CN109777494B - Method for producing high-quality gasoline and diesel oil by catalyzing diesel oil - Google Patents
Method for producing high-quality gasoline and diesel oil by catalyzing diesel oil Download PDFInfo
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Abstract
The invention discloses a method for producing high-quality gasoline and diesel oil by catalyzing diesel oil, which comprises the following steps: (1) mixing high aromatic catalytic diesel oil and recycle hydrogen, and allowing the mixture to enter a hydrofining reaction zone I for reaction; (2) mixing the generated oil obtained in the step (1) with recycle hydrogen, and allowing the mixture to enter a hydrofining reaction zone II for reaction, wherein the reaction temperature is 30-120 ℃ higher than that of the hydrofining reaction zone I; (3) cutting the generated oil obtained in the step (2) into a light component and a heavy component; (4) mixing the light components obtained in the step (3) with recycle hydrogen, allowing the mixture to enter a hydro-upgrading reaction zone, and separating the generated oil to obtain a gasoline fraction and a diesel fraction; (5) mixing the heavy components obtained in the step (3) with circulating hydrogen, allowing the mixed heavy components and the circulating hydrogen to enter a hydro-conversion reaction zone, allowing the generated oil to pass through a separation system to obtain gas, gasoline and diesel oil fractions, mixing the gasoline obtained in the step (4) with the gasoline obtained in the step (5) to obtain a qualified gasoline product, and mixing the diesel oil obtained in the step (4) with the diesel oil obtained in the step (5) to obtain a qualified diesel oil product. The method can produce high-quality fuel oil products, and has the characteristics of low chemical hydrogen consumption and flexible product structure adjustment compared with other technologies.
Description
Technical Field
The invention relates to the field of petroleum refining. In particular to a method for producing high-quality gasoline and high-quality diesel oil by treating catalytic diesel oil.
Background
Catalytic cracking is the most important secondary process in the petroleum refining industry at present, and is also the core process for heavy oil lightening. With the increasing weight of global petroleum, the processing capacity of the FCC device is continuously improved, various heavy oils are used as raw materials, the main product gasoline with high octane number is obtained through catalytic cracking reaction, and simultaneously, a large amount of catalytic diesel oil with high sulfur, nitrogen and aromatic hydrocarbon contents, low cetane number or cetane index and extremely poor stability is generated. And the requirements of environmental protection laws and regulations are increasingly strict, and the indexes of diesel products are gradually improved, so that strict requirements are imposed on the sulfur content, the aromatic hydrocarbon content, the cetane index and the like in the diesel products. Therefore, while the yield of the poor diesel oil is reduced, a proper method needs to be found for processing the poor diesel oil so as to meet the requirements of product delivery of enterprises.
The catalytic hydrogenation technology has important significance for improving the processing depth of crude oil, reasonably utilizing petroleum resources, improving product quality, improving yield of light oil and reducing atmospheric pollution, particularly has more remarkable importance for catalytic hydrogenation under the condition that the weight of the current petroleum resources is changed and the quality is deteriorated, can improve the hydrogen-carbon ratio in fuel oil products, optimizes product quality and improves emission standard through proper hydrogenation, becomes an indispensable component in the field of petrochemical industry at present, and can be divided into hydrogenation treatment and hydrocracking in the main process.
The catalytic diesel oil has very bad properties, so the current treatment means is single, and in China, the means which can be relied on mainly comprises the combined processing of the catalytic diesel oil and hydrogenation technology, such as the hydrofining after mixing the catalytic diesel oil and the straight-run diesel oil, the hydrocracking after mixing the catalytic diesel oil and the straight-run wax oil and the conversion technology which is used for producing gasoline by independently cracking the catalytic diesel oil in recent years.
CN1955257A introduces a method for producing high-quality chemical raw materials in a large quantity, which mainly mixes poor-quality catalytic cracking diesel oil and hydrogenation raw materials in proportion, and then produces catalytic reforming raw materials and high-quality ethylene raw materials by steam cracking through controlling reaction conditions. Although the catalytic cracking poor diesel oil can be processed, the processing path of poor raw materials is increased and the poor raw materials are converted into high-quality products, the proportion of blended catalytic diesel oil is still limited to a certain extent, the amount of the processable catalytic diesel oil is small, and the consumption of hydrogen for processing the catalytic diesel oil under the high-pressure condition is large.
CN103773455A the invention discloses a combined hydrogenation process of animal and vegetable oil and catalytic diesel, which essentially treats catalytic diesel through hydrofining, and although catalytic diesel can be processed through proper raw material proportion, the amount of catalytic diesel which can be blended is very small due to the limit of diesel product indexes, and the problem of treating a large amount of catalytic diesel of a large catalytic oil refining enterprise can not be thoroughly solved.
CN104611029A discloses a catalytic cracking diesel oil hydro-conversion method, wherein catalytic diesel oil and hydrogen gas are mixed and then enter a hydrofining reactor for hydrofining reaction, and then enter a hydrocracking reactor for hydrocracking reaction. Although the high-octane gasoline can be produced by processing and catalyzing diesel components through a certain catalyst grading action, the chemical hydrogen consumption is relatively high, and the requirement on hydrogen resources of enterprises is relatively high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a combined hydrogenation process method for processing catalytic diesel raw materials. On the basis that the system grasps the influence rule of operating conditions such as reaction pressure, reaction temperature and the like on aromatic hydrocarbon saturation, two different hydrofining reaction zones are arranged, and the problem of poor monocyclic aromatic hydrocarbon selectivity of a high aromatic hydrocarbon diesel raw material in the conventional hydrofining process is solved. On the basis, the hydrogenated catalytic diesel is cut and separated, the heavy aromatic components (containing a small amount of single-ring and double-ring aromatic hydrocarbons with long side chains) of three or more rings and the light aromatic components are separated, the heavy components directly generate high-octane gasoline after reaction, and the light components generate high-cetane diesel after ring-opening continuous chain modification reaction. When the catalytic diesel raw material is treated, all components are independently processed, the pertinence is strong, a high-quality fuel oil product can be produced, and compared with other technologies, the catalytic diesel oil production method has the characteristics of low chemical hydrogen consumption and flexible product structure adjustment.
The invention provides a method for producing high-quality gasoline and diesel oil by catalyzing diesel oil, which comprises the following steps:
(1) high aromatic catalytic diesel oilMixing the obtained product with recycle hydrogen, and allowing the obtained product to enter a hydrofining reaction zone I for reaction, wherein the reaction conditions are as follows: the hydrogen partial pressure is 3-12 MPa, the reaction temperature is 260-450 ℃, and the volume ratio of hydrogen to oil is 300-1500 Nm3/m3And the liquid hourly space velocity is 0.3-4.0 h-1(ii) a The preferable reaction conditions of the I hydrofining reaction zone are that the hydrogen partial pressure is 4-8 MPa, the reaction temperature is 280-350 ℃, and the volume ratio of hydrogen to oil is 500-1000 Nm3/m3The liquid hourly space velocity is 0.5-2.0 h-1；
(2) Mixing the generated oil obtained in the step (1) with recycle hydrogen, and allowing the mixture to enter a II hydrofining reaction zone for further reaction, wherein the reaction conditions are generally as follows: the hydrogen partial pressure is 3-12 MPa, the reaction temperature is 260-450 ℃, and the volume ratio of hydrogen to oil is 300-1500 Nm3/m3And the liquid hourly space velocity is 0.3-4.0 h-1Preferably, the reaction conditions of the II hydrofining reaction zone are that the hydrogen partial pressure is 4-8 MPa, the reaction temperature is 30-120 ℃ higher than that of the I hydrofining reaction zone, and the volume ratio of hydrogen to oil is 500-1000 Nm3/m3The liquid-time volume-air ratio is 0.5 to 1.5 hours lower than that of the hydrofining reaction zone I-1；
(3) The generated oil obtained in the step (2) enters a separation device and is cut into light components and heavy components;
(4) mixing the light components obtained in the step (3) with recycle hydrogen, allowing the mixture to enter a hydro-upgrading reaction zone for hydrocarbon hydrogenation reaction, and allowing the generated oil to pass through a separation system to obtain a gasoline fraction and a diesel fraction with a high cetane number;
(5) mixing the heavy components obtained in the step (3) with recycle hydrogen, allowing the mixture to enter a hydro-conversion reaction zone for hydrocarbon hydro-conversion reaction, allowing the generated oil to pass through a separation system to obtain gas, gasoline and diesel oil fractions, allowing part of the diesel oil fractions to recycle to a II hydro-refining reaction zone, and allowing part of the diesel oil to exit the device;
(6) and (3) mixing the gasoline obtained in the step (4) with the gasoline obtained in the step (5) to obtain a qualified gasoline product, and mixing the diesel oil obtained in the step (4) with the diesel oil obtained in the step (5) to obtain a qualified diesel oil product.
According to the method, the initial boiling point of the high aromatic hydrocarbon catalytic diesel oil in the step (1) is generally 160-240 ℃, and preferably 180-220 ℃; the final boiling point is generally 320 to420 ℃, preferably 350-390 ℃; the aromatic hydrocarbon content is generally more than 50wt%, preferably 60wt% to 99 wt%; the density of the diesel fuel feedstock is typically 0.91 g.cm-3Above, preferably 0.93 g.cm-3The above.
According to the method of the present invention, the high aromatic catalytic diesel oil in step (1) may be a catalytic cracking product obtained by processing any oil species of genus Basidious, for example, may be selected from catalytic diesel oils obtained by processing middle east crude oil, and specifically may be catalytic diesel oil components obtained by processing Iran crude oil, Sauter crude oil, and the like.
According to the method, the hydrofining catalyst adopted in the hydrofining reaction zone I in the step (1) comprises a carrier and a loaded hydrogenation metal. Based on the weight of the catalyst, the catalyst generally comprises a metal component of group VIB of the periodic table of elements, such as tungsten and/or molybdenum, accounting for 10-35 percent of oxide, preferably 15-30 percent; group VIII metals such as nickel and/or cobalt, in terms of oxides, are in the range of 1% to 7%, preferably 1.5% to 6%. The carrier is inorganic refractory oxide, and is generally selected from at least one of alumina, amorphous silica-alumina, silica, titanium oxide and the like. Wherein, the conventional hydrocracking pretreatment catalyst can be selected from various existing commercial catalysts, such as 3936, 3996, FF-16, FF-26, FF-36, FF-46, FF-56, FF-66, UDS-6 and other hydrofining catalysts developed by the Fushun petrochemical research institute (FRIPP); it can also be prepared according to the common knowledge in the field, if necessary.
According to the method of the present invention, the hydrofining catalyst used in the II hydrofining reaction zone in the step (2) and the hydrofining catalyst used in the II hydrofining reaction zone in the step (1) may be the same or different, preferably different.
According to the method, compared with the hydrofining catalyst used in the hydrofining reaction zone I in the step (1), the hydrofining catalyst used in the hydrofining reaction zone II in the step (2) is as follows: the content (calculated by oxide) of the active metal component is 3.0-8.0%; the total acid content of the catalyst is 1.0-2.0 mmol/g, wherein the content of strong acid in the catalyst is not limited, and is preferably 0.01-0.05 mmol/g; the pore volume of the catalyst is reduced by 0.20-0.40 mL/g; the specific surface area is 40-70 m high2/g。
According to the method, the weight ratio of the high aromatic catalytic diesel oil to the circulating diesel oil is 5: 1-1: 5, preferably 3: 1-1: 3.
According to the method of the present invention, the cutting separation in step (3) is a conventional distillation separation operation, and a flash separation or tray separation method well known in the art can be adopted, so as to separate the catalytic diesel into a light part and a heavy part. The cutting temperature of the light diesel oil and the heavy diesel oil is generally 290-350 ℃, and preferably 300-340 ℃. The light component is a liquid phase fraction below the division point, and the heavy component is a liquid phase fraction above the division point.
According to the method of the present invention, the hydro-upgrading catalyst used in the hydro-upgrading reaction zone in step (4) is a hydro-upgrading catalyst containing a molecular sieve, and refers to a general hydrocracking catalyst or a hydro-upgrading catalyst specially used in the present invention. The hydrogenation modification catalyst comprises hydrogenation active metal, a molecular sieve component and an alumina carrier. The general hydrogenation modification catalyst is composed of hydrogenation active metal components such as W, Mo, Co, Ni and the like, a molecular sieve component, an alumina carrier and the like, and the content of the hydrogenation components is 5-40% by taking the weight of the catalyst as a reference. The hydro-upgrading catalyst specially used in the invention comprises WO by weight3(or MoO)3) 13-25 wt%, NiO (or CoO) 3-10 wt%, molecular sieve 5-40 wt% and alumina 5-50 wt%, wherein the molecular sieve can be Y-type molecular sieve. The hydrogenation modification catalyst mainly plays a role in carrying out a saturated ring-opening but continuous chain-breaking hydrogenation modification process on the bicyclic aromatic hydrocarbon. The conventional hydrogenation reforming catalyst can be selected from various commercial catalysts, such as 3963, FC-18 and other catalysts developed by FRIPP. Specific hydro-upgrading catalysts may also be prepared as desired according to common general knowledge in the art.
According to the process of the present invention, the hydrocracking catalyst used in the hydroconversion reaction zone of step (5) is a hydroconversion catalyst comprising a molecular sieve, which is a catalyst specifically prepared according to the process. The hydrocracking catalyst comprises hydrogenation active metal, a molecular sieve component and an alumina carrier. The general hydrocracking catalyst is prepared from W, Mo, Co, Ni, etcHydrogenation active metal component, molecular sieve component and alumina carrier. Hydrocracking catalysts, especially for use in the present invention, comprise WO by weight3(or MoO)3) 8-20 wt%, NiO (or CoO) 4-10 wt%, molecular sieve 20-50 wt% and alumina 5-30 wt%.
In the preferred hydroconversion catalysts for use in accordance with the method of the present invention, the molecular sieve is a small-grained Y-type molecular sieve. The particle size of the small-grain Y-type molecular sieve is 400-600 nm, the infrared total acid is 0.2-0.5 mmol/g, and the proportion of the medium strong acid is more than 75%; the unit cell parameter is 2.430-2.436 nm; SiO 22/Al2O3The molar ratio is 10-70; the pore volume is 0.5-0.8 cm3The proportion of the secondary pore volume of 2-8 nm in the total pore volume is more than 55%. The Y-type molecular sieve has more accessible and exposed acid centers, is beneficial to the diffusion of hydrocarbon molecules, can improve the preferential conversion capacity of cyclic hydrocarbon, particularly tricyclic aromatic hydrocarbon, directionally saturates and breaks the aromatic ring in the tricyclic aromatic hydrocarbon, and produces the gasoline component with high octane number to the maximum extent. The hydroconversion catalyst containing the small-grain Y-shaped molecular sieve has the main function of performing selective reaction on tricyclic aromatic hydrocarbon in raw materials, and has poor selectivity on non-tricyclic two-ring and monocyclic aromatic hydrocarbon. The Y-type molecular sieve has a certain difference with the conventional Y-type molecular sieve, the grain size of the conventional modified molecular sieve is generally 800-1200 nm, and the pore volume is 0.35-0.50 cm3The proportion of the pore volume of the secondary pores of 2-8 nm to the total pore volume is generally 30-50%, and the proportion of the medium-strong acid is 50-70%. The hydroconversion catalyst may be used to prepare a satisfactory catalyst in accordance with common general knowledge in the art, as described above.
The "medium strong acids" are conventional knowledge well known to those skilled in the art in accordance with the process of the present invention. In the field of catalyst preparation, NH is adopted as medium-strong acid3TPD was analyzed, with 150 ℃ desorption defined as weak acid, 250 ℃ desorption defined as medium strong acid, and 400 ℃ desorption defined as strong acid.
According to the method of the present invention, the operation conditions of the hydro-upgrading reaction zone in the step (4) are as follows: the volume space velocity is 0.5-4.0 h-1Preferably 0.8 to 2.5 hours-1(ii) a HydrogenThe partial pressure is 4-13 MPa, preferably 6-10 MPa; the volume ratio of the hydrogen to the oil at the inlet is 300: 1-800: 1, preferably 400: 1-700: 1; the reaction temperature is 340-410 ℃, preferably 360-400 ℃.
According to the method of the present invention, the operating conditions of the hydroconversion reaction zone in step (5) are as follows: the space velocity is generally 0.5-4.0 h-1Preferably 0.8 to 2.5 hours-1The pressure is generally 4.0-13.0 MPa, preferably 6.0-10.0 MPa, the volume ratio of inlet hydrogen to oil is generally 300: 1-800: 1, preferably 400: 1-700: 1, and the reaction temperature is generally 360-430 ℃, preferably 380-420 ℃.
According to the general knowledge in the field, the aromatic hydrocarbon in the catalytic diesel mainly comprises monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon and aromatic hydrocarbon above three rings, wherein the ratio of the bicyclic aromatic hydrocarbon to the aromatic hydrocarbon above three rings is large. The hydrogenation of aromatic hydrocarbon is a reversible reaction and is controlled by dynamics and thermodynamics, the hydrogenation saturation reaction of aromatic hydrocarbon is mainly controlled by dynamics in a lower reaction temperature range, and the hydrogenation saturation reaction of aromatic hydrocarbon is mainly controlled by thermodynamics in a higher reaction temperature range. The reaction process parameters have a complex influence on the hydrogenation of aromatics. On the one hand, increasing the temperature in the kinetic control zone is beneficial to increasing the reaction rate; on the other hand, a certain increase in temperature leads to a limitation in thermodynamic equilibrium. In the existing hydrofining process, the problem of excessive saturation of aromatic hydrocarbon occurs no matter monocyclic aromatic hydrocarbon is not used as a main target product or monocyclic aromatic hydrocarbon is used as a main target product, so that the final content of monocyclic aromatic hydrocarbon is reduced, namely the problem of poor selectivity of monocyclic aromatic hydrocarbon is caused, and the problems of increase of hydrogen consumption and the like exist at the same time.
The inventors of the present invention have intensively studied and found that the rate constant of the hydrogenation saturation reaction of the first ring of the polycyclic aromatic hydrocarbon is generally larger than that of the hydrogenation saturation reaction of the monocyclic aromatic hydrocarbon, that is, the hydrogenation of the first ring of the polycyclic aromatic hydrocarbon is easier than that of the monocyclic aromatic hydrocarbon. In order to increase the saturation rate of the polycyclic aromatic hydrocarbon, the reaction severity needs to be increased properly, including the increase of the reaction temperature, but the increase of the reaction temperature can also make monocyclic aromatic hydrocarbon be hydrogenated and saturated, if the reaction temperature is further increased, the aromatic hydrocarbon hydrogenation and saturation reaction can enter a thermodynamic control region, and the saturation rate of the polycyclic aromatic hydrocarbon is reduced. At a lower reaction temperature, the polycyclic aromatic hydrocarbon saturation rate is increased along with the increase of the reaction temperature, the saturated polycyclic aromatic hydrocarbon is completely converted into monocyclic aromatic hydrocarbon, the monocyclic aromatic hydrocarbon selectivity is 100%, when the reaction temperature rises to a certain value, the reaction temperature is continuously increased, the polycyclic aromatic hydrocarbon saturation rate continues to rise, but the hydrogenation saturation of the monocyclic aromatic hydrocarbon begins to be converted into naphthenic hydrocarbon, the monocyclic aromatic hydrocarbon selectivity begins to fall, when the reaction temperature reaches a kinetic control critical value, the polycyclic aromatic hydrocarbon saturation rate reaches a maximum value, the monocyclic aromatic hydrocarbon selectivity reaches a minimum value, the reaction temperature is continuously increased, the aromatic hydrocarbon hydrogenation saturation reaction enters a thermodynamic control region, the reaction temperature is increased in the thermodynamic control region, the polycyclic aromatic hydrocarbon saturation rate is reduced, and the monocyclic aromatic hydrocarbon selectivity rises.
Based on the research, the invention is provided with at least two hydrofining reaction areas which respectively meet the reaction requirements of a kinetic control area and a thermodynamic control area. In the first reaction zone, under proper technological conditions, the reaction of converting the selective hydrogenation saturation of most polycyclic aromatic hydrocarbon into monocyclic aromatic hydrocarbon occurs, then in the second reaction zone, under proper technological conditions, the reaction of converting the hydrogenation saturation of polycyclic aromatic hydrocarbon into monocyclic aromatic hydrocarbon occurs further, the hydrogenation saturation reaction rate of low monocyclic aromatic hydrocarbon is controlled, and the monocyclic aromatic hydrocarbon is kept to the maximum extent.
Compared with the prior art, the method for producing high-quality gasoline and diesel oil by catalyzing diesel oil has the following advantages:
(1) the method treats the poor diesel raw oil with high aromatic hydrocarbon content by at least two hydrofining reaction zones, has high monocyclic aromatic hydrocarbon selectivity while keeping high polycyclic aromatic hydrocarbon saturation rate, has the total aromatic hydrocarbon removal rate of below 15 percent when the polycyclic aromatic hydrocarbon removal rate is 85 percent, and obviously keeps the monocyclic aromatic hydrocarbon content.
(2) The catalytic diesel oil after hydrotreating is subjected to a cutting process of light-heavy separation, heavy components with high content of bicyclic heavy aromatics and tricyclic heavy aromatics and light components are respectively processed, heavy components with high content of bicyclic heavy aromatics and tricyclic heavy aromatics which are most suitable as hydroconversion raw materials can be subjected to conversion reaction, the preparation, grading and technological parameter control of a catalyst are matched, high-octane gasoline components can be produced to the maximum extent, meanwhile, the light components are subjected to modification reaction, and the saturation ring opening and hydrogenation processes of the light components can be carried out in cooperation with the preparation and technological parameter control of the catalyst, so that the high-cetane diesel oil components can be produced to the maximum extent. The method can process different types of raw materials independently in a targeted manner through reasonable separation and processing processes, simplifies the complex petroleum refining process, and maximizes the processing suitability and pertinence of each component while considering the processing difficulty when processing poor-quality catalytic diesel oil, thereby having great advantages.
(3) The method effectively reduces the hydrogen consumption in the hydrogenation process, improves the utilization efficiency of the hydrogen and reduces the processing cost.
(4) The method deeply couples the separation, the hydro-upgrading and the hydro-conversion in the process flow, and obtains ideal comprehensive processing effect on the basis of pertinently treating raw materials and improving the product quality. Although each unit has stronger independence in the description process, different units can be organically combined and shared in practical application, so that the method has the advantages of equipment saving, low operation cost and the like, and simultaneously, due to the improvement of a heat exchange system brought by combination, the energy consumption of the device is reduced to a certain extent, the investment is reduced, and the method has wide application prospect.
(5) The small crystal grain molecular sieve used by the hydro-conversion catalyst has large specific surface area, particularly the external surface area is obviously increased, the ratio of the surface atomic number to the volume atomic number is sharply increased, the pore passage is shortened, and the exposed pore openings are increased, so that the small crystal grain molecular sieve has higher reactivity and surface energy and shows obvious volume effect and surface effect. Specifically, the following aspects are provided: because the area of the outer surface is increased, more active centers are exposed, the diffusion effect is effectively eliminated, the efficiency of the catalyst is fully exerted, and the reaction performance of macromolecules is improved; the surface energy is increased, so that the adsorption capacity of the molecular sieve is increased, the adsorption speed is accelerated, and the effective adsorption capacity of the molecular sieve is improved; the small-crystal molecular sieve has short pore passage and small in-crystal diffusion resistance, and the huge external surface area enables more orifices of the small-crystal molecular sieve to be exposed outside, so that the small-crystal molecular sieve is beneficial to the rapid in-and-out of reactant or product molecules, and can prevent or reduce the formation of carbon deposition caused by the accumulation of the product in the pore passage, thereby improving the turnover rate of the reaction and the service life of the molecular sieve; has uniform radial distribution of the skeleton components, thereby improving activity and selectivity; the method is more beneficial to the realization of the modification technology after the synthesis of the molecular sieve; for molecular sieve supported metal catalysts, the use of small crystallite molecular sieves is beneficial in increasing the effective loading of the metal component and improving the dispersion properties of the metal component. In addition, the proportion of secondary pores in the molecular sieve can be further increased through subsequent modification treatment, the pore structure of the molecular sieve is unblocked, macromolecule adsorption reaction and desorption are facilitated, the directional hydrogenation conversion capability of macromolecule polycyclic aromatic hydrocarbon is greatly enhanced, and the saturation and cracking of the intermediate ring can enable high-octane gasoline components in the product to be more.
Drawings
FIG. 1 is a schematic flow chart of a method for producing high-quality gasoline and diesel oil by catalyzing diesel oil according to the invention.
Detailed Description
The method of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in figure 1, in the method for producing high-quality gasoline and diesel oil by catalyzing diesel oil, high-aromatic-hydrocarbon catalytic diesel oil 1 is heated by a heating furnace 2, mixed with circulating hydrogen 25 and enters a hydrogenation refining reaction zone I3 for reactions such as hydrodesulfurization, polycyclic aromatic hydrocarbon saturation and the like; mixing the obtained generated oil 4 with recycle hydrogen 25, and allowing the mixture to enter a II hydrofining reaction zone 5 for further hydrodesulfurization reaction, wherein aromatic hydrocarbon selectively reacts; the obtained produced oil 6 enters a separation device 7 and is cut into a light component 8 and a heavy component 9; the light component 8 and recycle hydrogen 25 are mixed and enter a hydro-upgrading reaction zone 10 for hydrocarbon hydrogenation reaction, and the generated oil is separated by a separation system 12 to obtain gas 13, gasoline fraction 14 and diesel fraction 15 with high cetane number; the heavy component 9 and recycle hydrogen 25 are mixed and enter a hydro-conversion reaction zone 16 for hydrocarbon hydro-conversion reaction, the generated oil 17 passes through a separation system 18 to obtain gas 19, gasoline 20 and diesel fraction 21, part of the diesel fraction 22 is recycled to a II hydro-refining reaction zone 5, and the gas 13 and the gas 19 are recycled through a recycle hydrogen compressor 23. The gasoline is mixed with 14 and 20 to obtain the qualified gasoline product. And mixing the diesel oil 15 and the diesel oil 21 to obtain a qualified diesel oil product.
The method for producing high quality gasoline and diesel oil by catalyzing diesel oil according to the invention is further illustrated by the following specific examples.
Examples 1 to 3
Examples 1-3 all employ the process of the present invention, the combined process flow shown in FIG. 1. Heating high aromatic hydrocarbon catalytic diesel oil in a heating furnace, mixing with circulating hydrogen, and allowing the mixture to enter a hydrogenation refining reaction zone I for hydrodesulfurization, polycyclic aromatic hydrocarbon saturation and other reactions; mixing the obtained generated oil with recycle hydrogen, and allowing the mixture to enter a II hydrofining reaction zone for further hydrodesulfurization reaction, wherein aromatic hydrocarbon selectively reacts; the obtained generated oil enters a separation device and is cut into light components and heavy components; the light components and recycle hydrogen are mixed and enter a hydro-upgrading reaction zone for hydrocarbon hydrogenation reaction, and the generated oil is separated by a separation system to obtain gas, gasoline fraction and diesel fraction with high cetane number; the heavy components and the recycle hydrogen are mixed and enter a hydro-conversion reaction zone for hydro-conversion reaction of hydrocarbons, the generated oil passes through a separation system to obtain gas, gasoline and diesel oil fractions, part of the diesel oil fractions are recycled to a II hydro-refining reaction zone, and the gas are recycled by a recycle hydrogen compressor. The hydro-modified gasoline is mixed with hydro-converted gasoline to obtain qualified gasoline product. And mixing the hydro-modified diesel oil and the hydro-converted diesel oil to obtain a qualified diesel oil product.
In example I, the catalyst used in the hydrofining reaction zone is a commercial catalyst FF-36 hydrotreating catalyst, and the catalyst used in the hydrofining reaction zone II is a catalyst modified on the basis of the commercial catalyst FF-36: the content of Mo active metal components (calculated by oxide) is higher than 3.0 percent, the content of Ni active metal components (calculated by oxide) is higher than 2.0 percent, the total content of Mo-Ni active metal components (calculated by oxide) is higher than 5.0 percent, the total acid content of the catalyst is higher than 1.5mmol/g, the pore volume of the catalyst is lower than 0.25mL/g, and the specific surface area is higher than 50m2(ii) in terms of/g. The hydrogenation modification reaction zone is usedThe catalyst of (2) is a commercial catalyst FC-18 hydrocracking catalyst. The hydroconversion reaction zone uses a hydroconversion catalyst (a) specifically made by the present technique. The properties of the raw materials of the examples are shown in Table 1, the properties of the catalyst A are shown in Table 2, and the operating conditions and the properties of the main products are shown in Table 3.
Comparative examples 1 to 2
Comparative examples 1-2 are conventional catalytic diesel hydroconversion processes, and catalytic diesel as in the examples is selected as a raw material for hydrogenation production, and target products are high-quality gasoline and common diesel. The catalysts used in the comparative examples were a commercial catalyst FF-36 hydrotreating catalyst and a conventional commercial hydroconversion catalyst FC-24. The properties of the raw materials of the comparative examples are shown in Table 1, the properties of the catalysts are shown in Table 2, and the operating conditions and the properties of the main products are shown in Table 3.
TABLE 1 Properties of the raw materials
TABLE 2 hydroconversion catalyst properties prepared by the process of the invention
TABLE 3 operating conditions and Main product Properties
Polycyclic aromatic hydrocarbon saturation rate = (polycyclic aromatic hydrocarbon content in raw material-polycyclic aromatic hydrocarbon content in product)/polycyclic aromatic hydrocarbon content in raw material x 100%
Single ring aromatic selectivity = (content of single ring aromatic hydrocarbon in product-content of single ring aromatic hydrocarbon in raw material)/(content of polycyclic aromatic hydrocarbon in raw material-content of polycyclic aromatic hydrocarbon in product) × 100%.
Claims (13)
1. A method for producing high-quality gasoline and diesel oil by catalyzing diesel oil is characterized in that: the method comprises the following steps:
(1) mixing high aromatic catalytic diesel oil and recycle hydrogen, and allowing the mixture to enter a hydrofining reaction zone I for reaction, wherein the reaction conditions are as follows: the hydrogen partial pressure is 3-12 MPa, the reaction temperature is 260-450 ℃, and the volume ratio of hydrogen to oil is 300-1500 Nm3/m3And the liquid hourly space velocity is 0.3-4.0 h-1(ii) a The aromatic hydrocarbon content of the high aromatic hydrocarbon catalytic diesel oil is more than 50 wt%;
(2) mixing the generated oil obtained in the step (1) with recycle hydrogen, and allowing the mixture to enter a II hydrofining reaction zone for further reaction, wherein the reaction conditions are as follows: the hydrogen partial pressure is 4-8 MPa, the reaction temperature is 30-120 ℃ higher than that of a hydrofining reaction zone I, and the volume ratio of hydrogen to oil is 500-1000 Nm3/m3The liquid-time volume-air ratio is 0.5 to 1.5 hours lower than that of the hydrofining reaction zone I-1；
(3) The generated oil obtained in the step (2) enters a separation device and is cut into light components and heavy components;
(4) mixing the light components obtained in the step (3) with recycle hydrogen, allowing the mixture to enter a hydro-upgrading reaction zone for hydrocarbon hydrogenation reaction, and allowing the generated oil to pass through a separation system to obtain a gasoline fraction and a diesel fraction with a high cetane number;
(5) mixing the heavy components obtained in the step (3) with recycle hydrogen, allowing the mixture to enter a hydro-conversion reaction zone for hydrocarbon hydro-conversion reaction, allowing the generated oil to pass through a separation system to obtain gas, gasoline and diesel oil fractions, allowing part of the diesel oil fractions to recycle to a II hydro-refining reaction zone, and allowing part of the diesel oil to exit the device;
(6) and (3) mixing the gasoline obtained in the step (4) with the gasoline obtained in the step (5) to obtain a qualified gasoline product, and mixing the diesel oil obtained in the step (4) with the diesel oil obtained in the step (5) to obtain a qualified diesel oil product.
2. The method of claim 1, wherein: the reaction conditions of the hydrofining reaction zone in the step (1) I are that the hydrogen partial pressure is 4-8 MPa, the reaction temperature is 280-350 ℃, and the volume ratio of hydrogen to oil is 500-1000 Nm3/m3The liquid hourly space velocity is 0.5-2.0 h-1。
3. The method of claim 1, wherein: the initial boiling point of the high aromatic catalytic diesel oil in the step (1) is 160-240 ℃; the final distillation point is 320-420 ℃.
4. The method of claim 1, wherein: the high aromatic catalytic diesel oil in the step (1) is a catalytic cracking product obtained by processing any basic oil species.
5. The method of claim 1, wherein: the hydrofining catalyst adopted in the hydrofining reaction zone I in the step (1) takes the weight of the catalyst as a reference, and the VIB group metal component accounts for 10-35 percent of the oxide; the amount of the VIII family metal is 1-7% by oxide.
6. The method of claim 1, wherein: compared with the hydrofining catalyst used in the hydrofining reaction zone I in the step (1), the hydrofining catalyst used in the hydrofining reaction zone II in the step (2) is as follows: the content of the active metal component is 3.0-8.0% in terms of oxide; the total acid content of the catalyst is 1.0-2.0 mmol/g; the pore volume of the catalyst is reduced by 0.20-0.40 mL/g; the specific surface area is 40-70 m high2/g。
7. The method of claim 1, wherein: the weight ratio of the high aromatic catalytic diesel to the circulating diesel is 5: 1-1: 5.
8. The method of claim 1, wherein: the cutting separation in the step (3) is a conventional distillation separation operation, and a flash separation or tray separation mode is adopted.
9. The method of claim 1, wherein: the hydro-upgrading catalyst used in the hydro-upgrading reaction zone in the step (4) takes the weight as a reference, the content of the hydrogenation component is 5-40%, and the weight of the molecular sieve is 5-40%.
10. The method of claim 1, wherein: the hydrocracking catalyst used in the hydroconversion reaction zone in the step (5) consists of at least one hydrogenation active metal component of W, Mo, Co and Ni, a molecular sieve component and an alumina carrier.
11. The method of claim 10, wherein: the molecular sieve is a small-grain Y-shaped molecular sieve, the grain size of the small-grain Y-shaped molecular sieve is 400-600 nm, the infrared total acid is 0.2-0.5 mmol/g, and the proportion of the medium strong acid is more than 75%; the unit cell parameter is 2.430-2.436 nm; SiO 22/Al2O3The molar ratio is 10-70; the pore volume is 0.5-0.8 cm3The proportion of the secondary pore volume of 2-8 nm in the total pore volume is more than 55%.
12. The method of claim 1, wherein: the operation conditions of the hydro-upgrading reaction zone in the step (4) are as follows: the volume space velocity is 0.5-4.0 h-1(ii) a The hydrogen partial pressure is 4-13 MPa; the volume ratio of the hydrogen to the oil at the inlet is 300: 1-800: 1; the reaction temperature is 340-410 ℃.
13. The method of claim 1, wherein: the operating conditions of the hydroconversion reaction zone in the step (5) are as follows: the airspeed is 0.5-4.0 h-1The pressure is 4.0-13.0 MPa, the volume ratio of hydrogen to oil at the inlet is 300: 1-800: 1, and the reaction temperature is 360-430 ℃.
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