Fluid catalytic cracking process for converting crude oil into light olefins and aromatic compounds

Abstract

The present invention provides a process and reactor system for converting crude oil into light olefins and aromatic compounds in a single step. [Solution] The present invention relates to a process involving high-intensity catalytic cracking for converting whole crude oil into light olefins and aromatic compounds, and to a double catalytic cracking reactor system in which two reactors are connected in series with respect to the catalyst flow. This process allows refiners to maximize the production of high-value petrochemical raw materials and minimize the production of liquid fuels directly derived from crude oil using a single process unit. The reactor system consists of a fractionation column (A), a high-density fluidized bed reactor (B), an upward-flow reactor and stripper (C), a product separation section (E), and a combustor (D).

Description

Technical Field

[0001] The present invention relates generally to the field of the petroleum industry. Specifically, the present invention relates to a production method comprising a high-intensity catalytic cracking process for converting entire crude oil into light olefins and aromatic compounds, and a dual catalytic cracking system in which two reactors are connected in series with respect to catalyst flow. This process makes it possible to maximize the production of high value-added petrochemical feedstocks directly from crude oil and minimize the production of liquid fuels using a single process unit.

Background Art

[0002] The world is shifting to cleaner fuels, and in the transportation sector, remarkable progress has been made in recent years in the fields of electric vehicles and hybrid vehicles, which is affecting the future demand for liquid fuels such as gasoline and diesel. However, the demand for petrochemical products is increasing globally, and therefore, to improve refining margins, refiners need to maximize the conversion of crude oil to petrochemical feedstocks.

[0003] U.S. Patent No. 6979757B2 and U.S. Patent No. 7550642B2 disclose olefin production processes that use a pyrolysis process to use entire crude oil / condensate as feedstock. In U.S. Patent No. 6979757B2, the entire crude oil is sent to a pyrolysis furnace where cracking with mild and controlled cavitation is performed.

[0004] U.S. Patent No. 7550642B2 discloses an olefin production process, in which the entire crude oil is sent to a pyrolysis furnace after preheating to produce a mixture of hydrocarbon vapor and liquid. Further, gaseous hydrocarbons are separated from the liquid and sent to a severe cracking step. The liquid hydrocarbons are subjected to mild catalytic steam cracking (also using hydrogen) until substantially all are vaporized, and then sent to a severe cracking step. However, these processes have extremely high energy consumption, and operational limitations such as coking are unavoidable.

[0005] U.S. Patent No. 9550707B2 discloses an integrated process combining atmospheric distillation units, vacuum distillation units, catalytic cracking units, coking units, and reforming units. In this process, crude oil is sent to an ADU and VDU, where it is separated into gaseous, liquid, vacuum gas-oil, and vacuum residue. The vacuum gas-oil is sent to an atmospheric distillation unit (ADU) and a vacuum distillation unit (VDU), where it is separated into gaseous, liquid, vacuum gas-oil, and vacuum residue. The liquid from the VDU, catalytic cracking unit, and delayed coking unit, as well as C3 and C4 paraffin, are sent to a steam cracker.

[0006] U.S. Patent No. 10407629B2 discloses an integrated process for distilling crude oil to produce naphtha, kerosene, residue oil, and diesel fuel, which are then sent to hydrocrackers to produce ethane, LPG, and BTX. The residue oil is sent to a residue oil hydrocracker, and the middle distillates from the residue oil unit, along with the diesel fuel, are sent to an aromatic ring-opening unit. The LPG produced in this integrated process is then sent to an LPG aromaticization unit.

[0007] U.S. Patent No. 9,771,530,B2 discloses an integrated slurry hydrogenation and steam pyrolysis process for producing olefins and aromatic petrochemical feedstocks from crude oil. Crude oil is hydrogenated to produce a high-hydrogen content effluent, which is then sent to a steam pyrolysis unit to undergo pyrolysis. The mixed product stream is separated, and the olefins and aromatic products are recovered.

[0008] U.S. Patent No. 1,1359,149 discloses a process configuration for producing light olefins and aromatic compounds from a residual hydrocarbon stream. This configuration employs a high-intensity catalytic cracking process to produce higher yields of light olefins and various high-boiling fractions. The C4 hydrocarbon fluid separated from the gaseous products is aromaticized via metathesis to form monocyclic aromatic compounds. The high-boiling fractions are then processed in various apparatuses, such as HDT, delayed coking units, naphtha catalytic crackers, and hydrocrackers, to further increase the yields of light olefins and aromatic compounds.

[0009] U.S. Patent No. 11840672 utilizes a processing scheme that integrates desalination units, atmospheric and vacuum towers, high-intensity FCC processes, naphtha cracking processes, residue slurry hydrocracking processes, delayed coking processes, selective mild hydrocracking aromatic production units, dehydrogenation units, aromatic / olefin recovery sections, gasification units, and synthesis gas to olefin conversion sections. However, all of these processes describe numerous refining units for converting crude oil into chemical products, which involve significant capital investment and operating costs.

[0010] U.S. Patent No. 9,290,705 discloses an FCC process and system for directly converting entire crude oil raw materials into light olefins and other products. The raw materials are separated into high-boiling and low-boiling fractions, and each fraction is processed in a separate FCC downflow reactor. Because the downflow reactors operate with short residence times of approximately 1 second, the light fractions require longer residence times to decompose, resulting in lower yields. Light olefins (ethylene, propylene, C4 olefins) and aromatic compounds (benzene, toluene, xylene, ethylbenzene) are major components in the modern chemical industry. The demand for these chemicals continues to increase with the growing demand for polymers and other important intermediate chemicals.

[0011] Traditionally, ethylene has been produced by naphtha steam cracking at high temperatures exceeding 800°C, but this involves high energy consumption and low selectivity for light olefins. Propylene is mainly produced as a byproduct in steam cracking plants and fluid catalytic cracking plants.

[0012] With increasing demand for light olefins and the introduction of alternative fuels / energy sources to replace conventional gasoline and diesel, efforts are intensifying to develop cost-effective crude oil catalytic cracking processes that achieve high propylene-ethylene yields and flexible P / E ratios, enabling them to meet fluctuating market demand with relatively low energy consumption.

[0013] Known prior art does not describe a cost-effective method using a single process unit to maximize the production of high-value petrochemical raw materials while minimizing the production of liquid fuels from crude oil.

[0014] Therefore, it is necessary to develop a single process for converting crude oil into light olefins and aromatic compounds, and in that process, it is required to provide optimal conditions for the decomposition of each component of crude oil, based on their respective decomposition behaviors. [Overview of the project] [Problems that the invention aims to solve]

[0015] The primary objective of the present invention is to provide a process for converting crude oil into light olefins and aromatic compounds in a single step.

[0016] Another object of the present invention is to convert crude oil, preferably crude oil with a low organometallic content, into light olefins and aromatic compounds using a dual catalytic cracking reactor system.

[0017] A further objective of the present invention is to enable the production of high value-added petrochemical raw materials directly from crude oil and the production of liquid fuels to be maximized and minimized using a single process unit.

[0018] A further object of the present invention is to provide optimal reaction conditions for the decomposition of each component of crude oil, based on their respective decomposition behaviors. [Means for solving the problem]

[0019] This abstract is provided to introduce, in a simplified form, some of the concepts that will be further elaborated in the detailed description of the invention. This abstract is not intended to identify the main or essential inventive concepts of the invention, nor is it intended to define the scope of the invention.

[0020] The present invention provides a one-step process for converting crude oil into light olefins and aromatic compounds. The process includes fractionating a crude oil stream (1) into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3) using a fractional distillation column (A). Subsequently, the light oil (LO) fraction (2) is sent to a high-density fluidized bed reactor (B) together with a first co-treatment feed stream (4). Subsequently, the heavy oil (HO) fraction (3) is sent to the upflow reactor section of an upflow reactor / stripper (C) together with a second co-treatment feed stream (6). Next, catalytic cracking of the light oil (LO) fraction (2) is performed in the high-density fluidized bed reactor (B) in the presence of a cracking catalyst and the first co-treatment feed stream (4). In addition, catalytic cracking of the heavy oil (HO) fraction (3) is performed inside the upflow reactor (C) in the presence of a partially deactivated catalyst and the second co-treatment feed stream (6). Here, the high-density fluidized bed reactor (B) supplies the first reactor effluent (5), and the upflow reactor (C) supplies the second reactor effluent (7).

[0021] Subsequently, at the end of the high-density fluidized bed reactor (B), the first reactor effluent (5) is separated from the partially deactivated catalyst, and at the end of the upflow reactor section of the upflow reactor / stripper (C), the second reactor effluent (7) is separated from the spent catalyst. The first reactor effluent (5) and the second reactor effluent (7) are sent to the product separation unit (E), where the product separation unit (E) separates the first reactor effluent (5) and the second reactor effluent (7) into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10).

[0022] Next, the light liquid fraction (9) is fed into the high-density fluidized bed reactor (B), and the heavy liquid fraction (10) is fed into the upstream reactor (C). Here, the high-density fluidized bed reactor (B) and the upstream reactor (C) are arranged so that the catalyst flows in series and in contact with each other. Partially deactivated catalyst flows from the high-density fluidized bed reactor (B) to the upflow reactor (C) via the first conduit (11). Stripping of spent catalyst to remove hydrocarbons mixed between individual catalyst particles is performed using steam in the stripper section of the upflow reactor / stripper (C). The spent catalyst received from the stripper section of the upflow reactor is transferred to the combustor (D) via the second conduit (12), where it is combusted in the combustor (D) in the presence of oxygen-containing gas (14) to obtain a regenerated catalyst. Here, the regenerated catalyst is recycled back to the high-density fluidized bed reactor (B) via the third conduit (13).

[0023] The present invention provides optimal conditions for the decomposition of each component of crude oil based on their decomposition behavior. The heavy fraction of crude oil requires a short residence time and low temperature to maximize light olefins and reduce dry gas, while the light fraction of crude oil requires a longer residence time and higher temperature. The present invention provides optimal conditions by sending heavy oil to an upflow reactor with a short residence time of 2 to 5 seconds and a low temperature of 500 to 600°C, and sending light oil to a high-density fluidized bed reactor with a long residence time of 5 to 15 seconds and a high temperature of 600 to 700°C. The product gas (gas) resulting from the decomposition of light oil is not introduced into the decomposition section of heavy crude oil, and vice versa, so that over-decomposition of decomposition products can be prevented. Furthermore, the catalyst containing a small amount of coke supplied from the high-density fluidized bed reactor improves olefin selectivity in the decomposition of heavy oil in the upflow reactor.

[0024] The present invention provides a dual catalyst cracking reactor system for converting crude oil into light olefins and aromatic compounds in a single step. This reactor system is composed of a fractionation column (A), a high-density fluidized bed reactor (B), an upflow reactor (C), a product separation section (E), and a combustor (D).

[0025] The fractionation column (A) is configured to fractionate the crude oil stream (1) into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3). In the high-density fluidized bed reactor (B) connected to the fractionation column (A), the light oil (LO) fraction (2) from the fractionation column (A) is transferred to the high-density fluidized bed reactor (B), where catalytic cracking is carried out in the presence of a cracking catalyst to produce a first reactor effluent (5). Furthermore, to increase the yield of light olefins, a dimethyl ether or methanol stream (4) can be co-processed in the high-density fluidized bed reactor.

[0026] The upflow reactor (C) is connected to the fractionation column (A), and the heavy oil (HO) fraction (3) from the fractionation column (A) is transferred to the upflow reactor (C) for catalytic cracking in the presence of a partially deactivated catalyst and to generate a second reactor effluent (7). Furthermore, to increase the yield of light olefins, a diethyl ether or ethanol stream (6) can be co-treated in the upflow reactor / stripper. The injection of ethanol generates water during the ethanol dehydration reaction, which lowers the partial pressure of hydrocarbons, suppresses coke deposition, and improves the selectivity of the light olefin yield. In addition, the ethanol stream is treated in a catalyst layer located above the stripper section of the upflow reactor / stripper (C) prior to the stripping process, generating light olefins and contributing to the cooling of the combustor (D) because the ethanol dehydration reaction is an endothermic reaction. This allows the combustor temperature to be controlled by adjusting the amount of ethanol treated in the catalyst layer above the stripper section, making it effective for processing heavy crude oil. Stripping of the spent catalyst (a process to remove hydrocarbons adhering between individual catalyst particles) is performed using steam in the stripper section of the upflow reactor / stripper (C) before sending it to the combustor (D).

[0027] The product separation section (E) is connected to the high-density fluidized bed reactor (B) and the upflow reactor (C), and the product separation section (E) separates the first reactor effluent (5) and the second reactor effluent (7) into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10).

[0028] The combustor (D) is connected to the upflow reactor (C) via the second conduit (12), wherein the combustor (D) combusts the spent catalyst from the upflow reactor (C) to obtain a regenerated catalyst. Here, the regenerated catalyst is recirculated to the high-density fluidized bed reactor (B) via the third conduit (13). Here, the high-density fluidized bed reactor (B) and the upflow reactor (C) are arranged such that the catalyst flow is in serial contact, and the partially deactivated catalyst flows from the high-density fluidized bed reactor (B) to the upflow reactor (C) via the first conduit (11). BRIEF DESCRIPTION OF THE DRAWINGS

[0029] These features, aspects, and advantages of the present invention will be better understood when reading the following detailed description with reference to the accompanying drawings. Note that like numerals represent like parts throughout the drawings. [Figure 1] A process flow diagram of a dual catalytic cracking reactor system for converting crude oil into light olefins and aromatic compounds in a single step is shown. [Figure 2] The trend of CO2 concentration from synthetic air to the combustor against the gradual increase in the CCR processing suitability of the feedstock is shown. DETAILED DESCRIPTION OF EMBODIMENTS FOR CARRYING OUT THE INVENTION

[0030] The present invention solves the drawbacks of the prior art, and provides a method for converting crude oil into light olefins and aromatic compounds, as well as a system for converting crude oil into light olefins and aromatic compounds. Further, this conversion method in the dual catalytic cracking reactor is cost-effective, simple, efficient and rapid, and the time required for controlling the conversion rate is short. In addition, the present invention provides optimal conditions for the cracking of each component of crude oil based on their cracking behaviors.

[0031] While the heavy components of crude oil require short residence times and low temperatures, the light components require longer residence times and higher temperatures to maximize light olefins and reduce dry gases. This invention provides these optimal conditions by sending heavy oil to an upflow reactor with a short residence time of 2-5 seconds and a low temperature of 500-600°C, and light oil to a high-density layer reactor with a long residence time of 5-15 seconds and a high temperature of 600-700°C. The product gases generated from the cracking of light oil are not introduced into the cracking section of heavy crude oil, and vice versa, thus helping to prevent over-cracking of cracking products. Furthermore, a catalyst containing mild coke supplied from the high-density layer reactor improves olefin selectivity in the cracking of heavy oil in the upflow reactor.

[0032] For the purpose of facilitating the understanding of the principles of this disclosure, embodiments shown in the drawings will be referenced and specific terminology will be used to describe them. However, it should be understood that this is not intended to limit the scope of this disclosure, and such modifications and further improvements to the illustrated systems, as well as further applications of the principles of this disclosure that a person skilled in the art could ordinarily conceive of, are anticipated. Unless otherwise defined, all technical and scientific terms used herein have the meanings generally understood by a person skilled in the art to which this disclosure belongs. The systems, methods, and embodiments described herein are illustrative and not intended to limit the scope.

[0033] Methods and materials similar to or equivalent to those described herein may also be used in carrying out or testing the present invention, but preferred methods and materials are described here. All publications referenced herein are incorporated herein by reference to disclose and explain methods and / or materials relating to the cited publications.

[0034] It should be noted that, unless otherwise specified in this specification and the appended claims, the singular forms "a," "and," and "the" include multiple subjects. Therefore, for example, a reference to "compound" includes multiple such compounds, and a reference to "step" includes one or more steps and their equivalents well known to those skilled in the art.

[0035] As used herein, the term "some" is defined as "none, one, one or more, or all." Thus, terms such as "none," "one," "one or more," "one or more but not all," or "all" are all included in the definition of "some." The term "some embodiments" may refer to no embodiments at all, one embodiment, multiple embodiments, or all embodiments. Thus, the term "some embodiments" is defined as meaning "no embodiments at all, one embodiment, one or more embodiments, or all embodiments."

[0036] The terms and constructs used herein are for the purpose of describing, teaching, and clarifying certain embodiments and their specific features and elements, and are not intended to limit, restrict, or diminish the spirit and scope of the claims or their equivalents.

[0037] More specifically, any terms used herein, including but not limited to “contains,” “constitutes,” “has,” “spans,” and their grammatical variations, are inclusive or open and do not preclude any additional elements or steps of method not described herein. This specification is understood to also include embodiments having the conjunction “spans” or “essentially consists” instead of the conjunction “contains.” The conjunction “spans of” excludes any elements, steps, or components not expressed in the claim, except for any impurities associated with it. The conjunction “spans essentially of” limits the scope of the claim to the expressed materials or steps “and not substantially affect the basic and novel characteristics of the claimed disclosure.”

[0038] Regardless of whether a particular feature or element is limited to a one-time use or not, in either case, they may still be expressed as “one or more features” or “one or more elements,” or “at least one feature” or “at least one element.” Furthermore, the use of the terms “one or more” or “at least one” feature or element does not exclude cases where that feature or element is not present at all, unless otherwise specified by restrictive phrases such as “one or more are required” or “one or more elements are required.”

[0039] In this specification, the term "about" is used to indicate the degree or tolerance of variation in numerical or quantitative values. This is not intended to strictly limit the disclosed values, but rather to indicate that they may vary within ±5% without departing the scope of the invention. Unless otherwise defined, all terms used herein, in particular technical and / or scientific terms, shall be construed as having the same meaning as that generally understood by those skilled in the art.

[0040] This specification refers to several “embodiments.” It should be understood that embodiments are possible examples of any features and / or elements described in the appended claims. Some embodiments are described for the purpose of revealing one or more potential ways in which certain features and / or elements of the appended claims satisfy the requirements of originality, usefulness, and non-obviousness.

[0041] The use of “First Embodiment,” “Further Embodiment,” “Alternative Embodiment,” “One Embodiment,” “Embodiment,” “Multiple Embodiments,” “Several Embodiments,” “Other Embodiments,” “Further Embodiments,” “Even Further Embodiments,” “Additional Embodiments,” or variations thereof, does not necessarily refer to the same embodiment. Unless otherwise specified, one or more specific features and / or elements described in relation to one or more embodiments may be found in one embodiment, multiple embodiments, all embodiments, or none of any embodiment. Wherein this specification one or more features and / or elements are described in the context of a single embodiment only, in the context of multiple embodiments, or in the context of all embodiments, those features and / or elements may instead not be provided individually, in any suitable combination, or not at all. Conversely, features and / or elements described in the context of separate embodiments may be realized as coexisting in the context of a single embodiment.

[0042] In this specification, the term "cracking" refers to a technique or process for breaking down large, complex hydrocarbons into smaller, lighter components.

[0043] In this specification, the terms “method” and “process” are used interchangeably.

[0044] The present invention provides a method for converting crude oil into light olefins and aromatic compounds in a single step, and also provides a dual-catalyst cracker reactor consisting of two cracking reactors connected in series with respect to the flow of catalyst.

[0045] Specifically, the present invention provides a single-step process for converting crude oil into light olefins and aromatic compounds. This process includes fractionating a crude oil stream (1) into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3) using a fractional distillation column (A). Subsequently, the light oil (LO) fraction (2) is sent to a high-density fluidized bed reactor (B), and the heavy oil (HO) fraction (3) is sent to an upstream reactor (C).

[0046] In one embodiment, the present invention provides a process for converting crude oil into light olefins and aromatic compounds. This process includes the step of fractionating a crude oil stream (1) through a fractionation column (A) into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3). Subsequently, the light oil (LO) fraction (2) is sent to a high-density fluidized bed reactor (B) along with a first co-processing feed stream, such as a dimethyl ether or methanol stream (4), as is optional. Subsequently, the heavy oil (HO) fraction (3) is sent to an upflow reactor (C) along with a second co-processing feed stream, such as a diethyl ether or ethanol stream (6), as is optional.

[0047] Subsequently, catalytic cracking of the light oil (LO) fraction (2) is carried out in a high-density fluidized bed reactor (B) in the presence of a cracking catalyst, and catalytic cracking of the heavy oil (HO) fraction (3) is carried out in an upflow reactor (C) in the presence of a partially deactivated catalyst.

[0048] In another embodiment, a first co-processing stream is introduced into a high-density fluidized bed reactor along with a diesel (LO) fraction, and a second co-processing stream is introduced into an upflow reactor along with a heavy oil (HO) fraction. Subsequently, catalytic cracking of the diesel (LO) fraction (2) is performed in the high-density fluidized bed reactor (B) in the presence of a cracking catalyst and other co-processing feed streams such as dimethyl ether or methanol (4), and catalytic cracking of the heavy oil (HO) fraction (3) is performed inside the upflow reactor (C) in the presence of a partially deactivated catalyst and other co-processing feed streams such as diethyl ether or ethanol (6).

[0049] Here, the high-density fluidized bed reactor (B) supplies the first reactor effluent (5), and the upflow reactor (C) supplies the second reactor effluent (7). The catalyst is deactivated by the accumulation of carbonaceous material called coke. The amount of coke accumulation on the catalyst depends on the quality of the raw materials and the degree of cracking. Catalyst deactivation due to coke accumulation in the high-density fluidized bed reactor is minimized to less than 0.2% of the catalyst due to the use of light raw materials. The spent catalyst produced in the high-density fluidized bed reactor is sufficiently active to decompose heavier raw materials. On the other hand, with heavier raw materials, the amount of carbonaceous material accumulation is much greater, sometimes reaching 1% by weight of the catalyst. In addition, organometallic compounds contained in heavier raw materials also accumulate, leading to significant catalyst deactivation.

[0050] Subsequently, at the outlet of the high-density fluidized bed reactor (B), the first reactor effluent (5) is separated from the partially deactivated catalyst, and at the outlet of the rising-flow reactor (C), the second reactor effluent (7) is separated from the used catalyst, and the first reactor effluent (5) and the second reactor effluent (7) are sent to the product separation unit (E). Here, the product separation unit (E) separates the first reactor effluent (5) and the second reactor effluent (7) into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10).

[0051] Next, the light liquid fraction (9) is led to the high-density fluidized bed reactor (B), and the heavy liquid fraction (10) is led to the upstream reactor (C). Here, the high-density fluidized bed reactor (B) and the upstream reactor (C) are arranged in series with respect to the catalyst flow and are in fluid contact. Partially deactivated catalyst from the high-density fluidized bed reactor (B) is transferred to the upflow reactor (C) via the first conduit (11). Stripping of the spent catalyst to remove hydrocarbons adhering between individual catalyst particles is performed using steam in the stripper section of the upflow reactor / stripper (C). The spent catalyst received from the stripper section of the upflow reactor (C) is transferred to the combustor (D) via the second conduit (12), where it is combusted in the combustor (D) in the presence of an oxygen-containing gas including synthetic air consisting of O2, CO2, and N2 to obtain a regenerated catalyst. Here, the regenerated catalyst is recycled to the high-density fluidized bed reactor (B) via a third conduit (13).

[0052] In one embodiment, the diesel (LO) fraction (2) is composed of C5-C20 hydrocarbons, has a density in the range of 0.7-0.8 g / cc, a refractive index (RI) in the range of 1.4-1.45, a molecular weight in the range of 100-175, and a temperature range of 200°C-350°C.

[0053] In one embodiment, the heavy oil (HO) fraction (3) contains C21-C70 hydrocarbons, has a density in the range of 0.90-0.99 g / cc, a refractive index (RI) in the range of 1.45-1.55, a molecular weight in the range of 400-550, a Conradson carbon ratio of 2-10% by weight, and an initial boiling point in the range of 200-350°C.

[0054] In another embodiment, the heavy oil (HO) fraction (3) consists of C21-C70 hydrocarbons, has a density in the range of 0.90-0.99 g / cc, a refractive index (RI) in the range of 1.45-1.55, a molecular weight in the range of 400-550, a Conradson carbon content (CCR) of 2-10% by weight, and a boiling point in the range of 200°C-1000°C.

[0055] In another embodiment, the light olefin is selected from ethylene, propylene, and C4 olefins, and the aromatic compound is selected from benzene, toluene, ethylbenzene, and xylene (BTEX).

[0056] In another embodiment, catalytic decomposition of the diesel (LO) fraction (2) in a high-density fluidized bed reactor (B) is carried out with a residence time of 5 to 15 seconds, a pressure of 1 to 4 atmospheres (g), and a temperature of 600 to 700°C, where the first co-treatment feed stream (4) is selected from dimethyl ether, methanol, or a combination thereof.

[0057] In yet another embodiment, catalytic decomposition of the heavy oil (HO) fraction (3) in an upward-flow reactor (C) is carried out at a residence time of 2 to 5 seconds, a pressure of 1 to 4 atmospheres (g), and a temperature of 500 to 600°C, where the second co-treatment feed stream (6) is selected from diethyl ether, ethanol, or a combination thereof.

[0058] In another embodiment, the decomposition catalyst comprises 5-10% by weight of a pentasil-type selective zeolite, 5-10% by weight of a Y-type zeolite, iron, and a lanthanide metal, and the decomposition catalyst has a larger pore matrix component in the range of 1-20%.

[0059] In another embodiment of the present invention, the catalyst-to-oil ratio in the high-density fluidized bed reactor (B) is in the range of 10 to 25% by weight, and the catalyst-to-oil ratio in the upward-flow reactor (C) is in the range of 10 to 25% by weight.

[0060] In yet another embodiment, the gas fraction (8) consists of hydrogen, methane, ethane, ethylene, propane, propylene, and C4 fluids, where the light olefins are separated from the gas fraction (8). The light liquid fraction (9) includes cracked naphtha (C5-210°C), where the aromatic compounds are extracted from the light liquid fraction (9). The heavy liquid fraction (10) includes cycle oil and hydrocarbon streams with boiling points ranging from 210°C to 800°C.

[0061] In another embodiment, a first co-processing stream is introduced into a high-density layer reactor along with the light oil (LO) fraction, and a second co-processing stream is introduced into an upflow reactor along with the heavy oil (HO) fraction.

[0062] In another embodiment, the used catalyst received from the stripper is burned in a combustor (D), using air as the combustion gas source, and a regenerated catalyst is obtained at a temperature in the range of 650°C to 750°C. The exhaust gas (15) from the combustor, which contains 10-20% CO2, is sent to the chimney after heat recovery.

[0063] In another embodiment, the used catalyst received from the stripper is burned in a combustor (D) to obtain a regenerated catalyst at a temperature range of 650°C to 750°C using an oxygen-enriched gas stream consisting of 20-30% oxygen, CO2, and 0-5% nitrogen. In addition, some of the CO2-rich exhaust gas (15) from the combustor is recirculated back into the combustor before being sent to the chimney.

[0064] In yet another embodiment, the temperature of the high-density fluidized bed reactor (B) is maintained by adjusting the flow rate of the high-temperature regenerating catalyst.

[0065] In another embodiment, ethanol is dehydrated in a catalyst layer located above the stripper section of an upflow reactor / stripper (C) at a temperature in the range of 250-600°C, thereby lowering the temperature of the combustor (D) and enabling the processing of heavier crude oil.

[0066] Furthermore, the present invention provides a dual catalytic cracking reactor system for converting crude oil into light olefins and aromatic compounds. This reactor system comprises a fractionation column (A), a high-density fluidized bed reactor (B), an upflow reactor (C), a product separation section (E), and a combustor (D).

[0067] The fractionation column (A) is configured to fractionate the crude oil stream (1) into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3). A high-density fluidized bed reactor (B) is connected to the fractionation column (A), and the light oil (LO) fraction (2) from the fractionation column (A) is sent to the high-density fluidized bed reactor (B), where catalytic cracking takes place in the presence of a cracking catalyst, producing a first reactor effluent (5). An upflow reactor (C) is connected to the fractionation column (A), and the heavy oil (HO) fraction (3) from the fractionation column (A) is transferred to the upflow reactor (C) for catalytic cracking in the presence of a partially deactivated catalyst and to produce a second reactor effluent (7).

[0068] In one embodiment, there is a high-density fluidized bed reactor (B) connected to a fractional distillation column (A), and the diesel fuel (LO) fraction (2) from the fractional distillation column (A) is sent to the high-density fluidized bed reactor (B), where catalytic cracking is carried out in the presence of a cracking catalyst and a first co-treatment feed stream (4) to obtain a first reactor effluent (5).

[0069] In one embodiment, an upflow reactor (C) is connected to a fractional distillation column (A), and a heavy oil (HO) fraction (3) from the fractional distillation column (A) is transferred to the upflow reactor (C) for catalytic decomposition in the presence of a partially deactivated catalyst and a second co-treatment feed stream (6), and for generating a second reactor effluent (7).

[0070] The product separation unit (E) is connected to the high-density fluidized bed reactor (B) and the upflow reactor (C), and the product separation unit (E) separates the effluent (5) from the first reactor and the effluent (7) from the second reactor into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10).

[0071] The combustor (D) is connected to the upflow reactor (C) via a second conduit (12), where the combustor (D) burns the spent catalyst in the upflow reactor (C) to obtain a regenerated catalyst. The regenerated catalyst is then recycled to the high-density fluidized bed reactor (B) via a third conduit (13). The high-density fluidized bed reactor (B) and the upflow reactor (C) are arranged in series via a first conduit (11) to allow the partially deactivated catalyst to flow from the high-density fluidized bed reactor (B) to the upflow reactor (C), and the catalysts flow and come into contact with each other.

[0072] In one embodiment, a high-density fluidized bed reactor (B) is operated at a pressure in the range of 1 to 4 atmospheres, a temperature in the range of 600 to 700°C, and a residence time of 5 to 15 seconds, where the first co-processing feed stream (4) is selected from dimethyl ether, methanol, or a combination thereof.

[0073] In yet another embodiment, the upflow reactor (C) is operated at a pressure in the range of 1 to 4 atmospheres, a temperature in the range of 500 to 600°C, and a residence time of 2 to 5 seconds, where the second co-processing feed stream (6) is selected from diethyl ether, ethanol, or a combination thereof.

[0074] In yet another embodiment, the combustor (D) is operated at a temperature in the range of 650°C to 750°C to burn the spent catalyst of the upflow reactor (C) in the presence of an oxygen-containing gas (14), and the combustor (D) is supplied with exhaust gas (15) containing a regenerated catalyst and 10-20% CO2.

[0075] In one embodiment, a combustor (D) is operated at a temperature in the range of 650°C to 750°C to burn coke deposited on the spent catalyst of an upflow reactor (C) in the presence of an oxygen-containing gas (14), the oxygen-containing gas (14) being burned in the presence of an oxygen-containing gas (14) consisting of 20-30% oxygen, 70-80% CO2, and 0-5% nitrogen, the combustor (D) supplies a regenerated catalyst, and a portion of the CO2-rich exhaust gas (15) is recirculated to the combustor (D).

[0076] In another embodiment, the used catalyst received from the stripper is burned in a combustor (D) and a regenerated catalyst is obtained at a temperature range of 650°C to 750°C using an oxygen-enriched stream (14) consisting of 20-30% oxygen, 70-80% CO2, and 0-5% nitrogen. In addition, some of the CO2-rich exhaust gas (15) from the combustor is recirculated back into the combustor before being sent to the chimney.

[0077] In another embodiment of the present invention, the gas fraction (8) consists of hydrogen, methane, ethane, ethylene, propane, propylene, and C4 hydrocarbon fluids, where the light olefin is separated from the gas fraction (8).

[0078] In another embodiment of the present invention, the catalyst-to-oil ratio of the high-density fluidized bed reactor (B) is in the range of 10 to 25% by weight, and the catalyst-to-oil ratio of the upward-flow reactor (C) is in the range of 10 to 25% by weight.

[0079] In another embodiment, the decomposition catalyst comprises 5-10% by weight of a pentasil-type selective zeolite, 5-10% by weight of a Y-type zeolite, iron, and a lanthanide metal, and the decomposition catalyst has a larger pore matrix component in the range of 1-20%.

[0080] In another embodiment of the present invention, the light liquid fraction (9) comprises decomposed naphtha at C5-210°C, where aromatic compounds are extracted from the light liquid fraction (9), and after the extraction of aromatic compounds, the light liquid fraction (9) is transferred to a high-density fluidized bed reactor (B).

[0081] In another embodiment, the heavy liquid fraction (10) comprises a light cycle oil, a heavy cycle oil, and a hydrocarbon stream with a boiling point from 210°C to 800°C, and the heavy liquid fraction (10) is transferred to an upflow reactor (C).

[0082] In another aspect, the present invention provides a single-step dual-catalyst cracker reactor system for cracking crude oil or crude oil mixtures in a single process to produce light olefins (ethylene, propylene, C4 olefins) and benzene, toluene, ethylbenzene, and xylene (BTEX) in high yield. Benzene, toluene, ethylbenzene, and xylene (BTEX) are extracted from a naphtha stream. The dual-catalyst cracker reactor consists of two cracking reactors: a high-density fluidized bed reactor and an upflow reactor. The temperatures of the high-density fluidized bed reactor and the upflow reactor are maintained in the ranges of 600-700°C and 500-600°C, respectively. This single-stage dual-catalyst cracker reactor system process scheme allows refineries to maximize the production of high-value petrochemical feedstocks and minimize the production of liquid fuels directly produced from crude oil, using a single process unit.

[0083] In another embodiment, the present invention also provides a coupling catalytic cracking reaction of light oil (LO) and heavy oil (HO). In this reaction, the catalytic cracking reaction of light oil (LO) and heavy oil (HO) coupled with the production of dimethyl ether, diethyl ether, and dipropyl ether is carried out in a bubbling bed reactor and an upflow reactor, respectively, at high temperature in the presence of a catalyst to produce light olefins. Alternatively, short-chain alcohols, particularly methanol, ethanol, and propanol, are injected into the reactor to produce the respective ethers in situ. At high temperature in the presence of an acidic catalyst, the alcohols undergo a dehydration reaction to produce the respective light olefins and ethers. The olefinic light naphtha produced in this process is recycled to a high-density fluidized bed reactor to maximize the yield of light olefins, and the bottom fraction, which boils at 350°C or higher, is recycled to an upflow reactor for heat balance.

[0084] In another embodiment, a process is provided for the single-step conversion of crude oil into light olefins and aromatic compounds. In this process, ethanol is injected into an upflow reactor, and the water produced during the dehydration of ethanol reduces the partial pressure of hydrocarbons, thereby reducing coke buildup and improving the selectivity of the light olefin yield. Furthermore, since ethylene is produced by the dehydration of ethanol, the process and catalyst system disclosed herein are useful in adjusting the propylene-to-ethylene ratio of the product.

[0085] In another embodiment, the ethanol stream is treated in a catalyst layer located above the stripper section of the upflow reactor / stripper (C) to produce ethylene. Furthermore, since ethanol dehydration is an endothermic reaction, it is possible to lower the temperature of the combustor (D), and the combustor temperature can be controlled by changing the amount of ethanol treated in the catalyst layer located above the stripper section of the upflow reactor / stripper (C), making it useful for processing heavy crude oil. Stripping of the spent catalyst (removal of hydrocarbons adhering between individual catalyst particles) is performed using steam in the stripper section of the upflow reactor / stripper (C) before sending it to the combustor (D).

[0086] Another aspect is that the combustor temperature is controlled using the oxygen combustion method. In this method, oxygen is used instead of air in the combustor, and the CO2 produced during combustion is recirculated back into the combustor. In combustion with air, only O2 is consumed, while N2 acts as an inert gas and a heat absorber. However, in the proposed oxygen combustion method, air is replaced with synthesis gas containing oxygen and recirculated CO2. The composition of the synthesis gas is 20-30% oxygen, 70-80% carbon dioxide, and 0-5% nitrogen. By using carbon dioxide instead of nitrogen, the molecular weight (MW) and specific heat capacity (Cp) of the synthetic air flue gas increase, resulting in an increase in the amount of heat carried by the flue gas. This lowers the combustor temperature, which is helpful in processing heavy crude oil. [Examples]

[0087] The present invention is further described with reference to the following examples. These examples are for illustrative purposes only and do not limit the scope of the disclosure in any way. These examples are not intended to cover all aspects of the subject matter disclosed herein, but rather to illustrate representative features, methods, compositions, and results. These examples are not intended to exclude equivalents or modifications of the invention that would be obvious to those skilled in the art. Furthermore, the present invention is embodied by the following non-limiting examples.

[0088] material and method Raw materials: The process described herein is an improved fluid catalytic cracking process for converting crude oil, preferably crude oil with a low content of organometallic compounds, in two reactors. Before cracking, the crude oil or crude oil mixture is separated into a light oil (LO) fraction and a heavy oil (HO) fraction. LO is a fraction with a boiling point of 350°C or less and consists of molecules having 5 to 20 carbon atoms. The remaining crude oil fraction, i.e., HO, consists of molecules having up to 75 carbon atoms. The boiling points of LO and HO are adjusted according to the types of hydrocarbons contained in LO and the desired products. LO is catalytically cracked in a high-density fluidized bed reactor, and HO is catalytically cracked in an upflow reactor. The two cracking reactors are a high-density fluidized bed reactor (B) operated at a higher temperature and an upflow reactor (C) operated at a relatively lower temperature.

[0089] Dimethyl ether or methanol is co-treated with LO in a high-density fluidized bed reactor, while dimethyl ether, diethyl ether, or ethanol is co-treated with HO in an upward-flow reactor. Alternatively, methanol and ethanol can be injected into the reactor to produce dimethyl ether and / or diethyl ether in situ, respectively. Methanol is dehydrated to produce dimethyl ether (CH3OCH3), while ethanol is dehydrated to light olefins via diethyl ether and ethylene. Diethyl ether is further dehydrated to produce ethylene. The ratio of methanol to LO is in the range of 0 to 1.0 (by weight), and the ratio of ethanol to HO is in the range of 0 to 1.0 (by weight). The LO supplied to the high-density fluidized bed reactor has a density of 0.7 to 0.8 g / cc, a refractive index of 1.4 to 1.45, and a molecular weight of 100 to 175, depending on the type of crude oil and final boiling point. The density of HO supplied to the upflow reactor is 0.90–0.99 g / cc, the refractive index is 1.45–1.55, the molecular weight is 400–550, and the Conradson carbon ratio (CCR) is 2–10 wt%, which vary depending on the type of crude oil and the initial boiling point.

[0090] The decomposition of LO in a close-bed reactor and the decomposition of HO in an upflow reactor are mutually beneficial in maintaining the thermal stability of the entire process. The amount of coke produced in the close-bed reactor during LO decomposition is very small, as the carbon content in the catalyst is less than 0.2%, and is insufficient to provide the preheating, vaporization, and supply necessary for the endothermic decomposition of LO. Since coke deposition on the catalyst is minimal during LO decomposition, there is no significant adverse effect on HO decomposition in the upflow reactor. On the other hand, HO decomposition in the upflow reactor generates high concentrations of coke, reaching up to 1% by weight of the catalyst. This coke is burned in the combustor during catalyst regeneration, and the heat generated is supplied to the high-density bed reactor via the regenerated catalyst.

[0091] Process conditions: The high-density fluidized bed reactor and upflow reactor are arranged in series with respect to the catalyst flow, creating a fluid-contact structure. Because the feedstock oil (LO) contains low-boiling hydrocarbons, the formation of carbonaceous deposits (coke) within the catalyst's zeolite pores during cracking in the high-density fluidized bed reactor is minimized, and the reduction in catalytic efficiency is also minimized. Residence times in the high-density fluidized bed reactor and upflow reactor range from 5–15 seconds and 2–5 seconds, respectively. Temperatures in the high-density fluidized bed reactor and upflow reactor are maintained in the ranges of 600–700°C and 500–600°C, respectively. The decomposition reaction occurs in the gas phase. LO and HO are atomized using vapor as a dispersant. Ether or alcohol is injected into each reactor individually. The amount of vapor injected into the high-density fluidized bed reactor and upflow reactor varies from 5–100% of the feed rate. Since the decomposition reaction in both reactors is endothermic, the necessary heat must be generated in the combustor by burning the coke produced in the high-density fluidized bed reactor and the upward-flow reactor. In the absence of an external supply of coke or heat, the reactor's heat balance is ensured by adjusting the cut range of the LO and HO fractions in the crude oil, the amount of recycled material, and the decomposition temperature in the high-density fluidized bed reactor and the upward-flow reactor.

[0092] catalyst: The catalyst consists of 5-10 wt% pentasil-type selective zeolite, 5-10 wt% Y-type zeolite, iron, lanthanide metals, and a large-pore matrix. Long-chain hydrocarbons are broken down into smaller molecules by cleaving carbon-carbon bonds. The decomposition rate is highly dependent on the properties of the hydrocarbon, the catalyst, and the temperature. The catalyst composition in terms of zeolite content and temperature is optimized based on the type of hydrocarbon, the number of carbon atoms, and the boiling point of the crude oil.

[0093] Table 1 shows the typical physical properties of crude oil.

[0094] [Table 1] [Examples]

[0095] Disadvantages of processing all crude oil without pre-fractionation in a conventional high-severity FCC riser reactor: This example is presented as reference data for analyzing the cracking potential of total crude oil under catalytic cracking conditions. This example shows the case where total crude oil is processed without preliminary fractionation in a conventional high-severity FCC riser reactor.

[0096] In this embodiment, the riser outlet temperature was maintained at 580°C, and the yield of the target final product is shown in Table 2.

[0097] [Table 2]

[0098] Table 2 shows that when all crude oil is processed in a high-intensity riser-type catalytic cracking unit, a chemical conversion rate of 28-32% by weight can be obtained.

[0099] The present invention will be explained by the following examples. [Examples]

[0100] Process flow for converting crude oil into light olefins and aromatic compounds: Fractional distillation of crude oil into diesel (LO) and heavy fuel (HO) fractions: Crude oil or a crude oil mixture (1) is separated into a light oil (LO) fraction (2) and a heavy oil (HO) fraction (3) in a crude oil fractionation column (A). The boiling point ranges of LO and HO are adjusted according to the cracking properties of the raw materials and the composition of the LO·HO fractions in the crude oil.

[0101] The high-density fluidized bed reactor (B) is operated at 650°C, and the upflow reactor (C) is operated at a riser outlet temperature of 580°C. The high-density fluidized bed reactor (B) and the upflow reactor (C) are arranged in series with respect to the catalyst flow and are in fluid contact. Because LO contains low-boiling hydrocarbons, the formation of carbonaceous deposits (coke) in the zeolite pores of the catalyst in the high-density fluidized bed reactor (B) is minimized, and the partially deactivated catalyst after the decomposition of LO is sent to the upflow reactor through the first conduit (11). In the upflow reactor (C), HO comes into contact with the partially deactivated catalyst, producing light olefins. During cracking, carbonaceous deposits (coke) form in the zeolite pores of the catalyst, which leads to temporary deactivation of the catalyst and a decrease in catalytic efficiency, thus requiring regeneration. Coke deposition on the catalyst not only reduces catalytic activity and selectivity but also affects the product yield. Nickel, vanadium, and iron contained in HO also deposit on the circulating catalyst along with organometallic compounds. The coked or spent catalyst and decomposed hydrocarbons are separated at the end of the upflow reactor.

[0102] Dispensing of the LO and HO fractions to the reactor: The LO fraction (2) of the crude oil is sent separately with the catalyst to a high-density fluidized bed reactor (B), where it is decomposed into light olefins and aroma-rich naphtha in the presence of the catalyst. The heavy oil (HO) fraction of the crude oil is sent separately with the catalyst (3) to an upflow reactor / stripper (C), where it is catalytically decomposed to light olefins, aroma-rich naphtha, and various other products. Furthermore, a dimethyl ether or methanol stream (4) is co-processed with the LO fraction (2) in the high-density fluidized bed reactor to increase the yield of light olefins. A diethyl ether or ethanol stream (6) is co-processed with the HO fraction (3) in the upflow reactor to increase the yield of light olefins.

[0103] Transfer of decomposition products from the reactor to the product separation section for the separation of light olefins and aromatic compounds: Decomposition products or reactor effluent (5) from the high-density fluidized bed reactor (B) and decomposition products (7) from the upflow reactor are separated from the partially deactivated catalyst and then sent to the product separation section (E). Here, the product separation section (E) separates the decomposition product streams from the high-density fluidized bed reactor (stream 5) and the upflow reactor (stream 7) into the following fractions: gas fractions released from stream 8 (hydrogen, methane, ethane, ethylene, propane, propylene, and C4 stream), light liquid fractions released from stream 9 (decomposed naphtha C5 - 210°C) which are discharged from stream 9, and heavy liquid fractions (light and heavy cycle oils, 210°C). + ) is discharged from stream 10. C2, C3, and C4 olefins are separated from the gas fraction (8), while the C5-210°C stream, preferably the C5-150°C stream, of the light liquid fraction (9) is recycled to the high-density fluidized bed reactor (B). Heavy liquid product fraction (10), 210°C + Stream, preferably 370°C + The stream is returned to the upflow reactor for heat balance. Benzene, toluene, ethylbenzene, and xylenes (BTEX) are extracted from the unreacted light liquid product fraction (9). The desired residence time of hydrocarbons in the high-density fluidized bed reactor is achieved by adjusting the amount of catalyst, while the desired residence time of 2 to 5 seconds in the upflow reactor is achieved by adjusting the HO supply and vapor flow rate.

[0104] Injection of coke into the combustor and circulation of the regenerated catalyst to the dense-phase fluidized bed reactor (B): The spent catalyst from the upflow reactor is sent to the combustor (D) through a second conduit (12) after steam stripping to burn off the coke that has accumulated during the reaction. In the combustor (D), the coke is burned by supplying air or an oxygen-containing gas (14). Since the combustion of coke with an oxygen-containing gas is an exothermic reaction, the temperature of the combustor rises by 100-200°C. The temperature of the combustor is usually maintained in the range of approximately 650°C to 750°C. The exhaust gas (15) from the combustor is either discharged into the chimney or recirculated back into the combustor with pure oxygen.

[0105] The high-temperature regenerating catalyst is returned to the high-density fluidized bed reactor (B) through a third conduit (13), forming a circulating loop appropriately positioned between the combustor (D) and the upward-flow reactor (C). The temperature of the high-density fluidized bed reactor is maintained by adjusting the flow rate of the high-temperature regenerating catalyst. Figure 1 shows the process flow diagram.

[0106] The crude oil samples were fractionated according to ASTM D2892, and Table 3 shows the physical properties of the fractionated samples (LO and HO), such as density and distillation data.

[0107] [Table 3]

[0108] The light liquid fraction, consisting of light naphtha (C5-150°C) discharged from the fractionation column (E), is rich in olefins and is a promising raw material for the high-temperature dense-bed cracker reactor. Therefore, the light naphtha (C5-150°C) is recycled to the high-density fluidized bed reactor (B). The heavy oil fraction (stream with boiling points of 370°C to 1000°C) is recycled to the upflow reactor / stripper (C).

[0109] [Table 4]

[0110] Table 4 shows that treating the LO fraction and HO fraction in a high-density fluidized bed reactor and an upward flow reactor, respectively, improved the chemical yields of light olefins and aromatic compounds, with the greatest improvement in chemical yield observed in crude oil-3. [Examples]

[0111] Crude oil is fractionated into an LO fraction (boiling point up to 350°C) and an HO fraction (boiling point above 350°C). In this example, the entire crude oil was fractionated according to ASTM D2892 into light oil with a boiling point below 350°C and heavy oil with a boiling point above 350°C. Table 5 shows the characteristics of the fractionated samples (LO and HO).

[0112] [Table 5]

[0113] Here, the LO fraction is sent to a high-density fluidized bed reactor (B), and the HO fraction is sent to an upflow reactor / stripper (C). Similar to Example 2, the light liquid fraction consisting of light naphtha (C5-150°C) discharged from the fractionation column (E) is recirculated to the high-density fluidized bed reactor (B) to increase the olefin yield, and the heavy oil fraction is recirculated to the upflow reactor / stripper (C) to achieve thermal balance. The upflow reactor is operated at a riser outlet temperature of 580°C, and the high-density fluidized bed reactor is operated at 650°C. The yields of the main final products in this example are shown in Table 6.

[0114] [Table 6]

[0115] Table 6 shows that adjusting the cut points for LO and HO improves the chemical yield, and this process scheme achieves a chemical conversion rate of approximately 47% by weight of crude oil. [Examples]

[0116] Conversion of crude oil into light olefins and aromatic compounds in combination with alcohols. Example 4 is an extension of Examples 2 and 3, and in addition to the single-step process scheme shown in Examples 2 and 3, ethanol is also treated in an upward-flow reactor / stripper (C). The injection of ethanol generates water during ethanol dewatering, thereby lowering the partial pressure of hydrocarbons, reducing coke buildup, and improving the selectivity of the light olefin yield. The ethanol is decomposed in the upward-flow reactor at different temperatures in the range of 550-600°C, and the resulting ethylene yields are shown in Table 7.

[0117] [Table 7]

[0118] Treating with 20% by weight (crude oil basis) ethanol increases the ethylene yield by 9.8% by weight (crude oil basis). The total chemical yields of light olefins and aromatic compounds obtained by treating with 20% by weight ethanol in addition to the feedstock stream, as shown in Examples 2 and 3, are shown in Tables 8 and 9, respectively. Therefore, treating with ethanol in an upflow reactor allows for adjustment of the propylene / ethylene (P / E) ratio of the product stream, thereby increasing process flexibility.

[0119] [Table 8]

[0120] Table 8 shows the chemical yields (ethylene, propylene, C4 olefin, and BTEX) obtained by adding 20% ​​by weight of ethanol to crude oil fractions, such as the LO fraction with a boiling point below 200°C and the heavy oil (HO) fraction with a boiling point above 200°C, in an upflow reactor, according to the process flow diagram shown in Figure 1.

[0121] [Table 9]

[0122] Table 9 shows the chemical yields (ethylene, propylene, C4 olefin, and BTEX) obtained from crude oil fractions treated with the process shown in Figure 1, further by adding 20% ​​by weight of ethanol in an upflow reactor, i.e., the LO fraction with a boiling point below 350°C and the HO fraction with a boiling point above 350°C. From the above examples, it is clear that the simple process scheme disclosed in the present invention yields high yields of light olefins and aromatic compounds (ethylene, propylene, C4 olefin, and BTEX) of 53-57% by weight, and also provides flexibility in adjusting the propylene / ethylene (P / E) ratio of the product stream. [Examples]

[0123] Conversion of heavy crude oil into light olefins and aromatic compounds in combination with alcohols. This embodiment demonstrates that heavy crude oil can be processed in the present invention by injecting ethanol into a catalyst layer located at the top of the stripper section of an upflow reactor / stripper (C). The challenge in processing heavy crude oil is that the high content of coke precursors and residues (CCR) increases coke production, resulting in a rise in combustor temperature. By processing ethanol in the catalyst layer located at the top of the stripper, the catalyst coming from the upflow riser is cooled before reaching the combustor. The stripper temperature is maintained between 250 and 600°C, depending on the amount of ethanol dehydrated in the stripper. As the temperature difference between the stripper and the combustor increases, it becomes possible to process heavier raw materials while maintaining the combustor temperature below 750°C. Thus, catalyst activity can be maintained. As the residue (CCR) in the raw material increases, it is necessary to process more ethanol in the catalyst layer located at the top of the stripper in order to maintain the optimal regenerator temperature. Therefore, a symbiotic relationship arises between the CCR of the raw material and the processable ethanol rate, which makes it possible to process low-value, high-CCR crude oil and increase the olefin yield by supplying more ethanol. Table 10 shows that in the present invention, treating ethanol with a catalyst layer provided above the stripper section improves the CCR of the crude oil and increases the processable amount.

[0124] [Table 10]

[0125] Here, "base" refers to the CCR (Cumulative Cooling Rate) of crude oil corresponding to the case where ethanol treatment in the stripper is "zero". As shown in Table 10, by increasing the amount of ethanol treatment in the catalyst layer installed at the top of the stripper, it becomes possible to process heavier crude oil while maintaining the combustor temperature at the same level as in the case of base crude oil, and to produce additional ethylene. [Examples]

[0126] Conversion of heavy crude oil to light olefins and aromatic compounds by oxygen combustion in a combustor. This embodiment demonstrates that high-density crude oil can be processed in the present invention by utilizing oxygen combustion in the combustor (D). Here, coke deposited on the catalyst sent from the stripper is combusted in the combustor (D) at a temperature in the range of 650°C to 750°C using synthetic air containing oxygen and CO2 to obtain a regenerated catalyst. The CO2-rich exhaust gas (15) from the combustor (D) is partially recirculated back to the combustor along with oxygen. Depending on the CO2 recirculation rate, the CO2 concentration in the oxygen-rich gas supplied to the combustor (D) can be varied in the range of 0 to 80%. When carbon dioxide is used instead of nitrogen, the molecular weight (MW) and specific heat capacity (Cp) of the synthetic air exhaust gas increase compared to air. The corresponding Cp of the exhaust gas also increases, and the amount of heat carried over from the combustor increases. From Figure 2, it can be seen that as the CO2 concentration in the oxygen-enriched gas increases, the possibility of processing heavier crude oil increases.

Claims

1. A fluid catalytic cracking process for converting crude oil into light olefins and aromatic compounds, i. A step of fractionating the crude oil stream (1) into a diesel fuel (LO) fraction (2) and a heavy fuel oil (HO) fraction (3) using a fractional distillation column (A), ii. A step of sending the light oil (LO) fraction (2) to a high-density fluidized bed reactor (B) together with a first co-processing stream as needed, and sending the heavy oil (HO) fraction (3) to an upflow reactor (C) together with a second co-processing stream as needed, iii. A step of performing catalytic cracking of the light oil (LO) fraction (2) in the presence of a cracking catalyst in the high-density fluidized bed reactor (B), and performing catalytic cracking of the heavy oil (HO) fraction (3) in the presence of a partially deactivated catalyst in the upflow reactor (C), wherein the high-density fluidized bed reactor (B) is supplied with a first reactor effluent (5), and the upflow reactor (C) is supplied with a second reactor effluent (7). iv. The process of separating the first reactor effluent (5) from the partially deactivated catalyst at the end of the high-density fluidized bed reactor (B), and separating the second reactor effluent (7) from the spent catalyst at the end of the upflow reactor (C), v. A step of sending the first reactor effluent (5) and the second reactor effluent (7) to a product separation unit (E), wherein the product separation unit (E) separates the first reactor effluent (5) and the second reactor effluent (7) into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10), vi. A step of introducing the light liquid fraction (9) to the high-density fluidized bed reactor (B) and the heavy liquid fraction (10) to the upflow reactor (C), wherein the high-density fluidized bed reactor (B) and the upflow reactor (C) are connected in series via a flow channel, and the partially deactivated catalyst flows from the high-density fluidized bed reactor (B) to the upflow reactor (C) via the first conduit (11), vii. A step of transferring the spent catalyst received from the upflow reactor (C) to a combustor (D) via a second conduit (12), and burning the coke accumulated on the spent catalyst in the combustor (D) in the presence of an oxygen-containing gas (14) to obtain a regenerated catalyst, wherein the regenerated catalyst is recycled to the high-density fluidized bed reactor (B) via a third conduit. A fluid catalytic cracking process including a fluid catalytic cracking process.

2. A process according to claim 1, wherein the diesel fuel (LO) fraction (2) contains C5 to C20 hydrocarbons, has a density in the range of 0.7 to 0.8 g / cc, a refractive index (RI) in the range of 1.4 to 1.45, a molecular weight in the range of 100 to 175, and a boiling point range in the range of 200 to 350°C.

3. A process according to claim 1, wherein the heavy oil (HO) fraction (3) contains C21 to C70 hydrocarbons, has a density in the range of 0.90 to 0.99 g / cc, a refractive index (RI) in the range of 1.45 to 1.55, a molecular weight in the range of 400 to 550, a Conradson carbon ratio of 2 to 10% by weight, and a boiling point in the range of 200 to 1000°C.

4. The process according to claim 1, wherein the light olefin is selected from ethylene, propylene, and C4 olefins, and the aromatic compound is selected from benzene, toluene, ethylbenzene, and xylene.

5. The process according to claim 1, wherein the catalytic decomposition of the diesel fuel (LO) fraction (2) in the high-density fluidized bed reactor (B) is carried out at a residence time of 5 to 15 seconds, a pressure of 1 to 4 atmospheres (g), and a temperature of 600 to 700°C, and the first co-processing stream (4) is selected from dimethyl ether, methanol, or a combination thereof.

6. The process according to claim 1, wherein the catalytic decomposition of the heavy oil (HO) fraction (3) in the upflow reactor (C) is carried out at a residence time of 2 to 5 seconds, a pressure of 1 to 4 atmospheres (g), and a temperature of 500 to 600°C, and the second co-processing stream (6) is selected from diethyl ether, ethanol, or a combination thereof.

7. The process according to claim 1, wherein the cracking catalyst contains 5 to 10% by weight of a pentasil-type selective zeolite, 5 to 10% by weight of a Y-type zeolite, iron, and a lanthanide metal, and the cracking catalyst has a larger pore matrix component in the range of 1 to 20%.

8. A process according to claim 1, wherein the catalyst / oil ratio in the high-density fluidized bed reactor (B) is in the range of 10 to 25% by weight, and the catalyst / oil ratio in the upflow reactor (C) is in the range of 10 to 25% by weight.

9. A process according to claim 1, wherein the gas fraction (8) contains hydrogen, methane, ethane, ethylene, propane, propylene and C4 fluids, the light olefin is separated from the gas fraction (8), the light liquid fraction (9) consists of cracked naphtha C5-210°C, the aromatic compound is extracted from the light liquid fraction (9), and the heavy liquid fraction (10) consists of cycle oil, which is a hydrocarbon fluid with a boiling point in the range of 210°C to 800°C.

10. A process according to claim 1, wherein the used catalyst received from the stripper is burned in the combustor (D) using air as the combustion gas source at a temperature in the range of 650°C to 750°C to obtain the regenerated catalyst, and the exhaust gas (15) from the combustor containing 10-20% CO2 is sent to a chimney after heat recovery.

11. The process according to claim 1, wherein the spent catalyst received from the upflow reactor (C) and stripper is combusted in the combustor (D) at a temperature in the range of 650°C to 750°C using synthetic air consisting of 20-30% oxygen, 70-80% carbon dioxide, and 0-5% nitrogen, in order to obtain the regenerated catalyst, and CO from the combustor ２ A process in which a portion of the exhaust gas (15) rich in is recirculated to the combustor.

12. A process according to claim 1, wherein the temperatures of the high-density fluidized bed reactor (B) and the upflow reactor (C) are maintained by adjusting the flow rate of the high-temperature regenerating catalyst.

13. A process according to claim 1, wherein ethanol is dehydrated at a temperature in the range of 250 to 600°C in a catalyst layer provided above the stripper section of an upflow reactor and stripper (C) in order to lower the temperature of the combustor (D) and enable the processing of heavier crude oil.

14. A dual catalytic cracking reactor system for converting crude oil into light olefins and aromatic compounds, A fractionation column (A) for fractionating a crude oil stream (1) into a diesel fuel (LO) fraction (2) and a heavy fuel oil (HO) fraction (3), A high-density fluidized bed reactor (B) is connected to the fractional distillation column (A), and the light oil (LO) fraction (2) from the fractional distillation column (A) is sent to the high-density fluidized bed reactor (B) along with a first co-processing stream as needed, in order to perform catalytic cracking in the presence of a cracking catalyst to produce a first reactor effluent (5). An upflow reactor (C) connected to the fractional distillation column (A), wherein the heavy oil (HO) fraction (3) from the fractional distillation column (A) is sent to the upflow reactor (C) along with the first co-processing stream as needed, in order to perform catalyst cracking in the presence of a partially deactivated catalyst to produce a second reactor effluent (7), A product separation unit (E) is connected to the high-density fluidized bed reactor (B) and the upflow reactor (C), and separates the first reactor effluent (5) and the second reactor effluent (7) into a gas fraction (8), a light liquid fraction (9), and a heavy liquid fraction (10). A combustor (D) is connected to the upflow reactor (C) via a second conduit (12) and burns the spent catalyst of the upflow reactor (C) to obtain a regenerated catalyst, wherein the regenerated catalyst is recycled to the high-density fluidized bed reactor (B) via a third conduit (13). Equipped with, A reactor system in which the high-density fluidized bed reactor (B) and the upflow reactor (C) are connected as a series flow path in order to flow the partially deactivated catalyst from the high-density fluidized bed reactor (B) to the upflow reactor (C) via a first conduit (11).

15. A reactor system according to claim 14, wherein the first co-processing stream (4) is introduced into a high-density fluidized bed reactor and stripper together with the light oil (LO) fraction, and the second co-processing stream (6) is introduced into an upflow reactor and stripper together with the heavy oil (HO) fraction.

16. A reactor system according to claim 14, wherein the high-density fluidized bed reactor (B) is operated at a pressure in the range of 1 to 4 atmospheres, a temperature in the range of 600 to 700°C, and a residence time of 5 to 15 seconds, and the first co-processing feed stream (4) is selected from dimethyl ether, methanol, or a combination thereof.

17. A reactor system according to claim 14, wherein the upflow reactor (C) is operated at a pressure in the range of 1 to 4 atmospheres, a temperature in the range of 500 to 600°C, and a residence time of 2 to 5 seconds, and the second co-processing feed stream (6) is selected from diethyl ether, ethanol, or a combination thereof.

18. A reactor system according to claim 14, wherein the combustor (D) is operated at a temperature in the range of 650°C to 750°C to burn the spent catalyst of the upflow reactor (C) in the presence of an oxygen-containing gas (14), and the combustor (D) is supplied with exhaust gas (15) containing the regenerated catalyst and 10-20% CO2.

19. In the reactor system according to claim 14, the combustor (D) is operated at a temperature in the range of 650°C to 750°C to burn the spent catalyst of the upflow reactor (C) in the presence of an oxygen-containing gas (14), wherein the oxygen-containing gas (14) consists of 20-30% oxygen and 70-80% CO ２ The combustion chamber (D) contains the regenerative catalyst and CO ２ A reactor system in which exhaust gas (15) rich in is partially recirculated to the combustor (D).

20. A reactor system according to claim 14, wherein the gas fraction (8) consists of hydrogen, methane, ethane, ethylene, propane, propylene, and C4 hydrocarbon fluids, and the light olefin is separated from the gas fraction (8).

21. A reactor system according to claim 14, wherein the light liquid fraction (9) contains decomposed naphtha at C5-210°C, the aromatic compound is extracted from the light liquid fraction (9), and the light liquid fraction (9) is transferred to the high-density fluidized bed reactor (B) after the extraction of the aromatic compound.

22. A reactor system according to claim 14, wherein the heavy liquid fraction (10) contains cycle oil and a hydrocarbon stream having a boiling point from 210°C to 800°C, and the heavy liquid fraction (10) is sent to the upflow reactor (C).

23. In the reactor system according to claim 14, ethanol is processed in a catalyst layer provided above the stripper section of the upflow reactor and stripper (C) in order to lower the temperature of the combustor (D) and enable the processing of heavier crude oil.

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