Method for producing light olefins and low sulfur fuel oil components

Abstract

A method for producing propylene and a low-sulfur fuel oil component is provided, comprising: step i) contacting a hydrocarbon-containing feedstock oil with a catalytic conversion catalyst in a catalytic conversion reactor under effective conditions in the absence of hydrogen to obtain a reaction product containing propylene; step ii) separating the reaction product from step i) to obtain a catalytically cracked distillate oil; and step iii) subjecting the catalytically cracked distillate oil to hydrodesulfurization to obtain a low-sulfur hydrodistillate oil as a fuel oil component. The method can significantly increase propylene selectivity and propylene yield while producing more fuel oil components, and significantly reduce the yields of dry gas and coke, thus having better economic and social benefits.

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Patent Application No. 201911014993.7, filed October 24, 2019, entitled "Method for Producing Light Olefins and Low Sulfur Fuel Oil Components," which is incorporated herein by reference in its entirety.

[0002] [Technical Field] This application relates to the field of catalytic conversion of hydrocarbon oils, and in particular to a process for catalytically converting hydrocarbon-containing feedstock oils into light olefins and low sulfur fuel oil components.

[0003] [Prior Art] With the rapid development of national economies, environmental pollution issues are receiving increasing attention, and environmental regulations are becoming increasingly strict. According to the International Maritime Organization (IMO) International Convention for the Prevention of Pollution from Ships, starting January 1, 2020, all ships worldwide must use marine fuel with a sulfur content of 0.5% or less. This will undoubtedly revolutionize the global marine fuel market. According to BP forecasts, global marine fuel consumption in 2020 could reach approximately 300 million tons, which will undoubtedly pose a significant challenge to the supply of low-sulfur fuel oil. Furthermore, there remains a significant gap between the supply capacity announced by major global oil processing companies and global market demand.

[0004] CN109722303A discloses a method for producing a blending component for low-sulfur marine fuel from high-sulfur heavy oil, which includes the steps of: a) feeding high-sulfur heavy oil feedstock into a visbreaking device for visbreaking to obtain a visbreaking residue; b) adding a composite modifier to the visbreaking residue obtained in step a), and then continuously settling the mixture to obtain an overflow at the top and a bottom flow at the bottom; and c) sending the overflow obtained in step b) to a fixed-bed residue hydrotreating device for hydrodesulfurization to obtain a blending component for low-sulfur marine fuel.

[0005] As crude oil production increases, crude oil quality has become inadequate, primarily due to increases in crude oil density, viscosity, heavy metal content, sulfur content, nitrogen content, colloid content, and asphaltene content. As the shortage of petroleum resources becomes increasingly severe, the price gap between low-quality crude oil and high-quality crude oil is widening. Producing as many high-value products as possible from low-quality crude oil poses significant challenges to traditional crude oil processing technologies. However, the key to processing low-quality crude oil lies in how to process the atmospheric residue fraction, the heaviest of all crude oil fractions.

[0006] Catalytic cracking of residues is currently an important method for producing light olefins and high-octane gasoline in modern oil refineries, and light cycle oil (LCO) is produced as a by-product. Recently, LCO has been considered as a potential blending component for marine fuels. Blending vacuum residue with LCO can produce low-sulfur marine fuels, but the proportion of LCO used as a fuel component must not be too high due to LCO's lower viscosity. Simple blending of the two materials may result in phase separation during long-term storage because the distillation ranges of LCO and vacuum residue do not overlap. Furthermore, the use of vacuum residue as a fuel component may affect the economic profits of companies due to the high hydrogen content of saturated hydrocarbons in vacuum residue.

[0007] As the demand for derivatives such as polypropylene grows rapidly, the demand for propylene in China still exceeds its supply, and the production of more propylene through catalytic cracking of heavy oil plays a more important role. Because the price of marine fuel is lower than that of diesel oil for vehicles, the production of marine fuel cannot provide good economic benefits. It is important to pay attention to the component characteristics of feedstock oil and produce marine fuel together with high-value products such as propylene and butylene.

[0008] Considering China's current excess oil refining capacity, developing a method to produce higher-value propylene and provide low-sulfur marine fuel components by using core oil refining units, i.e., catalytic cracking units, is an important strategy for restructuring the oil refining industry, thereby meeting the requirements of improving environmental protection standards and market demand and improving corporate competitiveness. Summary of the Invention The objective of the present application is to provide a catalytic conversion process for producing propylene and low-sulfur fuel oil components, which can significantly improve propylene selectivity and propylene yield while producing more fuel oil components, and can significantly reduce the yields of dry gas and coke, bringing about good economic and social benefits.

[0009] In order to achieve the above object, the present application Step i) contacting a hydrocarbon-containing feedstock oil with a catalytic conversion catalyst for reaction in a catalytic conversion reactor in the absence of hydrogen to obtain a reaction product comprising propylene; step ii) separating the reaction product from step i) to obtain a catalytically cracked distillate oil, the catalytically cracked distillate oil having an initial boiling point of about 200°C or more, a final boiling point of about 550°C or less, and a hydrogen content of about 12.0 wt% or less; and Step iii) subjecting the catalytically cracked distillate oil to hydrodesulfurization to obtain a low-sulfur hydrodistillate oil suitable for use as a fuel oil component; the catalytic conversion catalyst comprises, based on the total weight of the catalyst, about 1 to 50 wt. % of a zeolite, about 5 to 99 wt. % of an inorganic oxide, and about 0 to 70 wt. % of a clay; The reaction conditions in step i) are a reaction temperature of about 460 to 750°C, and a reaction time of about 10 to 100 hours. -1 or a reaction time of about 1-10 seconds, and a catalyst to oil weight ratio of about 4-20.

[0010] Preferably, the reaction product obtained in step i) comprises about 8-25 wt % of propylene and about 15-50 wt % of the catalytically cracked distillate, based on the weight of the hydrocarbon-containing feedstock oil.

[0011] The method of the present application selectively cracks alkanes, hydrocarbons with alkyl side groups, and the like present in the hydrocarbon-containing feedstock oil, maximizing the production of propylene, while simultaneously producing polycyclic aromatic hydrocarbons with short side chains retained in the catalytically cracked distillate oil, which are suitable for use as fuel oil components. By using the method of the present application, the hydrocarbon-containing feedstock oil can be converted into propylene, butylene, and marine fuel components, while significantly reducing the yield of dry gas and coke. As a result, petroleum resources can be utilized more efficiently.

[0012] In particular, compared to the prior art, the method of the present application offers at least one of the following advantages: Advantages 1. While producing more fuel oil components, the propylene selectivity and propylene yield can be greatly improved, and thus some economic and social benefits can be achieved; Advantage 2. The production of high-value products such as propylene can be significantly increased while the yield of dry gas and coke can be significantly reduced; and Advantage 3. The total liquid yield can be significantly increased, thereby improving the utilization efficiency of petroleum resources.

[0013] BRIEF DESCRIPTION OF THE DRAWINGS The drawings that form part of this specification are provided to aid in the understanding of the application and should not be considered limiting. The application can be read with reference to the drawings in combination with the following detailed description. In the drawings: FIG. 1 is a schematic flow diagram of a preferred embodiment of the process for producing propylene and low sulfur fuel oil components of the present application.

[0014] Detailed Description of the Invention The present application will now be described in more detail with reference to specific embodiments and the accompanying drawings. It should be noted that the specific embodiments of the present application are provided for illustrative purposes only and are not intended to be limiting in any way.

[0015] Any specific numerical value, including the endpoints of a numerical range, described in the context of this application should be interpreted as not being limited to that exact value, but also encompassing all values ​​close to that exact value, for example, all values ​​within ±5% of that exact value. Furthermore, with respect to any numerical range described herein, any combination between the endpoints of the range, between each endpoint and any particular value within the range, or between any two particular values ​​within the range, can be made to provide one or more new numerical ranges, in which case the new numerical ranges should also be considered to be specifically described in this application.

[0016] Unless otherwise specified, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art; where terms are defined herein and those definitions differ from the common understanding in the art, the definitions provided herein shall control.

[0017] According to the present application, the term "catalytic cracking distillate oil" refers to a fraction in the reaction product having an initial boiling point of about 200°C or higher, preferably about 250°C or higher, and a final boiling point of about 550°C or lower, preferably about 520°C or lower, and most preferably about 500°C or lower, i.e., a fraction having a distillation range of about 200 to 550°C, preferably about 250 to 520°C, and more preferably about 250 to 500°C.

[0018] In this application, the term "fluidized-bed reactor," also referred to as "fluidized reactor," should be understood in its broadest sense and encompasses all types of reactors in which a gaseous feedstock can be brought into contact with solid catalyst particles in a fluidized state for chemical reaction, including, but not limited to, dense-phase beds, bubbling beds, ebullated beds, turbulent-flow beds, high-velocity beds, and gas-phase transport beds (e.g., upflow and downflow fluidized beds). Fluidized-bed reactors may be constant-linear-velocity fluidized-bed reactors, isodiameter fluidized-bed reactors, variable-diameter fluidized-bed reactors, and the like, and may also be composite reactors containing two or more different types of fluidized beds connected in series or parallel, such as, for example, riser reactors or composite reactors containing a riser reactor combined with a dense-phase bed. Typically, the gas velocity in a dense-phase bed can range from about 0.1 to 2 m / s, while the gas velocity in a riser reactor (excluding catalyst) can range from about 1 to 30 m / s.

[0019] In the context of this application, in addition to the explicitly described contents, any or undescribed contents shall be deemed to be the same as those known in the art without any modifications. Furthermore, any of the embodiments described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or concepts thus obtained shall be deemed to be part of the original disclosure or original description of this application, and shall not be deemed to be new matters not disclosed or anticipated herein, unless it is obvious to those skilled in the art that such combination is obviously unreasonable.

[0020] All patent and non-patent literature cited herein, including but not limited to textbooks and journal articles, is hereby incorporated by reference in its entirety.

[0021] Those skilled in the art have long understood that the higher the conversion rate of heavy oil during catalytic cracking, the better. However, through creative thinking and repeated experimentation, the present inventors discovered that the conversion rate of heavy oil during catalytic cracking should not be as high as possible. Once a certain level of conversion is reached, there is little increase in the desired products, but the yield of by-products, dry gas and coke, increases significantly. Therefore, the present inventors developed a mild catalytic cracking method based on the concept of selective cracking of alkane groups. In this method, the hydrocarbon feedstock is converted to a stage within an optimal range, the ratio of the total yield of dry gas and coke to the conversion rate is minimized, propylene selectivity is good, and difficult-to-convert polycyclic aromatic hydrocarbons are retained in the cracked product fraction with a distillation range of 300-500°C (referred to as "catalytic gas oil"), and coke formation is minimized. Due to the physicochemical properties of catalytic gas oil, it can be used as an effective blending component for marine fuels.

[0022] Therefore, the present application provides a method for producing a pharmaceutical composition comprising the steps of: step i) contacting a hydrocarbon-containing feedstock with a catalytic conversion catalyst for reaction under conditions effective in a catalytic conversion reactor in the absence of hydrogen to obtain a reaction product comprising propylene; step ii) separating the reaction product from step i) to obtain catalytically cracked distillate; and Step iii) subjecting the catalytically cracked distillate oil to hydrodesulfurization to obtain a low-sulfur hydrodistillate oil; The low sulfur hydrodistillate oil can be used as a low sulfur fuel oil component, and a method for producing propylene and a low sulfur fuel oil component is provided.

[0023] According to the present application, the hydrocarbon-containing feedstock oil may be selected from the group consisting of petroleum hydrocarbons, other mineral oils or mixtures thereof, said petroleum hydrocarbons may be selected from the group consisting of vacuum gas oils (VGOs), atmospheric gas oils, coker gas oils, deasphalted oils, vacuum residues (VRs), atmospheric residues, hydrogenated heavy oils or any mixtures thereof, and said other mineral oils may be selected from the group consisting of coal liquids, tar sands oil, shale oil or any mixtures thereof.

[0024] According to the present application, the catalytic conversion reactor can be selected from various types of fluidized bed reactors, such as a single fluidized bed reactor or a composite reactor including multiple fluidized bed reactors connected in series or parallel. In certain preferred embodiments, the fluidized bed reactor can be various types of variable diameter fluidized bed reactors or isodiameter riser reactors, such as the reactor disclosed in Chinese Patent No. 1078094C.

[0025] According to the present application, the catalytic conversion catalyst may contain, based on the total weight of the catalyst, about 1 to 50 wt% of zeolite, about 5 to 99 wt% of inorganic oxide, and about 0 to 70 wt% of clay. Preferably, the catalyst may contain about 5 to 45 wt% of zeolite, more preferably about 10 to 40 wt% of zeolite, about 5 to 80 wt% of inorganic oxide, and about 10 to 70 wt% of clay.

[0026] In a preferred embodiment, the zeolite may comprise about 51-100 wt%, preferably about 70-100 wt%, mesoporous zeolite, and about 0-49 wt%, preferably about 0-30 wt%, macroporous zeolite, based on the total weight of the zeolite. Preferably, the mesoporous zeolite has a silica-alumina ratio greater than about 10, preferably greater than about 50, and more preferably greater than about 100. The mesoporous zeolite is preferably selected from the group consisting of ZSM-type zeolite and ZRP-type zeolite; the macroporous zeolite is preferably Y-type zeolite. Optionally, the zeolite may be modified with a nonmetallic element such as phosphorus and / or a transition metal element such as iron, cobalt, or nickel. The inorganic oxide is preferably selected from the group consisting of silica, alumina, and a combination thereof; and the clay is preferably selected from kaolin and / or halloysite.

[0027] According to the present application, the "effective conditions" refer to conditions that allow the hydrocarbon-containing feedstock to undergo a catalytic conversion reaction to obtain a reaction product containing propylene and catalytically cracked distillate, preferably containing about 8 to 25 wt. % propylene and about 15 to 50 wt. % catalytically cracked distillate, based on the weight of the hydrocarbon-containing feedstock. In a preferred embodiment, the reaction conditions in the catalytic conversion step i) include a reaction temperature of about 460 to 750°C, preferably about 480 to 700°C, more preferably about 480 to 600°C, and most preferably about 500 to 560°C; a reaction time of about 5 to 100 h; -1 , preferably about 10 to 70 hours -1 , more preferably about 15 to 50 hours -1 , most preferably about 18 to 40 hours -1 (e.g., in the case of a dense phase bed reactor, a fast bed reactor, etc.), or a reaction time (e.g., in the case of a riser reactor) of about 1 to 10 seconds, preferably about 1.5 to 10 seconds, more preferably about 2.0 to 8.0 seconds, and most preferably about 4 to 8 seconds; and a catalyst to oil weight ratio of about 1 to 30, preferably about 5 to 15, and more preferably about 5 to 10.

[0028] In a preferred embodiment, step i) is carried out to the extent that the resulting reaction product has a propylene / propane mass ratio of about 4 or greater, preferably about 6 or greater, and most preferably about 8 or greater; and / or an isobutene / isobutane mass ratio of about 1 or greater, preferably about 1.5 or greater, and most preferably about 1.8 or greater.

[0029] In a preferred embodiment, step i) is carried out to such an extent that the yield of the catalytically cracked distillate oil in the resulting reaction product is about 15% or more, preferably about 20% or more, more preferably about 25% or more, and about 50% or less, based on the weight of the hydrocarbon-containing feedstock oil.

[0030] As is well known to those skilled in the art, the conversion rate of feedstock oil in a catalytic conversion process is generally expressed as the sum of the yields of gas, gasoline, and coke. In the present process, the final products of the catalytic conversion process include only dry gas, liquefied gas, gasoline, catalytically cracked distillate, and coke. Therefore, in the present process, the conversion rate of feedstock oil is substantially equal to 100% minus the yield of catalytically cracked distillate. Next, the conversion rate of the catalytic conversion process according to the present invention is controlled to about 85% or less, preferably about 80% or less, most preferably about 75% or less, and about 50% or more.

[0031] In certain preferred embodiments, the method further comprises separating the reaction products of step i) from spent catalyst, which is recycled to the reactor after stripping and regeneration by coke burning, and the separated reaction products comprise propylene, gasoline, and catalytic cracking distillate. Methods for separating materials such as propylene from the reaction products are well known to those skilled in the art and will not be described in detail herein.

[0032] In a preferred embodiment, a catalyst containing a Group VIB metal and / or a Group VIII metal supported on an alumina and / or amorphous silica-alumina support is used in the hydrodesulfurization step iii). More preferably, the catalyst used in the hydrodesulfurization step iii) contains about 0 to 10 wt. % of an additive, about 1 to 40 wt. % of at least one Group VIII metal (calculated as the metal oxide), and about 1 to 50 wt. % of at least one Group VIB metal (calculated as the metal oxide), with the remainder being a support selected from alumina and amorphous silica-alumina. The additive includes a nonmetallic element selected from fluorine, phosphorus, etc., a metallic element selected from titanium, platinum, etc., or a combination thereof. For example, the additive can be a phosphorus-containing additive or a fluorine-containing additive such as ammonium fluoride. The Group VIB metal is preferably selected from molybdenum, tungsten, or a combination thereof; and the Group VIII metal is preferably selected from nickel, cobalt, or a combination thereof.

[0033] In a preferred embodiment, the conditions for the hydrodesulfurization step iii) are a reaction pressure of about 2.0 to 24.0 MPa, preferably about 3.0 to 15.0 MPa; a reaction temperature of about 200 to 500°C, preferably about 300 to 400°C; and a reaction pressure of about 50 to 5000 Nm 3 / m 3 , preferably about 200 to 2000 Nm 3 / m 3 The volume ratio of hydrogen to oil is about 0.1 to 30.0 h -1 , preferably about 0.2 to 10.0 hours -1 Including the liquid hourly space velocity.

[0034] According to the present application, the catalytically cracked distillate oil has an initial boiling point of about 200°C or higher, a final boiling point of about 550°C or lower, and a hydrogen content of about 12.0% by weight or lower; preferably, the catalytically cracked distillate oil has an initial boiling point of about 250°C or higher, a final boiling point of about 520°C or lower, more preferably a final boiling point of about 500°C or lower, and a hydrogen content of about 11.5% by weight or lower.

[0035] In a preferred embodiment, the low sulfur hydrodistillate obtained through hydrodesulfurization of the catalytically cracked distillate has a sulfur content of about 0.1% or less, preferably about 0.05% or less, and is used as a blending component for fuel oil.

[0036] A particular embodiment of the method according to the present application is described below with reference to FIG.

[0037] A pre-lifting medium is introduced into the bottom of a variable diameter fluidized-bed reactor 2 (e.g., the reactor disclosed in Chinese Patent No. 1078094C) through a pipeline 1. The regenerated catalyst from the regenerated catalyst inclined pipe 16 moves upward along the reactor under the action of the pre-lifting medium. The feedstock oil, together with atomized steam from a pipeline 4, is supplied to the bottom of the first reaction zone 8 of the variable diameter fluidized-bed reactor 2 through a pipeline 3 and mixed with the existing flow in the reactor. The feedstock oil is cracked on a high-temperature catalyst and moves upward to the second reaction zone 9 of the variable diameter fluidized-bed reactor 2 for further reaction. The resulting oil gas and deactivated spent catalyst are passed through a cyclone separator in a disengager 7 to separate the spent catalyst from the oil gas. The oil and gas is passed through the main oil and gas pipeline 17, and the catalyst fines are returned to the separator 7 through the dipleg of the cyclone separator. The spent catalyst in the separator 7 passes through a stripping section 10 and contacts stripping steam from a pipeline 11. The oil and gas removed from the spent catalyst passes through the cyclone separator and is sent to the main oil and gas pipeline 17. The removed spent catalyst is sent to a regenerator 13 through a spent catalyst inclined pipe 12, and main air is introduced into the regenerator through a pipeline 14 to burn coke deposited on the spent catalyst. As a result, the deactivated spent catalyst can be regenerated. Exhaust gas is discharged through a pipeline 15. The regenerated catalyst is recycled to the variable diameter fluidized bed reactor 2 through the regenerated catalyst inclined pipe 16 for reuse.

[0038] The oil and gas is sent to the next fractionator 18 through the main oil and gas pipeline 17, and after separation, the resulting dry gas is discharged through pipeline 19; the resulting liquefied gas is discharged through pipeline 20 and separated into propylene, propane and C4 hydrocarbons in gas separator 25, and the propylene, propane and C4 hydrocarbons are discharged through pipelines 26, 27 and 28, respectively; the resulting gasoline is discharged through pipeline 21; the resulting light cycle oil fraction, which has a distillation range of 200-250°C, is recovered through pipeline 22 and then discharged from pipeline 32. the resulting slurry oil is recovered through pipeline 24 and recycled to the first reaction zone 8 of the variable diameter fluidized-bed reactor 2 for purification to regenerate the catalyst fines (optionally, it is passed to the first reaction zone 8 together with the feedstock oil from pipeline 3 through a feedstock nozzle); the resulting catalytic cracking distillate is passed to a hydrotreating unit 29 through pipeline 23, and the hydrodistillate obtained after the hydrotreatment is discharged through pipeline 30. The distillation range and processing scheme of each fraction can be adjusted according to the actual needs of the refinery, for example, gasoline can be split to obtain a light gasoline fraction, which can be recycled to the second reaction zone 9 of the variable diameter fluidized-bed reactor 2 through pipeline 6 together with the atomized steam from pipeline 5 for purification to increase the yield of propylene.

[0039] In certain preferred embodiments, the present application provides the following technical solutions: 1. A method for producing light olefins (especially propylene) and a low-sulfur fuel oil component comprises contacting a feedstock oil with a catalyst for reaction in a catalytic conversion reactor at a temperature, weight hourly space velocity, and weight ratio of catalyst to feedstock oil sufficient to produce a reaction product comprising 8 to 25 weight percent propylene and 15 to 50 weight percent catalytically cracked distillate oil, and subjecting the catalytically cracked distillate oil to hydrodesulfurization to obtain a low-sulfur hydrodistillate oil suitable for use as a fuel oil component.

[0040] 2. The method according to item 1, wherein the feedstock oil is selected from the group consisting of petroleum hydrocarbons selected from vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residue, atmospheric residue, hydrogenated heavy oil, or a mixture of two or more thereof, and / or other mineral oils selected from coal liquid oil, tar sand oil, shale oil, or a mixture of two or more thereof.

[0041] 3. The method according to item 1, wherein the catalytic conversion reactor is selected from the group consisting of a riser reactor, a constant linear velocity fluidized bed, an isodiameter fluidized bed, an upflow conveyor line, a downflow conveyor line, or a combination of two or more thereof, including a combination of reactors connected in series and / or in parallel, or a combination of two or more reactors of the same type, and the riser reactor is a conventional isodiameter riser reactor or various types of variable diameter fluidized beds.

[0042] 4. The method according to item 1, wherein the catalytic conversion catalyst comprises, based on the total weight of the catalyst, 1 to 50% by weight of a zeolite, 5 to 99% by weight of an inorganic oxide, and 0 to 70% by weight of a clay, the zeolite being a mesoporous zeolite and optionally a macroporous zeolite, the mesoporous zeolite accounting for 51 to 100% by weight of the total weight of the zeolite, the mesoporous zeolite having a silica-alumina ratio greater than 50, preferably greater than 80, and the macroporous zeolite accounting for 0 to 49% by weight of the total weight of the zeolite.

[0043] 5. The conditions for the catalytic conversion are a reaction temperature of 460 to 750°C, 10 to 100 hours -1 and a weight ratio of the catalyst to the catalytic conversion feedstock oil of 4 to 20.

[0044] 6. The conditions for the catalytic conversion are a reaction temperature of 480 to 700°C, 30 to 80 hours -1 and a weight ratio of the catalyst to the catalytic conversion feedstock oil of 5 to 12.

[0045] 7. The method according to item 1, wherein the catalytically cracked distillate oil has an initial boiling point of 200°C or higher and a hydrogen content of 12.0% by weight or less.

[0046] 8. The method according to item 7, wherein the catalytically cracked distillate oil has an initial boiling point of 250°C or higher and a hydrogen content of 11.5% by weight or less.

[0047] 9. The method according to item 1, wherein for the hydrodesulfurization, a catalyst containing a Group VIB metal and / or a Group VIII metal supported on an alumina and / or amorphous silica-alumina support is used.

[0048] 10. The method according to item 9, wherein the catalyst for hydrodesulfurization comprises 0 to 10 wt. % of an additive, 1 to 40 wt. % of one or more Group VIII metals, 1 to 50 wt. % of one or more Group VIB metals, and the remaining amount of an alumina and / or amorphous silica-alumina support, and the additive is selected from the group consisting of non-metallic elements such as fluorine and phosphorus, and metallic elements such as titanium and platinum.

[0049] 11. The hydrodesulfurization conditions are a reaction pressure of 2.0 to 24.0 MPa, a reaction temperature of 200 to 500°C, and a pressure of 50 to 5000 Nm 3 / m 3 The volume ratio of hydrogen to oil, and 0.1 to 30.0 h -1 2. The method according to item 1, comprising a liquid hourly space velocity of

[0050] 12. The hydrodesulfurization conditions are a reaction pressure of 3.0 to 15.0 MPa; a reaction temperature of 300 to 400°C; and a pressure of 200 to 2000 Nm 3 / m 3 The volume ratio of hydrogen to oil is 0.2 to 10.0 h -1 Item 12. The method according to item 11, comprising a liquid hourly space velocity of

[0051] 13. The method according to item 1, wherein the sulfur content in the hydrodistilled oil in step (3) is 0.1% or less, preferably 0.05% or less.

[0052] [Example] The present application is further illustrated with reference to the following examples, but is not limited thereto.

[0053] The properties of the feedstock oils and catalysts used in the following examples and comparative examples are shown in Tables 1 and 2, respectively. The catalytic conversion catalyst used in the comparative examples was MMC-1, a catalyst manufactured by Qilu Branch of Sinopec Catalyst Co., Ltd.

[0054] The hydrogen content of the catalytically cracked distillate oil obtained in each example is measured by a carbon and hydrogen analyzer according to the NB / SH / T 0656-2017 standard.

[0055] The catalytic conversion catalyst used in this example was prepared as follows: 969 g of halloysite (available from China Kaolin Clay Co., Ltd. with a solid content of 73%) was slurried in 4300 g of decationized water, and 781 g of pseudoboehmite (available from Shandong Zibo Bauxite Plant with a solid content of 64%) and 144 ml of hydrochloric acid (with a concentration of 30% and a specific gravity of 1.56) were added and stirred uniformly. The mixture was allowed to stand and aged at 60°C for 1 hour to maintain a pH value of 2-4. The mixture was then cooled to room temperature. 5000 g of a previously prepared slurry containing 1600 g of mesoporous shape-selective ZSM-5 zeolite (available from the Qilu Branch of Sinopec Catalyst Co., Ltd.) with a silica-alumina ratio of over 150 and chemical water was added and stirred uniformly. The resulting mixture was spray-dried to remove free Na. + The catalyst was then washed away to obtain a catalyst. The obtained catalyst was aged in 100% steam at 800°C. The aged catalyst is designated as Catalyst A, and its properties are shown in Table 2.

[0056] The hydrodesulfurization catalyst used in this example was prepared as follows: 1000 g of pseudoboehmite manufactured by the ChangLing Branch of Sinopec Catalyst Co., Ltd. was weighed out, and then 1000 ml of an aqueous solution containing 10 ml of nitric acid (chemically pure) was added. The mixture was extruded into a band shape using a twin-screw extruder, dried at 120°C for 4 hours, and calcined at 800°C for 4 hours to obtain a catalyst support. The support was immersed in 900 ml of an aqueous solution containing 120 g of ammonium fluoride for 2 hours, dried at 120°C for 3 hours, and calcined at 600°C for 3 hours; after cooling to room temperature, the resultant was immersed in 950 ml of an aqueous solution containing 133 g of ammonium metamolybdate for another 3 hours, dried at 120°C for 3 hours, and calcined at 600°C for 3 hours; after cooling to room temperature again, the resultant was finally immersed in 900 ml of an aqueous solution containing 180 g of nickel nitrate and 320 g of ammonium metatungstate for 4 hours, dried at 120°C for 3 hours, and calcined at 600°C for 4 hours to obtain Catalyst B.

[0057] [Table 1]

[0058] [Table 2]

[0059] Example 1-a This example was carried out using VGO+30% VR-1 as the feedstock oil and catalyst A as the catalytic conversion catalyst, in a medium-sized catalytic cracking unit including a variable diameter fluidized bed reactor, according to the process scheme shown in Figure 1. The resulting oil-gas and used catalyst were separated in a separator, and the oil-gas products were separated into propylene, butylene, gasoline, and catalytic cracking distillate (distillation range 250-500°C, with a hydrogen content of 11.2 wt%) according to the distillation range of these fractions in a fractionator. The reaction conditions and product distribution are listed in Table 3.

[0060] The resulting catalytically cracked distillate oil was sent to a hydrodesulfurization reactor together with hydrogen, where it was brought into contact with hydrodesulfurization catalyst B under conditions of reaction pressure of 6.0 MPa, reaction temperature of 350°C, volume ratio of hydrogen to oil of 350, and liquid hourly space velocity of 2.0 h -1 The resulting low-sulfur hydrodistillate was used as a fuel oil component and blended with another fuel oil component, "vacuum residue VR-2," to obtain an RMG 380 fuel oil product that meets the national standard GB 17411-2015, marine fuel oil. The properties are shown in Table 4.

[0061] Example 1-b This example was carried out in a medium-sized catalytic cracking unit containing a variable diameter fluidized bed reactor, using VGO as the feedstock oil and catalyst A as the catalytic conversion catalyst, according to the process scheme shown in Figure 1. The resulting oil-gas and spent catalyst were separated in a separator, and the oil-gas product was separated into propylene, butylene, gasoline, and catalytic cracking distillate (distillation range 250-500°C, hydrogen content 11.3 wt%) according to the distillation range of these fractions in a fractionator. The reaction conditions and product distribution are listed in Table 3.

[0062] Example 1-c This example was carried out in a medium-sized catalytic cracking unit equipped with an equal-diameter riser reactor, using VGO+30% VR-1 as the feedstock oil and catalyst A as the catalytic conversion catalyst, according to the process scheme shown in Figure 1. The resulting oil-gas and spent catalyst were separated in a separator, and the oil-gas products were separated into propylene, butylene, gasoline, and catalytic cracking distillate (distillation range 250-500°C, with a hydrogen content of 11.2 wt%) according to the distillation range of these fractions in a fractionator. The reaction conditions and product distribution are listed in Table 3.

[0063] Comparative Example 1 This comparative example was carried out in a medium-sized unit including a riser reactor combined with a dense-phase fluidized bed, using VGO as the feedstock oil and catalyst MMC-1 as the catalytic cracking catalyst, according to the conventional deep catalytic cracking process described in CN1004878B. The resulting oil-gas and spent catalyst were separated in a separator, and the oil-gas products were separated into propylene, butylene, gasoline, and light cycle oil (distillation range 200-350°C, with a hydrogen content of 9.8 wt%) according to the distillation range of these fractions in a fractionator. The reaction conditions and product distribution are listed in Table 3.

[0064] Example 2 This example uses hydrogenated heavy oil as the feedstock oil and catalyst A as the catalytic conversion catalyst, The process was carried out according to the process scheme shown in Figure 1 on a medium-sized catalytic cracking unit containing a variable diameter fluidized bed reactor. The resulting oil-gas mixture and spent catalyst were separated in a separator, and the resulting oil-gas product was separated into propylene, butylene, gasoline, and catalytic cracking distillate (distillation range: 250-500°C, with a hydrogen content of 10.9 wt%) according to the distillation range of these fractions in the fractionator. The reaction conditions and product distribution are listed in Table 3.

[0065] The resulting catalytically cracked distillate oil was sent to a hydrodesulfurization reactor together with hydrogen, where it was brought into contact with hydrodesulfurization catalyst B under conditions of reaction pressure of 9.0 MPa, reaction temperature of 330°C, volume ratio of hydrogen to oil of 650, and liquid hourly space velocity of 8.0 h -1 The resulting low-sulfur hydrodistillate was used as a fuel oil component and blended with another fuel oil component, "vacuum residue VR-3," to obtain an RMG 180 fuel oil product that meets the national standard GB 17411-2015, marine fuel oil. The properties are shown in Table 5.

[0066] [Table 3]

[0067] As can be seen from the results in Table 3, compared with Comparative Example 1, Examples 1-a and 1-c not only provide a high propylene yield of 14.42 wt% and 13.45 wt%, respectively, but also a high catalytic cracking distillate oil yield of 29.32 wt% and 28.32 wt%, respectively, using a lower feedstock oil, but the dry gas and coke yields are significantly reduced and the total liquid yield is significantly increased; on the other hand, Example 1-b can provide a high propylene yield of 15.00 wt% and a catalytic cracking distillate oil yield of 27.73 wt%, using the same feedstock oil, the dry gas and coke yields are significantly reduced and the total liquid yield is significantly increased.

[0068] [Table 4]

[0069] [Table 5]

[0070] Although the preferred embodiments of the present application have been described in detail above, the present application is not limited to the details of these embodiments. Various modifications can be made without departing from the spirit of the present application, and these modifications are also within the scope of the present application.

[0071] It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and for the sake of brevity, various possible combinations are not separately described in this application, but such combinations are also within the scope of this application.

[0072] In addition, the various embodiments of the present application may be combined in any manner without departing from the spirit of the present application, and such combinations should be considered part of the disclosure of the present application. [Brief explanation of the drawings]

[0073] [Figure 1] 1 is a schematic flow diagram of a preferred embodiment of the process for producing propylene and low sulfur fuel oil components of the present application.

Claims

1. Step i) contacting a hydrocarbon-containing feedstock with a catalytic conversion catalyst for reaction in a catalytic conversion reactor in the absence of hydrogen, The reaction conditions for step i) are a reaction temperature of 500 to 560°C, and 18 to 40 hours. －１ or a reaction time of 4 to 8 seconds, and a weight ratio of catalyst to oil of 5 to 10, wherein step i) is carried out to a degree of conversion of 50 to 75%, to obtain a reaction product containing 10.89 to 25 wt% of propylene and 25 to 50 wt% of catalytically cracked distillate oil, based on the weight of the hydrocarbon-containing feedstock oil; step ii) separating the reaction product from step i) to obtain a catalytically cracked distillate oil, wherein the catalytically cracked distillate oil has an initial boiling point of 250°C or more, a final boiling point of 520°C or less, and a hydrogen content of 12.0 wt% or less; Step iii) subjecting the catalytically cracked distillate to hydrodesulfurization to obtain a low-sulfur hydrodistillate having a sulfur content of 0.1% or less, suitable for use as a fuel oil component; and Step iv) obtaining the low sulfur hydrodistillate oil and using the obtained low sulfur hydrodistillate oil as a fuel oil component for fuel oil blending; The catalytic conversion catalyst comprises, based on the total weight of the catalyst, 1 to 50 wt. % of a zeolite, 5 to 99 wt. % of an inorganic oxide, and 0 to 70 wt. % of a clay, and the zeolite is not modified with phosphorus. A method for producing propylene and low sulfur fuel oil components.

2. 2. The method of claim 1, wherein in the catalytic conversion catalyst, the zeolite comprises 51 to 100 wt. % mesoporous zeolite and 0 to 49 wt. % macroporous zeolite, based on the total weight of the zeolite, and the mesoporous zeolite has a silica-to-alumina ratio greater than 10.

3. 3. The method according to claim 1 or 2, wherein step i) is carried out to such an extent that the resulting reaction product has a propylene / propane mass ratio of 4 or greater; and / or an isobutene / isobutane mass ratio of 1 or greater.

4. The method according to any one of claims 1 to 3, wherein step i) is carried out to such an extent that the yield of the catalytically cracked distillate oil in the resulting reaction product is 15% or more and 50% or less by weight, based on the weight of the hydrocarbon-containing feedstock oil.

5. 5. The method of claim 1, wherein the hydrocarbon-containing feedstock oil is selected from the group consisting of petroleum hydrocarbons, other mineral oils, or mixtures thereof, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residue, atmospheric residue, hydrogenated heavy oil, or any mixtures thereof, and the other mineral oils are selected from the group consisting of coal liquid oil, tar sand oil, shale oil, or any mixtures thereof.

6. The method of any one of claims 1 to 5, wherein the catalytic conversion reactor is a fluidized bed reactor, including a single fluidized bed reactor, or a composite reactor comprising multiple fluidized bed reactors connected in series or in parallel.

7. 3. The method of claim 2, wherein the mesoporous zeolite is selected from the group consisting of ZSM-type zeolite and ZRP-type zeolite, and the macroporous zeolite is Y-type zeolite.

8. The method according to any one of claims 1 to 7, wherein the catalytically cracked distillate oil has an initial boiling point of 250 ° C or higher, a final boiling point of 520 ° C or lower, and a hydrogen content of 11.5 wt% or less.

9. 9. The process according to claim 1, wherein in the hydrodesulfurization step iii) a catalyst is used comprising a Group VIB metal and / or a Group VIII metal supported on an alumina and / or amorphous silica-alumina support.

10. 10. The method of claim 9, wherein the catalyst used in hydrodesulfurization step iii) comprises 0 to 10 wt. % of an additive, 1 to 40 wt. % of at least one Group VIII metal (calculated as metal oxide), 1 to 50 wt. % of at least one Group VIB metal (calculated as metal oxide), the remainder being a support selected from alumina and amorphous silica-alumina, and wherein the additive comprises an element selected from the group consisting of fluorine, phosphorus, titanium, platinum or a combination thereof.

11. The conditions for the hydrodesulfurization step iii) are a reaction pressure of 2.0 to 24.0 MPa, a reaction temperature of 200 to 500°C, and a pressure of 50 to 5000 Nm ３ / m ３ The volume ratio of hydrogen to oil, and 0.1 to 30.0 h －１ The method of any one of claims 1 to 10, comprising a liquid hourly space velocity of

12. The conditions for the hydrodesulfurization step iii) are a reaction pressure of 3.0 to 15.0 MPa; a reaction temperature of 300 to 400°C; and a pressure of 200 to 2000 Nm ３ / m ３ the volume ratio of hydrogen to oil; and 0.2 to 10.0 h －１ The method of any one of claims 1 to 11, comprising a liquid hourly space velocity of

13. 13. The method according to any one of claims 1 to 12, wherein the hydrodistilled oil obtained in step iii) has a sulfur content of 0.1% or less.

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