KR20230124628A - Production of BTX aromatics and light gas olefins from crude oil and plastic pyrolysis oil - Google Patents

Abstract

A process for producing C ₆ to C ₈ aromatics and optionally light gas olefins from crude oil and/or pyrolysis oil is disclosed. The process comprises hydrotreating a first stream containing hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream containing saturated hydrocarbons boiling below 350°C, containing hydrocarbons boiling below 70°C. separating the second stream to obtain a third stream, a fourth stream containing hydrocarbons boiling between 70°C and 140°C and a fifth stream containing hydrocarbons boiling above 140°C; recycling at least one portion of the stream to a hydrotreating step, reforming a fourth stream to obtain a sixth stream containing C ₆ to C ₈ aromatics, and optionally a third stream to obtain light gas olefins. includes disassembling

Description

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

This application claims the benefit of priority from U.S. Provisional Patent Application Serial No. 63/131,270, filed on December 28, 2020, which is incorporated herein by reference in its entirety.

The present invention relates generally to processes for producing C ₆ to C ₈ aromatics and optionally light gas olefins. In one aspect, the invention relates to a process for producing C ₆ to C ₈ aromatics and light gas olefins from crude oil and/or pyrolysis oil using hydroprocessing.

C ₆ to C ₈ aromatics such as benzene, toluene and xylene are important commodity chemicals with ever-increasing demand. For example, benzene, toluene and/or xylene are used to make a variety of polymers (eg, polycarbonates, polyesters, nylons and polyurethanes, etc.) that have a variety of industrial uses. Light gas olefins such as ethylene, propylene and butylene are important raw materials for many end products such as polymers, rubbers, plastics and octane booster compounds.

Benzene, toluene and xylene are generally produced by reforming naphtha, such as continuous naphtha, from crude oil in a reformer. However, only a fraction (eg about 10-20% by weight) of crude oil is suitable for reforming and is used to make benzene, toluene and xylene. In addition, while naphthenes are more favored to form aromatics by reforming, typical reformer feeds from crude oil have a relatively low naphthene content. For example, typically less than 25% by weight of the reformer feed is naphthenic. For example Turaga, et al., (2003). Journal of Scientific and Industrial Research, 62 (10), 963-978; Mujtaba, et al., (2019). See Processes , 7 , 192.

Various attempts have been made to maximize aromatics production from crude oil. For example, processes with multiple hydrocracking units and other equipment have been used. However, these attempts may cause additional problems due to process complexity, reduced efficiency, and increased cost.

A discovery has been made that provides a solution to at least one of the problems associated with producing high value chemicals such as C ₆ to C ₈ aromatics and/or light gas olefins from crude oil. In one aspect, the solution may include placing a hydrotreating unit upstream of a reforming unit used to produce aromatics. In some aspects, a single hydrotreating unit may be used. The use of an upstream hydrotreating unit can i) increase the amount of reformer feed per unit of crude oil treated; ii) increase the amount of naphthenes suitable for producing C ₆ to C ₈ aromatics by reforming and/or iii) optionally increase the amount of steam cracker feed per unit crude oil treated. In addition, the use of a hydrotreating unit can reduce the amount of olefins in the reformer feed, which can serve to reduce the heating of the reforming unit, which can help conserve energy and increase the efficiency of the reforming unit. there is. This advantage is such that the product stream from the hydroprocessing unit is (i) a stream comprising hydrocarbons having a boiling point of less than 70°C; (ii) a stream comprising hydrocarbons having a boiling point between 70° C. and 140° C.; and (iii) a stream containing hydrocarbons with a boiling point greater than 140°C. Streams comprising hydrocarbons with a boiling point above 140° C. can be recycled back to the hydroprocessing unit. A stream comprising hydrocarbons having a boiling point between 70° C. and 140° C. may be sent to a reforming unit to produce C ₆ to C ₈ aromatics (eg, benzene, toluene and/or xylenes (BTX)). Streams comprising hydrocarbons boiling below 70° C. may be cracked (eg, via steam cracking or catalytic cracking) to produce light gas olefins.

In another aspect of the invention, the use of an upstream hydrotreating unit may not be used. In this aspect, the C ₆ to C ₈ aromatics and/or light gas olefins may be produced from plastics (eg, recycled blended thermoplastics) as a source. For example, the initial furnish may include a plastic (eg, a recycled blended thermoplastic). Plastics can be reactively extruded or melt cracked to form pyrolysis oil. The pyrolysis oil includes (i) a stream comprising hydrocarbons having a boiling point of less than 70°C; (ii) a stream comprising hydrocarbons having a boiling point between 70° C. and 140° C.; and (iii) a stream comprising hydrocarbons with a boiling point greater than 140°C. At least a portion of the stream comprising hydrocarbons having a boiling point greater than 140° C. may be recycled back to a reactive extrusion or melt cracking process (eg, a reaction process). A stream comprising hydrocarbons boiling between 70°C and 140°C may be sent to a reforming unit to produce C ₆ to C ₈ aromatics (eg BTX). A stream comprising hydrocarbons boiling below 70°C, or a portion thereof, may be sent to steam reforming to produce hydrogen; cracked in a catalytic cracking unit to produce light gas olefins; can be sent to a petrol pool; It may be any combination of these. Advantages of this process include not using a hydrotreating unit (although such a unit can be used in the context of the present invention) and/or using recycled plastics to efficiently produce BTX and optionally olefins. In some aspects, streams comprising hydrocarbons with a boiling point between 70° C. and 140° C. may contain chlorine, which may be beneficial for maintaining reforming catalytic activity. In some aspects, at least one portion of the chloride present in the stream comprising hydrocarbons having a boiling point between 70°C and 140°C may be sourced from a plastic.

Certain aspects relate to a first process for producing C ₆ to C ₈ aromatics and optionally light gas olefins. The first process may include 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 of crude oil and/or pyrolysis oil. The second stream may contain saturated hydrocarbons with a boiling point below 350°C. In some aspects, at least 70% by weight of the hydrocarbons in the second stream may be saturated hydrocarbons having a boiling point less than 350°C. In certain aspects, the second stream may further contain aromatics. In step (b), the second stream comprises a third stream containing hydrocarbons boiling below 70°C, a fourth stream containing hydrocarbons boiling between 70°C and 140°C, and a fifth stream containing hydrocarbons boiling above 140°C. can be separated to obtain a stream. 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 sixth stream containing C ₆ to C ₈ aromatics. The C ₆ to C ₈ aromatics may be benzene, toluene and xylene, and the sixth stream may include benzene, toluene and xylene. Optionally, in step (e) the third stream may be cracked, for example by steam cracking or catalytic cracking, to obtain light gas olefins. The reforming in step (d) may also produce non-aromatics and non-C ₆ to C ₈ aromatics (eg, aromatic hydrocarbons other than benzene, toluene and xylene). In some aspects, a seventh stream containing non-aromatics and at least one portion of non-C ₆ to C ₈ aromatics produced in step (d) may be recycled to hydrotreating step (a). Optionally, a portion of the fifth stream may be cracked, for example by steam cracking or catalytic cracking, into a third stream in step (e) to form light gas olefins.

The hydrotreating in step (a) may include hydrocracking and/or hydrotreating. The sulfur and/or nitrogen content of hydrocarbons containing sulfur and/or nitrogen may be reduced in the hydrotreating process. The hydrocracking process may include cracking hydrocarbons in the presence of H2. In some aspects, the hydrotreating may be performed at low pressure, such as at less than or equal to 100 barg. Without being bound by theory, it is believed that lower operating pressures may lead to lower investment costs and may have a beneficial effect on the economics of the process. In some aspects, the hydrotreating conditions of step (a) are a pressure of 30 barg to 100 barg; a temperature of 300°C to 600°C, preferably 350°C to 500°C; or a weight hourly space velocity (WHSV) of 0.5 to 2 hr ⁻¹ , or combinations thereof. In some aspects, the hydrotreating is performed in the presence of hydrogen (H2) having a H2 to hydrocarbon (eg, H2 and hydrocarbon feed to the hydrotreating step) volume ratio between 200 Nm ³ /m ³ and 20000 Nm ³ /m ³ . It can be. Hydrotreating can be carried out in the presence of a catalyst. 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, hydrotreating can be performed in the presence of a dissolved catalyst and/or a fixed bed catalyst. In some aspects, the dissolved catalyst is nickel (Ni) and/or molybdenum (Mo) In some aspects, the dissolved catalyst may contain metal naphthenates and/or octanoates In some aspects, the dissolved catalysts may contain Ni octanoate, Ni naphthenate, Mo octanoate can contain noate, or Mo naphthenate, or any combination thereof In some aspects, Ni octanoate, Ni naphthenate, Mo octanoate and/or Mo naphthenate are independently hydrocarbons In some aspects, the dissolved catalyst can be a catalyst dissolved in the feed and can form a homogeneous catalyst when mixed with the feed (e.g., hydrotreating feed). , no additional solvents can be used to dissolve catalysts that are, for example, metal naphthenates and/or octanoates in the feed. Ebullated bed catalysts can contain one or more transition metal(s) on a support. In certain aspects, the one or more transition metal(s) can be cobalt (Co), Ni, Mo and/or tungsten (W) In certain aspects, the ebullated bed catalyst comprises Co and Mo on a support; Ni and Mo; Co, Ni, and Mo on a support; Ni and W on a support; or Ni, W, and Mo on a support, or any combination thereof. In some aspects, the fixed bed The catalyst support can be alumina, silica, aluminosilicate or zeolite, or any combination thereof The zeolite can be type X zeolite, type Y or type USY zeolite, mordenite, faujasite, nanocrystalline zeolite, MCM mesoporous material , SBA-15, silico-alumino phosphate, gallophosphate, titanophosphate, ZSM-5, ZSM-11, ferrierite, furlandite, zeolite-A, erionite and chabazite, or any of these can be a combination.

In some aspects, the second stream may be separated into third, fourth and fifth streams in step (b) by atmospheric distillation with boiling cuts of 70°C and 140°C. The third stream may contain a hydrocarbon fraction with a high boiling point cutoff of 70°C from the second stream. The fourth stream may contain a hydrocarbon fraction with a low boiling point cut of 70°C and a high boiling point cut of 140°C in the second stream. The fifth stream may contain a hydrocarbon fraction with a lower boiling cutoff of 140° C. in the second stream.

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. Atmospheric distillation may be performed in a crude distillation unit (CDU) with boiling cuts of 70°C and 140°C. From the CDU, a first hydrocarbon fraction has a high boiling cut of 70°C, a second hydrocarbon fraction has a low boiling cut of 70°C and a high boiling cut of 140°C, and a third hydrocarbon fraction has a low boiling cut of 140°C. fraction 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 can be modified to form C ₆ to C ₈ aromatics. In certain aspects, an eighth stream containing a second hydrocarbon fraction may be reformed in step (d) with a 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 can be cracked, for example, by steam cracking or catalytic cracking to form light gas olefins. In some aspects, the first hydrocarbon fraction or a portion of the first hydrocarbon fraction can be hydrotreated. In certain aspects, crude oil may be distilled in a CDU, and a ninth stream containing a first hydrocarbon fraction is optionally cracked, e.g. steam in step (a) together with a third stream to form light gas olefins. It can be decomposed or decomposed catalytically. In certain aspects, crude oil and pyrolysis oil may be distilled in a CDU, and a ninth stream containing a first hydrocarbon fraction may be hydrotreated in step (a) together with the first stream 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 a crude hydrocarbon fraction having a high boiling point cut of 350° C., whole crude oil, or any combination thereof. In some aspects, the first stream may contain pyrolysis oil. Pyrolysis oil can be obtained from plastics by reactive extrusion or melt cracking. Reactive extrusion or melt cracking of plastics is the process of depolymerizing a plastic at a depolymerization temperature sufficient to produce a hydrocarbon-based wax stream and catalytically cracking the hydrocarbon-based wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce a pyrolysis oil. may include, wherein the decomposition conditions include a decomposition temperature lower than, equal to, or higher than the depolymerization temperature. In some aspects, depolymerization of plastics can be performed in an extruder/twin screw reactor/auger.

Certain aspects relate to a second process for producing C ₆ to C ₈ aromatics and optionally light gas olefins. The second process may include 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 carried out to obtain the pyrolysis oil. In step (ii), to obtain a stream A comprising hydrocarbons boiling below 70 °C, a stream B comprising hydrocarbons boiling between 70 °C and 140 °C and a stream C comprising hydrocarbons boiling above 140 °C A pyrolysis oil can be separated. In step (iii), stream B may be reformed to obtain stream D containing C ₆ to C ₈ aromatics. The C ₆ to C ₈ aromatics may be benzene, toluene and xylenes and stream D may include benzene, toluene and xylenes. In some aspects, stream A may be sent to a gasoline pool. Reactive extrusion or melt cracking of a plastic includes depolymerizing the plastic at a depolymerization temperature sufficient to produce a hydrocarbon wax stream and catalytically cracking the hydrocarbon-based wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce a pyrolysis oil. The decomposition conditions may include a decomposition temperature lower than, equal to, or higher than the depolymerization temperature. In some aspects, depolymerization of plastics can be performed in an extruder/twin screw reactor/auger. The pyrolysis oil can be separated into streams A, B and C by atmospheric distillation with boiling cutoffs at 70°C and 140°C. Stream A may contain a hydrocarbon fraction with a high boiling point cut of 70 °C from pyrolysis oil. Stream B may contain a hydrocarbon fraction with a low boiling cut of 70 °C and a high boiling cut of 140 °C from pyrolysis oil. The C stream may contain a hydrocarbon fraction with a low boiling point cutoff of 140°C from pyrolysis oil. In certain aspects, stream C may be recycled to the hydrocarbon-based wax catalytic cracking step. The reforming in step (iii) may also produce non-aromatics and non-C ₆ to C ₈ aromatics (eg aromatic hydrocarbons other than benzene, toluene and xylene). In some aspects, stream E containing at least one portion of non-aromatics and non-C ₆ to C ₈ aromatics produced during reforming may be recycled to the hydrocarbon wax catalytic cracking step. In some aspects, stream F containing one portion of the hydrogen (H2) containing gas from reforming step (iii) may be recycled to the hydrocarbon wax catalytic cracking step.

The modification can be performed with processes and systems known in the art (eg in step (d) of the first process and step (iii) of the second process). In some aspects, reforming conditions may include a temperature of 400°C to 600°C, preferably 450°C to 550°C, and/or a pressure of 2 barg to 30 barg. The reforming can be carried out in the presence of H2. In some aspects, the molar ratio of H2 to hydrocarbons (eg, H2 and hydrocarbons fed to the reforming step) during reforming may be 2:1 and 9:1. Reforming can be carried out 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 containing zeolite, or any combination thereof. Metal-bearing zeolites may contain one or more dehydrogenating metal(s) 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 reforming unit or a continuous catalytic reforming unit.

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

In some aspects, the plastic from which the pyrolysis oil (eg, the pyrolysis oil used in the first process and/or the second process) is produced may be obtained from a plastic containing waste, such as a post-consumer plastic containing waste. . In certain aspects, the plastic may contain chloride and at least one portion of the chloride is modified via a process step described herein (e.g., step (d) of the first process and step (iii) of the second process). )) can be sent to Chloride can increase the activity of reforming catalysts. In certain aspects, the chloride may be supplied to the reforming step (eg, step (d) of the first process and step (iii) of the second process) at a concentration of 0.1 ppm to 15 ppm.

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

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

The term "wt.%", "vol.%" or "mol.%" means the weight, volume or mole percentage of a component based on the total weight, total volume or total number of moles of the material containing the component, respectively. do. In a non-limiting example, 10 moles of a component in 100 moles of material is 10 mole percent of a component.

The term “substantially” and variations thereof is defined to include ranges within 10%, within 5%, within 1% or within 0.5%.

The terms "inhibiting" or "reducing" or "preventing" or "preventing" or any variations of these terms, when used in the claims and/or specification, refer to any measurable reduction to achieve a desired result. or complete inhibition.

The term “effective” as used in the specification and/or claims means adequate to achieve a desired, expected or intended result.

The use of "a" or "an" in conjunction with the terms "comprising", "comprising", "including" or "having" in the claims or specification may mean "a," but it also It also corresponds to the meaning of "one or more", "at least one", and "one or more".

The word “comprising” (and all forms of inclusion such as “comprises” and “includes”), “having” (and all forms of having such as “have” and “have”), “comprising” ( and all forms of inclusion such as “comprises” and “comprises”) or “including” (and all forms of inclusion such as “contains” and “contains”) are inclusive or open-ended and not further, uncited. Do not exclude elements or method steps.

The process of the present invention may "comprise", "consist essentially of" or "consist of" certain components, 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, description and examples, while representing specific embodiments of the invention, are provided by way of example only and are not intended to be limiting. Also, it is contemplated that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from the detailed description. In further embodiments, features of certain embodiments may be combined with features of other embodiments. For example, features of one embodiment may be combined with features of any other embodiment. In additional implementations, additional features may be added to the specific implementations described herein.

For a more complete understanding, reference is now made to the following description taken in conjunction with the accompanying drawings:
1 is a schematic diagram of an embodiment of the present invention for producing C ₆ to C ₈ aromatics and optionally light gas olefins.
FIG. 2 is a schematic diagram of System 100, an embodiment of the present invention for producing C ₆ to C ₈ aromatics and optionally light gas olefins using the system of FIG. 1 .
FIG. 3 is a schematic diagram of System 100, a second embodiment of the present invention for producing C ₆ to C ₈ aromatics and optionally light gas olefins using the system of FIG. 1 .
FIG. 4 is a schematic diagram of System 100, a third embodiment of the present invention for producing C ₆ to C ₈ aromatics and optionally light gas olefins using the system of FIG. 1 .
5 is a schematic diagram of a second embodiment of the present invention for producing C ₆ to C ₈ aromatics and optionally light gas olefins.

Discoveries have been made that provide solutions to at least some of the problems associated with producing high value chemicals such as C ₆ to C ₈ aromatics and/or light gas olefins from crude oil. Solutions may include using a hydroprocessing unit configured to hydrotreat hydrocarbons at pressures less than 100 barg. The hydrotreating unit may be located upstream of a cracking unit such as a reformer and/or cracking unit used to produce aromatics, for example a steam cracker or catalytic cracking unit used to produce light olefins. As shown in the examples and figures in a non-limiting manner, the use of an upstream hydrotreating unit can increase the naphthenic content of the reformer feed to, for example, 30% by weight or more, and increase single aromatics in the reformer feed. and/or enriches the reformer feed for producing aromatics, particularly C ₆ to C ₈ aromatics. In some aspects, higher aromatics (aromatics with two or more rings or branched chains) may be converted to single aromatics or naphthenes in a hydroprocessing unit to increase the naphthenic content of the reformer feed. The use of an upstream hydrotreating unit also increases the amount of hydrocarbons being reformed and reduces the olefin content in the reforming feed. In some aspects, the amount of hydrocarbons to be reformed can be increased by increasing the amount of 70-140°C boiling stream that can be fed to the reformer through upgrading of the heavy ends of crude oil in a hydroprocessing unit. there is.

In another aspect of the invention, the use of an upstream hydrotreating unit may not be used. In this aspect, C ₆ to C ₈ aromatics and optionally light gas olefins may be produced from pyrolysis oil obtained from plastics such as waste plastics. Advantages of this process include the use of recycled plastics to efficiently produce BTX and optionally olefins.

These and other non-limiting aspects of the invention are discussed in more detail in the following sections with reference to the drawings. The units shown in the drawings are one or more heating and/or cooling units (eg, insulation, electric heaters, wall jacketed heat exchangers) or controllers that can be used to control the temperature and pressure of the process. (eg, computers, flow valves, automatic values, etc.). Although generally only one unit is shown, it should be understood that several units may be accommodated in one unit. In some aspects, unless otherwise stated, a reactor shown or described is a fixed bed reactor, a moving bed reactor, a trickle-bed reactor, a rotating bed reactor, and the like. reactor, slurry reactor or fluidized bed reactor.

Referring to FIG. 1 , a system and process for producing C ₆ color C ₈ aromatics and optionally light gas olefins according to one embodiment of the present invention is described. System 100 may include a hydrotreating unit 120 , a separation unit 122 , a reforming unit 124 and an optional cracking unit 126 . 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 hydrotreating unit 120 first stream 101 may be hydrotreated to obtain a hydrotreated product. A second stream 102 containing hydrotreated products may exit the hydrotreating unit 120 and may be fed to a separation unit 122 . In the separation unit 122, the second stream may be separated into a third stream 103, a fourth stream 104, and a fifth stream 105. Third stream 103 may contain a hydrocarbon fraction with a high boiling point cutoff of 70°C. The fourth stream 104 may contain a hydrocarbon fraction with a low boiling point cut of 70°C and a high boiling point cut of 140°C. Fifth stream 105 may contain a hydrocarbon fraction with a low boiling point cutoff of 140°C. In certain aspects, third stream 103 may be fed to optional cracking unit 126 and cracked to form light gas olefins, for example via steam cracking or catalytic cracking. A light gas olefin stream 127 containing light gas olefins may exit cracking unit 126. At least one portion of fifth stream 105 may be recycled to hydroprocessing unit 120 and subjected to hydroprocessing. Optionally, a portion of fifth stream 105 may be sent to cracking unit 126 and cracked to produce light gas olefins, for example via steam cracking or catalytic cracking. Third stream 103 and an optional fifth stream portion may be fed to cracking unit 126 as separate streams or may be combined and fed as a combined stream (not shown). Fourth stream 104 may be fed to reforming unit 124 and may be reformed to form C ₆ color C ₈ aromatics. A sixth stream 106 containing C ₆ color C ₈ aromatics may exit reforming unit 124 . Reforming in reforming unit 124 may also produce non-aromatic and non-C ₆ C ₈ aromatics (eg, aromatics other than C ₆ C ₈ aromatics). A seventh stream 107 containing at least one portion of non-aromatics and non-C ₆ color C ₈ aromatics from reforming unit 124 may be recycled to hydroprocessing unit 120 and subjected to hydrotreating.

In certain aspects, first stream 101 may be obtained by atmospheric distillation of crude oil. Referring to FIG. 2 , a system and process for producing C ₆ color C ₈ aromatics and optionally light gas olefins using system 100 according to one embodiment of the present invention is described. System 200 may include crude oil distillation unit (CDU) 230 and system 100 . Stream 232 containing crude oil may be fed to CDU 230. In CDU 230, crude oil may be separated via atmospheric distillation to form first stream 101, eighth stream 208, and ninth stream 209. First stream 101 in system 200 may contain a hydrocarbon fraction with a low boiling point cutoff of 140° C. separated from crude oil in CDU 230 . The first stream may be supplied to hydroprocessing unit 120 of system 100 and may be processed in system 100, eg, as described above with respect to FIG. Eighth stream 208 may contain a hydrocarbon fraction having a low boiling cut of 70°C and a high boiling cut of 140°C separated from crude oil in CDU 230. Eighth stream 208 may be fed to reforming unit 124 of system 100 and reformed to obtain C6 to C8 hydrocarbons. Eighth stream 208 and fourth stream 104 may be fed to reforming unit 124 either individually or as a combined stream. Ninth stream 209 may contain a hydrocarbon fraction with a high boiling point cutoff of 70° C. separated from crude oil in CDU 230 . In some aspects, ninth stream 209 may be fed to optional cracking unit 126 of system 100 and may be cracked to obtain light gas olefins, for example via steam cracking or catalytic cracking. . Portions of the ninth stream 209, the third stream 103, and the optional fifth stream may be fed individually or in any combination to the optional cracking unit 126.

In certain aspects, first stream 101 may be obtained by atmospheric distillation of crude oil and pyrolysis oil. The pyrolysis oil can be, for example, a plastic pyrolysis oil obtainable from plastics. Referring to FIG. 3, a system and process for producing C6 to C8 aromatics and optionally light gas olefins using system 100 according to a second embodiment of the present invention is described. System 300 may include plastic depolymerization unit 342 , catalytic cracking unit 344 , CDU 330 and system 100 . Pyrolysis oil may be produced from plastics using a plastics depolymerization unit 342 and a catalytic cracking unit 344. Plastic 346 may be supplied to plastic depolymerization unit 342 . In the plastic depolymerization unit 342, the plastic may be depolymerized to form a hydrocarbon-based wax. The hydrocarbon-based wax 348 from the depolymerization unit 342 may be supplied to the catalytic cracking unit 344. In the catalytic cracking unit 344, hydrocarbon-based waxes can be cracked in the presence of a cracking catalyst to produce pyrolysis oil. Pyrolysis oil 350 from catalytic cracking unit 344 and stream 332 containing crude oil may be fed to CDU 330 . The pyrolysis oil and crude oil may be supplied to the CDU as separate feeds or as a combined feed. In CDU 330, the crude oil and pyrolysis oil mixture may be separated via atmospheric distillation to form a first stream 101, an eighth stream 308 and a ninth stream 309. In system 300, first stream 101 may contain a hydrocarbon fraction with a low boiling point cutoff of 140° C. separated from the crude oil and pyrolysis oil mixture in CDU 330. First stream 101 may be supplied to hydroprocessing unit 120 of system 100 and may be processed in system 100, for example as described above with respect to FIG. Eighth stream 308 may contain a hydrocarbon fraction having a low boiling cut of 70°C and a high boiling cut of 140°C separated from crude oil and pyrolysis oil in CDU 330. Eighth stream 308 may be fed to reforming unit 124 of system 100 and reformed to obtain C6 to C8 hydrocarbons. Eighth stream 308 and fourth stream 104 may be fed to reforming unit 124 either individually or as a combined stream. Ninth stream 309 may contain a hydrocarbon fraction with a high boiling point cutoff of 70° C. separated from crude oil and pyrolysis oil in CDU 330 . Ninth stream 309 may be fed to hydroprocessing unit 120 of system 100 . Ninth stream 309 and first stream 101 may be fed to hydroprocessing unit 120 as separate or combined feeds. In an alternative embodiment, plastics depolymerization unit 342 and catalytic cracking unit 344 are not a part of system 300, and pyrolysis oil, such as crude oil, is used using separate systems and processes. The pyrolysis oil produced with can be supplied to the CDU.

Through the use of hydroprocessing unit 120, additional C6 to C8 aromatics and/or light gas olefins may be produced from hydrocarbon fractions (from crude oil and/or pyrolysis oil) having a low boiling cutoff of 140°C, whereas On these hydrocarbon fractions are generally not used for reforming.

In certain aspects, first stream 101 may contain pyrolysis oil. The pyrolysis oil may be a plastic pyrolysis oil, for example a plastic pyrolysis oil obtainable from plastics. Referring to FIG. 4, a system and process for producing C6 to C8 aromatics and optionally light gas olefins using system 100 according to a third embodiment of the present invention is described. System 400 may include plastic depolymerization unit 442 , catalytic cracking unit 444 and system 100 . Pyrolysis oil may be produced from plastics using a plastics depolymerization unit 442 and a catalytic cracking unit 444. Plastic 446 may be supplied to plastic depolymerization unit 442 . In plastics depolymerization unit 442, plastics may be depolymerized to form hydrocarbon-based waxes. The hydrocarbon-based wax 448 from the depolymerization unit 442 may be supplied to the catalytic cracking unit 444. In cracking unit 444, hydrocarbon-based waxes may be cracked in the presence of a cracking catalyst to produce pyrolysis oil. Pyrolysis oil from catalytic cracking unit 444 may be supplied to system 100 via stream 101 and may be treated, for example, as described above in FIG. 1 .

Referring to Figure 5, a system and process for producing C6 to C8 aromatics and optionally light gas olefins according to another embodiment of the present invention is described. System 500 may include a plastics depolymerization unit 502 , a catalytic cracking unit 504 , a separation unit 506 , and a reforming unit 508 . Plastic 501 may be supplied to a plastic depolymerization unit 502 . In depolymerization unit 502, the plastic may be depolymerized to form a hydrocarbon-based wax. The hydrocarbon-based wax 503 from the depolymerization unit 502 may be supplied to the catalytic cracking unit 504. In catalytic cracking unit 504, hydrocarbon-based waxes 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 B (511) and stream C (512). Stream A (510) may contain a hydrocarbon fraction with a high boiling point cutoff of 70° C. separated from pyrolysis oil in separation unit (506). Stream B 511 may contain a hydrocarbon fraction having a low boiling point cut of 70° C. and a high boiling point cut of 140° C. separated from the pyrolysis oil in separation unit 506. Stream C 512 may contain a hydrocarbon fraction with a low boiling point cutoff of 140° C. separated from pyrolysis oil in separation unit 506. Stream C 512 may be recycled to catalytic cracking unit 504 and may be catalytically cracked to produce pyrolysis oil. Stream B 511 may be fed to reforming unit 508 and reformed to obtain C6 to C8 aromatics. Stream D 513 containing C6 to C8 aromatics may exit reforming unit 508. Reforming in reforming unit 508 may also produce non-aromatics and non-C6 to C8 aromatics (eg, aromatics other than C6 to C8 aromatics). Stream E 514 containing at least one portion of non-aromatics and non-C6 to C8 aromatics from reforming unit 508 may be recycled to catalytic cracking unit 504 and may be catalytically cracked to produce pyrolysis oil. can Stream F 515 containing H2 containing gas from reforming unit 508 may be recycled to catalytic cracking unit 504. The H2 containing gas from the reforming unit may contain at least one portion of H2 added and/or produced H2 during reforming. In some aspects, stream A 510 may be sent to and/or mixed with a gasoline pool, such as a refinery's gasoline pool.

Hydrotreating in hydrotreating unit 120 may include hydrotreating and/or hydrocracking of the feed. In unit 120 the hydrocarbon feed (e.g., introduced via streams 101, 105, 107, and/or 309) is subjected to hydrotreating in the presence of a dissolved catalyst and an ebullated bed catalyst to form a hydrotreated product. can The hydrotreating in unit 120 may be performed at low pressures, such as pressures below 100 barg. In some aspects, the hydrotreating conditions in unit 120 are: i) at least any one of 30 barg to 100 barg or 30,40,50,60,70,80,90 and 100 barg, the same as any one , the pressure between any two; ii) a temperature between 300°C and 600°C, preferably between 350°C and 500°C, or at least one of, equal to, or between any two of 300,350,400,450,500,550 and 600°C; or iii) 0.5 to 2 hr ^-1 or at least any one of 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 2 hr ^-1 ; weight hourly space velocity (WHSV) equal to any one, or between any two, or any combination thereof. Hydrogenation treatment may be performed in the presence of hydrogen (H2). H2 may be supplied to hydroprocessing unit 120 individually and/or via one or more of the hydrocarbon feed streams (eg, 101 , 105 , 107 and/or 309 ). In some aspects, H2 and hydrocarbons (eg, introduced via stream(s) 101, 105, 107, and/or 309) have a volume ratio between 200 Nm ³ :1 m ³ and 2000 Nm ³ :1 m ³ ; or 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, 2000:1 Nm ³ : m3 at least any one, equal to any one, or in a volume ratio between any two It may be supplied to the hydrotreating unit 120. In some aspects, the dissolved catalyst may contain Ni and/or Mo. In some aspects, the dissolved catalyst may contain metal octanoates and/or naphthenates. In some aspects, the dissolved catalyst may contain Ni octanoate, Ni naphthenate, Mo octanoate, or Mo naphthenate, or any combination thereof. In some aspects, Ni octanoate, Ni naphthenate, Mo octanoate, and/or Mo naphthenate can independently be present in a hydrocarbon base. In some aspects, the dissolved catalyst can be a catalyst dissolved in the feed and can form a homogeneous catalyst when mixed with the feed (eg, hydrotreating feed). In some aspects, no additional solvent may be used to dissolve the catalyst, eg naphthenates and/or octanoates in the feed. Metal octanoates and/or naphthenates may be present in the liquid hydrocarbons of the feed as dissolved organic salts.

The ebullated bed catalyst may include Co, Ni, Mo and/or W on a support. In certain aspects, the ebullated bed catalyst comprises Co and Mo on a support; Ni and Mo on the support; Co, Ni and Mo on the support; Ni and W on the support; or Ni, W and Mo, or any combination thereof, on the support. In some aspects, the ebullated bed catalyst support can be alumina, silica, aluminosilicate or zeolite or any combination thereof. Zeolites include type X zeolites, type Y or type USY zeolites, mordenites, faujasites, nanocrystalline zeolites, MCM mesoporous materials, SBA-15, silico-alumino phosphates, gallophosphates, titanophosphates, ZSM-5, ZSM- 11, ferrierite, hulandite, zeolite-A, erionite, and chabazite, or any combination thereof.

In a reforming unit (eg, 124 and/or 508), hydrocarbons may be reformed to form C6 to C8 aromatic hydrocarbons such as benzene, toluene and xylene. In some aspects, reforming conditions in units (e.g., 124 and/or 508) may include temperatures from 400 to 600, preferably from 450 to 550, or from 400, 450, 500, 550 and 600°C. at least any one, the same as any one, or between any two, and/or a pressure of 2 barg to 30 barg or 2, 4, 6, 8, 10, 12, 14, 16, 18 , 20, 22, 24, 26, 28 and 30 barg, at least any one, equal to any one, or between any two. The reforming can be carried out in the presence of H2. H2 is supplied to the reforming unit via one or more hydrocarbon feed streams (e.g., stream 104 to unit 124; stream 511 to unit 508) and/or individually to the reforming unit. It can be. In some aspects, H2 and hydrocarbons are present in a molar ratio of 2:1 to 9:1 or 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 and 9:1 At least any one of them, the same as any one, or a molar ratio between any two may be supplied to the reforming unit. Reforming can be carried out in the presence of a reforming catalyst. In some aspects, the reforming catalyst comprises Pt and Re on alumina; Pt on alumina; metal-containing zeolites; or any combination thereof. Metal-bearing zeolites may contain one or more dehydrogenating metals including but not limited to Pt, Pd, Ga and/or Ni. Reforming in units 124 and 508 may be performed according to systems and processes known in the art. The reforming process may be a semi-regenerative reforming process or a continuous catalytic reforming process, and the reforming units (eg, 124 and/or 508) may be semi-regenerative reforming units or continuous catalytic reforming units. The reforming catalyst can be included in a semi-regenerative reforming unit as a fixed bed catalyst and can be included in a continuous catalytic reforming unit as a moving bed catalyst. The reforming catalyst may be regenerated according to methods known in the art. In some aspects, reforming units (eg, 124 and/or 508) can include multiple reactors, such as three or more reactors. The hydrocarbon feed to the reactor may be heated before being fed to the reactor.

The selective cracking unit 126 may be a steam cracking unit or a catalytic cracking unit. The hydrocarbon feed to cracking unit 126 (e.g., introduced to unit 126 via optional portions of 103, 209, 105) may be cracked, for example steam cracking or catalyst to form light gas olefins. It can be broken down through disassembly. In some aspects, light gas olefins may include ethylene, propylene and/or butylene. 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 cracking unit 126 are i) equal to or equal to any one of, any one of, 750°C to 900°C or at least any one of 750, 775, 800, 825, 850, 875 and 900°C. temperature between the two of; ii) a pressure from 6 barg to atmospheric pressure, or at least any one, equal to any one or between any two of atmospheric pressure, 2 barg, 3 barg, 4 barg, 5 barg and 6 barg; iii) or from 0.05 seconds to 1 second, or from 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1 second, at least any one, equal to any one or between any two ; or the residence time of any combination thereof. In certain aspects, the catalytic cracking conditions in cracking unit 126 are i) 500 °C to 800 °C or at least 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775 and 800 °C. a temperature of any one, equal to any one, or between any two; ii) from 10 barg to atmospheric pressure or from 2 barg, 3 barg, 4 barg, 5 barg, 6 barg, 7 barg, 8 barg, 9 barg and 10 barg, any one, equal to any one, or any two pressure between; iii) a contact time of less than 5 seconds; or a combination thereof.

The pyrolysis oil is used for reactive extrusion/melt cracking of plastics using a plastic depolymerization unit (eg, 342, 442, and/or 502) and a catalytic cracking unit (eg, 344, 444, and/or 504). can be produced by In some aspects, the plastic feed (e.g., 346, 446, and/or 501) can be a mixed plastic feed and is a polyolefin (e.g., polyethylene, ethylene alpha-olefin copolymer, polypropylene, etc.), polystyrene, It may contain one or more of polyester (eg poly alkylene terephthalate), polyvinyl chloride and polyamide (eg nylon, polyphthalamide, etc.). The plastic may be obtained from a plastic containing waste, such as a plastic containing post-consumer waste.

In a plastics depolymerization unit (eg, 342, 442 and/or 502) the plastic feed may be depolymerized to form a hydrocarbon wax. The average molecular weight of the hydrocarbon-based wax (e.g., of the compounds in the hydrocarbon-based wax) may be at least 50 times lower than the average molecular weight of the plastic feed (e.g., of the compounds in the plastic feed), such as 20 to 50 times lower. can In some aspects, depolymerization can be performed in the presence of a catalyst. Catalysts may include liquid catalysts and/or solid catalysts. In some specific aspects, the liquid catalyst may contain one or more organometallic compounds, such as octanoates and/or naphthenates of transition metals, such as Ni, Mo, Co or W. In some aspects, the liquid catalyst can be a catalyst dissolved in a plastic melt. In some aspects, the liquid catalyst can be a homogeneous catalyst in a plastic melt. The solid catalyst may contain inorganic oxides, aluminosilicates, zeolites, MCM mesoporous materials, SBA-15, silico-alumino phosphates, gallium phosphates, titanophosphates, or molecular sieves, or combinations thereof. . The zeolite can be a ZSM-5, X-type zeolite, Y-type zeolite, USY-zeolite, mordenite, faujasite, or nano-crystalline zeolite, or any combination thereof. In some aspects, the solid catalyst can be a heterogeneous catalyst in a plastic melt. In some aspects, the solid catalyst may remain in a solid state in the plastic melt. In some aspects, depolymerization units 342, 442 and/or 502 may include an extruder. The plastic and catalyst may be fed into the extruder using one or more feeders, for example from a throat hopper and/or any side feeder. The plastic and catalyst may be fed to the extruder, eg a barrel of the extruder, individually or in any combination, eg a mixed combination. The extruder is single screw, left handed screw, right handed screw, neutral screw, kneading screw, multiple screws, meshing co-rotation ( intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins (screws with pins), screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, It may have 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 arranged along the length of the extruder barrel. In the extruder barrel, the plastic feed may be heated, melted, and depolymerized to form a hydrocarbon-based wax. In some aspects, the plastic feed in the extruder barrel is subjected to a temperature of 300 to 500°C, or at least any one, any one of 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 and 500°C. It can be depolymerized at the same temperature as, or any temperature between the two. The residence time of the plastic in the extruder may be less than an hour, such as from 1 minute to 15 minutes. In certain aspects, an extruder may contain one or more vents configured to introduce and/or withdraw one or more gases into and/or from the extruder barrel. The plastic melt and/or hydrocarbon-based wax may be extruded from an extruder through a die. The hydrocarbon-based wax from the extruder of the depolymerization unit may be fed to the catalytic cracking unit.

In a catalytic cracking unit (eg, 344, 444 and/or 504) the hydrocarbon-based wax may be catalytically cracked in the presence of a cracking catalyst to form a pyrolysis oil. In some aspects, the cracking catalyst may contain zeolites and/or metal containing zeolites. In some specific aspects, the zeolite can be ZSM-5. In certain aspects, the metal can be a transition metal such as Mg, Ni and/or Co. In the catalytic cracking units (eg, 344, 444 and/or 504) the hydrocarbon-based wax may be catalytically cracked in a fixed bed reactor or a fluidized bed reactor. In certain aspects, the catalytic cracking of hydrocarbon-based waxes (e.g., in catalytic cracking units 344, 444, and/or 504) causes the plastics feed to contain hydrocarbon-based waxes (e.g., in depolymerization units 342, 442, and/or at 502) at a temperature that is lower than, equal to, or higher than the temperature at which the depolymerization may be performed. In certain aspects, the catalytic cracking conditions in the catalytic cracker 344, 444 and/or 504 are a temperature between 350 and 500°C, or 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460 , at least any one of 470, 480, 490 and 500° C., a temperature equal to any one, or between any two, a pressure of 1 to 6 bara, or any combination thereof. In some aspects, the average molecular weight of the pyrolysis oil (eg, of the compounds in the pyrolysis oil) can be at least 3 times lower than the average molecular weight of the hydrocarbon-based wax (eg, of the compounds in the hydrocarbon-based wax). The pyrolysis oil may contain paraffins, isoparaffins, olefins, naphthenes and aromatic hydrocarbons.

In certain aspects, the plastic furnish may contain a plastic containing chloride such as polyvinyl chloride. In some aspects, a portion of chloride from the plastics feed may be fed to a reforming unit (eg, 124 and/or 508) via process steps described herein. Chloride can increase the activity of reforming catalysts. In certain aspects, the chloride is present at a concentration of 0.1 ppm to 15 ppm, or at least any one, equal to any one, or between any two of 0.1, 1, 2, 4, 6, 8, 10, 12, 14 and 15 ppm. may be supplied to the reforming units 124 and 508 at a concentration of

Second stream 102 may contain saturated hydrocarbons having a boiling point less than 350°C. In some aspects, at least 70% by weight of the hydrocarbons in second stream 102 may be saturated hydrocarbons with a boiling point of less than 350°C. In some aspects, the second stream is: i) from 10 wt% to 40 wt%, or at least any one, the same as any one, or any of 10, 15, 20, 25, 30, 35 and 40 wt% naphthenes between the two; ii) from 2 wt.% to 20 wt.%, or at least any one of 2, 3, 4, 6, 8, 10, 12, 14, 16, 18 and 20 wt%, equal to any one, or any Aromatic between the two of; and iii) from 50 to 85 wt%, or from 50, 55, 60, 65, 70, 75, 80 and 85 wt%, based on the total weight of the second stream, of at least any one, equal to any one, or It may contain paraffins and isoparaffins with total concentrations anywhere between the two. In some aspects, the olefin content of second stream 102 may be less than 8 wt%, or less than 5 wt%, or less than 3 wt%, or less than 1 wt%, or the second stream may be essentially free of olefins. there is. The naphthenes described herein may include branched and non-branched naphthenes.

The fourth stream (104) and stream B (511) may contain hydrocarbons having a boiling point between 70°C and 140°C. The fourth stream 104 is: i) 25% to 50% by weight, or at least any one of 25, 30, 35, 40, 45 and 50% by weight, the same as any one, or between any two naphthenes; 10 wt % to 35 wt %, or at least any one of 10, 15, 20, 25, 30 and 35 wt %, the same as any one, or between any two aromatics; and iii) at least any one, equal to any one, or any of from 30% to 50%, or from 30, 35, 40, 45, 50 and 55% by weight, each based on the total weight of the fourth stream. may contain paraffins and isoparaffins with a total concentration between the two of In some aspects, the olefin content of fourth stream 104 may be less than 8 wt%, or less than 5 wt%, or less than 3 wt%, or less than 1 wt%, or fourth stream 104 may be essentially free of olefins. there is. In certain aspects, the components of stream B (511) may be similar to fourth stream (104).

Third stream 103 and stream A 510 may contain hydrocarbons with a boiling point less than 70°C. The third stream 103 has a total concentration of 90 to 100 wt % or 90, 95, 96, 97, 98, 99, 99.3, 99.5, 99.8, 99.9 and 100 wt %, each based on the total weight of the third stream. It may contain paraffins and isoparaffins having at least any one of, equal to any one, or total concentrations between any two. In some aspects, the olefin content of third stream 103 may be less than 8 weight percent, or less than 5 weight percent, or less than 1 weight percent, or the third stream may be essentially olefin free. In some aspects, the aromatics content of third stream 103 may be less than 8 wt%, or less than 5 wt%, or less than 3 wt%, or less than 1 wt%, or the third stream may be essentially free of aromatics. In certain aspects, the components of stream A (510) may be similar to third stream (103).

Fifth stream 105 and stream C 512 may contain hydrocarbons with boiling points greater than 140°C.

In certain aspects, the ethylene, propylene and/or butylenes from light gas olefins stream 127 are purified/purified by one or more steps to obtain a separated stream containing polymer grade ethylene, propylene and/or butylenes. can be separated

In certain aspects, the benzene, toluene and xylenes from sixth stream 106 and/or stream D 513 are purified by one or more steps to obtain separate streams containing benzene, toluene and xylenes. /Can be separated.

Although implementations of the present invention have been described with reference to blocks in FIGS. 1-5, as shown in FIGS. 1-5, the operation of the present invention is limited to specific blocks and/or the order of specific blocks. You have to understand that it doesn't. Accordingly, implementations of the present invention may use various blocks in a different order than that of FIGS. 1-5 to provide functionality as described herein.

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

Example

As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. One skilled in the art will readily recognize parameters that can be altered or modified to yield essentially the same results.

Example 1

Production of benzene, toluene, xylenes and light gas olefins from crude hydrocarbon fractions with a high boiling cutoff of 350 °C

A hydrocarbon fraction with a high boiling cutoff of 350 °C from crude oil is obtained at 380 °C 60 barg, 1 h ⁻¹ and a H ₂ /hydrocarbon feed ratio of 400 Nm ³ /m ³ and of a hydrotreating catalyst to obtain a hydrotreated stream. Hydrogenated in presence. The hydrotreated stream was distilled in an atmospheric column and a first hydrocarbon fraction with a high boiling cut of 70 °C, fraction 1, a second hydrocarbon fraction with a low boiling cut of 70 °C and a high boiling cut of 140 °C, frac It was separated into section 2 and a third hydrocarbon fraction, fraction 3, with a low boiling point cutoff of 140°C. The paraffinic, isoparaffinic, olefinic, naphthenic and aromatic (PIONA) components of hydrocarbon fractions 1, 2 and 3, based on the total weight of the hydrotreated stream, are given in Table 1. Hydrocarbon fraction 1 was steam cracked to obtain light gas olefins. Hydrocarbon fraction 2 was reformed in a naphtha reformer to obtain benzene, toluene and xylene. Hydrocarbon fraction 2 had more naphthenes compared to the two commonly used reformer feeds (Table 2). Accordingly, higher amounts of aromatics (eg, benzene, toluene and xylenes) may be produced from reforming hydrocarbon fraction 2 compared to the reforming feed of Table 2. Also, as can be seen in Table 1, hydrocarbon fraction 1 is completely paraffinic and free of aromatics and olefins, making it an excellent feed for steam cracking/catalytic cracking.

Table 1 : PIONA components obtained by hydrotreating hydrocarbon fractions with a high boiling point cutoff of 350 ° C obtained from crude oil

Component
Components hydrocarbon fraction 1
Hydrocarbon fraction 1 hydrocarbon
fraction 2
Hydrocarbon fraction 2 hydrocarbon
fraction 3
Hydrocarbon fraction 3 plain paraffin
Normal Paraffin 6.8 4.6 3.3 isoparaffin
Isoparaffin 30.8 10.9 2.6 naphthene
Naphthenes 0 11.6 0.1 branched naphthenes
Branched Naphthenes 0 14.8 2.7 Dynaphthen
DiNaphthenes 0 0.1 0.4 monoaromatic
Monoaromatics 0 7.8 3.4 naphthenic aromatics
Naphthenic aromatics 0 0 0.1 heteroaromatic
Diaromatics 0 0 0 naphthenic diaromatic
Naphthenic diaromatics 0 0 0 triaromatic
Triaromatics 0 0 0 gun
Total 37.6 49.8 12.6

Table 2 : Typical PIONA components fed to a naphtha reformer.

Literature data Turaga et al. Mujtaba et al. paraffin
Paraffins 63 59 naphthene
Naphthenes 23 20 aromatic
Aromatics 14 21 boiling range
Boiling range ℃ 85-160 88-180

Example 2

Production of benzene, toluene, xylene and light gas olefins from crude oil

West Texas Blended Crude Oil with an end boiling point of 750 °C was hydrotreated at 450 °C 40 barg, 1 h ^-1 and H ₂ /hydrocarbon feed ratio 400 Nm ³ /m ³ to obtain a hydrotreated stream. Hydrogenation was performed in the presence of a catalyst (combination of hydrocracking catalyst Ni/W and hydrotreating catalysts Co, Ni, Mo). The hydrotreated stream was distilled in an atmospheric column and a first hydrocarbon fraction with a high boiling cut of 70 °C, fraction 4, a second hydrocarbon fraction with a low boiling cut of 70 °C and a high boiling cut of 140 °C, frac It was separated into section 5 and a third hydrocarbon fraction, fraction 6, with a low boiling point cutoff of 140°C. The PIONA components of hydrocarbon fractions 4 and 5, based on the total weight of the hydrotreated stream, are provided in Table 3. Hydrocarbon fraction 4 was steam cracked to obtain light gas olefins. Hydrocarbon fraction 5 was reformed in a naphtha reformer to obtain benzene, toluene and xylene. 19.7% and 31% by weight of the hydrotreated stream were fractionated into fractions 4 and 5 respectively and the remaining amount was fractionated into fraction 6. Hydrocarbon fraction 5 is predominantly paraffinic and naphthenic, providing a good feed for reforming at -70% by weight when normalized. In addition, 31% by weight of the hydrocarbon fraction 5 was naphthenic, providing a good reforming feed to form benzene, toluene and xylene. The olefin content of hydrocarbon fraction 4 was low and, when normalized, mainly paraffinic -94% by weight, providing a good feed for steam cracking/catalytic cracking.

Table 3 : PIONA components obtained by hydrotreating crude oil

Component
Components hydrocarbon fraction 4
Hydrocarbon fraction 4 hydrocarbon fraction 5
Hydrocarbon fraction 5 plain paraffin
Normal Paraffin 8.3 4.6 isoparaffin
Isoparaffin 10.3 7.3 olefin
Olefin 0.5 0.1 naphthene
Naphthenes 0.5 9.8 aromatic
Aromatics 0.0 9.3 gun
Total 19.7 31

Example 3

Production of benzene, toluene, xylenes and light gas olefins from pyrolysis oil

Commercial pyrolysis oils with a boiling range of 85 °C to 470 °C are prepared at 400 °C 60 barg, 1 h ⁻¹ and a H ₂ /hydrocarbon feed ratio of 400 Nm ³ /m ³ to obtain a hydrotreated stream and in the presence of a hydrogenation catalyst. (combination of hydrocracking catalyst Ni/W and hydrotreating catalysts Co, Ni, Mo). The hydrotreated stream was distilled in an atmospheric column and a first hydrocarbon fraction with a high boiling cut of 70 °C, fraction 7, a second hydrocarbon fraction with a low boiling cut of 70 °C and a high boiling cut of 140 °C, frac It was separated into section 8 and a third hydrocarbon fraction, fraction 9, with a low boiling point cutoff of 140°C. The PIONA components of hydrocarbon fractions 7, 8 and 9, based on the total weight of the hydrotreated stream, are given in Table 4. Hydrocarbon fraction 7 was steam cracked to obtain light gas olefins. Hydrocarbon fraction 8 was reformed in a naphtha reformer to obtain benzene, toluene and xylene. Hydrocarbon fraction 9 was recycled to the hydrotreating stage. 43.6 wt%, 39 wt% and 17.3 wt% of fraction 8 were paraffinic, naphthenic and aromatic, respectively. Compared to the typical reforming feed (Table 2), hydrocarbon fraction 8 had more naphthenes and was therefore more suitable for benzene, toluene and xylene production by reforming. Also, as can be seen in Table 4, hydrocarbon fraction 7 is completely paraffinic and free of aromatics and olefins, making it an excellent feed for steam cracker/catalytic cracking.

Table 4 : PIONA composition by hydrotreating pyrolysis oil.

Component
Components hydrocarbon fraction 7
Hydrocarbon fraction 7 hydrocarbon fraction 8
Hydrocarbon fraction 8 hydrocarbon fraction 9
Hydrocarbon fraction 9 plain paraffin
Normal Paraffin 4.84 5.41 24.25 isoparaffin
Isoparaffin 11.21 6.75 18.18 naphthene
Naphthenes 0 4.17 1.07 branched naphthenes
Branched Naphthenes 0 6.67 6.86 Dynaphthen
DiNaphthenes 0 0.03 1.21 monoaromatic
Monoaromatics 0 4.83 2.92 naphthenic aromatics
Naphthenic aromatics 0 0 1.33 heteroaromatic
Diaromatics 0 0 0.09 naphthenic diaromatic
Naphthenic
diaromatics 0 0 0 triaromatic
Triaromatics 0 0 0 gun
Total 16.05 27.86 55.91

In the context of the present invention, at least the following 20 embodiments are described. Embodiment 1 is a process for selectively producing C ₆ to C ₈ aromatics and optionally light gas olefins. The process includes hydrotreating a first stream containing hydrocarbons from crude oil and/or pyrolysis oil to obtain a second stream containing saturated hydrocarbons below 350°C. The process yields a third stream containing hydrocarbons boiling less than 70°C, a fourth stream containing hydrocarbons boiling between 70°C and 140°C, and a fifth stream containing hydrocarbons boiling greater than 140°C. It further includes separating the second stream to do so. The process further includes recycling at least one portion of the fifth stream to the hydrotreating step (a). The process also includes reforming the fourth stream to obtain a sixth stream containing C ₆ to C ₈ aromatics. The process also includes optionally cracking a portion of the third stream and/or fifth stream to obtain light gas olefins. Embodiment 2 is the process of Embodiment 1, wherein at least 70% by weight of the second stream contains saturated hydrocarbons having a boiling point less than 350 °C. Embodiment 3 is the process of embodiment 1 or 2, wherein reforming step d) obtains a seventh stream containing non-aromatics and non-C ₆ to C ₈ aromatics, and optionally at least one portion of the seventh stream. to the hydrotreating step (a). Embodiment 4 is the process of any of embodiments 1 to 3, wherein the hydrotreating conditions in step (a) are a pressure of less than 100 barg, preferably 30 barg to 100 barg, a temperature of 300 °C to 600 °C, weight per hour a space velocity of 0.5 to 2 hr ⁻¹ , or a H ₂ :hydrocarbon volume ratio of 200 Nm ³ :1 m ³ to 2000 Nm ³ :1 m ³ of liquid feed, or any combination or all thereof. Embodiment 5 is the process of any of Embodiments 1 to 4, wherein the hydrogenation treatment in step (a) is performed on a dissolved catalyst containing Ni and/or Mo, and Co, Mo, Ni, W or any of these on a support. This is done using a fixed bed catalyst containing any combination. Embodiment 6 is the process of any of embodiments 1 to 5, wherein the reforming conditions in step (b) are a temperature of 450° C. to 550° C., a pressure of 2 barg to 30 barg, or 2:1 to 9:1 H ₂ : hydrocarbon molar ratio, or any combination or all of them. Embodiment 7 is any of Embodiments 1 to 6 wherein the reforming in step (d) is performed using a reforming catalyst containing Pt-Re on alumina, Pt on alumina, a metal containing zeolite, or a combination thereof. do. Embodiment 8 is the process of any of Embodiments 1 to 7, wherein the pyrolysis oil may be obtained from a plastic. Embodiment 9 is the process of any of Embodiments 1-8, wherein the pyrolysis oil is subjected to depolymerization of the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-based wax stream and in the presence of a cracking catalyst under cracking conditions sufficient to produce a pyrolysis oil. It can be obtained from plastics by cracking a hydrocarbon-based wax stream in , wherein the cracking conditions include a cracking temperature that is higher than, equal to, or lower than the row polymerization temperature. Embodiment 10 is any of Embodiments 1 to 9, wherein the first stream contains hydrocarbons having a boiling point greater than 140° C. separated from crude oil and/or pyrolysis oil by atmospheric distillation. Embodiment 11 is the process of any of embodiments 1 to 10, wherein the atmospheric distillation further produces an eighth stream containing hydrocarbons having a boiling point between 70°C and 140°C, and the process further comprises reforming the eighth stream. include Embodiment 12 is any of Embodiments 1 to 11 wherein the eighth stream is reformed with a fourth stream to form a sixth stream and a seventh stream. Embodiment 13 is any of Embodiments 1-12 wherein atmospheric distillation further produces a ninth stream containing hydrocarbons having a boiling point less than 70°C. Embodiment 14 is any of Embodiments 1 to 3 wherein stream zero is cracked into a third stream to produce light gas olefins and sent to a hydrotreating step. Embodiment 15 is the process of any of Embodiments 1-14, wherein the first stream contains pyrolysis oil. Embodiment 16 is the process of any of embodiments 1 to 15, wherein the first stream is condensate, naphtha, light crude oil, or a crude hydrocarbon fraction having a high boiling point of 350° C. or whole crude oil, or any combination or contains all of

Embodiment 17 is a process for the selective production of C ₆ to C ₈ aromatics and optional light gas olefins from plastics. The process includes a) performing reactive extrusion or melt cracking of the plastic to form a pyrolysis oil; b) pyrolysis to obtain a stream A containing hydrocarbons with a boiling point below 70° C., a stream B containing hydrocarbons with a boiling point between 70 and 140° C. and a stream C containing hydrocarbons with a boiling point above 140° C. separating oil; c) reforming stream B to obtain stream D containing C ₆ to C ₈ aromatics; and d) optionally mixing stream A into the refinery's gasoline pool. Embodiment 18 is the process 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-based wax stream; and catalytically cracking the hydrocarbon-based wax in the presence of a cracking catalyst under cracking conditions sufficient to produce a pyrolysis oil, wherein the cracking conditions include a cracking temperature that is greater than, equal to, or less than the depolymerization temperature. Embodiment 19 is the process of any of Embodiments 17 or 18 further comprising recycling stream C to the catalytic cracking step. Embodiment 20 is the process of any of embodiments 17 to 19, wherein at least one portion of the hydrogen containing gas, non-aromatics, non C ₆ to C ₈ aromatics obtained from reforming in step (c) is recycled to the catalytic cracking step. do.

All of the embodiments described above and herein can be combined in any way unless explicitly excluded.

Although embodiments of this application and their advantages have been described in detail, it should be understood that various changes, substitutions and modifications may be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of this application is not intended to be limited to the specific embodiments of the processes, machines, manufacture, construction of materials, means, methods and steps described herein. One of ordinary skill in the art will readily understand from the above disclosure that any process, machine, manufacture, composition of matter, means, method or step that performs substantially the same function or achieves substantially the same results as the corresponding embodiments described herein will be readily apparent to those skilled in the art. Existing or future developments may be used. Accordingly, the appended claims are intended to encompass within their scope such processes, machines, manufactures, compositions of matter, means, methods or steps.

Claims (20)

A process for selectively producing C ₆ to C ₈ aromatics and optionally light gas olefins, comprising:
a) hydrotreating a first stream comprising hydrocarbons from crude oil and/or pyrolysis to obtain a second stream comprising saturated hydrocarbons having a boiling point of less than 350°C;
b) obtaining a third stream comprising hydrocarbons boiling below 70°C, a fourth stream comprising hydrocarbons boiling between 70 and 140°C, and a fifth stream comprising hydrocarbons boiling above 140°C separating the second stream for;
c) recycling at least a portion of the fifth stream to the hydrotreating step (a);
d) reforming said fourth stream to obtain a sixth stream comprising C ₆ to C ₈ aromatics; and
e) optionally cracking a portion of said third stream and/or said fifth stream to obtain light gas olefins;
process. According to claim 1,
wherein at least 70% by weight of the second stream consists of saturated hydrocarbons having a boiling point of less than 350 °C;
process. According to claim 1 or 2,
Reforming step d) further comprises obtaining a seventh stream comprising non-aromatics and non C ₆ to C ₈ aromatics and optionally recycling at least a portion of said seventh stream to said hydrotreating step (a). doing,
process. According to claim 1 or 2,
The hydrogenation treatment conditions in step (a) are less than 100 barg, preferably 30 barg to 100 barg pressure, 300 ° C to 600 ° C temperature, 0.5 to 2 hr ^-1 or H ₂ weight hourly space velocity: liquid hydrocarbon volume ratios of the liquid feed from 200 Nm ³ :1 m ³ to 2000 Nm ³ :1 m ³ , or any combination or all thereof;
process. According to claim 4,
The hydrogenation process of step (a) produces a dissolved catalyst comprising Ni and/or Mo and a fixed bed catalyst comprising Co, Mo, Ni, W or any combination thereof on a support. which is done using
process. According to claim 1 or 2,
The reforming conditions in step (b) include a temperature of 450 ° C to 550 ° C, a pressure of 2 barg to 30 barg, or a H ₂ : hydrocarbon molar ratio of 2.1 to 9.1, or any combination thereof,
process. According to claim 1 or 2,
The reforming in step (d) is performed using a reforming catalyst comprising Pt-Re on alumina, Pt on alumina, metal loaded zeolite, or a combination thereof,
process. According to claim 1 or 2,
The pyrolysis oil is obtained from plastics,
process. According to claim 8,
the pyrolysis oil depolymerizes the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-based wax stream; and obtained from the plastic by cracking the hydrocarbon-based wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions comprise a cracking temperature higher than, equal to, or lower than the depolymerization temperature. doing,
process. According to claim 1 or 2,
wherein the first stream comprises hydrocarbons having a boiling point greater than 140°C separated from the crude oil and/or the pyrolysis oil by atmospheric distillation;
process. According to claim 10,
wherein the atmospheric distillation further produces an eighth stream comprising hydrocarbons having a boiling point between 70°C and 140°C, and the process further comprises reforming the eighth stream;
process. According to claim 10,
an eighth stream is reformed to the fourth stream to form the sixth stream and the seventh stream;
process. According to claim 10,
wherein the atmospheric distillation further produces a ninth stream comprising hydrocarbons having a boiling point of less than 70 °C.
process. According to claim 13,
wherein the ninth stream is cracked into the third stream or sent to the hydroprocessing step to produce the light gas olefins.
process. According to claim 1 or 2,
The first stream comprises pyrolysis oil,
process. According to claim 1 or 2,
The first stream is condensate, naphtha, light crude oil, or a crude oil hydrocarbon fraction having a high boiling point cut of 350°C or whole crude oil. , or any combination or all of these,
process. A process for the selective production of C ₆ to C ₈ aromatics and optionally light gas olefins from plastics,
a) performing reactive extrusion or melt cracking of a plastic to form a pyrolysis oil;
b) to obtain a stream A comprising hydrocarbons boiling below 70°C, a stream B comprising hydrocarbons boiling between 70°C and 140°C, and a stream C comprising hydrocarbons boiling above 140°C. separating the pyrolysis oil;
c) reforming said stream B to obtain a stream D comprising C ₆ to C ₈ aromatics; and
d) optionally mixing the stream A into a gasoline pool of a refinery;
process. According to claim 17,
The reactive extrusion or melt cracking of the plastic depolymerizes the plastic at a depolymerization temperature sufficient to produce a hydrocarbon-based wax stream; and catalytically cracking the hydrocarbon-based wax stream in the presence of a cracking catalyst under cracking conditions sufficient to produce the pyrolysis oil, wherein the cracking conditions include a cracking temperature that is higher than, equal to, or lower than the depolymerization temperature. doing,
process. According to claim 18,
Further comprising recycling the stream C to the catalytic cracking step.
process. The method of claim 18 or 19,
wherein at least one portion of the hydrogen-containing gas, non-aromatics, and non-C ₆ to C ₈ aromatics obtained from the reforming of step (c) is recycled to the catalytic cracking step.
process.