, it is assumed that the decrease in the adsorption capacity of the zeolite hexafluoride (SF6after steam treatment is due to the decrease of the crystallinity of the zeolite or the size of micropores or availability of micropores of the zeolite. This measurement correlates with changes in the zeolite, which may be undesirable, and therefore, SF6the adsorption capacity of hydrocracking catalysts used in the methods disclosed here preferably is relatively high. In one of the embodiments of the methods of hydrocracking disclosed here, SF6the adsorption capacity of the beta zeolite used in the catalyst hydrocracking, regardless of whether he was subjected to steam treatment or not, is at least 28% of the mass. (for example, from 30% to 50 wt. -%).
Although in one embodiment of the method disclosed here, the beta zeolite is not subjected to the steam treatment, in other embodiments, implementation of the beta zeolite could expose the soft, relatively traditional methods used in the art, the steam processing. It was found that under appropriate conditions and with appropriate duration of treatment with beta-zeolite PA is ω ensures catalyst, which can be used in the methods of hydrocracking with achieving the preferred results described here. As mentioned earlier, there is an obvious correlation between total yield of distillate, on the one hand, and the release of LPG and activity of the catalyst, on the other hand, which limits the improvement of the system, which is available when steaming.
Processing of beta-zeolite steam can be successfully implemented in a variety of ways, the method that is actually used in industry, often highly dependent and may be determined by the type and performance of the available hardware. Steaming can be done in the case of zeolite held in the form of a fixed mass or zeolite transported by conveyor belt or mixed in a rotary kiln. Important factors are of equal treatment of all particles of the zeolite under appropriate conditions, duration, temperature and concentration of steam. For example, the zeolite should not be placed so that there is a significant difference between the amount of steam in contact with the surface and internal area of the zeolite mass. In one of the embodiments of the invention beta-zeolite is steamed in an atmosphere containing steam, passing through the equipment, obespechivaya the low concentration of steam. It can be described as stay in the atmosphere with a given concentration of the pair is less than 50 mol%. Concentrations of vapor can be in the range from 1 to 20 mol%. in one of the embodiments of the invention and from 5 to 10 mol%. in another embodiment, and small-scale laboratory operations are distributed in the area of higher concentration. In one of the embodiments of the invention the steam treatment is carried out for a period of time equal to 2 hours or less, or in another embodiment, during the period of time from 1 to 2 hours, in any of these options at a temperature of 600°C (1112°F) or less at atmospheric pressure and a given water vapor content of 5 mol%. or less. In another embodiment of the invention the steam treatment is carried out for a period of time equal to 2 hours or less at a temperature equal to 650°C (1202°F) or less at atmospheric pressure and a given water vapor content is 10 mol%. or less. The magnitude of the water vapor content is determined based on the mass of the vapor in contact with beta-zeolite. Steam treatment at temperatures above 650°C (1202°F), it turns out, leads to the production of zeolite, which cannot be applied in the way described here, because SF6the adsorption capacity obtained beta-zeolite is too low. You can use temperature n the same 650°C (1202°F), moreover, the characteristic temperature of the steam treatment is from 600°C (1112°F) to 650°C (1202°F) in one of the embodiments and below 600°C (1112°F) in another embodiment. To achieve good results, you can use the period of time from 1/2 to 2 hours in one of the embodiments from 1 to 1 1/2 hours in another embodiment. Usually is mutual dependence between time and temperature of the steam treatment, and the temperature increase leads to a reduction in the required time. In a specific embodiment, the method of carrying out the steam treatment on an industrial scale is carried out using a rotary kiln, in which the steam is injected at a rate sufficient to maintain an atmosphere with a concentration of pair 10 mol%.
In one embodiment of the invention, the beta zeolite used in the composition of hydrocracking catalysts described herein are not treated with the acid solution for the implementation of dealumination. In this regard, it should be noted that almost all of the crude (synthesized) zeolite is subjected to treatment with acid in order to reduce the concentration of sodium that remains after the synthesis. This stage of the process of obtaining zeolite is not considered as part of processing the obtained zeolite described here. In one embodiment of the invention, the zeolite is subjected to treatment with acid during the process the AE processing and the preparation of the catalyst only when carrying out additional process steps, such as peptidase, when forming or impregnation of metals. In another embodiment, the zeolite is not acid washed after treatment, steam treatment, for example, to remove the "remains" of aluminum of the day.
In laboratory scale demonstration procedure steam treatment carried out with zeolite, placed in a quartz tube (for example, with a diameter of 6.4 cm (2½ inches), located in the furnace. The furnace temperature is slowly increased by the controller. After the temperature of the zeolite reaches 150°C (302°F), in the lower part of the quartz tube serves pairs generated in the flask with deionized water, and put it up. To achieve the desired water vapor content in the tube can ignore other gas. The flask refill water as needed. In the demonstration procedure, the time interval between the beginning of the steam supply and the achievement of the zeolite to temperatures of 600°C (1112°F) is one hour. At the end of the steam supply temperature of the furnace can be reduced by reinstalling the controller 20°C (68°F). The furnace allowed to cool down to 400°C (752°F) (for example, 2 hours), and then cease transmission of the steam flow in a quartz tube. The sample is removed from the oven at 100°C (212°F) and placed in a laboratory oven, stand over night at 110°C (230°F), in the mode of blowing air.
The beta zeolite used in SOS the Ave of hydrocracking catalysts, described here, can also be characterized from the point of view of the adsorption of SF6. It is a generally accepted method of determining characteristics of microporous materials such as zeolites. It is similar to other measurements of adsorption capacity, such as capacity, the fact that they use the difference in mass to determine the number of SF6that is adsorbed by the sample, which was subjected to pre-treatment to achieve the state, practically free of adsorbate. SF6use in this test due to the fact that the size and shape of the molecule prevents its penetration into the pores with a diameter of less than 6 angstroms. Thus, this technique can be used within a single measurement to determine the reduction of the size of the mouths of available pores and pore size, which is, in turn, measure impact on the zeolite to treatment with steam. In a simplified description of this method, preferably, the sample previously dried in vacuum at 350°C (662°F) and weighed. Then it is subjected to the processing of SF6within one hour, while the temperature of the sample support is 20°C (68°F). The vapor pressure of SF6support with a consistent liquid state SF6equal to 400 Torr (53,3 kPa). The sample is weighed again to determine the amount of adsorbed SF . To facilitate the sample can be left on the Cup weights.
In any mass production process, including methods such as steaming and heating, there is a likelihood that the individual particles will be subjected to various degrees of processing. For example, particles on the bottom of the pile, moving along with the conveyor belt may not be exposed to the same atmosphere or temperature as the particles that cover the top of the pile. This factor should be taken into account during production, as well as the analysis and testing of the finished product. Therefore, it is recommended that when testing any measurement performed on a sample composed of a large number of randomly taken individual granules of the catalyst, in order to avoid misleading measurements, carried out on non-representative sample. For example, measurement of adsorption capacity when using multiple granules, gives an idea of the average adsorption characteristics of all granules and does not show whether the criteria adsorption of an individual particle. The average value of the adsorption characteristics may fit this description, while individual particles, in the case of large differences from particle to particle, its properties are beyond the scope of the data description.
In the layer of catalyst for hydrocracking or reaction region of the heavy hydrocarbon feedstock is subjected to contacting with the above-described hydrocracking catalyst to obtain a stream coming from a hydrocracking unit. Usually heavy hydrocarbons combine with the hydrogen-containing gas stream prior to contact with the hydrocracking catalyst. Most often this hydrogen-containing gas stream is combined hydrogen-containing recycle gas stream, which in General is a combination of (i) enriched hydrogen gas stream separated in the course of the subsequent gas-liquid separation (e.g., in the high pressure separator), and (ii) a relatively small amount of fresh make-up hydrogen is added to replenish the amount of hydrogen consumed in the hydrocracking reactions, and loss process in the form of dissolved hydrogen.
Therefore, the methods of the invention generally relate to the hydrocracking hydrocarbon streams typically used as sources of raw materials hydrocracking (for example, gas oils, such as straight-run gas oil or VGO) in oil refining processes, in which the flow coming from the hydrocracking unit, divided into one or more low-boiling fractions in the form of products (for example, n is fty and diesel fuel) and high-boiling fraction in the form is not turned oil. Separation processes are generally carried out using one or more operations of evaporation and/or distillation, depending on the particular heavy hydrocarbons and streams of the desired product. In a typical embodiment, the invention is not converted oil is obtained as a bottom fraction at the stage of allocation, including a single evaporation flow coming from the hydrocracking unit (optional, after separation of the enriched hydrogen gas stream described above), while the fraction originating from the upper part of the column and containing the transformed (or brakirovochnye) hydrocarbons with lower molecular weight, direct further fractionation to isolate the product flows are usually more valuable than not turned into oil. As described in the aforementioned U.S. patent US 6432297, a single evaporation can be made by the distillation of light fractions, for example, using hydrogen-containing gas stream. The criteria used for selection, is turned oil, determine its composition and the initial boiling point.
Therefore, the converted hydrocarbon fraction isolated in the form of relatively low-boiling fraction (e.g., at least on the temperature of the end of the distillation) flow coming from the hydrocracking unit. This support is giving you can do, for example, after separation of the enriched hydrogen gas stream, as described above, and it is possible after separation of the other recycle gas components and/or after other stages of the removal of light and heavy fractions. In the distillation converted hydrocarbon fraction, therefore, can be obtained as the products of naphtha and diesel fuel. Depending on the needs in the products that define the conditions of fractionation, the final temperature of the distillation product stream containing naphtha, can be varied. For example, the product stream containing relatively light naphtha can be separated from the converted hydrocarbon fraction, with this product is characterized by a finite temperature distillation 149°C (300°F) (for example, fraction from 132°C (270°F) to 160°C (320°F)). According to other variants of the invention, it is possible to separate the product stream containing relatively heavy naphtha characterized by a finite temperature distillation 204°C (400°F) (for example, the fraction of 193°C (380°F) to 216°C (420°F)). The naphtha can be subjected to fractionation to obtain one or more fractions of naphtha, for example, light naphtha, gasoline and heavy naphtha, and specific end-temperature distillation range from 132°C (270°F) to 160°C (320°F), from 168°C (335°F) up to 191°C (375°F) and from 193°C (380°F) to 216°C (420°F) ratio is estwenno. In any nafta or its fractions, characterized discussed above, the final temperature of distillation, initial boiling point typical "head of the faction" or initial boiling point 85°C (185°F) (for example, the fraction of 70°C (158°F) to 100°C (212°F)). According to a characteristic variation of the invention the yield of naphtha (characterized by initial and/or final temperature distillation, in the above-described limits) is generally at least 15% vol. (for example, from 20% to 50% vol.), and usually at least 25%. (for example, from 30% to 45% vol.) in the calculation of the flow coming from the hydrocracking unit.
In the high-boiling fraction is usually desirable to separate from the flow coming from the hydrocracking of hydrocarbons, which boil at temperatures above characteristic limits boiling hydrocarbons diesel fraction. Therefore, not turned into oil, in most cases, is characterized by an initial boiling point (or "head of the faction"), at least 288°C (550°F), typically at least 316°C (600°F), and often at least 343°C (650°F). As discussed above, in many cases, this high-boiling fraction is a smaller part (for example, less than 45% vol.) flow coming from the hydrocracking unit, due to large amount of cracking reactions occurring in the reactor, g is dragracing or reaction zone with the formation of products of lower molecular weight. The final temperature of distillation is not turned oil, usually close to the corresponding temperature VGO, especially in cases where VGO is used as the main component, or the entire fresh component raw materials. Therefore, usually not turned oil is characterized by a finite temperature distillation is not above 593°C (1100°F) (for example, in the range of 510°C (950°F) up to 593°C (1100°F), and often not above 566°C (1050°F).
Not into the oil separated in the form of a high-boiling component (at least in its initial boiling point) of the total flow coming from the hydrocracking unit, from the given output stream, optionally after separation of the enriched hydrogen gas stream (for example, in the high pressure separator). Not into the oil contains a significant quantity of hydrocarbons that are suitable for intermediate basic components of lubricating oils, specifically saturated and isomerized (branched) hydrocarbons. The low content of sulfur, nitrogen and metals are not converted oil in comparison with fresh raw material hydrocracking, and combined with the heavy hydrocarbon feedstock is also favorable for intermediate basic components of lubricating oils.
Therefore, while the part not turned by the oil return in the hydrocracking reactor to increase efficiency the efficiency, narziklov part can be used as intermediate basic components of lubricating oils, optionally after one or more additional stages of processing, such as Hydrotreating to further improve the content of saturated compounds not converted oil and additional lowering of the content of impurities of nitrogen and sulfur. According to some versions of the invention precisava part is a lower part (for example, from 5% to 45% wt.) not into oil, while in other embodiments of the invention precisava part is the main part (for example, at least 50% to 95% of the mass.) not turned into oil. Running process (i.e. no recycling is not converted oil) is another variant of the invention, according to which you can implement the methods of hydrocracking. Therefore, precisava part is not converted oil may constitute all or substantially all (for example, more than 95%) are not converted oil emitted as high-boiling fractions of the flow coming from the hydrocracking unit.
Preferably, not turned into oil according to some variants of the invention are used as intermediate basic components of lubricating oils without separate stages hydro is somersalo or dewaxing, due to the significant degree of isomerization of heavy hydrocarbons, already achieved in combination with cracking according to the methods described above. Specifically, not into the oil secreted directly from the stream coming from the hydrocracking unit, can be characterized by a sufficiently low pour point for use as intermediate basic components of lubricating oils, without contact with a catalyst containing a noble metal (e.g. platinum or palladium), traditionally used to lower the freezing temperature.
Stage Hydrotreating, when it is used, as described above, includes contacting nerusilova part not turned oil with a Hydrotreating catalyst in the reactor moderate or reaction zone. Specifically, at least some, and usually all narziklov share not turned oil, optionally in combination with another hydrocarbon stream for which the Hydrotreating can also be effective, is subjected to contact with a catalyst for Hydrotreating feedstock to Hydrotreating reactor with the aim of obtaining intermediate basic components of lubricating oils. Therefore, the intermediate base components of lubricating oils may contain at least part nerusilova part not turned oil PEFC is the implementation of Hydrotreating for example, to reduce the sulfur content. Hydrotreating in most cases includes introduction to the Hydrotreating reactor or reaction zone separate hydrogen-rich gas stream, which may contain enriched hydrogen gas stream or the combined recycle gas stream obtained by hydrocracking, as described above.
Hydrotreating generally carried out in the presence of a Hydrotreating catalyst at an average temperature from 288°C (550°F) to 454°C (850°F), partial pressure of hydrogen is from about 6.2 MPa (800 psi) to 17.2 MPa (2500 psi) and flow rate of the liquid (LHSV) of 0.5 h-1up to 3 h-1. Suitable Hydrotreating catalysts typically contain a metal selected from the group consisting of platinum, palladium, Nickel, cobalt, tungsten, molybdenum and mixtures thereof, on a refractory inorganic oxide carrier. The Hydrotreating catalyst may be the same as the hydrocracking catalyst, or otherwise. Hydrotreating at least part nerusilova part not turned by the oil obtained in the hydrocracking process may lead to additional improve the various properties of semi-basic components of lubricating oils, for example, higher viscosity index, resistance to oxidation, thermal stability and/or low-temperature fluidity and lower lettuces and toxicity.
Intermediate basic components of lubricating oils obtained by the above methods, containing hydrocracking and, optionally, Hydrotreating, preferably complies with the standards established by the American petroleum Institute (API) base oil lubricants group II or group III. Technical specifications for oil, group II and group III include at least 90% of the mass. saturated hydrocarbons and not more than 300 ppm of the mass. total sulfur. According to the technical conditions, the viscosity index (VI) for oils group II and group III is within (i) from 80 to less than 120 and (ii) at least 120 respectively. A high index VI is important from the point of view of resistance grease to the "dilution" at higher temperatures of the engine. Intermediate basic components of lubricating oils, as a rule, is transparent and colorless.
Therefore, aspects of this invention involve hydrocracking of various types of heavy hydrocarbons during their simultaneous hydroisomerization. The catalyst used for the implementation of the combined reactions, can be placed in a single reactor. In some cases it may be desirable to use different, from the point of view of their composition, types of catalysts in different layers inside the reactor. Various types of catalysts can also be mixed, for example, to get on the popular mixed catalyst layer. According to other variants of the invention, it is possible to use two or more separate reactor for implementing the above-described reactions of hydrocracking and hydroisomerization depending on the need for different reactions or different stages of these reactions in individual operating conditions (e.g., total pressure or partial pressure of hydrogen) and/or a need to add or remove threads (for example, hydrogen or hydrocarbons) between stages or reactors.
As discussed above, the specific aspects of the invention relate to methods, which eliminate traditional single stage hydroisomerization selected relatively high-boiling fraction stream coming from the hydrocracking unit (for example, nerusilova part not turned oil, as described above). Therefore, according to certain variants of the invention are not converted oil is not subjected to any catalytic hydroisomerization or catalytic dewaxing to reduce its pour point. Alternatively, according to other variants of the invention are not transformed the oil is subjected to contact with a catalyst containing an expensive noble metal such as platinum or palladium, to reduce its pour point. In d the natives additional embodiments of the invention, in which the hydrocracking unite with Hydrotreating, as described above, the raw material hydrotreater unit is characterized by almost the same pour point, and that precisava part not turned by the oil separated from the flow coming from the hydrocracking unit. For example, the freezing temperature can be identical or differ by a maximum 5°C (9°F), indicating the feasibility of the elimination of the intermediate stage (for example, hydroisomerization or dewaxing)designed to substantially lower the pour point of the feedstock Hydrotreating.
The drawing shows a simplified typical technological scheme of the process, illustrating a variant implementation of the methods described above. Details, including pumps, measuring and control equipment, circuit heat exchange and heat recovery, and other items not essential to the understanding of the invention, not shown. You must understand that this drawing is an illustration of the invention and/or its principles. As is obvious to a person skilled in the art having knowledge of the details of the present description, the methods according to various other variants of the invention include configurations, components, and operating parameters determined, in part, specific types ishodnoj the raw materials, products and technical requirements for the quality of products.
According to a variant of embodiment shown in the drawing, the source of heavy hydrocarbon raw material 1 contains a mixture of (i) recycle part 11 is not turned oil 16 and (ii) VGO 12 as fresh component raw materials. Heavy hydrocarbon feedstock 1 is added to the combined recycle gas stream 2, which is a mixture of enriched hydrogen gas stream 5, is obtained from the separator 30 to the high pressure, and fresh make-up hydrogen stream 4. As shown in the diagram, and dedicated enriched hydrogen gas stream 5, and fresh make-up hydrogen stream 4 is fed to the suction or input (or alternatively, served on the discharge or output) cycle compressor 40. United raw stream 17 is then subjected to contact with a hydrocracking catalyst in a hydrocracking zone 20. As noted above, the conditions and the catalyst in the hydrocracking zone 20 are such that the conversion of the hydrocarbons with lower boiling points (e.g., boiling within the diesel boiling fraction and below)contained in the stream 3, extending from hydrocracking, is significant. In addition, the degree of hydroisomerization hydrocarbons contained in the thread 3 extending from the hydrocracking unit is sufficient for ponies who placed the freezing temperature of the high-boiling fraction or not converted oil 16, as also noted above.
Part of the thread 3 extending from hydrocracking, namely the liquid part 6 (or degassed part), after separation of the enriched hydrogen gas stream 5 in the separator 30 high-pressure, direct to the stage 50 separation (for example, the second separator evaporation or distillation column) to obtain in the form of liquid cubic product is not converted oil 16 in the form of vaporous head product fractions 7 converted hydrocarbons, including products subjected to hydrocracking and contains hydrocarbons with lower boiling point, which can be divided into the following flows of products, such as light naphtha 8, gasoline 9 and diesel fuel 10 fractionation in a distillation column 60. To the specified stream split products fraction 7 converted hydrocarbons from the stage 50 of the separation can be subjected to one or more additional operations division, for example in the low pressure separator (not shown), which enables the removal of additional quantities of dissolved hydrogen and lower side of hydrocarbons, LPG and other light gases such as hydrogen sulfide. You can use one or more distillation columns for separation of naphtha, diesel fuel and other fuel components shall now, depending on the type of processed heavy hydrocarbon feedstock and the desired state of the product. In some cases, using the fractionation may be desirable allocation of the aggregate of the fuel components, such as the overall product naphtha with an end boiling point of 204°C (400°F) can be used to produce a gasoline blending or separation into fractions of light naphtha, gasoline and heavy naphtha otherwise.
The separator 30 is a high pressure, typically operate at almost the same pressure as the hydrocracking zone 20, and a temperature of 38°C (100°F) to 71°C (160°F). Enriched hydrogen gas stream 5 usually provide the major portion of the total quantity of hydrogen in the combined recycle gas stream 2, and the hydrogen consumed in the hydrocracking zone 20 and lost by dissolution, reimburse fresh make-up hydrogen stream 4. In some cases, the thread 3 extending from hydrocracking, is subjected to contact with a water stream (not shown) for the dissolution of ammonium salts (e.g. ammonium chloride)generated in the hydrocracking zone 20 and which may condense in the form of solid by-products on the colder surfaces. This water stream is then removed from the separator 30 to the high pressure as a separate water leaving the second stream.
Not into the oil 16 is divided into recycle part 11, which return the reactor 20 hydrocracking, and narziklov part 13, which can be used as intermediate basic components of lubricating oils. In an alternative embodiment of the invention, representing the instantaneous operating mode, not into the oil 16 is not shared by all not into the oil 16 is subjected to further processing, as discussed below in relation to nerusilova share 13. As shown in the drawing, narziklov part 13 is subjected to contacting with the second hydrogen-containing gas stream 14 (which may contain a portion of the enriched hydrogen gas stream 5, the make-up hydrogen stream 4 and/or combined cycle gas stream 2) prior to the introduction of the combined raw materials 18 in Hydrotreating reactor hydrocity or reaction zone 70. Hydrotreating reduces the content of unsaturated hydrocarbons and other beautification nerusilova share of 13, as discussed above, with the aim of obtaining product 15 Hydrotreating, specifically as intermediate basic components of lubricating oils.
In General, aspects of the invention are intended for use of hydrocracking catalysts and operating conditions with the aim of turning the original heavy hydrocarbons into valuable products, is also hydroisomerization high-boiling fraction, which is identified as the intermediate base component lubricating oils, optionally, after the stage hydrotreatment. Specialists in the art will recognize the advantages of the methods described here, from the point of view of the possible exceptions of the traditional stage of the process, namely a separate stage of hydroisomerization not turned oil and the resultant catalyst and equipment, to achieve the effect of this substantial savings. Therefore, the processes described herein may consist of or mainly composed of the stages of hydrocracking and, optionally, Hydrotreating order to obtain intermediate basic components of lubricating oils, without any significant additional process steps, including hydroisomerization or dewaxing.
From the point of view of this disclosure it is seen that it is possible to extract some of the other benefits, and other preferred results. The applicability of the disclosed here are methods to any number of processes hydrocracking and especially the processes, including the production of semi-basic components of lubricating oils, it becomes obvious from the point of view of the present disclosure. Specialists in this field of technology, with information gleaned from the present disclosure, understand that in the above-mentioned methods, you can make various treason the Oia within the scope of the present disclosure. The mechanisms used to explain theoretical or observed phenomena or results are interpreted only as illustrative and in no way limit the scope of the attached claims.
The following examples are set forth as typical examples of the present invention. These examples should not be construed as limiting the scope of the invention, since these and other equivalent embodiments of the invention are obvious from the point of view of this disclosure and the accompanying claims,
The vacuum gas oil was subjected to hydrocracking in the presence of (i) traditional hydrocracking catalyst (catalyst A)containing Nickel and tungsten on a bound zeolite LZ-15 and (ii) of the catalyst (the catalyst)containing these metals, but put on associated beta-zeolite. For each of the two tested catalysts hydrocracking conditions were changed in order to achieve a pass 55%, 70% and 85% (by volume) VGO conversion into hydrocarbons boiling within the diesel fraction, and lighter substances. Not into the oil, characterized by the boundary boiling point of the head of the faction of 382°C. (720°F), then analyzed in each case and the results of this analysis for different values of conversion per pass to the following tables:
|Conversion of 55% for passage in the calculation of the total volume of liquid|
Properties of products with boundary boiling point >720°F. (382°C)
|The total mass conversion, %||52,5||53,2|
|Hydrogen, wt. -%||14,1||14,0|
|Aromatics, wt. -%||6,4||4,4|
|Sulfur, ppm mass.||<10||10,0|
|Viscosity @ 38°C, cSt (mm2/(C)||N/A||30,9|
|Viscosity @ 50°C, cSt (mm2/(C)||the 17.3||19,4|
|Viscosity @ 60°C, cSt (mm2/(C)||12,8||the 13.4|
|Viscosity @ 99°C, cSt (mm2/(C)||5,2||of 5.4|
|Flash point, °F||429,8||404,6|
|Pour point, °F||102,2||48,2||-54,0|
|Microagility residue, % mass.||0,2||0,0|
|Nickel, mass. ppm for ICP||0,0||0,01|
|Vanadium, ppm wt. for ICP||0,01||0,01|
|Initial boiling point, °F||627||604|
|Final boiling point, °F||1039||1033|
|The viscosity index (50-99°C)||138,8||the 122.7|
|The correlation coefficient according to the standards of the US Mining Bureau||12,3||14,6|
|Conversion of 70% per pass in the calculation of the total volume of liquid|
Properties of products with boundary boiling point >720°F. (382°C)
|The total mass conversion, %||67,6||67,6|
|Density, the API||37,1||35,9|
|Hydrogen, wt. -%||14,5||14,0|
|Aromatics, wt. -%||3,3||4,3|
|Sulfur, ppm mass.||7,0||11,0|
|Viscosity @ 38°C, cSt (mm2/(C)||23,7||28,5|
|Viscosity @ 50°C, cSt (mm2/(C)||15,4||18,0|
|Viscosity @ 60°C, cSt (mm2/(C)||11,5||12,4|
|Viscosity @ 99°C, cSt (mm2/(C)||4,8||5,1|
|Flash point, °F||408,2||to 426.2|
|Pour point, °F||96,8||26,6||-70,2|
|Microagility residue, % mass.||0,0||0,0|
|Nickel, mass. ppm for ICP||<0,01||0,01|
|Vanadium, ppm wt. For ICP||0,01||0,01|
|Initial boiling point, °F||580||612|
|Final boiling point, °F||1046||1030|
|The viscosity index (50-99°C)||143,2||120,4||/td>|
|The viscosity index (38-99 degrees C)||136,2||116,8|
|The correlation coefficient according to the standards of the US Mining Bureau||8,7||11,8|
|Conversion of 85% for passage in the calculation of the total volume of liquid|
Properties of products with boundary boiling point >720°F. (382°C)
|The total mass conversion, %||82,1||83,0|
|Hydrogen, wt. -%||14,3||13,9|
|Aromatics, wt. -%||2,3||a 3.9|
|Sulfur, ppm mass.||<5||10,0|
|Viscosity @ 38°C, cSt (mm2/(C)||19,1||25,5|
|Viscosity @ 50°C, cSt (mm2/(C)||12,9||16,2|
|Viscosity @ 60°C, cSt (mm2/(C)||the 9.7||11,3|
|Viscosity @ 99°C, cSt (mm2/(C)||4,2||the 4.7|
|Flash point, °F||408,2||415,0|
|Pour point, °F||86,0||26,6||-59,4|
|Microagility residue, % mass.||0,3||0,0|
|Nickel, ppm wt. for ICP||0,01||0,01|
|Vanadium, ppm wt. for ICP||0,01||0,01|
|Initial boiling point, °F||629||613|
|Final boiling point, °F||996||1014|
|The viscosity index (50-99°C)||137,9||115,2|
|The viscosity index (38-99 degrees C)||136,7||111,1|
The vacuum gas oil was subjected to hydrocracking in the presence of (i) catalyst As described in example 1 and (ii) of the catalyst described in example 1, and (iii) the layer sequence is determined as being the placement of catalysts, including the catalyst, described in example 1, and the catalyst containing Nickel and tungsten in different amounts relative to the catalyst, but also applied to the related beta-zeolite. The sequential placement of the layer of hydrocracking catalysts used a ratio of 70% / 30% of the mass. the catalyst/catalyst C. For the tested layers of catalysts for hydrocracking conditions made it possible to achieve 70%conversion per pass (by volume) VGO in hydrocarbons boiling within the diesel fraction, and lighter substances. Not into the oil, characterized by the boundary boiling point of the head of the faction of 382°C. (720°F) and then analyzed in each case and the results of this analysis are summarized below in table 4:
|Conversion of 70% per pass in the calculation of the total volume of fluid Properties products with boundary boiling point >720°F. (382°C)|
|The total mass conversion, %||67,6||67,6||68,1|
|Hydrogen, wt. -%||14,5||14,0||14,2|
|Aromatics, wt. -%||3,3||4,3||3,7|
|Sulfur, ppm mass.||7,0||11,0||21,0|
|Viscosity @ 38°C, cSt (mm2/(C)||23,7||28,5||24,9|
|Viscosity @ 50°C, cSt (mm2/(C)||15,4||18,0||16,2|
|Viscosity @ 60°C, cSt (mm2/(C)||11,5||12,4||the 11.6|
|Viscosity @ 99°C, cSt (mm2/(C)||4,8||5,1||4,8|
|Flash point, °F||408,2||to 426.2||437,0|
|Temperature tasty the project, °F||96,8||26,6||27,0|
|Microagility residue, % mass.||0,0||0,0||0,0|
|Nickel, ppm wt. for ICP||0,01||0,01||0,0|
|Vanadium, ppm wt. for ICP||0,01||0,01||0,01|
|Initial boiling point, °F||580||612||706|
|Final boiling point, °F||1046||1030||1028|
|The viscosity index||135||117,||128,4|
As shown by the results obtained in examples 1 and 2, when comparing the values of conversion of each of the tested catalysts hydrocracking produces similar values of density (API gravity); hydrogen, aromatic compounds, sulfur and impurities of metals (Nickel and vanadium); characteristics of distillation, flash point and other characteristics. But not into the oil separated from the flow coming from the hydrocracking reactor containing the catalyst in examples 1 and 2, or sequentially placed layers of catalyst b and catalyst C in example 2, was characterized by a significantly lower pour point, and in each case it was below 10°C (50°F), whereas a conventional catalyst, catalyst A, was provided not turned oil, characterized in all cases, the pour point above 29°C (85°F). A significant lowering of the freezing temperature is not turned oil, the resulting zone hydrocracking catalyst In one or in sequential placement with catalyst (C)comprising a carrier containing a beta zeolite, has important implications for the use of this not converted oil as intermediate basic components of the blur is cnyh oils. In particular, low pour point indicates the product, traditionally subjected hydroisomerization or dewaxing (for example, on a separate reaction stage), which can be used as intermediate basic components of lubricating oils after a small hydroisomerization or without additional hydroisomerization (for example, in a separate reactor after hydrocracking, and possibly in the presence of platinum or palladium metal catalyst).
Moreover, the results obtained for the successive layers of catalysts b/C demonstrate that the catalysts described here can be used in separate layers or areas for additional improvement or optimization of properties not developed oil, as shown in the example of high viscosity index, obtained using the sequential placement of the catalyst layer, compared with the same catalyst Century, Specialists in the art taking into account that the conditions used for Hydrotreating not turned oil, characterized by the properties described in the examples and described herein in other places, can be modified to meet desired technical specifications that includes saturated hydrocarbons and sulfur and a viscosity index.
1. The method according to the teachings of the base oil,
(a) hydrocracking a heavy hydrocarbon feedstock in the presence of a hydrocracking catalyst containing a predetermined amount less than 15% of the mass. beta zeolite with obtaining flow coming from the hydrocracking unit containing at least 40% of the mass. hydrocarbons boiling at a temperature below 382°C (720°F), and
b) separation from the flow coming from the hydrocracking unit, not into the oil with a pour point not higher than 18°C (65°F) in the form of a high-boiling fraction containing the base oil.
2. The method according to claim 1, wherein the base oil contains narziklov part is not turned oil, separated in stage (b).
3. The method according to claim 1 or 2, in which the base oil characterized by a viscosity index equal to at least 100.
4. The method according to claim 2, in which narziklov part is not converted oil is subjected to Hydrotreating, obtaining a base oil containing at least 90% of the mass. saturated hydrocarbons.
5. The method according to claim 3, in which narziklov part is not converted oil is subjected to Hydrotreating, obtaining a base oil containing at least 90% of the mass. saturated hydrocarbons.
6. The method according to claim 1, in which the heavy hydrocarbon feedstock contains vacuum gasoil.
7. The method according to claim 1, in which the heavy hydrocarbon feedstock contains the recycle part is not preveden the oil, separated in stage (b).
8. The method according to any one of claims 1, 2, 4-6, in which the hydrocracking is carried out in the presence of a specified hydrocracking catalyst containing a metal selected from the group consisting of Nickel, cobalt, tungsten, molybdenum and mixtures thereof.
9. The method according to claim 3, in which the hydrocracking is carried out in the presence of a hydrocracking catalyst containing a metal selected from the group consisting of Nickel, cobalt, tungsten, molybdenum and mixtures thereof.
10. The method according to claim 1, containing:
the hydrocracking of the specified heavy hydrocarbon feedstock containing vacuum gas oil and recycle the part not turned oils, hydrocracking zone containing hydrocracking catalyst to obtain a stream coming from the hydrocracking unit and containing at least 55% of the mass. hydrocarbons boiling at a temperature below 382°C (720°F);
passing at least part of the flow coming from the hydrocracking unit, the separator evaporation for the implementation of the said stage of separation of obtaining (i) of the said high-boiling fraction in the form of liquid cubic product and (ii) a vaporous head product;
the return cycle of the part not turned oil in a hydrocracking zone; and Hydrotreating nerusilova parts are not converted oil to reduce the content of unsaturated hydrocarbons in reciclavel part and obtaining a base oil;
the hydrocracking catalyst contains a metal selected from the group consisting of Nickel, cobalt, tungsten, molybdenum and mixtures thereof, deposited on a beta-zeolite.
11. The method according to claim 10, in which not transformed the oil obtained in stage (b), do not put hydroisomerization or dewaxing.
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
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
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: power engineering.
SUBSTANCE: method is described to produce hydrocarbon fractions, which may be used as diesel fuel or as components of diesel fuel, based on a mixture of biological origin, containing ethers of fatty acids, possibly, with a certain amount of free fatty acids, which includes the following stages: 1) hydrodesoxygenation of a mixture of organic origin; 2) hydroisomerisation of a mixture produced at the stage (1), after possible treatment for cleaning; besides, the specified stage of hydroisomerisation is carried out in presence of a catalytic system, which contains the following: a) a carrier of acid nature, including a fully amorphous micro-mesoporous silicon-aluminium oxide, having a mole ratio SiO2/Al2O3 in the range from 30 to 500, the surface area of more than 500 m2/g, volume of pores in the range from 0.3 to 1.3 ml/g, the average diameter of pores below 40 Ǻ, b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of the group VIII.
EFFECT: production of a hydrocarbon fraction, which may be applied as diesel fuel or as a component of diesel fuel.
55 cl, 4 tbl, 3 dwg, 2 ex
SUBSTANCE: invention relates to a method of producing jet fuel for supersonic aircraft via hydrogenation and subsequent hydrodewaxing of secondary petroleum material in the presence of a hydrogen-containing gas and catalysts, at high temperature and pressure in two hydrogenation reactors and in a hydrodewaxing reactor. The secondary material used is a mixture of gas oils from catalytic cracking and delayed coking in ratio from 90%-10% to 70%-30% and straight-run gas oil is further added in amount of not more than 30 wt % based on the total load of the material, wherein the straight-run gas oil is fed into the top part of the first or second hydrogenation reactor or in different fractions into the top part of the first and second hydrogenation reactors, wherein the hydrogenation reactors are loaded with nickel sulphide - tungsten catalyst, and the hydrodewaxing reactor is 70% loaded with a molybdenum catalyst on a zeolite support, and 30% by a nickel sulphide - tungsten catalyst.
EFFECT: wider range of raw material resources for producing scarce jet fuel for supersonic aircraft, improved technological effectiveness of the process owing to a simple temperature control scheme in the reaction zone and high output of the end jet fuel.
3 cl, 3 ex
SUBSTANCE: invention relates to a method for synthesis of branched olefins, said method involving dehydrogenation of an isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms on a suitable catalyst. Said isoparaffin composition is obtained via hydroisomerisation a paraffin composition and contains paraffin containing 7-18 carbon atoms. Said paraffins, at least some of their molecules, are branched, where content of branched paraffins in the isoparaffin composition is equal to at least 50% of the weight of the isoparaffin composition. The average number of branches per paraffin molecule is between 0.5 and 2.5 and the branches include methyl and optional ethyl branches. Said branched olefins contain 0.5% or less quaternary aliphatic carbon atoms. Said paraffin composition is obtained using Fischer-Tropsch method. The invention also relates to methods of producing a branched alkyl aromatic hydrocarbon and branched alkylaryl sulphonates including the method described above.
EFFECT: high versatility and cost effectiveness of the method.
7 cl, 19 ex
FIELD: oil and gas production.
SUBSTANCE: procedure consists in following stages: (a) there is performed hydrocarbon raw stock hydraulic processing by means of gas enriched with hydrogen for production of hydraulically treated output flow containing mixture of fluid and vapour; mixture of fluid and vapour is separated into liquid phase and vapour phase; (b) liquid phase is separated to controlled liquid part and excessive liquid part; (c) vapour phase is connected with excessive liquid part for production of vapour-liquid part; (d) there is extracted fraction containing raw stock for FCC from controlled liquid part and simultaneously there is performed hydro-cracking of vapour-liquid part for production of diesel-containing fraction or there is performed hydro-cracking of controlled liquid part for production of diesel containing fraction and simultaneously there is extracted fraction containing raw stock for FCC from vapour-liquid part. The invention also refers to the device for implementation of the procedure of hydraulic cracking with partial conversion.
EFFECT: production of diesel fuel with ultra-low content of sulphur and substantially better combustibility.
9 cl, 3 ex, 4 tbl, 4 dwg
FIELD: oil and gas industry.
SUBSTANCE: invention refers to production of hydrocarbon fuel. The invention relates to the method including heavy charge suspension hydrocracking with obtained products of suspension hydrocracking; separation of the above products of suspension hydrocracking with obtainment of a tar pitch flow and a flow of heavy vacuum gas oil; mixing of at least a part of tar pitch with solvent in order to dissolve a part of tar pitch in the solvent; mixing of the dissolved part of tar pitch with at least a part of heavy vacuum gas oil with production of a composite product. The invention is related also to a device for hydrocarbon fuel and composite production.
EFFECT: producing turbine or bunker fuel with characteristics acceptable for burning in gas turbines or for producing different grades of bunker fuel.
1 cl, 1 dwg, 4 tbl, 3 ex
FIELD: oil and gas industry.
SUBSTANCE: invention refers to a hydrocracking method of hydrocarbon raw material containing 200 ppm - wt 2% of asphaltenes and/or more than 10 ppm wt of metals. The method involves hydrodemetallisation at least in two reaction zones of periodic action, which contain a hydrodemetallisation catalyst and possibly hydrodenitration; then, hydraulic cleaning to reduce content of organic nitrogen with further hydrocracking in a fixed bed and by a distillation stage.
EFFECT: invention provides a possibility of direct treatment of raw material types containing the amounts considerably exceeding known specifications; those raw material types can be treated individually or in a mixture, thus maintaining durability of a traditional cycle.
18 cl, 4 ex, 1 dwg
SUBSTANCE: invention relates to a method of converting heavy hydrocarbon material to lighter hydrocarbon products and separating coal tar, which involves hydrocracking the heavy hydrocarbon material suspended with a granular solid material in the presence of hydrogen in a hydrocracking reactor to form a hydrocracked stream containing vacuum gas oil and coal tar. Gas oil is separated from coal tar in a first vacuum column and further separation of vacuum gas oil from coal tar is carried out in a second vacuum column. The invention also relates to apparatus for converting heavy hydrocarbon material to lighter hydrocarbon products and separating coal tar.
EFFECT: obtaining coal tar from which particles capable of being transformed without sticking can be prepared.
10 cl, 2 dwg, 1 tbl, 1 ex
SUBSTANCE: invention relates to a sinter composition suitable for transportation, which contains hydrocarbon material which boils at temperature higher than 538°C and which contains not more than 30 wt % vacuum gas oil, 1-20 wt % organic residue which is insoluble in toluene, and having hydrogen concentration of not more than 7.3 wt % with respect to an ash-free base, having initial softening temperature of at least 66°C.
EFFECT: less sticky sinter composition which can be granulated and transported without agglomeration.
7 cl, 3 dwg, 2 tbl, 2 ex
FIELD: oil and gas industry.
SUBSTANCE: invention refers to oil stock quality improvement. This invention relates to method of improvement of refining residues quality including residues hydrocracking at the first stage (14) of reaction with formation of flow passing from the first stage; hydrocracking of fraction of asphalt-free oil at the second stage (22) of reaction with formation of flow passing from the second stage; supply of flow passing from the first stage and the flow passing from the second stage to separating system (26); fractioning of flow passing from the first stage and the flow passing from the second stage in separating system (26) with extraction of at least one distillate hydrocarbon fraction and residual hydrocarbon fraction; and supply of residual hydrocarbon fraction to the plant (32) of grout deasphalting obtaining fraction of asphaltens and fraction of asphalt-free oil.
EFFECT: increasing general conversion of residue.
17 cl, 4 dwg, 1 tbl, 1 ex
SUBSTANCE: invention relates to the improved method of obtaining the metal nanoparticles for use in thermocatalytic processes of hydrocarbon crude refining. The method of obtaining the metal nanoparticles includes their recovery from organic metal salt in the thermal treatment conditions in a hydrocarbon crude medium, and the recovery is carried out of the organic salt having the formula M(OOC-R)n or M(SOC-R)n, wherein R represents alkyl, aryl, C17H33-, isoalkyl, tert-alkyl, alkylaryl, diethylamino-, possibly comprising a hydroxyl or amino group, n=1-3, and M represents a metal of the elements of the periodic table, at a temperature above the decomposition temperature of the said organic salt. The size of the nanoparticles obtained is preferably 1-100 nm.
EFFECT: improvement of the method of obtaining.
4 cl, 11 ex, 4 dwg, 1 tbl
SUBSTANCE: invention relates to a method for hydroconversion of heavy oil selected from crude oil, heavy crude oil, asphalt from tar sands, distillation residues, distillation heavy fractions, deasphalted distillation residues, plant oils, oils obtained from coal and oil shale, oils obtained by thermal decomposition of wastes, polymers, biomass, involving feeding heavy oil into a hydroconversion zone, said hydroconversion being carried out in one or more fluidised-bed reactors in which hydrogen is fed, in the presence of a suitable heterogeneous supported hydrogenation catalyst which is made of a support and an active phase which consists of a mixture of sulphides, one of which is obtained from a group VIB metal and at least one more is obtained from a group VIII metal, and a suitable hydrogenation catalyst which is a Mo or W sulphide-based catalyst, which is nanodispersed in said heavy oil, and feeding a stream from the hydroconversion zone into a separation zone in which the separated liquid fraction containing the nanodispersed catalyst is recycled into the fluidised-bed reactor(s).
EFFECT: high degree of hydrodenitrogenation and hydrodesulphurisation, high output of the diesel fraction.
15 cl, 1 dwg, 1 ex, 2 tbl
FIELD: oil and gas industry.
SUBSTANCE: invention refers to the method for obtaining hydrogen-bearing gaseous fuel in a turbine-generator plant. The invention refers to a multistage method for obtaining hydrogen-bearing gaseous fuel with a closed cycle, which involves start-up of the process in a forced warm-up mode and implementation of the process in a standard self-heating mode involving the introduction of hydrocarbon component and water by pressure injection, heating, fuel return to the ignition zone for formation of flame. The fuel obtaining process is performed at many stages with separate introduction of hydrocarbon component and water to a process cylinder heated with the flame and separated into isolated steps as per the number of stages of the fuel obtaining process; water is introduced at the first stage, heated till water vapour is formed; at further stages, hydrocarbon component is introduced and mixed with water vapour; then, vapour and hydrocarbon mixture is heated additionally and warmed up to the temperature of formation of hydrogen-bearing gaseous fuel, the flow of which is returned to the ignition zone to provide flame combustion. The invention also deals with heat gas generator plant to obtain hydrogen-bearing gaseous fuel.
EFFECT: stable and safe processes of obtaining hydrogen-bearing gaseous fuel is aimed at reducing power consumption and flow rate of hydrocarbon component in fuel.
11 cl, 6 dwg, 1 tbl
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: oil and gas industry.
SUBSTANCE: invention refers to the method implemented in vortex reactor with volume of 1-20 litres, through which processed raw material is passed together with hydrogen of 0.1 to 0.8 wt % of weight of initial raw material at excess pressure of 0.01-0.5 MPa and temperature of 380-450°C, rotor speed of vortex reactor of 2000 to 10 000 rpm and power of rotor drive of 30 kW to 5 MW.
EFFECT: increasing the output of light distillate fractions and obtaining only commercial products: diesel fractions and tar oil - raw material for bitumen production at considerable simplicity of method and high process technological effectiveness.
4 ex, 1 dwg
SUBSTANCE: claimed invention relates to synthesis of molecular sieves. Claimed is molecular-sieve material EMM-13, which has framework of tetrahedral atoms, connected with bridges from oxygen atoms, characterised by specific atomic coordinates of elementary cell in nanometers. Material is characterised by specific X-ray image. Claimed material is used as catalyst of hydrocarbon conversion.
EFFECT: obtaining novel material, possessing activity and stability in catalytic reactions of hydrocarbon conversion.
13 cl, 17 dwg, 8 tbl, 17 ex