CN116917442A - Production of BTX aromatics and light gas olefins from crude oil and plastic pyrolysis oil - Google Patents

Abstract

Disclosed is a process for producing C from crude oil and/or pyrolysis oil ₆ To C ₈ A process for the production of aromatics and optionally light gaseous olefins. The method may include: hydrotreating a first stream containing hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream containing saturated hydrocarbons having a boiling point below 350 ℃, separating the second stream to obtain a third stream containing hydrocarbons having a boiling point below 70 ℃, a fourth stream containing hydrocarbons having a boiling point between 70 ℃ and 140 ℃ and a fifth stream containing hydrocarbons having a boiling point above 140 ℃, recycling at least a portion of the fifth stream to the hydrotreating step, reforming the fourth stream to obtain a stream containing C ₆ To C ₈ A sixth stream of aromatics, and optionally cracking the third stream to obtain light gaseous olefins.

Description

Production of BTX aromatics and light gas olefins from crude oil and plastic pyrolysis oil

Cross Reference to Related Applications

The present application claims the benefit of priority from U.S. provisional patent application No.63/131,270, filed on 12/28/2020, which is incorporated herein by reference in its entirety.

Technical Field

The present application relates generally to the production of C ₆ To C ₈ A process for the production of aromatics and optionally light gaseous olefins. In one aspect, the application relates to the production of C from crude oil and/or pyrolysis oil using hydrotreating ₆ To C ₈ Aromatic compounds and light gaseous olefins.

Background

C ₆ To C ₈ Aromatic compounds such as benzene, toluene and xylene are important commodity chemicals with a continuously growing demand. For example, benzene, toluene, and/or xylene are used to make various polymers (e.g., polycarbonates, polyesters, nylons, polyurethanes, etc.) that have many industrial uses. Light gaseous olefins such as ethylene, propylene and butenes are important raw materials for a variety of end products such as polymers, rubber, plastics, octane booster compounds, and the like.

Benzene, toluene and xylenes are typically produced by reforming naphtha (e.g., straight run naphtha) from crude oil in a reformer. However, only a portion (e.g., about 10 to 20 wt%) of the crude oil is suitable for reforming and for use in the production of benzene, toluene, and xylenes. Furthermore, while naphthenes are more conducive to the formation of aromatics by reforming, typical reformer feeds from crude oil have relatively low naphthene content. For example, typically less than 25 wt% of the reformer feed is naphthenes. See, for example, turaga et al, (2003) Journal of Scientific and Industrial Research,62 (10), 963-978; mujtaba et al, (2019) Process, 7,192.

Various attempts have been made to maximize aromatics production from crude oil. For example, processes having multiple hydrocracking units and other equipment are used. However, such attempts may create additional problems that result from complexity, reduced efficiency, and increased cost of the process.

Disclosure of Invention

A discovery has been made that provides a method for producing high value chemicals such as C from crude oil ₆ To C ₈ A solution to at least one or more problems associated with aromatics and/or light gas olefins. In one aspect, the solution may include disposing a hydroprocessing unit upstream of the reforming unit for producing aromatics. In some aspects, a single hydroprocessing unit may be used. The use of an upstream hydroprocessing unit may: i) Increasing reformer feed per unit of crude processed; ii) increasing the suitability for production of C by reforming ₆ To C ₈ The amount of naphthenes of the aromatic compounds; and/or iii) optionally increasing the amount of steam cracker feed per unit of processed crude oil. Furthermore, the use of a hydroprocessing unit may reduce the amount of olefins in the reformer feed, which may serve to reduce exotherms in the reforming unit, which may help to save energy and increase the efficiency of the reforming unit. These advantages may be obtained by separating the product stream from the hydroprocessing unit into: (i) a stream comprising hydrocarbons having a boiling point below 70 ℃; (ii) a stream comprising hydrocarbons having a boiling point of 70 ℃ to 140 ℃; and (iii) a stream comprising hydrocarbons having a boiling point above 140 ℃. The stream comprising hydrocarbons having a boiling point above 140 ℃ may be recycled back to the hydroprocessing unit. Streams comprising hydrocarbons having boiling points of 70 ℃ to 140 ℃ may be sent to a reforming unit to produce C ₆ To C ₈ Aromatic compounds (e.g., benzene, toluene, and/or xylene (BTX)). Streams containing hydrocarbons having boiling points below 70 ℃ may be cracked (e.g., by steam cracking or catalytic cracking) to produce light gaseous olefins.

In another aspect of the invention, an upstream hydroprocessing unit may not be used. In this respect, C ₆ To C ₈ Aromatic and/or light gaseous olefinsMay be produced from plastics (e.g., recycled mixed thermoplastic material) as a feed source. For example, the initial charge may include plastic (e.g., recycled mixed thermoplastic). The plastic may be reactively extruded or melt cracked to form pyrolysis oil. Pyrolysis oil may be separated into: (i) a stream comprising hydrocarbons having a boiling point below 70 ℃; (ii) a stream comprising hydrocarbons having a boiling point of 70 ℃ to 140 ℃; and (iii) a stream comprising hydrocarbons having a boiling point above 140 ℃. At least a portion of the stream comprising hydrocarbons having a boiling point greater than 140 ℃ may be recycled back to the reactive extrusion or melt cracking process (e.g., reaction process). Streams comprising hydrocarbons having boiling points of 70 ℃ to 140 ℃ may be sent to a reforming unit to produce C ₆ To C ₈ Aromatic compounds (e.g., BTX). The stream comprising hydrocarbons having a boiling point below 70 ℃ or a portion thereof may be sent to steam reforming to produce hydrogen; or cracking in a catalytic cracking unit to produce light gaseous olefins; or to a gasoline pool; or any combination thereof. Benefits of the process include the efficient production of BTX and optionally olefins without the use of a hydrotreating unit (although such a unit may be used in the context of the present invention) and/or with recycled plastic. In some aspects, the stream containing hydrocarbons having a boiling point of 70 ℃ to 140 ℃ may contain chlorine, which is advantageous to maintain the activity of the reforming catalyst. In some aspects, at least a portion of the chlorides present in the stream comprising hydrocarbons having a boiling point of 70 ℃ to 140 ℃ may be derived from plastics.

Certain aspects relate to the production of C ₆ To C ₈ A first process for aromatics and optionally light gaseous olefins. The first method may comprise any one, any combination or all of steps (a) to (e). In step (a), the first stream may be hydrotreated to obtain a second stream. The first stream may contain hydrocarbons from crude oil and/or pyrolysis oil. The second stream may contain saturated hydrocarbons having a boiling point below 350 ℃. In some aspects, at least 70wt% of the hydrocarbons in the second stream may be saturated hydrocarbons having a boiling point below 350 ℃. In certain aspects, the second stream can further comprise an aromatic compound. In step (b), the second stream may be separated to obtain a third stream comprising hydrocarbons having a boiling point below 70 ℃, a third stream comprising hydrocarbons having a boiling point between 70 ℃ and 140 DEG CA fourth stream and a fifth stream containing hydrocarbons having a boiling point above 140 ℃. In step (c), at least a portion of the fifth stream may be recycled to the hydrotreating step (a). In step (d), the fourth stream may be reformed to obtain a stream containing C ₆ To C ₈ A sixth stream of aromatic compounds. C (C) ₆ To C ₈ The aromatic compounds may be benzene, toluene and xylenes and the sixth stream may contain benzene, toluene and xylenes. Optionally, in step (e), the third stream may be cracked (e.g. steam cracked or catalytic cracked) to obtain light gaseous olefins. Reforming in step (d) may also produce non-aromatics and non-C ₆ To C ₈ Aromatic compounds (e.g., aromatic compounds other than benzene, toluene, and xylene). In some aspects, the product produced in step (d) may be combined with a catalyst comprising at least a portion of the non-aromatic compound and the non-C ₆ To C ₈ The seventh stream of aromatic compounds is recycled to the hydrotreating step (a). Optionally, a portion of the fifth stream may be cracked (e.g., steam cracked or catalytic cracked) with the third stream in step (e) to form light gaseous olefins.

The hydrotreating in step (a) may comprise hydrocracking and/or hydrotreating. The sulfur and/or nitrogen content of sulfur-and/or nitrogen-containing hydrocarbons may be reduced during hydrotreating. The hydrocracking process may be included in H ₂ Cracking of hydrocarbons in the presence of a catalyst. In some aspects, the hydrotreating may be performed at low pressure, for example, at a pressure of 100 bar or less. Without wishing to be bound by any theory, it is believed that lower operating pressures may result in lower investment costs and may have a beneficial effect on the economics of the process. In some aspects, the hydrotreating conditions in step (a) may comprise a pressure of from 30 bar to 100 bar; a temperature of 300 ℃ to 600 ℃, preferably 350 ℃ to 500 ℃; or 0.5 to 2hr ^-1 Weight Hourly Space Velocity (WHSV); or any combination thereof. In some aspects, the hydrotreating can be performed in the presence of hydrogen (H ₂ ) In the presence of H ₂ With hydrocarbons (e.g. H fed to the hydrotreatment step ₂ And hydrocarbon) of 200Nm ³ /m ³ Up to 2000Nm ³ /m ³ . The hydrotreatment can be catalyzedIn the presence of an agent. In some aspects, the catalyst may contain a hydrocracking catalyst and/or a hydrotreating catalyst. In some aspects, the hydrocracking catalyst may contain Ni and/or W. In some aspects, the hydrotreating catalyst may contain Co, ni, and/or Mo. In some aspects, the hydrotreating can be performed in the presence of a dissolved catalyst and/or a fixed bed catalyst. In some aspects, the dissolved catalyst may contain nickel (Ni) and/or molybdenum (Mo). In some aspects, the dissolved catalyst may contain a metal naphthenate and/or a octanoate. In some aspects, the dissolved catalyst may contain nickel octoate, nickel naphthenate, molybdenum octoate, or molybdenum naphthenate, or any combination thereof. In some aspects, nickel octoate, nickel naphthenate, molybdenum octoate, and/or molybdenum naphthenate independently may be in the hydrocarbon based body. In some aspects, the dissolved catalyst may be a catalyst that is dissolved in the feed and may form a homogeneous catalyst when mixed with the feed (e.g., a hydrotreated feed). In some aspects, no additional solvent may be used to dissolve the catalyst in the feed, such as metal naphthenates and/or octoates. The fixed bed catalyst may contain one or more transition metals on a support. In certain aspects, the one or more transition metals may be cobalt (Co), nickel, molybdenum, and/or tungsten (W). In certain aspects, the fixed bed catalyst may contain Co and Mo on a support; ni and Mo on a support; co, ni and Mo on a support; ni and W on a carrier; or Ni, W and Mo on a support, or any combination thereof. In some aspects, the fixed bed catalyst support may be alumina, silica, aluminosilicate, or zeolite, or any combination thereof. The zeolite may be an X-type zeolite, a Y-type or USY-type zeolite, mordenite, faujasite, nanocrystalline zeolite, MCM mesoporous material, SBA-15, silicoaluminophosphate, gallium phosphate, titanophosphate, ZSM-5, ZSM-11, ferrierite, heulandite, zeolite-A, erionite and chabazite, or any combination thereof.

In some aspects, in step (b), the second stream may be separated into third, fourth and fifth streams by atmospheric distillation with a boiling fraction of 70 ℃ to 140 ℃. The third stream may contain a hydrocarbon fraction from the second stream having an upper boiling point fraction of 70 ℃. The fourth stream may contain a hydrocarbon fraction from the second stream having a lower limit boiling fraction at 70 ℃ and an upper limit boiling fraction at 140 ℃. The fifth stream may contain a hydrocarbon fraction from the second stream having a lower boiling point fraction of 140 ℃.

The first stream may be obtained from crude oil. In some aspects, the first stream may be obtained by atmospheric distillation of i) crude oil or ii) crude oil and pyrolysis oil. The atmospheric distillation may be carried out in a Crude Distillation Unit (CDU) with a boiling point fraction of 70 ℃ to 140 ℃. From the CDU, a first hydrocarbon fraction having an upper boiling point fraction of 70 ℃, a second hydrocarbon fraction having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃ and a third hydrocarbon fraction having a lower boiling point fraction of 140 ℃ can be obtained. In some aspects, the third hydrocarbon fraction may form the first stream, and may be hydrotreated, for example, in step (a). The second hydrocarbon fraction may be reformed to form C ₆ To C ₈ An aromatic compound. In certain aspects, the eighth stream comprising the second hydrocarbon fraction may be reformed in step (d) with the fourth stream to form a sixth stream and a seventh stream. In some aspects, the first hydrocarbon fraction or a portion of the first hydrocarbon fraction may be cracked (e.g., steam cracked or catalytic cracked) to form light gas olefins. In some aspects, the first hydrocarbon fraction or a portion of the first hydrocarbon fraction may be hydrotreated. In certain aspects, the crude oil may be distilled in a CDU, and the ninth stream comprising the first hydrocarbon fraction may optionally be cracked (e.g., steam cracked or catalytic cracked) with the third stream in step (a) to form light gas olefins. In certain aspects, crude oil and pyrolysis oil can be distilled in a CDU, and a ninth stream comprising the first hydrocarbon fraction can be hydrotreated with the first stream in step (a) to form a second stream. In some aspects, pyrolysis oil may be obtained from plastics by reactive extrusion or melt cracking, and may contain chlorides and olefins.

In some aspects, the first stream may contain condensate, naphtha, light crude oil, or crude oil hydrocarbon fraction having an upper boiling point fraction of 350 ℃, whole crude oil, or any combination thereof. In some aspects, the first stream can contain pyrolysis oil. Pyrolysis oil may be obtained from plastics by reactive extrusion or melt cracking. Reactive extrusion or melt cracking of plastics may include depolymerizing the plastics at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and catalytically cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, where the cracking conditions may include a cracking temperature that is less than, equal to, or greater than the depolymerization temperature. In some aspects, depolymerization of the plastic may be performed in an extruder/twin screw reactor/auger.

Certain aspects relate to the production of C ₆ To C ₈ A second process of aromatic compounds and optionally light gaseous olefins. The second method may comprise any one, any combination or all of steps (i), (ii) and (iii). In step (i), reactive extrusion or melt cracking of the plastic may be performed to obtain pyrolysis oil. In step (ii), the pyrolysis oil may be separated to obtain a stream a containing hydrocarbons having a boiling point below 70 ℃, a stream B containing hydrocarbons having a boiling point between 70 ℃ and 140 ℃ and a stream C containing hydrocarbons having a boiling point above 140 ℃. In step (iii), stream B may be reformed to obtain a catalyst containing C ₆ To C ₈ Stream D of aromatic compounds. C (C) ₆ To C ₈ The aromatic compounds may be benzene, toluene and xylenes and stream D may contain benzene, toluene and xylenes. In some aspects, stream a may be sent to a gasoline pool. Reactive extrusion or melt cracking of plastics may include depolymerizing the plastics at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and catalytically cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, where the cracking conditions may include a cracking temperature that is less than, equal to, or greater than the depolymerization temperature. In some aspects, depolymerization of the plastic may be performed in an extruder/twin screw reactor/auger. Pyrolysis oil may be separated into streams A, B and C by atmospheric distillation with a boiling point fraction of 70 ℃ to 140 ℃. Stream a may contain a hydrocarbon fraction from pyrolysis oil having an upper boiling point fraction of 70 ℃. Stream B may contain hydrocarbon fractions from pyrolysis oil having a lower limit boiling fraction at 70 ℃ and an upper limit boiling fraction at 140 ℃. Stream C may contain hydrocarbon fractions from pyrolysis oil having a lower boiling point fraction of 140 ℃. In certain aspects, stream C can be recycled toA step of catalytic cracking of hydrocarbon-containing wax. Reforming in step (iii) may also produce non-aromatics and non-C ₆ To C ₈ Aromatic compounds (e.g., aromatic compounds other than benzene, toluene, and xylene). In some aspects, a catalyst may be produced during reforming that contains at least a portion of non-aromatic compounds and non-C ₆ To C ₈ Stream E of aromatics is recycled to the hydrocarbon-containing wax catalytic cracking step. In some aspects, the hydrogen-containing portion (H) from the reforming step (iii) ₂ ) The gaseous stream F is recycled to the hydrocarbon-containing wax catalytic cracking step.

Reforming (e.g., in step (d) of the first process and in step (iii) of the second process) may be performed using methods and systems known in the art. In some aspects, the reforming conditions may include a temperature of 400 ℃ to 600 ℃, preferably 450 ℃ to 550 ℃, and/or a pressure of 2 bar to 30 bar. Reforming can be carried out at H ₂ Is carried out in the presence of (3). In some aspects, during reforming H ₂ With hydrocarbons (e.g. H fed to the reforming step ₂ And hydrocarbons) may be 2:1 and 9:1. Reforming may be performed in the presence of a reforming catalyst. The reforming catalyst may be a reforming catalyst known in the art. In some aspects, the reforming catalyst may contain platinum (Pt) and rhenium (Re) on alumina, pt on alumina, a metal-loaded zeolite, or any combination thereof. The metal-loaded zeolite may contain one or more dehydrogenation metals including, but not limited to, pt, palladium (Pd), gallium (Ga), and/or nickel (Ni). The reforming process may be a semi-regenerative reforming process or a continuous catalytic reforming process, and the reforming may be performed in a semi-regenerative reformer unit or a continuous catalytic reformer unit.

The cracking (e.g. in optional step (e) of the first process) may be steam cracking or catalytic cracking. In some aspects, steam cracking may be performed using dilution steam, using processes and systems known in the art. In certain aspects, steam cracking conditions may include a temperature of 750 ℃ to 900 ℃, a pressure of atmospheric pressure to 6 bar, a residence time of 50ms to 1s or less, or any combination thereof. In some aspects, catalytic cracking may be performed in a Fluid Catalytic Cracking (FCC) unit or a fixed bed catalytic cracking unit. In certain aspects, the catalytic cracking conditions may include a temperature of 500 ℃ to 800 ℃, a pressure of atmospheric pressure to 10 bar, a contact time of less than 5s, or any combination thereof.

In some aspects, the plastic that produces the pyrolysis oil (e.g., the pyrolysis oil used in the first and/or second methods) may be obtained from waste-containing plastic, such as post-consumer waste-containing plastic. In certain aspects, the plastic may contain chlorides, and at least a portion of the chlorides may be sent to the reforming step (e.g., step (d) of the first process and step (iii) of the second process) by the process steps described herein. The chloride may increase the activity of the reforming catalyst. In certain aspects, chlorides may be fed to the reforming step (e.g., to step (d) of the first process and step (iii) of the second process) at a concentration of 0.1ppm to 15 ppm.

The following includes definitions of various terms and phrases used throughout this specification.

The term "about" or "approximately" is defined as proximal, as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term is defined as within 10%, preferably within 5%, more preferably within 1%, most preferably within 0.5%.

The terms "wt%", "vol%" or "mol.%" refer to weight, volume or mole percent of a component based on the total weight, total volume or total moles of the material comprising the component, respectively. In a non-limiting example, 10 mole of the component in 100 mole of the material is 10 mole of the component.

The term "substantially" and variants thereof are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

The term "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms, when used in the claims and/or the specification, includes any measurable reduction or complete inhibition to achieve a desired result.

The term "effective" as used in the specification and/or claims means sufficient to achieve a desired, intended or intended result.

The use of the terms "a" or "an" when used in conjunction with the terms "comprising," including, "" containing, "or" having "in the claims or specification may mean" one "but it also has the meaning of" one or more, "" at least one, "and" one or more than one.

The terms "comprises," "comprising," "and any form of containing," such as "comprises," "including," "has," "having," "including," or any form of containing, such as "contains" and "containing," are inclusive or open-ended, and do not exclude additional, unrecited elements or method steps.

The methods of the present invention may "comprise," consist essentially of, or "consist of the particular ingredients, components, compositions, etc., disclosed throughout the specification.

Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed description and examples. It should be understood, however, that the drawings, detailed description and examples, while indicating specific embodiments of the invention, are given by way of illustration only and not by way of limitation. In addition, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In a further embodiment, features from a particular embodiment may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any other embodiment. In further embodiments, additional features may be added to the specific embodiments described herein.

Drawings

For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a schematic diagram of a conventional gas turbineProduction of C by the invention ₆ To C ₈ Schematic of one example of an aromatic compound and optionally a light gas olefin.

FIG. 2 is a schematic diagram of the present invention for producing C using the system (system 100) of FIG. 1 ₆ To C ₈ Schematic of one embodiment of an aromatic compound and optionally a light gas olefin.

FIG. 3 is a schematic diagram of the present invention for producing C using the system (system 100) of FIG. 1 ₆ To C ₈ Schematic of a second embodiment of an aromatic compound and optionally a light gas olefin.

FIG. 4 is a schematic diagram of the present invention for producing C using the system (system 100) of FIG. 1 ₆ To C ₈ Schematic representation of a third embodiment of aromatic compounds and optionally light gaseous olefins.

FIG. 5 is a schematic diagram of the production C of the present invention ₆ To C ₈ Schematic of a second example of an aromatic compound and optionally a light gas olefin.

Detailed Description

A discovery has been made that provides a method for producing high value chemicals such as C from crude oil ₆ To C ₈ Solutions to at least some of the problems associated with aromatics and/or light gas olefins. The solution may include using a hydroprocessing unit configured to hydroprocessing hydrocarbons at pressures below 100 bar. The hydrotreating unit may be located upstream of a reformer for producing aromatics and/or a cracking unit (e.g., a steam cracker or catalytic cracking unit) for producing light olefins. As shown in the examples and figures by way of non-limiting example, the use of an upstream hydroprocessing unit can increase the naphthene content of the reformer feed, e.g., to 30wt% or more, increase monoaromatic compounds in the reformer feed, and/or enrich the reformer feed to produce aromatics, particularly C ₆ To C ₈ An aromatic compound. In some aspects, higher aromatics (2-ring or higher, or pendant aromatics) can be converted to monoaromatics or naphthenes in a hydroprocessing unit, thereby increasing the naphthene content of the reformer feed. The use of an upstream hydroprocessing unit also increases the amount of hydrocarbons being reformed and decreasesOlefin content in the reformer feed. In some aspects, the amount of hydrocarbons reformed may be increased by increasing the amount of a boiling stream at 70 to 140 ℃ that may be fed to the reformer by upgrading a heavy fraction of crude oil in a hydroprocessing unit.

In another aspect of the invention, an upstream hydroprocessing unit may not be used. In this regard, C ₆ To C ₈ Aromatics and optionally light gaseous olefins may be produced from pyrolysis oil obtained from plastics such as waste plastics. Advantages of this process include the efficient production of BTX and optionally olefins using recycled plastics.

These and other non-limiting aspects of the invention are discussed in further detail in the following sections with reference to the drawings. The units shown in the figures may include one or more heating and/or cooling devices (e.g., insulation, electrical heaters, jacketed heat exchangers in walls) or controllers (e.g., computers, flow valves, automatic valves, etc.) that may be used to control the temperature and pressure of the process. Although only one unit is generally shown, it should be understood that a plurality of units may be accommodated in one unit. In some aspects, unless otherwise indicated, the reactors shown or described may be fixed bed reactors, moving bed reactors, trickle bed reactors, rotating bed reactors, slurry reactors, or fluidized bed reactors.

With reference to FIG. 1, a process for producing C according to one example of the invention is described ₆ To C ₈ Systems and methods for aromatics and optionally light gas olefins. The system 100 may include a hydroprocessing unit 120, a separation unit 122, a reforming unit 124, and an optional cracking unit 126. The optional cracking unit 126 may be a steam cracking unit or a catalytic cracking unit. A first stream 101 containing hydrocarbons from crude oil and/or pyrolysis oil may be fed to a hydroprocessing unit 120. In the hydroprocessing unit 120, the first stream 101 can be hydrotreated to obtain a hydrotreated product. The second stream 102 comprising the hydrotreated product can exit the hydrotreating unit 120 and can be fed to a separation unit 122. In separation unit 122, the second stream can be separated into a third stream 103, a fourth stream 104, and a fifth stream 105. First, theThe three streams 103 may contain a hydrocarbon fraction having an upper boiling point fraction of 70 ℃. The fourth stream 104 can contain a hydrocarbon fraction having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃. The fifth stream 105 can contain a hydrocarbon fraction having a lower boiling point fraction of 140 ℃. In certain aspects, the third stream 103 can be fed to an optional cracking unit 126 and can be cracked, for example, by steam cracking or catalytic cracking, to form light gaseous olefins. Light gas olefin stream 127 containing light gas olefins can leave cracking unit 126. At least a portion of fifth stream 105 can be recycled to hydroprocessing unit 120 and can be hydrotreated. Optionally, a portion of the fifth stream 105 can be sent to a cracking unit 126 and can be cracked, e.g., via steam cracking or catalytic cracking, to produce light gaseous olefins. The third stream 103 and optional fifth stream portions may be fed to the cracking unit 126 as separate streams or may be combined and fed as a combined stream (not shown). The fourth stream 104 can be fed to a reforming unit 124 and reformed to form C ₆ To C ₈ An aromatic compound. Containing C ₆ To C ₈ The sixth stream of aromatics 106 may exit the reforming unit 124. Reforming in reforming unit 124 may also produce non-aromatics and non-C ₆ To C ₈ Aromatic compounds (e.g. other than C ₆ To C ₈ Aromatic compounds other than aromatic compounds). Contains at least a portion of non-aromatics and non-C from reforming unit 124 ₆ To C ₈ The seventh stream of aromatics 107 can be recycled to the hydroprocessing unit 120 and can be hydrotreated.

In certain aspects, the first stream 101 can be obtained by atmospheric distillation of crude oil. Referring to FIG. 2, the production of C using system 100 is depicted in accordance with one embodiment of the present invention ₆ To C ₈ Systems and methods for aromatics and optionally light gas olefins. The system 200 may include a Crude Distillation Unit (CDU) 230 and the system 100. Crude oil containing stream 232 can be fed to CDU 230. In CDU 230, crude oil can be separated by atmospheric distillation to form first stream 101, eighth stream 208, and ninth stream 209. First charge in system 200Stream 101 may contain a hydrocarbon fraction having a lower boiling point fraction of 140 c, which is separated from the crude oil in CDU 230. The first stream may be fed to the hydroprocessing unit 120 of the system 100 and may be processed in the system 100 as described above, for example, with respect to fig. 1. Eighth stream 208 can contain a hydrocarbon fraction having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃ that is separated from the crude oil in CDU 230. Eighth stream 208 can be fed to reforming unit 124 of system 100 and can be reformed to obtain C ₆ To C ₈ And (3) hydrocarbons. Eighth stream 208 and fourth stream 104 can be fed to reforming unit 124 separately or as a combined stream. The ninth stream 209 may contain a hydrocarbon fraction having an upper boiling point fraction of 70 c that is separated from the crude oil in CDU 230. In certain aspects, the ninth stream 209 can be fed to the optional cracking unit 126 of the system 100 and can be cracked, for example, by steam cracking or catalytic cracking, to obtain light gaseous olefins. Ninth stream 209, third stream 103, and optional fifth stream portion may be fed to optional cracking unit 126 alone or in any combination.

In certain aspects, the first stream 101 can be obtained by atmospheric distillation of crude oil and pyrolysis oil. The pyrolysis oil may be a plastic pyrolysis oil, such as may be obtained from plastic. Referring to FIG. 3, the production of C using the system 100 according to a second embodiment of the present invention is described ₆ To C ₈ Systems and methods for aromatics and optionally light gas olefins. The system 300 may include a plastic depolymerization unit 342, a catalytic cracking unit 344, a CDU 330, and the system 100. Pyrolysis oil may be produced from plastics using a plastic depolymerization unit 342 and a catalytic cracking unit 344. The plastic 346 may be fed to the plastic depolymerization unit 342. In the plastic depolymerization unit 342, the plastic may be depolymerized to form a hydrocarbon-containing wax. Hydrocarbon-containing wax 348 from depolymerization unit 342 can be fed to catalytic cracking unit 344. In the catalytic cracking unit 344, the hydrocarbonaceous wax can be cracked in the presence of a cracking catalyst to produce pyrolysis oil. Pyrolysis oil 350 and crude oil containing stream 332 from catalytic cracking unit 344 can be fed to CDU 330. Pyrolysis oil and crude oil may be fed to the CDU as separate feeds or as a combined feed. In CDU 330, crude oil and pyrolysis oil are mixed The compounds can be separated by atmospheric distillation to form first stream 101, eighth stream 308, and ninth stream 309. The first stream 101 in the system 300 may contain a hydrocarbon fraction having a lower boiling point fraction of 140 ℃ that is separated from the crude oil and pyrolysis oil mixture in the CDU 330. The first stream 101 can be fed to the hydroprocessing unit 120 of the system 100 and can be processed in the system 100 as described above, for example, with respect to fig. 1. Eighth stream 308 can contain a hydrocarbon fraction having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃ that is separated from the crude oil and pyrolysis oil in CDU 330. Eighth stream 308 can be fed to reforming unit 124 of system 100 and can be reformed to obtain C ₆ To C ₈ And (3) hydrocarbons. Eighth stream 308 and fourth stream 104 can be fed to reforming unit 124 separately or as a combined stream. The ninth stream 309 may contain a hydrocarbon fraction having an upper boiling point fraction of 70 ℃ that is separated from the crude oil and pyrolysis oil in the CDU 330. The ninth stream 309 may be fed to the hydroprocessing unit 120 of the system 100. The ninth stream 309 and the first stream 101 may be fed to the hydroprocessing unit 120 either alone or as a combined feed. In alternative embodiments, the plastic depolymerization unit 342 and the catalytic cracking unit 344 are not part of the system 300, and pyrolysis oil (e.g., pyrolysis oil produced using separate systems and processes) may be fed to the CDU along with the crude oil.

By using the hydrotreating unit 120, additional C may be produced from a hydrocarbon fraction (from crude oil and/or pyrolysis oil) having a lower boiling point fraction of 140C ₆ To C ₈ Aromatics and/or light gas olefins, while such hydrocarbon fractions are not typically used for reforming.

In certain aspects, the first stream 101 can contain pyrolysis oil. The pyrolysis oil may be a plastic pyrolysis oil, such as may be obtained from plastic. Referring to FIG. 4, the production of C using the system 100 according to a third embodiment of the present invention is described ₆ To C ₈ Systems and methods for aromatics and optionally light gas olefins. System 400 may include a plastic depolymerization unit 442, a catalytic cracking unit 444, and system 100. Pyrolysis oil may be produced from plastics using a plastic depolymerization unit 442 and a catalytic cracking unit 444. Plastic 446 may be introduced intoTo a plastic depolymerization unit 442. In a plastic depolymerization unit 442, the plastic may be depolymerized to form a hydrocarbon-containing wax. Hydrocarbon-containing wax 448 from depolymerization unit 442 can be fed to catalytic cracking unit 444. In the cracking unit 444, the hydrocarbon-containing wax may be cracked in the presence of a cracking catalyst to produce pyrolysis oil. Pyrolysis oil from catalytic cracking unit 444 may be fed to system 100 via stream 101 and may be processed as described above, for example, in fig. 1.

With reference to FIG. 5, a process for producing C according to another example of the invention is described ₆ To C ₈ Aromatic and optionally light gas olefin systems and methods. The system 500 may include a plastic depolymerization unit 502, a catalytic cracking unit 504, a separation unit 506, and a reforming unit 508. The plastic 501 may be fed to a plastic depolymerization unit 502. In the depolymerization unit 502, the plastic may be depolymerized to form a hydrocarbon-containing wax. The hydrocarbonaceous wax 503 from the depolymerization unit 502 can be fed to a catalytic cracking unit 504. In the catalytic cracking unit 504, the hydrocarbon-containing wax may be cracked in the presence of a cracking catalyst to produce pyrolysis oil. Stream 505 containing pyrolysis oil from catalytic cracking unit 504 may be fed to separation unit 506. In separation unit 506, stream 505 can be separated into stream a 510, stream B511, and stream C512. Stream a 510 may contain a hydrocarbon fraction having an upper boiling point fraction of 70 ℃ that is separated from pyrolysis oil in separation unit 506. Stream B511 may contain a hydrocarbon fraction having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃ that is separated from pyrolysis oil in separation unit 506. Stream C512 may contain a hydrocarbon fraction having an upper boiling point fraction of 140℃, which is separated from the pyrolysis oil in separation unit 506. Stream C512 may be recycled to the catalytic cracking unit 504 and may be catalytically cracked to produce pyrolysis oil. Stream B511 may be fed to reforming unit 508 and may be reformed to obtain C ₆ To C ₈ An aromatic compound. Containing C ₆ To C ₈ Stream D513 of aromatics may leave reforming unit 508. Reforming in reforming unit 508 may also produce non-aromatics and non-C ₆ To C ₈ Aromatic compounds (e.g. other than C ₆ To C ₈ Aromatics other than aromaticsA compound). From reforming unit 508 containing at least a portion of non-aromatics and non-C ₆ To C ₈ Stream E514 of aromatics may be recycled to catalytic cracking unit 504 and may be catalytically cracked to produce pyrolysis oil. May contain H from the reforming unit 508 ₂ Stream F515 of gas is recycled to catalytic cracking unit 504. H-containing from reforming unit ₂ The gas may contain H added during reforming ₂ And/or H produced ₂ At least a portion of (a) is provided. In some aspects, stream a 510 may be sent to and/or mixed with a gasoline pool, such as a refinery's gasoline pool.

The hydrotreating in the hydrotreating unit 120 may include hydrotreating and/or hydrocracking of the feedstock. The hydrocarbon feed in unit 120 (e.g., introduced via streams 101, 105, 107, and/or 309) can be hydrotreated in the presence of a dissolved catalyst and a fixed bed catalyst to form a hydrotreated product. The hydrotreatment in unit 120 can be carried out at low pressure, for example at a pressure lower than 100 bar. In some aspects, the hydrotreating conditions in unit 120 may include: i) 30 bar to 100 bar, or at least any one of 30, 40, 50, 60, 70, 80, 90 and 100 bar, equal to any one of them or a pressure between any two of them; ii) a temperature of 300 ℃ to 600 ℃, preferably 350 ℃ to 500 ℃, or at least any one of 300, 350, 400, 450, 500, 550 and 600 ℃, equal to any one of them or between any two of them; or iii) 0.5 to 2hr ^-1 Or at least 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2hr ^-1 A Weight Hourly Space Velocity (WHSV) equal to any one of them or between any two of them, or any combination thereof. The hydrotreatment can be carried out in hydrogen (H) ₂ ) In the presence of a catalyst. H ₂ May be fed to the hydroprocessing unit 120 via one or more hydrocarbon feed streams (e.g., 101, 105, 107, and/or 309) and/or separately. In some aspects, H ₂ And hydrocarbons (e.g., introduced via streams 101, 105, 107, and/or 309) may be fed to hydroprocessing unit 120 at a volume ratio of 200Nm ³ :1m ³ Up to 2000Nm ³ :1m ³ Or at least 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1, 1400:1, 1500:1, 1600:1, 1700:1, 1800: 1. 1900:1 and 2000:1Nm ³ :m ³ Any one of them, or any two in between. In some aspects, the dissolved catalyst may contain Ni and/or Mo. In some aspects, the dissolved catalyst may contain metal octoates and/or naphthenates. In some aspects, the dissolved catalyst may contain nickel octoate, nickel naphthenate, molybdenum octoate, or molybdenum naphthenate, or any combination thereof. In some aspects, nickel octoate, nickel naphthenate, molybdenum octoate, and/or molybdenum naphthenate independently may be in the hydrocarbon based body. In some aspects, the dissolved catalyst may be a catalyst that is dissolved in the feed and may form a homogeneous catalyst when mixed with the feed (e.g., a hydrotreated feed). In some aspects, no additional solvent may be used to dissolve the catalyst in the feed, such as metal naphthenates and/or octoates. The metal octoates and/or naphthenates may be present as dissolved organic salts in the liquid hydrocarbon feed.

The fixed bed catalyst may comprise Co, ni, mo and/or W on a support. In certain aspects, the fixed bed catalyst may contain Co and Mo on a support; ni and Mo on a support; co, ni and Mo on a support; ni and W on a carrier; or Ni, W and Mo on a support, or any combination thereof. In some aspects, the fixed bed catalyst support may be alumina, silica, aluminosilicate, or zeolite, or any combination thereof. The zeolite may be an X-type zeolite, a Y-type or USY-type zeolite, mordenite, faujasite, nanocrystalline zeolite, MCM mesoporous material, SBA-15, silicoaluminophosphate, gallium phosphate, titanophosphate, ZSM-5, ZSM-11, ferrierite, heulandite, zeolite-A, erionite and chabazite, or any combination thereof.

In the reforming unit (e.g., 124 and/or 508), the hydrocarbons may be reformed to form C ₆ To C ₈ Aromatic compounds such as benzene, toluene and xylene. In some aspects, the reforming conditions in the units (e.g., 124 and/or 508) may include:400 ℃ to 600 ℃, preferably 450 ℃ to 550 ℃, or at least any one of 400, 450, 500, 550 and 600 ℃, equal to any one of them or between any two of them, and/or 2 bar to 30 bar, or at least any one of 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30 bar, equal to any one of them or between any two of them. Reforming can be carried out at H ₂ In the presence of a catalyst. H ₂ The reforming unit may be fed by one or more hydrocarbon feed streams to the reforming unit (e.g., stream 104 of unit 124; stream 511 of unit 508) and/or separately. In some aspects, H ₂ And hydrocarbons may be fed to the reforming unit in a molar ratio of 2:1 to 9:1, or any one of, equal to, or between any two of 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, and 9:1. Reforming may be performed in the presence of a reforming catalyst. In some aspects, the reforming catalyst may contain Pt and Re on alumina; platinum on alumina; metal-loaded zeolite; or any combination thereof. The metal-loaded zeolite may contain one or more dehydrogenation metals including, but not limited to, pt, pd, ga, and/or Ni. Reforming in units 124, 508 may be performed according to systems and methods known in the art. The reforming process may be a semi-regenerative reforming process or a continuous catalytic reforming process, and the reforming units (e.g., 124 and/or 508) may be semi-regenerative reforming units or continuous catalytic reforming units. The reforming catalyst may be contained as a fixed bed catalyst in a semi-regenerative reforming unit and may be contained as a moving bed catalyst in a continuous catalytic reforming unit. The reforming catalyst may be regenerated according to methods known in the art. In some aspects, the reforming unit (e.g., 124 and/or 508) may include a plurality of reactors, such as 3 or more reactors. The hydrocarbon feed to the reactor may be heated prior to feeding to the reactor.

The optional cracking unit 126 may be a steam cracking unit or a catalytic cracking unit. The hydrocarbon feed entering the cracking unit 126 (e.g., introduced into the unit 126 via an optional portion of the streams 103, 209, 105) can be cracked, such as by steam cracking or catalytic cracking, to form light gas olefins. In some aspects, the light gas olefins may include ethylene, propylene, and/or butene. In some aspects, the hydrocarbon feed may be steam cracked in the presence of steam, such as dilution steam. In certain aspects, the steam cracking conditions in the cracking unit 126 may include: i) 750 ℃ to 900 ℃, or at least any one of, equal to any one of, or between any two of, 750, 775, 800, 825, 850, 875, and 900 ℃; ii) atmospheric pressure to 6 bar, or at least any one of 2 bar, 3 bar, 4 bar, 5 bar and 6 bar, equal to any one of them or a pressure between any two of them; iii) Or 0.05s to 1s, or at least any one of, equal to, or between any two of 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 s; or any combination thereof. In certain aspects, the catalytic cracking conditions in the cracking unit 126 may include: i) 500 ℃ to 800 ℃, or at least any one of, equal to any one of, or between any two of 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, and 800 ℃; ii) atmospheric pressure to 10 bar, or at least 2 bar, 3 bar, 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar and 10 bar, equal to any one of them or a pressure between any two of them; iii) A contact time of less than 5 s; or any combination thereof.

Pyrolysis oil may be produced by reactive extrusion/melt cracking of plastics using a plastic depolymerization unit (e.g., 342, 442, and/or 502) and a catalytic cracking unit (e.g., 344, 444, and/or 504). In some aspects, the plastic feed (e.g., 346, 446, and/or 501) can be a mixed plastic feed, and can contain one or more polyolefins (e.g., polyethylene, ethylene alpha-olefin copolymer, polypropylene, etc.), polystyrene, polyesters (e.g., polyalkylene terephthalates), polyvinylchloride, and polyamides (e.g., nylon, polyphthalamides, etc.). The plastic may be derived from waste-containing plastic, such as post-consumer waste-containing plastic.

In a plastic depolymerization unit (e.g., 342, 442, and/or 502), the plastic feed can be depolymerized to form a hydrocarbonaceous wax. The average molecular weight of the hydrocarbon-containing wax (e.g., the compounds in the hydrocarbon-containing wax) may be at least 50 times lower, such as 20 to 50 times lower, than the average molecular weight of the plastic feed (e.g., the compounds in the plastic feed). In some aspects, depolymerization may be carried out in the presence of a catalyst. The catalyst may comprise a liquid catalyst and/or a solid catalyst. In some particular aspects, the liquid catalyst may contain one or more organometallic compounds, for example octoates and/or naphthenates of transition metals such as Ni, mo, co or W. In some aspects, the liquid catalyst may be a catalyst that is dissolved in a plastic melt. In some aspects, the liquid catalyst may be a homogeneous catalyst in a plastic melt. The solid catalyst may contain inorganic oxides, aluminosilicates, zeolites, MCM mesoporous materials, SBA-15, silicoaluminophosphates, gallium phosphate, titanium phosphate, or molecular sieves, or combinations thereof. The zeolite may be ZSM-5, X-type zeolite, Y-type zeolite, USY zeolite, mordenite, faujasite or nanocrystalline zeolite, or any combination thereof. In some aspects, the solid catalyst may be a heterogeneous catalyst in a plastic melt. In some aspects, the solid catalyst may remain solid in the plastic melt. In some aspects, the depolymerization unit (342, 442, and/or 502) can include an extruder. One or more feeders can be used to feed the plastic and catalyst to the extruder, for example from a throat hopper and/or any side feeder. The plastic and catalyst may be fed to the extruder, such as to the barrel of the extruder, alone or in any combination (e.g., a blending combination). The extruder can have a single screw, a left-handed screw, a right-handed screw, a neutral screw, a kneading screw, a multi-screw, intermeshing co-or counter-rotating screws, non-intermeshing co-or counter-rotating screws, reciprocating screws, pinned screws, screened screws, pinned barrels, rolls, pistons, helical rotors, co-kneaders, disc pack processors, various other types of extrusion equipment, or a combination comprising at least one of the foregoing. The plastic feed in the extruder barrel may be heated with one or more heaters disposed along the length of the extruder barrel. In the extruder barrel, the plastic feed may be heated, melted, and depolymerized to form the hydrocarbonaceous wax. In some aspects, the plastic feed in the extruder barrel may be depolymerized at a temperature of 300 to 500 ℃, or at least any one of 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, and 500 ℃, equal to any one of them, or between any two of them. The residence time of the plastic in the extruder may be less than 1 hour, for example 1min to 15min. In certain aspects, the extruder may contain one or more vents configured to introduce and/or withdraw one or more gases from the extruder barrel. The plastic melt and/or hydrocarbon-containing wax may be extruded from the extruder through a die. The hydrocarbonaceous wax from the extruder of the depolymerization unit may be fed to a catalytic cracking unit.

In a catalytic cracking unit (e.g., 344, 444, and/or 504), the hydrocarbonaceous wax can be catalytically cracked in the presence of a cracking catalyst to form pyrolysis oil. In some aspects, the cracking catalyst may contain zeolite and/or metal-loaded zeolite. In some particular aspects, the zeolite may be ZSM-5. In certain aspects, the metal can be a transition metal, such as Mg, ni, and/or Co. The hydrocarbonaceous wax in the catalytic cracking unit (e.g., 344, 444, and/or 504) can be catalytically cracked in a fixed bed reactor or a fluidized bed reactor. In certain aspects, catalytic cracking of the hydrocarbonaceous wax (e.g., in catalytic cracking units 344, 444, and/or 504) can be performed at a temperature below, equal to, or above the temperature at which the plastic feedstock depolymerizes to form hydrocarbonaceous wax (e.g., in depolymerization units 342, 442, and/or 502). In certain aspects, the catalytic cracking conditions in catalytic cracking units 344, 444, and/or 504 may include: 350 to 500 ℃, or at least any one of 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, and 500 ℃, a temperature equal to any one of them or between any two of them, a pressure of 1 to 6 bar, or any combination thereof. In some aspects, the average molecular weight of the pyrolysis oil (e.g., compounds in the pyrolysis oil) may be at least 3 times lower than the average molecular weight of the hydrocarbonaceous wax (e.g., compounds in the hydrocarbonaceous wax). Pyrolysis oils may contain paraffins, isoparaffins, olefins, naphthenes, and aromatics.

In certain aspects, the plastic feed may contain chlorine-containing plastics, such as polyvinyl chloride. In some aspects, a portion of the chlorides from the plastic feedstock can be fed to the reformer (e.g., 124 and/or 508) through the process steps described herein. The chloride may increase the activity of the reforming catalyst. In certain aspects, the chloride may be fed to the reformer units 124, 508 at a concentration of 0.1ppm to 15ppm, or at least any one of, equal to, or between any two of 0.1, 1, 2, 4, 6, 8, 10, 12, 14, and 15 ppm.

The second stream 102 may contain saturated hydrocarbons having a boiling point below 350 ℃. In some aspects, at least 70wt% of the hydrocarbons in the second stream 102 can be saturated hydrocarbons having a boiling point below 350 ℃. In some aspects, the second stream can contain: i) 10wt% to 40wt%, or at least any one of 10, 15, 20, 25, 30, 35, and 40wt%, equal to any one of them or between any two of them, naphthenes, based on the total weight of the second stream; ii) from 2wt% to 20wt%, or at least any one of 2, 3, 4, 6, 8, 10, 12, 14, 16, 18, an aromatic compound equal to any one of them or between any two of them; and iii) a total concentration of from 50 to 85wt%, or at least any one of, equal to, or between any two of, 50, 55, 60, 65, 70, 75, 80 and 85wt% of paraffins and isoparaffins. In some aspects, the olefin content of the second stream 102 can be less than 8wt%, or less than 5wt%, or less than 3wt%, or less than 1wt%, or the second stream can be substantially free of olefins. Naphthenes as described herein may include branched and unbranched naphthenes.

The fourth stream 104 and the stream B511 may contain hydrocarbons having a boiling point of 70 ℃ to 140 ℃. The fourth stream 104 can contain: i) 25wt% to 50wt%, or at least any one of 25, 30, 35, 40, 45 and 50wt%, equal to any one of them or between any two of them, respectively, based on the total weight of the fourth stream; ii) 10wt% to 35wt%, or at least any one of 10, 15, 20, 25, 30 and 35wt%, or any one of them or any two in between, aromatic compounds; and iii) a total concentration of from 30 to 55wt%, or at least any one of 30, 35, 40, 45, 50 and 55wt%, equal to any one of them or between any two of them, of paraffins and isoparaffins. In some aspects, the olefin content of the fourth stream 104 can be less than 8wt%, or less than 5wt%, or less than 3wt%, or less than 1wt%, or the fourth stream can be substantially free of olefins. In certain aspects, the composition of stream B511 can be similar to fourth stream 104.

Third stream 103 and stream a 510 can contain hydrocarbons having a boiling point below 70 ℃. The third stream 103 can contain paraffins and isoparaffins in a total concentration of from 90 to 100wt%, or at least any one of, equal to, or between any two of 90, 95, 96, 97, 98, 99, 99.3, 99.5, 99.8, 99.9, and 100wt%, based on the total weight of the third stream, respectively. In some aspects, the olefin content of the third stream 103 can be less than 8wt%, or less than 5wt%, or less than 3wt%, or less than 1wt%, or the third stream can be substantially free of olefins. In some aspects, the aromatic content of the third stream 103 can be less than 8wt%, or less than 5wt%, or less than 3wt%, or less than 1wt%, or the third stream can be substantially free of aromatics. In certain aspects, the composition of stream a 510 can be similar to third stream 103.

Fifth stream 105 and stream C512 may contain hydrocarbons having a boiling point above 140 ℃.

In certain aspects, ethylene, propylene, and/or butene from the light gas olefin stream (127) can be purified/separated in one or more steps to obtain a separated stream containing polymer grade ethylene, propylene, and/or butene.

In certain aspects, benzene, toluene, and xylenes from sixth stream 106 and/or stream D513 can be purified/separated by one or more steps to obtain a separated stream containing benzene, toluene, and xylenes.

While embodiments of the present invention have been described with reference to the blocks of fig. 1-5, it should be understood that the operation of the present invention is not limited to the specific blocks and/or the sequence of specific blocks illustrated in fig. 1-5. Accordingly, embodiments of the invention may use the various blocks in a different order than the order of fig. 1-5 to provide the functionality as described herein.

The systems and methods described herein may also include various equipment not shown and known to those skilled in the chemical processing arts. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, etc. may not be shown.

Examples

The following include specific embodiments as part of the disclosure. The examples are for illustrative purposes only and are not intended to limit the invention. One of ordinary skill in the art will readily recognize parameters that may be changed or modified to produce substantially the same results.

Example 1

Benzene, toluene, xylenes and light gaseous olefins from crude hydrocarbon fraction having an upper boiling point fraction of 350 DEG C

At 380 ℃ at 60 bar for 1h ^-1 And H ₂ Hydrocarbon feed ratio 400Nm ³ /m ³ The crude hydrocarbon fraction having an upper boiling fraction of 350 ℃ is hydrotreated in the presence of a hydrotreating catalyst (combination of hydrocracking catalyst Ni/W and hydrotreating catalyst Co, ni, mo) to obtain a hydrotreated stream. The hydrotreated stream is distilled in an atmospheric column and separated into a first hydrocarbon fraction (fraction 1) having an upper boiling point fraction of 70 ℃, a second hydrocarbon fraction (fraction 2) having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃, and a third hydrocarbon fraction (fraction 3) having a lower boiling point fraction of 140 ℃. The paraffin, isoparaffin, olefin, naphthene, and aromatic (PIONA) compositions of hydrocarbon fractions 1, 2, and 3 based on the total weight of the hydrotreated stream are provided in table 1. Hydrocarbon fraction 1 is steam cracked to obtain light gaseous olefins. Hydrocarbon fraction 2 is reformed in a naphtha reformer to obtain benzene, toluene and xylenes. Hydrocarbon fraction 2 contained more naphthenes than the two common reformer feeds (table 2). Thus, reformed hydrocarbon fraction 2 produced higher amounts of aromatics (e.g., benzene, toluene, and xylenes) than the reformed feed of table 2. Furthermore, as can be seen from Table 1, hydrocarbon fraction 1 is entirely paraffinic, The absence of aromatics and olefins provides a good feed for steam cracking/catalytic cracking.

Table 1. PIONA composition of a hydrocarbon fraction having an upper boiling point fraction of 350 ℃ obtained from crude oil by hydrotreating.

Component (A)	Hydrocarbon fraction 1	Hydrocarbon fraction 2	Hydrocarbon fraction 3
				N-paraffins	6.8	4.6	3.3
Isoparaffins	30.8	10.9	2.6
				Cycloalkane (CNS)	0	11.6	0.1
Branched cycloalkanes	0	14.8	2.7
				Di-cycloalkane	0	0.1	0.4
Monoaromatic compounds	0	7.8	3.4
				Cycloalkane aromatic compounds	0	0	0.1
Diaryl compounds	0	0	0
				Cycloalkane biaromatic compounds	0	0	0
Triaromatics	0	0	0
				Totals to	37.6	49.8	12.6

Table 2: typical PIONA composition of naphtha reformer feed.

Example 2

Benzene, toluene and xylene and light gaseous olefins from crude oil

At 450 ℃ under 40 bar for 1h ^-1 And H ₂ Hydrocarbon feed ratio 400Nm ³ /m ³ The SiTexas mixed crude oil having a final boiling point fraction of 750 ℃ is hydrotreated in the presence of a hydrotreating catalyst (combination of a hydrocracking catalyst Ni/W and hydrotreating catalysts Co, ni, mo) to obtain a hydrotreated stream. The hydrotreated stream is distilled in an atmospheric column and separated into a first hydrocarbon fraction (fraction 4) having an upper boiling point fraction of 70 ℃, a second hydrocarbon fraction (fraction 5) having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃, and a third hydrocarbon fraction (fraction 6) having a lower boiling point fraction of 140 ℃. The PIONA compositions of hydrocarbon fractions 4 and 5 based on the total weight of the hydrotreated stream are provided in table 3. Hydrocarbon fraction 4 is steam cracked to obtain light gaseous olefins. The hydrocarbon fraction 5 is reformed in a naphtha reformer to obtain benzene, toluene and xylenes. 19.7wt% and 31wt% of the hydrotreated stream are fractionated into fractions 4 and 5, respectively, and the remainder is fractionated into fraction 6. The hydrocarbon fraction 5 is mainly paraffinic and naphthenic, about 70wt% after standardization, providing a good feed for reforming. In addition, 31wt% of hydrocarbon fraction 5 is naphthenes, providing a good reforming feed for benzene, toluene and xylenes formation. The hydrocarbon fraction 4 is low in olefin content and is mainly paraffinic, about 94.6% after standardization, providing a good feed for steam cracking/catalytic cracking.

Table 3: PIONA composition obtained by hydrotreating crude oil

Component (A)	Hydrocarbon fraction 4	Hydrocarbon fraction 5
			N-paraffins	8.3	4.6
Isoparaffins	10.3	7.3
			Olefins	0.5	0.1
Cycloalkane (CNS)	0.5	9.8
			Aromatic compounds	0.0	9.3
Totals to	19.7	31

Example 3

Benzene, toluene and xylene and light gaseous olefins from pyrolysis oil

At 400℃at 60 bar for 1h ^-1 And H ₂ Hydrocarbon feed ratio 400Nm ³ /m ³ In the following, commercial pyrolysis oil having a boiling point range of 85 ℃ to 470 ℃ is hydrotreated in the presence of a hydrotreating catalyst (combination of a hydrocracking catalyst Ni/W and hydrotreating catalysts Co, ni, mo) to obtain a hydrotreated stream. Hydrotreating a streamThe mixture was distilled in an atmospheric column and separated into a first hydrocarbon fraction (fraction 7) having an upper boiling point fraction of 70 ℃, a second hydrocarbon fraction (fraction 8) having a lower boiling point fraction of 70 ℃ and an upper boiling point fraction of 140 ℃, and a third hydrocarbon fraction (fraction 9) having a lower boiling point fraction of 140 ℃. The PIONA compositions of hydrocarbon fractions 7, 8 and 9 based on the total weight of the hydrotreated stream are provided in table 4. Hydrocarbon fraction 7 is steam cracked to obtain light gaseous olefins. The hydrocarbon fraction 8 is reformed in a naphtha reformer to obtain benzene, toluene and xylenes. The hydrocarbon fraction 9 is recycled to the hydrotreating step. 43.6wt%,39wt% and 17.3 wt% of fraction 8 are paraffins, naphthenes and aromatics, respectively. Hydrocarbon fraction 8 has more naphthenes than typical reforming feedstock (table 2) and is therefore more suitable for producing benzene, toluene and xylenes by reforming. Furthermore, as can be seen from table 4, hydrocarbon fraction 7 is entirely paraffinic, free of aromatics and olefins, providing a good feed for steam cracking/catalytic cracking.

Table 4: PIONA composition obtained by hydrotreating pyrolysis oil

In the context of the present invention, at least the following 20 embodiments are described. Embodiment 1 is an alternative production C ₆ To C ₈ A process for the production of aromatics and optionally light gaseous olefins. The process comprises hydrotreating a first stream containing hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream containing saturated hydrocarbons having a boiling point below 350 ℃. The process further comprises separating the second stream to obtain a third stream comprising hydrocarbons having a boiling point below 70 ℃, a fourth stream comprising hydrocarbons having a boiling point between 70 ℃ and 140 ℃, and a fifth stream comprising hydrocarbons having a boiling point above 140 ℃. The process further comprises recycling at least a portion of the fifth stream to the hydrotreating step (a). The process further comprises reforming a fourth stream to obtain a C-containing stream ₆ To C ₈ A sixth stream of aromatic compounds. In addition, the process comprises optionally cracking the third stream and/or a portion of the fifth stream to obtain light gas olefinsAnd (3) hydrocarbons. Embodiment 2 is the method of embodiment 1, wherein at least 70wt% of the second stream contains saturated hydrocarbons having a boiling point below 350 ℃. Embodiment 3 is the method of any one of embodiments 1 or 2, wherein the reforming step d) further comprises obtaining a catalyst comprising a non-aromatic compound and a non-C ₆ To C ₈ A seventh stream of aromatic compounds and optionally recycling at least a portion of the seventh stream to the hydrotreating step (a). Embodiment 4 is the method of any one of embodiments 1 to 2, wherein the hydrotreating conditions in step (a) comprise: a pressure of less than 100 bar, preferably 30 bar to 100 bar, a temperature of 300 ℃ to 600 ℃, a pressure of 0.5 to 2hr ^-1 Or 200Nm ³ :1m ³ Up to 2000Nm ³ :1m ³ Is fed with liquid H ₂ Hydrocarbon volume ratio, or any combination or all thereof. Embodiment 5 is the method of any one of embodiments 1 to 4, wherein the hydrotreating in step (a) is performed using a dissolved catalyst comprising Ni and/or Mo and a fixed bed catalyst comprising Co, mo, ni, W on a support or any combination thereof. Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the reforming conditions in step (b) comprise: a temperature of 450 ℃ to 550 ℃, a pressure of 2 bar to 30 bar, or an H of 2:1 to 9:1 ₂ Hydrocarbon molar ratio, or any combination or all thereof. Embodiment 7 is the method of any one of embodiments 1 to 6, wherein the reforming in step (d) is performed using a reforming catalyst comprising Pt-Re on alumina, pt on alumina, a metal-loaded zeolite, or a combination thereof. Embodiment 8 is the method of any one of embodiments 1 to 7, wherein the pyrolysis oil is obtained from a plastic. Embodiment 9 is the method of any one of embodiments 1 to 8, wherein the pyrolysis oil is obtained from plastic by: depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, wherein the cracking conditions include a cracking temperature that is greater than, equal to, or less than the depolymerization temperature. Embodiment 10 is the method of any one of embodiments 1 to 9, wherein the first stream Contains hydrocarbons with boiling points higher than 140 ℃ separated from crude oil and/or pyrolysis oil by atmospheric distillation. Embodiment 11 is the method of any one of embodiments 1 to 10, wherein the atmospheric distillation further produces an eighth stream comprising hydrocarbons having a boiling point of 70 ℃ to 140 ℃, and the method further comprises reforming the eighth stream. Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the eighth stream is reformed with the fourth stream to form a sixth stream and a seventh stream. Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the atmospheric distillation further produces a ninth stream comprising hydrocarbons having a boiling point below 70 ℃. Embodiment 14 is the process of any one of embodiments 1 to 3, wherein the ninth stream is cracked with the third stream to produce light gaseous olefins or sent to a hydrotreating step. Embodiment 15 is the method of any one of embodiments 1 to 14, wherein the first stream contains pyrolysis oil. Embodiment 16 is the method of any one of embodiments 1 to 15, wherein the first stream contains condensate, naphtha, light crude oil, or crude oil hydrocarbon fraction having an upper boiling point fraction of 350 ℃, or whole crude oil, or any combination or all thereof.

Embodiment 17 is a selective production of C from plastics ₆ To C ₈ A process for the production of aromatics and optionally light gaseous olefins. The method comprises the following steps: a) Performing reactive extrusion or melt cracking of the plastic to form pyrolysis oil; b) Separating pyrolysis oil to obtain a stream a containing hydrocarbons having a boiling point below 70 ℃, a stream B containing hydrocarbons having a boiling point between 70 ℃ and 140 ℃ and a stream C containing hydrocarbons having a boiling point above 140 ℃; c) Reforming stream B to obtain a stream containing C ₆ To C ₈ Stream D of aromatic compounds; and d) optionally mixing stream A into the refinery's gasoline pool. Embodiment 18 is the method of embodiment 17, wherein the reactive extrusion or melt cracking of the plastic comprises: depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and catalytically cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, wherein the cracking conditions include a cracking temperature that is greater than, equal to, or less than the depolymerization temperatureDegree. Embodiment 19 is the method of any one of embodiments 17-18, further comprising recycling stream C to the catalytic cracking step. Embodiment 20 is the method of any one of embodiments 17 to 19, wherein at least a portion of the hydrogen-containing gas, non-aromatic compounds, and non-C obtained from the reforming in step (C) ₆ To C ₈ Aromatics are recycled to the catalytic cracking step.

All embodiments described above and herein can be combined in any manner unless explicitly excluded.

Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Furthermore, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure above, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims (20)

1. Selective production C ₆ To C ₈ A process for aromatic compounds and optionally light gaseous olefins, the process comprising:

a) Hydrotreating a first stream comprising hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream comprising saturated hydrocarbons having a boiling point below 350 ℃;

b) Separating the second stream to obtain a third stream comprising hydrocarbons having a boiling point below 70 ℃, a fourth stream comprising hydrocarbons having a boiling point between 70 ℃ and 140 ℃, and a fifth stream comprising hydrocarbons having a boiling point above 140 ℃;

c) Recycling at least a portion of the fifth stream to the hydrotreating step (a);

d) Reforming a fourth stream to obtain a stream comprising C ₆ To C ₈ A sixth stream of aromatic compounds; and

e) Optionally cracking the third stream and/or a portion of the fifth stream to obtain light gaseous olefins.

2. The process of claim 1, wherein at least 70wt% of the second stream consists of saturated hydrocarbons having a boiling point below 350 ℃.

3. The process of claim 1 or 2, wherein reforming step d) further comprises obtaining a catalyst comprising a non-aromatic compound and a non-C ₆ To C ₈ A seventh stream of aromatic compounds and optionally recycling at least a portion of the seventh stream to the hydrotreating step (a).

4. The process of any one of claims 1 to 2, wherein the hydrotreating conditions in step (a) comprise: a pressure of less than 100 bar, preferably 30 bar to 100 bar, a temperature of 300 ℃ to 600 ℃, a pressure of 0.5 to 2hr ^-1 Or 200Nm ³ :1m ³ Up to 2000Nm ³ :1m ³ Is fed with liquid H ₂ Hydrocarbon volume ratio, or any combination or all thereof.

5. The process of claim 4, wherein the hydrotreating in step (a) is performed using a dissolved catalyst comprising Ni and/or Mo and a fixed bed catalyst comprising Co, mo, ni, W on a support or any combination thereof.

6. The method according to any one of claims 1 to 2, wherein the reforming conditions in step (b) comprise: a temperature of 450 ℃ to 550 ℃, a pressure of 2 bar to 30 bar, or an H of 2:1 to 9:1 ₂ Hydrocarbon molar ratio, or any combination or all thereof.

7. The method of any one of claims 1 to 2, wherein the reforming in step (d) is performed using a reforming catalyst comprising Pt-Re on alumina, pt on alumina, a metal-loaded zeolite, or a combination thereof.

8. The method of any one of claims 1 to 2, wherein the pyrolysis oil is obtained from a plastic.

9. The method of claim 8, wherein the pyrolysis oil is obtained from plastic by: depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, wherein the cracking conditions include a cracking temperature that is greater than, equal to, or less than the depolymerization temperature.

10. The process of any one of claims 1 to 2, wherein the first stream comprises hydrocarbons having a boiling point above 140 ℃ separated from crude oil and/or pyrolysis oil by atmospheric distillation.

11. The method of claim 10, wherein the atmospheric distillation further produces an eighth stream comprising hydrocarbons having a boiling point of 70 ℃ to 140 ℃, and the method further comprises reforming the eighth stream.

12. The process of claim 10, wherein the eighth stream is reformed with the fourth stream to form a sixth stream and a seventh stream.

13. The method of claim 10, wherein the atmospheric distillation further produces a ninth stream comprising hydrocarbons having a boiling point below 70 ℃.

14. The process of claim 13, wherein the ninth stream is cracked with the third stream to produce light gaseous olefins or sent to a hydrotreating step.

15. The process of any one of claims 1-2, wherein the first stream comprises pyrolysis oil.

16. The method of any one of claims 1-2, wherein the first stream comprises condensate, naphtha, light crude oil, or crude hydrocarbon fraction having an upper boiling point fraction of 350 ℃, or whole crude oil, or any combination or all thereof.

17. Selective production of C from plastics ₆ To C ₈ A process for aromatic compounds and optionally light gaseous olefins, the process comprising:

a) Performing reactive extrusion or melt cracking of the plastic to form pyrolysis oil;

b) Separating pyrolysis oil to obtain a stream a comprising hydrocarbons having a boiling point below 70 ℃, a stream B comprising hydrocarbons having a boiling point between 70 ℃ and 140 ℃ and a stream C comprising hydrocarbons having a boiling point above 140 ℃;

c) Reforming stream B to obtain a stream comprising C ₆ To C ₈ Stream D of aromatic compounds; and

d) Stream a is optionally mixed into the refinery's gasoline pool.

18. The method of claim 17, wherein reactive extrusion or melt cracking of the plastic comprises: depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-containing wax stream, and catalytically cracking the hydrocarbon-containing wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce pyrolysis oil, wherein the cracking conditions include a cracking temperature that is greater than, equal to, or less than the depolymerization temperature.

19. The process of claim 18, further comprising recycling stream C to the catalytic cracking step.

20. The process of any one of claims 18 to 19, wherein at least a portion of the hydrogen-containing gas, non-aromatic compounds, and non-C obtained from the reforming in step (C) ₆ To C ₈ Aromatics are recycled to the catalytic cracking step.