Flexible benzene production via selective higher olefin oligomerization of ethylene

Abstract

The present disclosure relates to integration of systems and methods related to steam cracking, oligomerization, hydrogenation, and aromatization to produce benzene via hydrogenation of oligomers produced from ethylene. In some aspects, the disclosed systems and methods utilize one or more of an oligomerization process, a hydrotreating process, and an aromatization process to produce an effluent comprising benzene. In further aspects, the systems and methods disclosed herein utilize one or more selective oligomerization catalyst systems.

Description

Technical Field

[0001] This disclosure relates to the integration of systems and processes associated with steam cracking, oligomerization, hydrogenation and aromatization reactions, enabling the production of benzene via hydrogenation of oligomers produced from ethylene. Background Technology

[0002] Benzene, also known as crude benzene, mineral naphtha, phenylhydride, and anthracene, is an aromatic compound of significant commercial importance. Found in crude oil, it is a component of gasoline and is widely used in the manufacture of plastics, resins, synthetic fibers, rubber lubricants, dyes, detergents, pharmaceuticals, pesticides, glues, adhesives, cleaning products, paint removers, and other commercial products. Due to increasing demand for crude oil, conventional methods for producing benzene from substances present in crude oil are becoming increasingly costly. Methods using natural gas as a starting material offer a more cost-effective alternative. Therefore, new and improved systems and methods for benzene production are desired. Summary of the Invention

[0003] Therefore, this disclosure provides novel and non-obvious methods and systems for benzene production, including systems and methods for producing reformate effluents comprising benzene and additional commercially valuable hydrocarbons. For example, in some aspects, this disclosure provides a method comprising: a) in an oligomerization process, contacting ethylene with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising 1) a C6 hydrocarbon comprising 1-hexene and 2) a C8 hydrocarbon comprising 1-octene; b) recovering 1-hexene and 1-octene from the oligomerization reactor effluent; c) in a hydrotreating process, contacting the 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrotreating catalyst to produce an aromatized feed comprising hexane, octane, or both; and d) in an aromatization process, contacting the aromatized feed with an aromatization catalyst to produce a reformate effluent comprising benzene. In related aspects, the C6 hydrocarbons in the oligomerization reactor effluent account for about 20% to about 99% by weight of the total weight of the oligomerization reactor effluent, while the C8 hydrocarbons account for about 0.1% to about 75% by weight of the total weight of the oligomerization reactor effluent. Among related characteristics, the advantageous features of the resulting 1-hexene and 1-octene streams are significant purity levels, including 1) a purity level of about 60% to about 99.9% by weight relative to the total weight of C6 hydrocarbons in the oligomerization reactor effluent, and 2) a purity level of about 95% to about 99.3% by weight relative to the total weight of C8 hydrocarbons in the oligomerization reactor effluent.

[0004] In some respects, in addition to C6 and C8 hydrocarbons, the oligomerizing reactor effluent generated according to this disclosure may further contain C6 hydrocarbons. 10 Hydrocarbons, C 12Hydrocarbons and / or C 14+ One or more of the hydrocarbons, including combinations thereof. For example, the effluent from an oligomerization reactor may be characterized by one or more of the following: 1) C comprising about 1% (wt%) to about 4% (wt%) of C. 10 Hydrocarbon stream; 2) C comprising approximately 0.1% to approximately 3% by weight 12 Hydrocarbon stream; and / or 3) C comprising about 0% to about 3.5% by weight. 14+ Hydrocarbon streams, all of which are based on the total weight of the oligomer reactor effluent.

[0005] Additional features of the disclosed methods involve the use of catalysts and / or catalyst systems capable of producing oligomerizing reactor effluents characterized by the components and component concentrations described herein. For example, catalysts used in the disclosed methods may include selective oligomerizing catalysts such as PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PN Guan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNPDPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, and PNP DPh-1MeiPR-DPh, as well as combinations of one or more of these selective oligomerizing catalysts. In a further aspect, the aromatization catalysts described above may comprise one or more of a zeolite support, a Group VIII transition metal according to the periodic table, and one or more halides. In some aspects, the disclosed method may further include a step of contacting ethylene with a selective oligomerization catalyst in the presence of a diluent (such as isobutane, cyclohexane, methylcyclohexane, isobutene, and / or 1-hexene, including combinations thereof). Additionally, the step of contacting ethylene with the selective oligomerization catalyst may be carried out in the presence of a diluent, including but not limited to a diluent recovered from reforming effluent, wherein the diluent is selected from one or more of the following: raffinate, benzene, toluene, xylene, and one or more branched alkanes and combinations thereof. Alternatively, the method may further include 1) flowing raffinate recovered from the aromatization process into a steam cracker; and 2) cracking the raffinate in the steam cracker. The ethylene stream used in the disclosed method may be pure ethylene or substantially pure ethylene, or alternatively, the stream may contain ethylene and one or more additional hydrocarbons. For example, in some aspects, ethylene contacted in the oligomerization process is received in a stream containing ethylene and ethane. Furthermore, the method may benefit from the use of one or more removal, purification, and / or separation systems. For example, a sulfur removal system may or may not be used in one or more steps or processes characterizing the method. In some aspects, for example, it is advantageous to avoid using a sulfur removal system between the oligomerization process and the aromatization process.

[0006] Further features of the method may encompass the recovery of one or more hydrocarbons of interest, including but not limited to 1-hexene and 1-octene, from the oligomerization reactor effluent via fractionation into 1) a first stream containing heavy hydrocarbons and spent catalyst; 2) a second stream containing octene; and 3) a third stream containing hexene. In this relevant feature, only a portion of the third stream (with respect to the first, second, and third streams as described above) is used as feedstock for the hydrotreating process. Alternatively, the recovery of 1-hexene and 1-octene from the oligomerization reactor effluent may comprise fractionation into 1) a first stream containing heavy hydrocarbons and spent catalyst; 2) a second stream containing octene; and 3) a third stream containing hexene, wherein, with respect to the first, second, and third streams, only a portion of the second stream and only a portion of the third stream are fed to the hydrotreating process.

[0007] In a further aspect, the recovery of 1-hexene and 1-octene from the effluent of the oligomerization reactor as described herein includes fractionating the effluent of the oligomerization reactor into 1) a first stream containing heavy hydrocarbons and spent catalyst; and 2) a second stream containing hexene and octene, wherein only a portion of the second stream is fed to a hydrotreating process. In a further aspect, the recovery of 1-hexene and 1-octene from the effluent of the oligomerization reactor as described herein includes fractionating the effluent of the oligomerization reactor into 1) a first stream containing spent catalyst; and 2) a second stream containing hexene, octene, and heavy hydrocarbons, and further feeding only a portion of the second stream to a hydrotreating process. Additional features associated with the methods described herein further include the recovery of 1-hexene and 1-octene from the oligomerization reactor effluent, comprising separating the oligomerization reactor effluent into 1) a first stream containing heavy hydrocarbons and spent catalyst; 2) a second stream containing octene; and 3) a third stream containing hexene; fractionating the third stream to produce a high-purity 1-hexene stream and a C6 feed stream; and feeding the C6 feed stream into a hydrotreating process. In some aspects, the method may further include fractionating a refinery stream to recover a naphtha stream; feeding the naphtha stream into a hydrotreating process; and contacting the naphtha with a hydrotreating catalyst in the hydrotreating process to produce one or more of n-hexane and n-octane in the aromatization feed.

[0008] In some aspects, in addition to benzene, the reformate produced according to this disclosure may further comprise one or more commercially valuable hydrocarbons, which can be separated and / or directed for further processing. For example, the reformate may further comprise one or more of toluene, ethylbenzene, xylene, 1-hexene, and 1-octene, including combinations thereof. Depending on certain characteristics, the reformate may be further fractionated or separated into separate streams corresponding to one or more of the hydrocarbons described herein, such as a benzene stream, a toluene stream, a xylene stream, and / or a raffinate stream. Thus, the resulting hydrocarbon stream may be characterized by the presence of one or more additional hydrocarbons. For example, 1-hexene may be present in the benzene stream and / or toluene stream produced according to the disclosed method, while 1-octene may be present in the xylene stream and / or raffinate stream.

[0009] According to additional features of the disclosed method, the aromatization process can be further configured to advantageously generate a hydrogen effluent, which can be achieved by: 1) allowing a portion of the benzene stream and a portion of the hydrogen effluent to flow into a hydrogenation process to produce cyclohexane; and 2) recycling the cyclohexane to an oligomerization process.

[0010] As described in this article, the effluent from an oligomerization reactor can be characterized by the presence of various hydrocarbons. In some respects, the effluent from an oligomerization reactor can... especially Hexane substances, such as cyclohexane, can be recovered or separated from the oligomerization reactor effluent into cyclohexane and / or other (non-cyclohexane) hexane. Additionally, non-cyclohexane substances can be recovered from the oligomerization reactor effluent—either during processing or when the fluid is fed to the hydrotreating process described herein—while any residual cyclohexane can be recovered from the oligomerization reactor effluent and recycled or fed to the oligomerization process.

[0011] Additional features, processes, and operations may be incorporated into the methods described herein, for example, to enhance their value and / or utility. For example, in a non-limiting aspect, the method may further include 1) cracking one or more (including mixtures thereof) of ethane, propane, butane, pentane, and / or naphtha in a steam cracker to produce a cracker-derived effluent containing ethylene; and 2) causing the resulting ethylene recovered or separated from the cracker effluent to flow into or otherwise deliver it to the oligomerization process described herein. In some aspects, the resulting cracker effluent may further contain one or more light hydrocarbons, wherein the method may advantageously further include 1) using the light hydrocarbons recovered from the cracker effluent as a cooling source for the oligomerization reactor in the oligomerization process, including for a first fractionation process downstream of the oligomerization process, a second fractionation process downstream of the aromatization process, or for use in combination with the first and second fractionation processes. In a related aspect, the thermal energy associated with the methods of this disclosure may be advantageously recycled and / or recovered for one or more steps or processes associated therewith. For example, the method may further include 1) recovering steam from a steam pyrolyzer; and 2) using the recovered steam as a heat source for the aforementioned oligomerization process for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or for a combination of the first and second fractionation processes, as further described herein.

[0012] As described herein, the oligomerization reactor effluent produced according to this disclosure may contain a variety of hydrocarbons and their derivatives. Depending on certain characteristics, the oligomerization reactor effluent may contain or additionally contain one or more C... 9+ Hydrocarbons. Therefore, the method may further include steps or processes utilizing the C9+ hydrocarbons, including but not limited to 1) blending the C9+ hydrocarbons into a fuel stream (such as an electric motor fuel stream). In an additional aspect, the C9+ hydrocarbon stream may first be blended with an additional hydrocarbon stream (such as a raffinate stream separated from reformate effluent), followed by the resulting C9+ hydrocarbons being... 9+ The hydrocarbon / raffinate stream is blended into the fuel stream (e.g., motor fuel stream).

[0013] In some aspects, the disclosed methods may further include recycling, reintroducing or utilizing the chemical substances or portions thereof produced therein, including 1) allowing hydrogen obtained from the reforming effluent to flow into or be recycled to an oligomerization process, a hydrotreating process or both (i.e., an oligomerization process and a hydrotreating process).

[0014] This disclosure further provides systems configured to perform and capable of performing methods such as those disclosed herein. According to certain features, a system is provided comprising: 1) an oligomerization reactor configured to contact ethylene with a selective oligomerization catalyst to produce an oligomerization reactor effluent comprising C6 hydrocarbons (including 1-hexene) and C8 hydrocarbons (including 1-octene); 2) a first separation unit configured to recover 1-hexene and 1-octene from the oligomerization reactor effluent; 3) a hydrogenation reactor configured to contact 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to produce an aromatization feed comprising one or more of hexane, octane, and alkylcyclopentane; and 4) an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce a reforming effluent comprising benzene, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides. In an additional aspect, the system may further include a steam pyrolyzer configured to produce a pyrolyzer effluent containing ethylene, and the resulting ethylene may be recovered from the pyrolyzer effluent for oligomerization in an oligomerization reactor. According to a further feature, the pyrolyzer effluent may contain one or more light hydrocarbons, such that one or more of the oligomerization reactor, the first separation unit, the second separation unit (configured to receive and separate the reforming effluent), or a combination of two or more of these components may be configured to advantageously use light hydrocarbons as a cooling source.

[0015] A steam pyrolyzer can be configured to optimally perform the disclosed method, including the following aspects: wherein the steam pyrolyzer is configured to produce a steam effluent, and wherein an oligomerizing reactor, a first separation unit, a second separation unit configured to receive and separate the reformed effluent, or a combination thereof, are configured to advantageously utilize the steam effluent as an internally derived heat source.

[0016] The publicly disclosed system can especially It further includes a fractionator configured to fractionate the refinery stream to recover the naphtha stream, such that the naphtha can be effectively contacted with the hydrogenation catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0017] In an additional aspect, the reforming effluent produced by the disclosed system may further comprise toluene, ethylbenzene, xylene, 1-hexene, and 1-octene, including combinations thereof, and the system may further include a second separation unit for optimally processing the reforming effluent, such as a second separation unit configured to fractionate the reforming effluent into a benzene stream, a toluene stream, a xylene stream comprising ethylbenzene and xylene, and a raffinate stream. In a related aspect, 1-hexene may be present in the benzene stream and / or the toluene stream, while 1-octene may be present in the xylene stream, the raffinate stream, or both.

[0018] The disclosed system can be additionally arranged or customized according to certain features, such that the aromatization reactor is configured to produce a hydrogen effluent, the hydrogenation reactor is configured to receive a portion of the benzene stream and a portion of the hydrogen effluent for subsequent production of cyclohexane, and the oligomerization reactor is configured to receive the cyclohexane produced by the hydrogenation reactor. Alternatively, the system may further include a second separation unit optimized or configured to fractionate the oligomerization reactor effluent to produce a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein only a portion of the third stream (containing hexene) is fed to the aromatization reactor.

[0019] According to further features, the system may additionally include a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein only a portion of the second stream (containing octene) is fed to the aromatization reactor. In some aspects, the system may further include a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein only a portion of the second stream (containing octene) and at least a portion of the third stream (containing hexene) are fed to the aromatization reactor. In some aspects, the system further includes a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream containing heavy hydrocarbons and spent catalyst and a second stream containing hexene and octene, wherein only a portion of the second stream (containing hexene and octene) is fed to the aromatization reactor. In an additional aspect, the system further includes a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing spent catalyst and a second stream containing hexene, octene, and heavy hydrocarbons, wherein only a portion of the second stream (containing hexene, octene, and heavy hydrocarbons) is fed to the aromatization reactor.

[0020] According to some features of the disclosed system, the first separation unit of the system is configured to recover a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene and hexane, wherein the system further includes 1) a C6 separator configured to split the third stream into a) a high-purity 1-hexene stream; and b) a hexane stream; and 2) a cyclohexane recovery tower configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle stream, wherein 1) the residual C6 feed is fed to an aromatization reactor, and 2) the cyclohexane recycle stream is fed to an oligomerization reactor. In a further aspect, the selective oligomerization catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PN Guan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh, or combinations thereof; and the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides, as further described herein. Attached Figure Description

[0021] Figure 1 A schematic diagram of an integrated conversion system is provided.

[0022] Figure 2 A schematic diagram of the pyrolysis process is shown.

[0023] Figure 3 A schematic diagram of the oligomerization process is shown.

[0024] Figure 4 A schematic diagram of the aromatization process is shown.

[0025] Figure 5 A schematic diagram of another integrated conversion system is shown.

[0026] Figure 6 A schematic diagram of an additional integrated conversion system is provided.

[0027] Figure 7 A schematic diagram of an integrated conversion system is provided.

[0028] Figure 8 A schematic diagram of another integrated conversion system is shown.

[0029] Figure 9 A schematic diagram of an additional integrated conversion system is provided.

[0030] Figure 10 A schematic diagram of an integrated conversion system is provided.

[0031] Figure 11 A schematic diagram of another integrated conversion system is shown.

[0032] Figure 12 A schematic diagram of an additional integrated conversion system is provided.

[0033] Figure 13 A schematic diagram of an integrated conversion system is provided.

[0034] Figure 14 A graph showing the conversion rate of 1-hexene to benzene is presented.

[0035] Figure 15 A graph showing the selectivity for the conversion of 1-hexene to benzene is presented. Detailed Implementation

[0036] First, it should be understood that although exemplary embodiments of one or more aspects are provided below, the disclosed systems, processes, and / or methods can be implemented using any number of techniques, whether currently known or existing. This disclosure should not be limited to the exemplary embodiments, drawings, and techniques exemplified below, including the exemplary designs and embodiments illustrated and described herein, but modifications can be made within the full scope of the appended claims, together with their equivalents.

[0037] This document discloses systems, processes, apparatus, and methods for multi-step chemical conversions, wherein several chemical conversions, which are typically performed in discrete processes, are integrated into a single continuous flow system. The integrated conversion systems, along with their associated processes, apparatus, and methods, generally relate to continuous flow systems that integrate the conversion of C4 hydrocarbons (such as hydrocarbons derived from natural gas (e.g., ethane)) into oligomeric intermediates (e.g., 1-hexene and / or 1-octene), which are further converted into aromatic hydrocarbons (e.g., benzene).

[0038] As disclosed herein, methods utilizing integrated conversion systems generally include one or more of the following: (a) cracking a hydrocarbon feedstock in a cracking process to produce a cracker effluent containing monomers; (b) feeding monomers recovered from the cracker effluent into an oligomerization process; (c) contacting the monomers with an oligomerization catalyst in the oligomerization process to produce an oligomerization reactor effluent containing oligomer products; (d) feeding oligomer products recovered from the oligomerization reactor effluent into a hydrotreating process; (e) contacting the oligomer products with a hydrotreating catalyst in the hydrotreating process to produce an aromatization feedstock containing hexane, octane, or both; (f) feeding the aromatization feedstock into an aromatization process; and (g) contacting the aromatization feedstock with an aromatization catalyst in the aromatization process to produce a reforming effluent containing aromatics. In one aspect, the integrated conversion system disclosed herein is a continuous, serial-flow system, for example, a cracking process connected to an oligomerization process, an oligomerization process connected to a hydrotreating process, and a hydrotreating process connected to an aromatization process.

[0039] In the systems, processes, and methods disclosed herein, multiple streams and products (e.g., ethylene, 1-hexene, 1-octene, benzene) are recovered from reactors and / or process streams. Those skilled in the art will recognize that a stream or product can be recovered directly from the reactor or process that forms it; alternatively, the stream or product can be recovered from another process and / or stream located downstream of where it is formed.

[0040] The following definitions are provided to assist those skilled in the art in understanding the detailed description of this disclosure. Unless otherwise defined herein, scientific and technical terms used in conjunction with this disclosure should have the meanings commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, unless the context otherwise requires, singular terms should include the plural (form) and plural terms should include the singular (form).

[0041] Furthermore, for clarity, certain features of this disclosure described herein in the context of separate aspects may also be provided in combination in a single aspect. Conversely, for the sake of brevity, the various features of this disclosure described in the context of a single aspect may also be provided separately or in any sub-combination.

[0042] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise specified, the following definitions apply to this disclosure. If a term is used in this disclosure but is not explicitly defined herein, the definition in IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or unenforceable. If any definition or usage provided by reference to any document incorporated herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0043] Use, for example Chemical and Engineering News The numbering scheme indicated in the version of the periodic table published in 63(5), 27, 1985 indicates the groups of elements in the periodic table. In some cases, the groups of elements may be indicated by the common names assigned to the groups; for example, alkaline earth metals (or alkali metals) of Group 1 elements, alkaline earth metals (or alkali metals) of Group 2 elements, transition metals of Groups 3-12 elements, and halogens of Group 17 elements.

[0044] General formula C A+ and C A- A represents the number of carbon atoms in the molecular formula of an organic molecule (e.g., a hydrocarbon), where A is an integer or a whole number. For example, C 3+ This indicates a compound in which each molecule contains 3 or more carbon atoms, while C 5- This indicates a compound whose molecule contains 5 or fewer carbon atoms.

[0045] Unless otherwise expressly stated in the prescribed circumstances, all percentages, parts, ratios and similar quantities used herein are defined by weight.

[0046] Whenever used in this specification and claims, the term "olefin" refers to a compound having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Unless explicitly stated otherwise, the term "olefin" includes aliphatic and aromatic, acyclic and cyclic, and / or straight-chain and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Unless explicitly indicated, the term "olefin" itself does not indicate the presence of heteroatoms and / or the presence of other carbon-carbon double bonds. Olefins having only one, two, three, etc., carbon-carbon double bonds can be identified by using the terms "mono," "di," "tri," etc., within the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bonds (one or more).

[0047] The term "reactor effluent" and its derivatives (e.g., oligomer reactor effluent) generally refer to all substances leaving the reactor. The term "reactor effluent" and its derivatives may also be preceded by other descriptive terms that limit the scope of the reactor effluent. For example, while the term "reactor effluent" refers to all substances leaving the reactor (e.g., products and solvents or diluents), the term "olefin reactor effluent" refers to reactor effluent containing olefin (i.e., carbon-carbon) double bonds.

[0048] The term "oligomer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight (70 wt%) a product comprising 2 to 30 monomer units. Similarly, "oligomer" is a product containing 2 to 30 monomer units, while "oligomeric product" includes all products produced by an "oligomer" process, including both "oligomers" and products that are not "oligomers" (e.g., products containing more than 30 monomer units). It should be noted that the monomer units in an "oligomer" or "oligomeric product" need not be identical. For example, an "oligomer" or "oligomeric product" produced by an "oligomer" process using ethylene and propylene as monomers may contain both ethylene and / or propylene units.

[0049] The term "trimer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing three and only three monomer units. A "trimer" is a product containing three and only three monomer units, while a "trimer product" includes all products produced by a trimer process, including trimers and products that are not trimers (e.g., dimers and / or tetramers). Generally, olefin trimer reduces the number of olefin bonds by two when considering the number of olefin bonds in the monomer units and the number of olefin bonds in the trimer. It should be noted that the monomer units in a "trimer" or "trimer product" need not be identical. For example, a "trimer" produced by a trimer process using ethylene and butene as monomers may contain ethylene and / or butene monomer units; that is, a "trimer" may include C6, C8, C96 ... 10and C 12 Products. In another example, the "trimer" produced by a "trimerization" process using ethylene as a monomer may contain ethylene monomer units. It should also be noted that a single molecule may contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomer units within a single molecule.

[0050] The term "tetramer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing four and only four monomer units. A "tetramer" is a product containing four and only four monomer units, while a "tetramer product" includes all products produced by a tetramer process, including tetramers and products that are not tetramers (e.g., dimers or trimers). Generally, olefin tetramerization reduces the number of olefin bonds by three when considering the number of olefin bonds in the monomer unit and the number of olefin bonds in the tetramer. It should be noted that the monomer units in a "tetramer" or "tetramer product" need not be identical. For example, a "tetramer" from a "tetramer" process using ethylene and butene as monomers may contain ethylene and / or butene monomer units. In one instance, a "tetramer" from a "tetramer" process using ethylene as a monomer may contain ethylene monomer units. It should also be noted that a single molecule may contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomer units within a molecule.

[0051] The term "monomer" refers to a C4 hydrocarbon whose molecular structure contains a single carbon-carbon double bond. For example, a monomer can be a C2 monoalkene.

[0052] The term "oligomer" refers to a C0 group of molecules containing at least one carbon-carbon double bond. 6+ Hydrocarbons. For example, oligomers can be C6 monoolefins.

[0053] The term "aromatic hydrocarbon" refers to monocyclic C6 to C6 hydrocarbons. 14 Aromatic compounds.

[0054] "Cetane number" is the ratio of diesel fuel to cetane (C60). 16 H 34 ( ) is a measure of the ignition properties of a standard (product).

[0055] The term "smoke point," used for oils or fats, refers to the temperature at which, under specific and defined conditions, the oil or fat begins to produce a continuous, clearly visible blue smoke.

[0056] A further understanding of aspects of this disclosure can be obtained by referring to the accompanying flow diagrams in conjunction with the following description. Those skilled in the art will recognize the various additional pumps, valves, heaters, coolers, and other conventional devices required to implement this disclosure. For clarity, these additional devices have been omitted from the figures. The description of the figures provides a method for operating the process. However, it should be understood that while these figures are a general representation of the process, minor modifications may be made to adapt the figures to various conditions within the scope of this disclosure. It should also be understood that the numbering references in the figures are consistent throughout all figures. For example, inlet flow 10 containing hydrocarbon feed is a hydrocarbon feed inlet flow in all figures. Unless explicitly disclosed otherwise, the function and components of a process in one integrated conversion system are substantially the same as those in another integrated conversion system including the process. In other words, unless explicitly disclosed otherwise, the function and components of cracking process 200 in integrated conversion system 1000 are substantially the same as those in integrated conversion system 1100, or in integrated conversion system 1200, etc.

[0057] refer to Figure 1 The integrated conversion system 1000 is described. The integrated conversion system 1000 generally includes a cracking process 200, an oligomerization process 300, an aromatization process 400, a first fractionation process 50, a hydrotreating process 70, and a second fractionation process 80.

[0058] In the integrated conversion system disclosed herein, various system components can be fluidly connected via one or more conduits (e.g., pipes, tubes, streamlines, etc.) suitable for conveying specific flows, for example, such as Figure 1 The numbering stream is displayed in detail.

[0059] Hydrocarbon feed 10 flows into cracking process 200, where the hydrocarbons are converted (i.e., cracked) into monomers. In one aspect, the monomers include ethylene. Cracking process 200 may include any cracking process suitable for producing ethylene as disclosed herein. U.S. Patent No. 6,790,342 discloses a method for converting hydrocarbons into ethylene, which is incorporated herein by reference in its entirety. Any method for producing ethylene disclosed in U.S. Patent No. 6,790,342 may be utilized herein. Hydrocarbon feed 10 contains any one or more hydrocarbons suitable for the uses disclosed herein. For example, the hydrocarbons may include non-aromatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. The hydrocarbons may be derived from natural gas, gas condensates, oil, or combinations thereof. In one aspect, the hydrocarbons include ethane, propane, butane, pentane, naphtha, or combinations thereof. In a further aspect, hydrocarbon feed 10 contains ethane, wherein the ethane may be derived from a natural gas source.

[0060] In one specific aspect, based on the total weight of the hydrocarbon feedstock 10, the amount of ethane in the hydrocarbon feedstock 10 ranges from about 10% by weight to about 95% by weight; alternatively, from about 20% by weight to about 80% by weight, or alternatively, from about 40% by weight to about 60% by weight.

[0061] refer to Figure 2 This describes aspects of the cracking process 200. The hydrocarbon feed 10 is combined with the hydrocarbon recycle stream 201. The hydrocarbon recycle stream 201 can be combined with other streams of the integrated reforming system disclosed herein. For example, the hydrocarbon recycle stream 201 can be combined with the C0 of the cracking process 200. 3+ Flow 262 and / or alternative C 3+ Stream 282 merged (not shown); or alternatively, with Figure 12 and Figure 13 The heavy recycle 180 is combined; alternatively, as further described herein. Some aspects of the cracking process 200 can be considered for operation in the absence of hydrocarbon recycle 201.

[0062] Hydrocarbon feed 10 flows into pyrolysis zone 205, which includes a steam cracker, where it comes into contact with high temperatures to produce cracker effluent 210. Pyrolysis zone 205 includes one or more radiant furnace reactors capable of producing cracker effluent 210. In one aspect, the temperature of pyrolysis zone 205 may be in the range of about 600°C to about 1500°C; or, about 750°C to about 900°C. In a further aspect, pyrolysis zone 205 may have an inlet pressure in the range of about 5 psig to about 400 psig (about 0.03 MPag to about 2.76 MPag); or alternatively, about 29 psig to about 45 psig (about 0.19 MPag to about 0.31 MPag); and an outlet pressure in the range of about 0.5 psig to about 40 psig (about 0.0034 MPag to about 0.28 MPag); or alternatively, about 3.5 psig to about 11 psig (about 0.024 MPag to about 0.076 MPag). Radiation furnace reactors are disclosed in U.S. Patent Nos. 5,151,158; 4,780,196; 4,499,055; 3,274,978; 3,407,789; and 3,820,955; each of which is incorporated herein by reference in its entirety. In one aspect, the pyrolysis effluent 210 comprises one or more monomers, hydrogen, methane, acetylene, ethane, C 3+ Saturated hydrocarbons and combinations thereof. In a further aspect, the monomer comprises ethylene, propylene, butene, or combinations thereof; or alternatively, ethylene.

[0063] Based on the total weight of the pyrolysis effluent 210, the amount of ethylene in the pyrolysis effluent 210 may range from about 10% by weight to about 95% by weight; alternatively, from about 20% by weight to about 80% by weight; or alternatively, from about 40% by weight to about 70% by weight. In a further aspect, the pyrolysis effluent 210 may contain about 1% by weight to about 20% by weight of hydrogen, about 1% by weight to about 30% by weight of methane, about 1% by weight to about 30% by weight of acetylene, about 3% by weight to about 45% by weight of ethane, and about 0% by weight to about 25% by weight of C. 3+ hydrocarbon.

[0064] The pyrolysis effluent 210 flows into a quenching zone 215 to generate a quenched gas flow 220. In one aspect, the operating temperature of the quenching zone 215 may be below the temperature required to sustain the pyrolysis reaction occurring within the pyrolysis effluent 210. In another aspect, the pyrolysis effluent 210 is cooled to a temperature below about 595°C; alternatively, it is cooled to a temperature in the range of about 30°C to about 110°C to form the quenched gas flow 220. Quenching can be performed by any means suitable to a person skilled in the art. For example, the pyrolysis effluent 210 may be fed to a quenching boiler and a quenching tower, in which fuel oil and dilution streams may be removed. U.S. Patent Nos. 3,407,798; 5,427,655; 3,392,211; 4,351,275; and 3,403,722 disclose methods for cooling the pyrolysis effluent 210, all of which are incorporated herein by reference in their entirety. The quenched gas flow 220 flows into a first compression zone 225 to generate a pressurized gas flow 230. In one aspect, the pressurized gas flow 230 may include pressures ranging from about 150 psig to about 650 psig (about 1.034 MPag to about 4.48 MPag). The first compression zone 225 includes one or more gas compressors, wherein the gas compressors may be any gas compressors suitable as disclosed herein.

[0065] A pressurized gas stream 230 flows into a deacidification zone 235, where hydrogen sulfide (H2S) and carbon dioxide (CO2) are removed to produce a humidified gas stream 240. In one aspect, the deacidification zone 235 removes a portion of the H2S and CO2 from the pressurized gas stream 230. In a further aspect, the H2S concentration of the humidified gas stream 240 may be less than about 0.1 ppm by weight; alternatively, it may be in the range of about 25 ppb to about 100 ppb by weight. In yet another aspect, the CO2 concentration of the humidified gas stream 240 may be less than about 5 ppm by weight. The removal of H2S and CO2 can be achieved by any suitable means as determined by those skilled in the art and by means of this disclosure. In yet another aspect, diethanolamine or a caustic contactor may be used to remove at least a portion of the H2S and CO2 constituting the pressurized gas stream 230. The humidified gas stream 240 flows into a drying zone 245, producing a cracked gas stream 250. In one aspect, the water content of the cracked gas stream 250 is below the amount required to cause problems in downstream operations. In a further aspect, the water content of the pyrolysis gas stream 250 is less than about 10 ppm by weight. Drying in the drying zone 245 can be achieved by any suitable means as determined by those skilled in the art and by means of this disclosure. In one aspect, water can be removed from the humid gas stream 240 using a molecular sieve bed.

[0066] The cracked gas stream 250 flows into the de-ethanizer section 255 to produce C 2- Stream 260 and C 3+ Stream 262. Deethaner section 255 includes sections capable of producing C 2- Stream 260 and C 3+ Fractionator of flow 262. C 2- Stream 260 may contain hydrogen, methane, ethane, acetylene, ethylene, or combinations thereof. 3+ Stream 262 contains C3 hydrocarbons and heavier components, and in one respect, can be combined with hydrocarbon recycling stream 201 (not shown). 2- Flow 260 flows into hydrogenation zone 265, where C can be removed. 2- A portion of the acetylene in stream 260. Ethylene stream 270 is recovered from hydrogenation zone 265. This can be done by any suitable means as determined by a person skilled in the art and by means of this disclosure. 2- Hydrogenation at 260°C. For example, an acetylene reactor containing a catalyst can be used for C... 2-A portion of the acetylene in stream 260 is hydrogenated. Group VIII metal hydrogenation catalysts are typically used. Hydrogenation catalysts are disclosed in U.S. Patent Nos. 3,679,762; 4,571,442; 4,347,392; 4,128,595; 5,059,732; 5,488,024; 5,489,565; 5,520,550; 5,583,274; 5,698,752; 5,585,318; 5,587,348; 6,127,310 and 4,762,956, each of which is incorporated herein by reference in its entirety. The operating conditions in hydrogenation zone 265 may encompass any suitable combination of conditions as determined by a person of ordinary skill in the art with the aid of this disclosure. In one aspect, the temperature and pressure in hydrogenation zone 265 may be at a level capable of supporting C 2- A portion of the acetylene in stream 260 is hydrogenated. Further, the temperature of hydrogenation zone 265 can range from about 10°C to about 205°C. Further, the pressure of hydrogenation zone 265 can range from about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag). In some aspects, the residual acetylene in ethylene stream 270 can be less than about 5 ppm by weight; alternatively, it can range from about 0.5 ppm to about 3 ppm by weight.

[0067] Alternatively, C 2- Flow 260 passes through pipeline 266 (valves are provided in pipelines 260 and 268) and flows into the second compression zone 267 to generate pressurization C. 2- Flow 268. Pressurized C 2- The pressure of flow 268 can range from about 100 psig to about 750 psig (about 0.68 MPag to about 5.17 MPag); alternatively, from about 200 psig to about 650 psig (about 1.37 MPag to about 4.48 MPag). The second compression zone 267 includes one or more gas compressors, wherein the gas compressors can be any gas compressor suitable as disclosed herein. Pressurization C 2- Flow 268 flows into hydrogenation zone 265, where the components constituting pressurized C are removed. 2- A portion of the acetylene in stream 268. As described herein, ethylene stream 270 can be recovered from hydrogenation zone 265. In another alternative embodiment, the effluent from drying zone 245 is a substitute (positive) stream 272. Substitute stream 272 flows into substitute (positive) hydrogenation zone 275, where a portion of the acetylene constituting substitute stream 272 is removed to produce reducing stream 276. In one aspect, substitute hydrogenation zone 275 operates comparable to hydrogenation zone 265. Reducing stream 276 flows into substitute (positive) deethanerization zone 277, where substitute (positive) ethylene stream 280 is recovered and substitute (positive) C3+ Stream 282. In one aspect, the alternative deethaneration zone 277 operates equivalent to the deethaneration zone 255. In a further aspect, the alternative ethylene stream 280 and the alternative C... 3+ The composition of stream 282 is similar to that of ethylene stream 270 and C. 3+ The composition of Stream 262 is quite similar. In one respect, it replaces C. 3+ Stream 282 may be combined with hydrocarbon recycling stream 201 (not shown). Ethylene stream 270 and / or alternative ethylene stream 280 flow into cracking process effluent 25.

[0068] In one aspect, the cracking process effluent 25 contains ethylene. Based on the total weight of the cracking process effluent 25, the amount of ethylene in the cracking process effluent 25 may range from about 30% by weight to about 95% by weight; alternatively, from about 30% by weight to about 70% by weight; or alternatively, from about 40% by weight to about 60% by weight.

[0069] according to Figure 1 In one aspect, the cracking process effluent 25 flows into the oligomerization process 300. In another aspect, the cracking process effluent 25 continuously flows out of the cracking process 200 and into the oligomerization process 300. Those skilled in the art will understand that, as described herein with respect to the cracking process effluent 25, each stream described in this disclosure flows continuously from one process to the next. For simplicity, the continuous flow of each stream is not explicitly stated, but it is a characteristic of each stream. Ethylene effluent 29 originates from the cracking process effluent 25. In one aspect, the ethylene effluent 29 contains ethylene and may be sent for storage and / or for sale. In the oligomerization process 300, monomers may be contacted with an oligomerization catalyst in an oligomerization reactor to produce one or more oligomer products. In one aspect, the monomer may be an α-olefin; alternatively, a linear α-olefin; or alternatively, a n-α-olefin. In a further aspect, the monomer may include ethylene, propylene, or a combination thereof. When the monomer includes ethylene, the oligomerization process 300 may be an ethylene oligomerization process. In one aspect, the ethylene oligomerization process can be an ethylene trimerization process, an ethylene tetramerization process, or a combination thereof. When the process is an ethylene trimerization process, the oligomer product can be hexene, 1-hexene, or both. When the process is an ethylene tetramerization process, the oligomer product can be octene, 1-octene, or both. When the process is both an ethylene trimerization and tetramerization process, the olefin product can comprise hexene, octene, 1-hexene, 1-octene, or any combination thereof. In a further aspect, the oligomerization process 300 includes an oligomerization reaction, wherein the oligomerization reaction can be a trimerization reaction, a tetramerization reaction, or a combination thereof. U.S. Patent No. 8,680,003 discloses a method for ethylene oligomerization using an oligomerization catalyst, which is incorporated herein by reference in its entirety.

[0070] refer to Figure 3The text describes aspects of the oligomerization process 300. The cracking process effluent 25 may be combined with the ethylene recycle stream 306 to form the oligomer feed 301. In one aspect, the ethylene recycle stream 306 may be combined with the ethylene recovery stream 335 (not shown), as further described herein. Alternatively, the ethylene recycle stream 306 may be combined with an ethylene source from outside the integrated reforming process 1000. In a further aspect, the ethylene recycle stream 306 comprises a light effluent from the polyethylene polymerization process. Some aspects of the oligomerization process 300 can be considered for operation without the ethylene recycle stream 306. The oligomer feed 301 flows into the oligomerization reactor 305. In one aspect, the oligomer feed 301 comprises ethane, ethylene, or a combination thereof. The hydrogen feed 302 flows into the oligomerization reactor 305. In one aspect, the hydrogen feed 302 may be combined with a stream from another part of the integrated reforming system of this disclosure. For example, the hydrogen feed 302 may be combined with... Figure 1 The hydrogen effluent 81 is combined, as further described herein. It is not intended to be theoretically limited, but carrying out oligomerization in the presence of hydrogen can enhance product selectivity, reduce the formation of polymeric products, or both. Some aspects of the oligomerization process 300 can be considered for operation in the absence of hydrogen feed 302. Oligopolymerization catalyst stream 304 flows into oligomerization reactor 305. In one aspect, ethylene is contacted with the oligopolymerization catalyst in oligomerization reactor 305 in the presence of a solvent. In such aspects, solvent feed 308 is combined with oligopolymerization catalyst stream 304. For the purposes of this disclosure, "solvent" means a diluent or medium in which the oligomerization reaction occurs. The solvent can be any inert solvent suitable for the oligomerization reaction disclosed herein. In one aspect, the solvent can be a hydrocarbon solvent, a halohydrocarbon solvent, an aliphatic hydrocarbon solvent, a haloaliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a haloaromatic solvent, or any combination thereof. In a further aspect, the solvent may be isobutane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, or a combination thereof. In one aspect, solvent feed 308 may be combined with solvent recycle 345 (not shown), as further disclosed herein; alternatively, with cyclohexane effluent 67 (e.g., see...). Figure 10 or Figure 11 Alternatively, it can be combined with raffinate stream 88 (see, for example, see...). Figure 1 or Figures 5-11 (any of the above), as further disclosed herein. Some aspects of the oligomerization process 300 can be operated in the absence of solvent feed 308.

[0071] In one aspect, the oligomeric catalyst includes a selective oligomeric catalyst system. The selective oligomeric catalyst system suitable for use herein may comprise an N-oxophosphine-amidine compound, a metal salt, and an alkyl metal; alternatively, an N-oxophosphine-amidine compound, a metal salt, and an aluminoxane; alternatively, an N-oxophosphine-amidine metal salt complex and an alkyl metal; or alternatively, an N-oxophosphine-amidine metal salt complex and an aluminoxane. In a further aspect, the selective oligomeric catalyst system may comprise one or more neutral ligands. As previously disclosed, a selective oligomeric catalyst system suitable for use herein is described in U.S. Patent No. 8,680,003; therein are listed all the components constituting the selective oligomeric catalyst system, the ratios of these components, and methods of combining these components to produce the selective oligomeric catalyst system. In one aspect, the selective oligomerization catalyst system may comprise [4-tert-butyl-N1-(2,4,6-trimethylphenyl)-N2(diisopropylphosphino)benzamide](THF)CrCl3 (i.e., PN Mes-tBuPh-DIP), [4-methoxy-N1-(2,4,6-trimethylphenyl)-N2(diisopropylphosphino)benzamide](THF)CrCl3 (i.e., PNMes-MeOPh-DIP), N1-(2,6-dimethylphenyl)-N2-(di-n-butylphosphino)-2-p-tolylacetamide](THF)CrCl3 (i.e., PN Xyl-Bz-DnB), [N1-(2,6-dimethylphenyl)-N2-(diphenylphosphino)-2-p-tolylacetamide](THF)CrCl3; (i.e., PN Xyl-Bz-DPh), 7-(diisopropylphosphino)-1,5,7-triazabicyclo[4.4.0]dec-5-ene](THF)CrCl3 (i.e., PN Guan-DIP), [1-[bis(1-methylethyl)phosphino-κP]-1,3,4,6,7,8-hexahydro-2H-pyrimidino[1,2-a]pyrimidin-κN9]trichloro(tetrahydrofuran)-chromium (i.e., PN Guan-DIP), [N1-(2,4,6-trimethylphenyl)-N2-(diisopropylphosphino)benzamide](THF)CrCl3 (i.e., PN Mes Ph-DIP), [N1-(2,6-dimethylphenyl)-N2-(diethylphosphino)benzamide](THF)CrCl3 (i.e., PN Xyl-Ph-Det), [bis(diphenylphosphino)(n-hexyl)amine]trichlorochromium trichloro[ N- (diphenylphosphine-κ) P )- N -(Jiji)- P , P -Diphenylphosphine-κ P ]-Chromium (i.e., PNP DPh-Hex-DPh), [bis(diphenylphosphino)(cyclohexyl)amine]trichlorochromium, PNP trichloro[ N-Cyclohexyl- N -(diphenylphosphine-κ) P ) P , P -Diphenylphosphine-κ P ]-Chromium (i.e., PNP DPh-Cy-DPh), PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh, or combinations thereof.

[0072] Contact between ethylene and the selective oligomerization catalyst system within the oligomerization reactor 305 can be carried out in any suitable manner and by means of this disclosure. In some aspects, the oligomerization reactor 305 may include a loop reactor, a tubular reactor, a continuous stirred tank reactor (CSTR), or a combination thereof. In one specific aspect, the suspension formed between the selective oligomerization catalyst system and the solvent may be stirred to maintain a uniform concentration of the selective oligomerization catalyst system throughout the suspension; or alternatively, the solution formed between the selective oligomerization catalyst system and the solvent may be stirred to maintain the selective oligomerization catalyst system in solution throughout the oligomerization process. In one aspect, the oligomerization reaction may be carried out in one or more oligomerization reactors. In one aspect, the oligomerization reaction may be carried out under suitable reaction conditions, said reaction conditions encompassing one or more of catalyst concentration, reaction temperature, reaction pressure, and / or reaction time. In one aspect, the concentration of the selective oligomerization catalyst system may be at least 1 × 10⁻⁶ Eq / L; alternatively, at least 2 × 10⁻⁶ Eq / L; or alternatively, at least 5 × 10⁻⁶ Eq / L. The temperature within the oligomerization reactor 305 may be any temperature suitable for the ethylene oligomerization reaction. In one aspect, the temperature is within a range that is low enough to minimize or avoid a decrease in the activity of the selective oligomerization catalyst system, and high enough to minimize or avoid the formation and / or precipitation of polymer products. In a further aspect, the temperature within the oligomerization reactor 305 may be at least 0°C; alternatively, at least 10°C; alternatively, at least 20°C; or alternatively, at least 30°C. In some aspects, the temperature within the oligomerization reactor 305 may be in the range of about 0°C to about 200°C; alternatively, about 10°C to about 160°C; alternatively, about 20°C to about 140°C; or alternatively, about 30°C to about 120°C. The pressure within the oligomerization reactor 305 may be any pressure suitable for the ethylene oligomerization reaction. In one aspect, the pressure is within a range that is high enough to avoid a decrease in the activity of the selective oligomerization catalyst system. In a further aspect, the pressure within the oligomerization reactor 305 can range from about atmospheric pressure (about 0 psig) to about 5000 psig (about 0.101 MPag to about 34.5 MPag); alternatively, from about 50 psig to about 4000 psig (about 0.345 MPag to about 27.6 MPag); alternatively, from about 100 psig to about 3600 psig (about 0.68 MPag to about 24.8 MPag); or alternatively, from about 150 psig to about 2000 psig (about 1.03 MPag to about 13.8 MPag). Specifically, the oligomerization reaction can have a single-pass ethylene conversion of at least about 30% by weight; alternatively, at least about 35% by weight; alternatively, at least about 40% by weight; or alternatively, at least about 45% by weight.

[0073] like Figure 3 As shown, the oligomerization reactor effluent 310 flowing from the oligomerization reactor 305 contains all components that can be present in and removed from the oligomerization reactor. The oligomerization reactor effluent 310 may contain oligomer products, by-products, co-products, side-products, light hydrocarbons, heavy hydrocarbons, unreacted monomers, selective oligomerization catalyst systems, solvents, and other reactor components. In one aspect, the oligomerization reactor effluent 310 contains hexene, octene, 1-hexene, 1-octene, alkylcyclopentanes, solvents, cyclohexane, unreacted ethylene, and combinations thereof. In a further aspect, the oligomerization reactor effluent 310 contains C 10 Hydrocarbons, C 12 Hydrocarbons, C 14+ Hydrocarbons or combinations thereof. Those skilled in the art will understand that streams 301, 302, 304, and 310 may be located at any position on the oligomerization reactor 305 suitable for allowing sufficient contact between ethylene and the selective oligomerization catalyst system within the oligomerization reactor 305. A catalyst killstream 312 may be combined with the oligomerization reactor effluent 310. The catalyst killstream 312 comprises a catalyst deactivation composition that can partially or completely deactivate the selective oligomerization catalyst system. Some aspects of the oligomerization process 300 may not utilize the catalyst killstream 312. A filter 315 may remove particulate matter (e.g., catalyst fines and undesirable polymer products) from the oligomerization reactor effluent 310. While not wishing to be bound by theory, it is believed that higher reactor and stream temperatures can suppress the solidification of undesirable polymer particles. When the oligomerization reactor effluent 310 is maintained at high temperatures, less particulate matter can be formed, and the filter 315 may not be necessary. Filter 315 may be used where process conditions favor particulate formation (e.g., cooling of the oligomerization reactor effluent 310). Filter 315 may not be necessary for some aspects of the oligomerization process 300.

[0074] Process stream 320 comprises the effluent from filter 315 or a continuation of oligomer reactor effluent 310, wherein process stream 320 contains very little or no particulate matter. Process stream 320 flows into first separator 330 to produce ethylene recovery stream 335 and oligomer effluent 338. Ethylene recovery stream 335 may contain methane, ethane, ethylene, propane, propylene, butane, or combinations thereof. In one aspect, ethylene recovery stream 335 may be further processed (not shown) to recover its ethylene concentrate(s) of higher purity. Ethylene recovery stream 335 may be combined with ethylene recirculation stream 306 as disclosed herein (not shown). In one aspect, heavy feed 322 may optionally be combined with process stream 320 to form an inlet into first separator 330. Heavy feed 322 may contain desired oligomer products and heavy hydrocarbons, as further described herein. In one aspect, heavy feed 322 may be an effluent from a polyethylene production facility. Oligopolymer effluent 338 flows into a second separator 340 to produce solvent recycle 345 and oligomerization process effluent 36. Solvent recycle 345 may be combined with the solvent feed 308 disclosed herein (not shown). In one aspect, solvent recycle 345 may contain cyclohexane. The first separator 330 and the second separator 340 may operate in any manner suitable for producing their effluents. In a further aspect, the first separator 330 and the second separator 340 each include at least one fractionator.

[0075] Effluent composition In one aspect, the oligomerization process effluent 36 contains an oligomer product comprising C6 and C8 olefins. In one aspect, the C6 olefin comprises hexene, 1-hexene, or a combination thereof, while the C8 olefin comprises octene, 1-octene, or a combination thereof. In one aspect, the oligomerization process effluent 36 contains an oligomer product comprising at least 60% by weight of C6 and C8 olefins; alternatively, at least 70% by weight of C6 and C8 olefins; alternatively, at least 80% by weight of C6 and C8 olefins; alternatively, at least 85% by weight of C6 and C8 olefins; or alternatively, at least 90% by weight of C6 and C8 olefins.

[0076] In one aspect, the oligomerization process effluent 36 may contain C6 olefins, wherein, based on the total weight of the oligomerization process effluent 36, the amount of C6 olefins may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the oligomerization process effluent 36 may contain 1-hexene, wherein the amount of 1-hexene may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In one aspect, the amount of 1-hexene in the oligomerization process effluent 36 may range from about 85 wt% to about 99.9 wt%; alternatively, from about 87.5 wt% to about 99.9 wt%; alternatively, from about 90 wt% to about 99.9 wt%; alternatively, from about 92.5 wt% to about 99.9 wt%; alternatively, from about 95 wt% to about 99.9 wt%; alternatively, from about 97 wt% to about 99.9 wt%; or alternatively, from about 98 wt% to about 99.9 wt%.

[0077] In a further aspect, the oligomerization process effluent 36 may contain C8 olefins, wherein, based on the total weight of the oligomerization process effluent 36, the amount of C8 olefins may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the oligomerization process effluent 36 may contain 1-octene, wherein the amount of 1-octene may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In one aspect, the amount of 1-octene in the oligomerization process effluent 36 may range from about 85 wt% to about 99.9 wt%; alternatively, from about 87.5 wt% to about 99.9 wt%; alternatively, from about 90 wt% to about 99.9 wt%; alternatively, from about 92.5 wt% to about 99.9 wt%; alternatively, from about 95 wt% to about 99.9 wt%; alternatively, from about 97 wt% to about 99.9 wt%; or alternatively, from about 98 wt% to about 99.9 wt%.

[0078] for Figure 1The oligomerization process effluent 36 flows into the first fractionation process 50, where hexene effluent 52 and octene effluent 54 are recovered. The first fractionation process 50 produces a heavy effluent 56, which may contain heavy hydrocarbons and spent selective oligomerization catalyst system. The heavy hydrocarbons may contain C 9+ Hydrocarbons, C formed through oligomerization 9+ Oligomers, polymer products formed by oligomerization reactions, or combinations thereof. In one aspect, C 9+ Oligomers include decene, dodecene, tetradecene, and combinations thereof. Those skilled in the art will understand that the first fractionation process 50 can be operated in any manner suitable for producing the disclosed effluent. For example, the first fractionation process 50 may include a series of separation units, such as flash distillation columns, fractionating distillation columns, and liquid-liquid extraction units.

[0079] In one aspect, a first portion of the hexene effluent 52 is used as hexene feed 53. The remaining portions of the hexene effluent 52 and octene effluent 54 may be sent for storage or for sale. In one aspect, the hexene feed 53 is optionally combined with naphtha feed 60 to form a treater feed 65. In one aspect, the naphtha feed 60 may contain non-aromatic hydrocarbons containing at least six carbon atoms. In a further aspect, the naphtha feed 60 may contain a hydrocarbon mixture comprising C6 to C8 hydrocarbons, said hydrocarbon mixture containing up to about 15% by weight of C6 hydrocarbons. 5- Hydrocarbons and up to about 10% by weight of C 9+ Hydrocarbons, wherein the weight percentage is based on the total weight of naphtha feed 60. Specifically, naphtha feed 60 may be light naphtha with a boiling range of about 20°C to about 235°C, wherein the naphtha feed may contain one or more aliphatic, cycloalkanes, and / or alkanes. Some aspects of the integrated conversion system 1000 can be considered for operation without naphtha feed 60.

[0080] Hydrogenation process 70 like Figure 1As further shown, processor feed 65 flows into hydrotreating process 70. In one aspect, hydrotreating process 70 includes at least one hydrotreating reactor. At least a portion of the oligomer product in processor feed 65 may flow into the hydrotreating reactor and contact with a hydrotreating catalyst to produce a hydrotreating effluent (not shown). In the case where the oligomer product contains hexene, the hydrotreating effluent contains hexane. In the case where the oligomer product contains octene, the hydrotreating effluent contains octane. In such aspects, the oligomer product may be contacted with the hydrotreating catalyst in any manner suitable for forming hexane. In one aspect, the hydrotreating catalyst contains one or more of a hydrotreating catalyst comprising nickel (Ni), palladium (Pd), platinum (Pt), iridium (Ir), and / or ruthenium (Ru). In hydrotreating process 70, the hydrotreating effluent undergoes a purification stage to recover the aromatized feed 75 containing hexane (e.g., n-hexane). Further processes in the hydrotreating process 70 (e.g., fractionation) can affect the amount or concentration of sulfur, nitrogen, and / or aromatic compounds entering the hydrotreating process 70, thereby reducing the amount of sulfur, nitrogen, and / or aromatic compounds in the aromatization feed 75. In one aspect, the hydrotreating process 70 includes a sulfur removal system. Undesirably, lower amounts of sulfur, nitrogen, and / or aromatic compounds in the feedstock of the aromatization process 400 can lead to slower degradation and deactivation of the aromatization catalyst in the aromatization process, thus advantageously resulting in less facility turnaround and higher aromatic compound selectivity. In a further aspect, processes in the hydrotreating process 70 can enhance the cetane number, density, and / or smoke point of the components in the aromatization feed 75.

[0081] In one aspect, the amount of sulfur in the aromatization feed 75 may be in the range of about 0.01 ppm to about 5 ppm; or alternatively, in the range of about 0.05 ppm to about 0.5 ppm. In one aspect, the amount of nitrogen in the aromatization feed 75 may be in the range of about 0.01 ppm to about 5 ppm; or alternatively, in the range of about 0.05 ppm to about 0.5 ppm. In one aspect, the amount of aromatic components in the aromatization feed 75 may be in the range of about 0.01 ppm to about 1 ppm; or alternatively, in the range of about 0.02 ppm to about 0.2 ppm. The ppm values ​​are weight-to-weight values ​​based on the total weight of the aromatization feed 75.

[0082] refer to Figure 1Aromatization feed 75 flows into aromatization process 400. Aromatization process 400 includes an aromatization reactor system in which acyclic oligomers are contacted with an aromatization catalyst and undergo an aromatization reaction to produce aromatics. In a further aspect, the aromatization reaction converts 1-hexene to benzene. For example, U.S. Patent No. 7,932,425 discloses a method for converting 1-hexene to benzene, which is incorporated herein by reference in its entirety. Any suitable method for producing benzene disclosed in U.S. Patent No. 7,932,425 may be utilized herein. It is considered that aromatization process 400 may be coupled with acyclic hydrocarbons other than 1-hexene to produce aromatics other than benzene.

[0083] refer to Figure 4 This describes an aspect of the aromatization process 400. In the illustrated aspect, the aromatization reactor system includes a catalytic reactor system in which four aromatization reactors are connected in series (i.e., reactors 410, 420, 430, and 440). However, the catalytic reactor system may include any suitable number and / or configuration of aromatization reactors, including one, two, three, five, six, or more reactors, which may be arranged in series or in parallel. Because the aromatization reaction is highly endothermic, a significant temperature drop can occur across reactors 410, 420, 430, and 440. Therefore, each reactor 410, 420, 430, and 440 connected in series may include a corresponding furnace 411, furnace 421, furnace 431, and furnace 441, respectively, for reheating the components back to the desired temperature to maintain the desired reaction rate. Alternatively, where feasible, one or more reactors 410, 420, 430, and 440 may share a common furnace. Reactors 410, 420, 430 and 440, furnaces 411, 421, 431 and 441, and related piping are all referred to herein as the aromatization zone.

[0084] In one aspect, as further disclosed herein, aromatization feed 75 and optional raffinate recycle 90 are combined to form a mixed feed 402 flowing into purification process 480. Purification process 480 employs known processes (including fractionation) to purify mixed feed 402 to remove impurities such as oxygen (compounds), sulfur, and / or metals. In one aspect, purification process 480 includes a sulfur removal system. In a further aspect, the sulfur removal system includes a staged combustion air (SCA) pre-processor, an SCF / SCG sulfur guard, or both. Purified feed 403 originates from purification process 480. Purified feed 403 may be combined with a dry hydrogen recycle stream 465 to produce a hydrogen-rich purified feed 404. Oxygen (compounds) and / or nitrogen (compounds) stream 405 (i.e., O / N stream) may be combined with hydrogen-rich purified feed 404 to produce aromatization reactor feed 406. In addition to, or instead of, the O / N stream 405, oxygen-containing (compounds) and / or nitrogen-containing (compounds) may be fed to one or more locations in the catalytic reactor system, as described in more detail herein. Some aspects of the aromatization process 400 can be considered for operation without the purification process 480, wherein the mixed feed 402 continues directly into stream 403.

[0085] In some aspects, the aromatization reactor feed 406 is preheated in a first furnace 411, which heats the contents of feed 406 to a desired temperature, thereby producing a first aromatization reactor feed 412. The first aromatization reactor feed 412 flows into a first aromatization reactor 410, where it is contacted with an aromatization catalyst under suitable reaction conditions (e.g., suitable temperature and pressure) to aromatize one or more components in the feed, thereby increasing its aromatic content. A first aromatization reactor effluent 415, comprising aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the first aromatization reactor 410.

[0086] The first aromatization reactor effluent 415 is then preheated in a second furnace 421, which heats the contents of effluent 415 to a desired temperature, thereby producing a second aromatization reactor feed 422. The second aromatization reactor feed 422 flows into a second aromatization reactor 420, where it is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase their aromatic content. A second aromatization reactor effluent 425, comprising aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the second aromatization reactor 420.

[0087] The effluent 425 from the second aromatization reactor is then preheated in a third furnace 431, which heats the contents of effluent 425 to a desired temperature, thereby producing a third aromatization reactor feed 432. The third aromatization reactor feed 432 flows into a third aromatization reactor 430, where it is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. The third aromatization reactor effluent 435, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the third aromatization reactor 430.

[0088] The effluent 435 from the third aromatization reactor is then preheated in a fourth furnace 441, which heats the contents of effluent 435 to a desired temperature, thereby producing a fourth aromatization reactor feed 442. The fourth aromatization reactor feed 442 is then fed to a fourth aromatization reactor 440, where it is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. The fourth aromatization reactor effluent 445, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the fourth aromatization reactor 440.

[0089] The effluent 445 from the fourth aromatization reactor flows into a hydrogen separation process 450, where the recovered hydrogen stream 455 is separated from the reformate effluent 45. The reformate effluent 45 comprises aromatization reaction products from reactors 410, 420, 430, and 440, as well as optionally aromatization reaction byproducts and / or by-products, unreacted feed, other hydrocarbons, or combinations thereof. In one aspect, the aromatization reaction byproducts include toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, hexamethylbenzene, or combinations thereof. The recovered hydrogen stream 455 is dried in a dryer 460 to form a dry hydrogen recirculation stream 465, which can be recycled to the purified feed 403 as disclosed herein. Hydrogen separation processes are known in the art and described, for example, in U.S. Patent Nos. 5,401,386; 5,877,367; and 6,004,452, each of which is incorporated herein by reference in its entirety. For simplicity, Figure 4 Byproduct streams removed from the catalytic reactor system at various sites throughout the system are not illustrated. However, those skilled in the art are aware of the composition and location of such byproduct streams. Furthermore, although... Figure 4The diagram shows the addition of O / N stream 405 to the hydrogen-rich purification feed 404, but those skilled in the art will understand that oxygen-containing (compounds) and / or nitrogen-containing (compounds) can be added to any of streams 402, 403, 404, 406, 412, 415, 422, 425, 432, 435, 442, 445, 455, and 465, or combinations thereof. Some aspects of the aromatization process can be operated without hydrogen separation process 450 and dryer 460, where there is no recovered hydrogen stream 455 and dried hydrogen recirculation stream 465. In such aspects, the fourth aromatization reactor effluent 445 flows directly into and constitutes the composition of reformate effluent 45.

[0090] In various aspects, the catalytic reactor systems described herein may include fixed catalyst bed systems, moving catalyst bed systems, fluidized catalyst bed systems, or combinations thereof. Such reactor systems may be batch or continuous systems. In one aspect, the catalytic reactor system is a fixed-bed system comprising one or more fixed-bed reactors. In a fixed-bed system, the aromatization reactor feed may be preheated in a furnace tube and enter at least one reactor containing a fixed catalyst bed. The aromatization reactor feed flow may pass upward, downward, or radially through the reactor. In various aspects, the catalytic reactor systems described herein may operate as adiabatic or isothermal catalytic reactor systems. As used herein, the terms “catalytic reactor” and “reactor” are used interchangeably to refer to reactor vessels, reactor interiors, and associated process units, including but not limited to catalysts, inert packing, pits, flow distributors, central tubes, reactor ports, catalyst transfer and distribution systems, furnaces and other heating devices, heat transfer devices, and piping.

[0091] In one aspect, a catalytic reactor system is an aromatization reactor system comprising at least one aromatization reactor and its corresponding process unit. As used herein, the terms "aromatization" and "reforming" refer to the treatment of a feed to provide an aromatic-rich product, wherein the aromatic content of the product is higher than that of the feed. Typically, one or more components of the feed undergo one or more reforming reactions to produce aromatics. Some reforming reactions occurring within an aromatization reactor system include dehydrogenation cyclization reactions of acyclic hydrocarbons to aromatics (e.g., 1-hexene to benzene), dehydrogenation reactions of cyclohexane to aromatics, dehydrogenation isomerization reactions of alkylcyclopentanes to aromatics, or combinations thereof. Depending on the composition of the feed, additional reactions may also occur, including dealkylation reactions of alkylbenzenes, isomerization reactions of alkanes, hydrocracking reactions to produce light gaseous hydrocarbons (e.g., methane, ethane, ethylene, propane, propylene, and butane), or combinations thereof. A specific aspect of the integrated reforming system described herein utilizes the dehydrogenation cyclization reaction of 1-hexene, n-hexane, or a combination thereof to produce benzene. In a further aspect, the integrated reforming system utilizes the dehydrogenation reaction of cyclohexane to produce benzene.

[0092] In one respect, the aromatization reaction occurs under process conditions that are thermodynamically favorable for dehydrogenation cyclization and limit undesirable hydrocracking reactions. The pressure within the reactor can range from about 0 psig to about 500 psig (about 0 MPag to about 3.45 MPag), such as from about 25 psig to about 300 psig (about 0.17 MPag to about 2.07 MPag). Operating temperatures include reactor inlet temperatures in the range of about 370°C to about 565°C, including from about 480°C to about 540°C. The molar ratio of hydrogen to hydrocarbons (e.g., 1-hexene) in the aromatization reactor feed can range from about 0.1:1 to about 20:1, such as from about 1:1 to about 6:1.

[0093] In some aspects, the aromatization reaction of this disclosure is characterized in that, based on the total weight of the C6 feed stream (including 1-hexene) fed to the aromatization reactor, part or all of the C6 stream (including, but not limited to, 1-hexene) is converted to benzene. In one aspect, the conversion of C6 substances (such as 1-hexene) to benzene is greater than about 40% by weight; alternatively, greater than about 50% by weight; alternatively, greater than about 60% by weight; or alternatively, greater than about 70% by weight.

[0094] The aromatization reaction of this disclosure is characterized by a selectivity of the C6 feed stream material (e.g., 1-hexene) to benzene based on the total amount of 1-hexene converted in the aromatization reactor by weight. In one aspect, the selectivity of 1-hexene to benzene is greater than about 50% by weight; alternatively, greater than about 60% by weight; alternatively, greater than about 70% by weight; or alternatively, greater than about 75% by weight.

[0095] Various types of aromatization catalysts can be used with the catalytic reactor systems disclosed herein. In one aspect, the aromatization catalyst is a non-acidic catalyst comprising an inorganic support, a Group VIII metal, and one or more halides. Suitable halides include chlorides, fluorides, bromides, iodides, or combinations thereof. Suitable Group VIII metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, and combinations thereof. An example of a catalyst suitable for the catalytic reactor systems described herein is AROMAX. ® Branded catalysts (Chevron Phillips Chemical Company LLC, The Woodlands, TX, USA), including the catalysts discussed in U.S. Patent Nos. 6,812,180; 7,153,801; and 7,932,425, each of which is incorporated herein by reference in its entirety.

[0096] The inorganic support used in the aromatization catalyst of this disclosure may generally include any inorganic oxide. These inorganic oxides include bonded macroporous aluminosilicates (zeolite supports), amorphous inorganic oxides, and mixtures thereof. Macroporous aluminosilicates include, but are not limited to, L-type zeolites, Y-type zeolites, mordenite, ω-zeolites, β-zeolites, etc. Amorphous inorganic oxides include, but are not limited to, alumina, silica, and titanium dioxide. Suitable binders for the inorganic oxides include, but are not limited to, silica, alumina, clay, titanium dioxide, and magnesium oxide.

[0097] In one aspect, the support is a bound potassium (K) L-type zeolite or KL zeolite. As used herein, the term "KL zeolite" refers to an L-type zeolite in which the dominant cation "M" incorporated into the zeolite is potassium. KL zeolite can be cation exchanged or impregnated with another metal and one or more halides to produce, for example, platinum (Pt) impregnated halide-containing zeolites or KL-supported Pt halide zeolite catalysts.

[0098] In one aspect, Group VIII metals can be platinum. Platinum and optionally one or more halides can be added to the zeolite support by any suitable method, for example, by impregnation with a solution of a platinum-containing compound and one or more halide-containing compounds. For example, the platinum-containing compound can be any decomposable platinum-containing compound. Examples of such compounds include, but are not limited to, ammonium tetrachloroplatinate, chloroplatinic acid, diammonium platinum nitrite (II), bis(ethylenediamine)platinum chloride (II), platinum acetylacetonate (II), diammonium dichloroplatinum, platinum chloride (II), tetraammonium platinum hydroxide (II), tetraammonium platinum chloride, and tetraammonium platinum nitrate (II).

[0099] In a further aspect, the catalyst may be a macroporous zeolite support having a platinum-containing compound and at least one organoammonium halide compound. The organoammonium halide compound may include one or more compounds represented by the formula N(R)4X, where X is a halogen group, R represents hydrogen or a substituted or unsubstituted carbon chain molecule having 1-20 carbons, and each R may be the same or different. In one aspect, R is selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof, more specifically methyl. Examples of suitable organoammonium compounds are represented by the formula N(R)4X and may include ammonium chloride, ammonium fluoride, and tetraalkylammonium halides, such as tetramethylammonium chloride, tetramethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium fluoride, methyltriethylammonium chloride, methyltriethylammonium fluoride, and combinations thereof.

[0100] In certain aspects of this disclosure, oxygen-containing (compounds), nitrogen-containing (compounds), or both, can be added to one or more process streams and / or components in a catalytic reactor system. While not bound by theory, oxygen-containing (compounds) and / or nitrogen-containing (compounds) (e.g., water) may be beneficial for activating, preserving, and / or increasing the productivity of certain types of aromatization catalysts, as described, for example, in U.S. Patent No. 7,932,425. In one aspect, the aromatization feed 75 and optional raffinate recycle 90 are substantially free of sulfur, metals, and other known aromatization catalyst poisons, and are initially substantially free of oxygen-containing (compounds) and nitrogen-containing (compounds). If present, such poisons can be removed using methods known to those skilled in the art. In some aspects, the aromatization feed 75 and optional raffinate recycle 90 can be purified by first utilizing conventional hydrorefining techniques and then using an adsorbent to remove residual poisons. Such hydrorefining techniques and adsorbents are included in the purification processes related to oxygen-containing (combinations) and / or nitrogen-containing (combinations) described below.

[0101] As used herein, the term "oxygen-containing (compound)" refers to water or any chemical compound that forms water under catalytic aromatization conditions, such as oxygen, oxygen-containing compounds, hydrogen peroxide, alcohols, ketones, esters, ethers, carbon dioxide, aldehydes, carboxylic acids, lactones, ozone, and carbon monoxide, including combinations thereof. In one aspect, water and / or steam are used as the oxygen-containing (compound). In another aspect, oxygen can be used as the oxygen-containing (compound), wherein such oxygen is used under general aromatization conditions in one or more aromatization reactors, or under normal hydrorefining conditions in one or more hydrorefining catalyst or adsorbent beds. In situ It is converted to water. Furthermore, the oxygen-containing (compound) can be any alcohol-containing compound. Specific examples of suitable alcohol-containing compounds are methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, amyl alcohol, hexanol, cyclohexanol, phenol, or combinations thereof.

[0102] As used herein, the term "nitrogen-containing (compound)" refers to ammonia or any chemical compound that forms ammonia under catalytic aromatization conditions, such as nitrogen (gaseous), nitrogen-containing compounds, alkylamines, aromatic amines, pyridines, pyridazines, pyrimidines, pyrazines, triazines, heterocyclic N-oxides, pyrroles, pyrazoles, imidazoles, triazoles, nitriles, amides, ureas, imides, nitro compounds, and nitroso compounds, including combinations thereof. While not wishing to be theoretically limited, it is believed that ammonia enhances catalyst activity in much the same manner as water. Furthermore, all methods for adding and controlling oxygen-containing (compounds) described herein can also be applied, alternatively or entirely, to methods for adding and controlling nitrogen-containing (compounds).

[0103] Those skilled in the art will understand that any oxygen-containing (compound), nitrogen-containing (compound), or mixture thereof described herein can be used alone, in combination, or further combined to produce other suitable oxygen-containing (compound) or nitrogen-containing (compound). In some aspects, the oxygen-containing (compound) and nitrogen-containing (compound) may be contained in a single bifunctional compound. The oxygen-containing (compound) and / or nitrogen-containing (compound) may be added to any suitable physical phase, such as a gas, liquid, or combination thereof. The oxygen-containing (compound) and / or nitrogen-containing (compound) may be added to one or more process streams and / or components via any suitable means of addition, such as pumps, syringes, distributors, bubblers, etc. The oxygen-containing (compound) and / or nitrogen-containing (compound) may be introduced as a blend with a carrier. In some aspects, the carrier is selected from hydrogen (gas), hydrocarbons, nitrogen (gas), rare gases, or mixtures thereof. In one aspect, the carrier is hydrogen (gas). In a further aspect, oxygen-containing (compounds) and / or nitrogen-containing (compounds) can be added at various locations within the aromatization process, at any time during the lifetime of the aromatization catalyst, and in any suitable manner. In yet another aspect, the addition of oxygen-containing (compounds) and / or nitrogen-containing (compounds) is used to activate the aromatization catalyst, increase the lifetime of the aromatization catalyst, increase the selectivity and / or productivity of the aromatization catalyst, and combinations thereof.

[0104] In one aspect, prior to the addition of oxygen-containing compounds and / or nitrogen-containing compounds, the existing oxygen-containing compound and / or nitrogen-containing compound content of the stream to be added is measured and / or adjusted. For example, refer to Figure 4 Before adding oxygen-containing and / or nitrogen-containing compounds, the oxygen-containing and / or nitrogen-containing compound content of one or more feed streams (such as aromatization feed 75, raffinate recycle 90, mixed feed stream 402, or dry hydrogen recycle stream 465) can be measured and adjusted. Similarly, before adding nitrogen-containing compounds, the nitrogen-containing compound content of the aforementioned streams can be measured and / or adjusted. Generally, raw or untreated feed streams (such as aromatization feed 75) may contain a certain amount of oxygen-containing or nitrogen-containing compounds when flowing into the catalytic reaction system described herein. Furthermore, depending on one or more of the facility configuration, feed storage time, and / or weather / storage conditions, the feed may absorb oxygen-containing or nitrogen-containing compounds from the air. In order to accurately control the amount of oxygen-containing (compounds) or nitrogen-containing (compounds) flowing into one or more aromatization reactors (e.g., reactors 410, 420, 430, 440), the amount of oxygen-containing (compounds) and / or nitrogen-containing (compounds) in one or more feed streams of the reactor can be measured, adjusted, or both can be performed.

[0105] In one aspect, the oxygen and / or nitrogen content of a given stream (such as a feed stream) can be measured, for example using a real-time online analyzer (not shown). In response to such a measurement, the oxygen and / or nitrogen content of the stream can be adjusted by processing and / or adding oxygen and / or nitrogen to the stream to obtain a desired amount of oxygen and / or nitrogen. In another aspect, a control loop connects the analyzer to a processor and an oxygen and / or nitrogen injector, such that the amount of oxygen and / or nitrogen in one or more streams can be controlled in response to an oxygen and / or nitrogen setpoint in such streams. In some aspects, the measurement and / or adjustment of the content of oxygen-containing compounds and / or nitrogen-containing compounds, as well as related equipment (such as processors and / or chemical injectors), are included as part of purification process 480. The oxygen-containing and / or nitrogen-containing compound processor varies depending on the type and amount of the oxygen-containing and / or nitrogen-containing compounds. In cases where the oxygen-containing compounds contain water, adsorbent material beds can be used. These adsorbent beds are often referred to as dryers. In cases where the oxygen-containing compounds contain oxygen, the use of a processor to convert oxygen into water can be combined with a dryer. In a further aspect where the nitrogen-containing compounds contain alkaline chemicals, one or more adsorbent material beds can be used.

[0106] In one aspect, one or more streams, such as aromatization feed 75, raffinate recycle 90, mixed feed 402, and / or dry hydrogen recycle stream 465, are treated before the addition of oxygen-containing (compounds) and / or nitrogen-containing (compounds). In this aspect, the oxygen-containing (compounds) and / or nitrogen-containing (compounds) content of the streams is measured before such treatment can optionally be omitted. Without equipment for easily measuring the oxygen-containing (compounds) and / or nitrogen-containing (compounds) content in the feed, it may be difficult to reliably maintain the desired levels in the aromatization reactor.

[0107] Pretreatment of one or more streams prior to the addition of oxygenates and / or nitrogenates can help to comprehensively control the amount of water and / or ammonia flowing into one or more streams of the aromatization reactor by removing variations in the oxygenate and / or nitrogenate content in such streams. Pretreatment of such streams provides a consistent, baseline amount of oxygenates and / or nitrogenates in such streams for the addition of oxygenates and / or nitrogenates to form an oxidizing stream, such as aromatization reactor feed 406. When the reactor feed is sufficiently free of oxygenates and / or nitrogenates, precise amounts of oxygenates and / or nitrogenates can be added to the reactor feed so that the amount of oxygenates and / or nitrogenates in the reactor can be reliably maintained. In one aspect, purification process 480 may include a hydrocarbon dryer that dries the feed stream (e.g., aromatization feed 75) to a suitable moisture content. In other aspects, purification process 480 may include a reduced copper bed or a triethylaluminum bed over silica for removing oxygen-containing compounds. In a further aspect, the reduced copper bed or the triethylaluminum bed over silica may be used in combination with a hydrocarbon dryer. Similarly, dryer 460 may be used to dry the recovered hydrogen stream 455 and / or other process streams (e.g., aromatization feed 75) to a suitable moisture content. In one aspect, a suitable oxygen-containing compound level in one or more streams (such as aromatization feed 75, raffinate recycle 90, mixed feed 402, or dried hydrogen recycle stream 465) results in a water concentration of less than about 1 part per million (ppmv) in the untreated recovered hydrogen stream 455, or alternatively less than about 0.5 ppmv, or alternatively less than about 0.1 ppmv. In one aspect, one or more streams fed to the aromatization reactor, aromatization feed 75, raffinate recycle 90, mixed feed 402, or dried hydrogen recycle stream 465, are substantially free of water after drying. In another aspect, precise amounts of oxygen-containing (compounds) and / or nitrogen-containing (compounds) can be added by partially or completely bypassing such processing. Alternatively, this can be achieved by partially or completely passing the recovered hydrogen stream 455 through a wet... ( For example, waste molecular sieve beds can be used to add precise amounts of oxygen-containing (compounds) and / or nitrogen-containing (compounds).

[0108] The reformate effluent 45 may contain C6 aromatics. In one aspect, based on the total weight of the reformate effluent 45, the concentration of C6 aromatics in the reformate effluent 45 may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the concentration of C6 aromatics in the reformate effluent 45 may be in the range of about 60 wt% to about 99.9 wt%; alternatively, about 70 wt% to about 99.8 wt%; alternatively, about 75 wt% to about 99.7 wt%; or alternatively, about 80 wt% to about 99.6 wt%; or alternatively, about 85 wt% to about 99.5 wt%. In a further aspect, the benzene concentration in the reformate effluent 45 may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In one aspect, the benzene concentration in the reformate effluent 45 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0109] Back Figure 1 The reformate effluent 45 flows into the second fractionation process 80, where benzene stream 82, toluene stream 84, xylene stream 86, and raffinate stream 88 are recovered. Benzene stream 82, toluene stream 84, and xylene stream 86 may be sent for storage and / or for sale. In one aspect, xylene stream 86 comprises xylene (one or more types). In a further aspect, xylene stream 86 further comprises ethylbenzene, for example, in embodiments for recovering 1-octene from oligomerization reactor effluent 36 and / or receiving naphtha feed 60 in hydrotreating process 70. In one aspect, raffinate stream 88 comprises C 9+ Aromatic hydrocarbons, non-aromatic C 9+Hydrocarbons or combinations thereof. In a further aspect, stream 88 comprises benzene, toluene, xylene, or combinations thereof. In a further aspect, raffinate stream 88 comprises ethylbenzene, for example, in embodiments for recovering 1-octene from oligomerization reactor effluent 36 and / or receiving naphtha feed 60 in hydrotreating process 70. As disclosed herein, raffinate stream 88 may be fed to hydrocarbon recycling 201 of cracking process 200, or alternatively, may be sent for storage and / or for sale. In one aspect, as disclosed herein, a portion of raffinate stream 88 is optionally fed to raffinate recycling 90. In some aspects, as disclosed herein, raffinate recycling 90 flows into aromatization process 400.

[0110] Those skilled in the art will understand that the second fractionation process 80 can be adapted to operate in any manner that produces its effluent. For example, the second fractionation process 80 may include a series of separation units, such as flash distillation columns, fractionating distillation columns, liquid-liquid extraction units, etc. Some aspects of the second fractionation process 80 may include... Figure 4 The hydrogen separation process 450 is substantially similar to the hydrogen separation process in this respect. In this respect, hydrogen effluent 81 is recovered from the second fractionation process 80. As disclosed herein, hydrogen effluent 81 can be... Figure 3 The hydrogen feed 302 is combined. In a further aspect, the hydrogen effluent 81 may be sent for storage and / or for sale.

[0111] refer to Figure 5 The integrated conversion system 1100 is described, where the same number represents the same information as... Figure 1 The same components. With Figure 1 In contrast, the first portion of octene effluent 54 is used as octene feed 55. The remaining portions of octene effluent 54 and hexene effluent 52 may be sent for storage and / or for sale. In one aspect, octene feed 55 may optionally be combined with naphtha feed 60 to form processor feed 65, which is fed to aromatization process 400. In the aspect where the oligomer product in processor feed 65 contains octene, the hydrotreated effluent (not shown) produced in hydrotreatment process 70 contains octane. In such aspects, the oligomer product may be contacted with a hydrotreating catalyst in any manner suitable for forming octane. In hydrotreatment process 70, the hydrotreated effluent passes through a purification stage to recover the aromatization feed 75 containing octane (e.g., n-octane).

[0112] refer to Figure 6 The integrated conversion system 1200 is described, where the same number represents the same information as... Figure 1The same components are described. A first portion of hexene effluent 52 is used as hexene feed 53, and a first portion of octene effluent 54 is used as octene feed 55. The remaining portions of each of hexene effluent 52 and octene effluent 54 may be sent for storage and / or for sale. In one aspect, hexene feed 53 and octene feed 55 are optionally combined with naphtha feed 60 to form processor feed 65, which is sent to hydrotreating process 70. In hydrotreating process 70, the hydrotreating effluent passes through a purification stage to recover aromatized feed 75 containing hexane (e.g., n-hexane), octane (e.g., n-octane), or combinations thereof.

[0113] refer to Figure 7 The document describes an integrated conversion system 1300, where the same number represents the same information as... Figure 1 The same components are described above. A middle-cut feed 57 exits from the first fractionation process 50 and is optionally combined with a naphtha feed 60 to form a processor feed 65 fed to the hydrotreating process 70. In one aspect, the middle-cut feed 57 comprises C6 to C8 hydrocarbons. In a further aspect, the middle-cut feed 57 comprises C6 and C8 olefins, wherein the C6 and C8 olefins include hexene, octene, or combinations thereof. In a specific aspect, the middle-cut feed 57 comprises 1-hexene and 1-octene.

[0114] refer to Figure 8 The integrated conversion system 1400 is described, where the same number represents the same information as... Figure 7 The same components are described above. A heavy-cut feed 59 exits from the first fractionation process 50 and is optionally combined with a naphtha feed 60 to form a processor feed 65 fed to the hydrotreating process 70. In one aspect, the heavy-cut feed 59 comprises C6 to C6. 12 Hydrocarbons. Further, the heavy fraction feed 59 contains C6 and C2. 12 Olefins, in which C6 and C2 are olefins 12 Olefins include hexene, octene, decene, dodecene, or combinations thereof. In one specific aspect, the heavy fraction feed 59 comprises 1-hexene and 1-octene.

[0115] Integrated conversion systems 1300 and 1400 do not contain hexene effluent 52 and octene effluent 54. Integrated conversion systems 1300 and 1400 integrate all hexene and octene produced in oligomerization process 300 into hydrotreating process 70.

[0116] refer to Figure 9 The document describes an integrated conversion system 1500, where the same number represents the same information as... Figure 1The same components are described. Cyclohexane recycled 62 flows into oligomerization process 300, where cyclohexane is used as a solvent (i.e., a diluent). In one aspect, as disclosed herein, cyclohexane recycled 62 and... Figure 3 The solvent feed 308 is combined. The C6 fraction (C6-cut) feed 58 flows from the first fractionation process 50 and into the C6 separator 151. In one aspect, the C6 fraction feed 58 contains C6 hydrocarbons. In the C6 separator 151, hexene effluent 52 and depleted C6 fraction 61 are recovered from the C6 fraction feed 58. In one aspect, the composition and disposal of hexene effluent 52 are consistent with those described herein. Figure 1 The same as disclosed. Lean C6 fraction 61 flows from C6 separator 151 and into cyclohexane recovery (CHR) column 153, where residual C6 feed 63 and cyclohexane recycle 62 are recovered from lean C6 fraction 61. Residual C6 feed 63 is optionally combined with naphtha feed 60 to form processor feed 65, which is sent to aromatization process 400. In one aspect, residual C6 feed 63 contains C6 hydrocarbons (e.g., hexane). C6 separator 151 and CHR column 153 can be operated in any manner suitable for producing their effluents. In one aspect, C6 separator 151 and CHR column 153 each include at least one fractionator.

[0117] As disclosed herein, all C6 fraction feed 58 enters C6 separator 151. This configuration of the integrated conversion system 1500 advantageously produces hexene effluent 52 at full load. Some aspects of the integrated conversion system 1500 are configured to operate in the absence of C6 separator 151, wherein no hexene effluent 52 is produced. In such aspects, an optional bypass line 51 delivers all C6 fraction feed 58 to CHR column 153, wherein C6 fraction feed 58 enters CHR column 153 via line 61. This configuration of the integrated conversion system 1500 can be utilized when, for example, the demand for C6 olefins (e.g., 1-hexene) is low, and / or when the supply of naphtha feed 60 is low, or alternatively to avoid costs associated with the source of naphtha feed 60. In a further aspect, the flow (rate) of the C6 fraction feed 58 is divided between the C6 separator 151 and the CHR tower 153 by metering the flow rate of the optional bypass line 51.

[0118] In one respect, the flexible configuration of the Integrated Conversion System 1500 advantageously allows operators to respond quickly to factors such as business (market), weather, and / or production.

[0119] refer to Figure 10 The document describes an integrated conversion system 1500, where the same number represents the same information as... Figure 9The same components are described. Cyclohexane feed 64 flows into oligomerization process 300, where cyclohexane is used as a solvent (i.e., a diluent). In one aspect, as disclosed herein, cyclohexane feed 64 and Figure 3 The solvent feed 308 is combined. The C6 fraction feed 58 exits from the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form the processor feed 65, which is fed to the hydrotreating process 70. Regarding the second fractionation process 80, a portion of the benzene stream 82 is conveyed through the benzene feed 83, and a portion of the hydrogen stream effluent 81 is conveyed through the reduction feed 85. The benzene feed 83 and the reduction feed 85 flow into the benzene hydrotreating process 160, where the hydrogenation of benzene produces a cyclohexane effluent 67. In one aspect, the cyclohexane effluent 67 contains cyclohexane and may be sent for storage or sale. As disclosed herein, a portion of the cyclohexane effluent 67 may be fed to the cyclohexane feed 64. Benzene hydrogenation can be carried out by any suitable means determined by those skilled in the art and by means of this disclosure. For example, in a non-limiting aspect, a hydrogenation catalyst may be utilized. The operating conditions in the hydrotreating process 160 can be any suitable combination of conditions as determined by those skilled in the art by means of this disclosure. In one respect, the temperature and pressure in the hydrogenation process 160 can be at levels capable of hydrogenating benzene. The temperature in the hydrogenation process 160 can be in the range of about 10°C to about 205°C. The pressure in the hydrogenation process 160 can be in the range of about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag).

[0120] In one aspect, based on the total weight of the cyclohexane effluent 67, the concentration of cyclohexane in the cyclohexane effluent 67 may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In a further aspect, the concentration of cyclohexane in the cyclohexane effluent 67 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0121] refer to Figure 11 The integrated conversion system 1700 is described, where the same number represents the same information as... Figure 9 and Figure 10The same components are described. A second solvent recycle 68 flows into oligomerization process 300, where cyclohexane is used as a solvent (i.e., a diluent). In one aspect, as disclosed herein, the second solvent recycle 68 is... Figure 3 The solvent feed 308 is combined. The second solvent recycle 68 may be formed by a combination of cyclohexane recycle 62 and cyclohexane feed 64 as described herein.

[0122] refer to Figure 12 The integrated conversion system 1800 is described, where the same number represents the same information as... Figure 1 The same components. With Figure 1 In comparison, hydrocarbon feedstock 10 flows into cracking process 290, and its operation method is similar to... Figure 2 The cracking process 200 is similar, unless otherwise explicitly disclosed. As previously stated, raffinate recycle 90 flows out from the second fractionation process 80, while heavy recycle 180 flows into the cracking process 290. In one aspect, raffinate recycle 90 and heavy recycle 180 are similar to... Figure 2 The hydrocarbon recycle 201 is combined. Heavy recycle 180 can be obtained from the first fractionation process 50. Heavy recycle 180 may contain heavy hydrocarbons, said heavy hydrocarbons containing C 9+ Hydrocarbons, C formed through oligomerization 9+ Oligomers, polymer products formed by oligomerization reactions, or combinations thereof. In one aspect, C 9+ Oligomers include decene, dodecene, tetradecene, and combinations thereof.

[0123] The following streams flow from cracking process 290: cracking process effluent 25 as described above, refrigerant stream 146, crude pyrolysis gasoline (CPG) stream 142, fuel gas stream 144, and vapor stream 148. Refrigerant stream 146 can be obtained from... Figure 2 210, C of the pyrolyzer effluent 3+ Flow 262 and / or alternative C 3+ Stream 282 is recovered. In one aspect, refrigerant stream 146 comprises light hydrocarbons produced by cracking process 290, wherein said light hydrocarbons include methane, ethane, ethylene, propane, propylene, butane, and combinations thereof. Three portions 146a, 146b, and 146c of refrigerant stream 146 may be fed to oligomerization process 300 and / or aromatization process 400, where they are used for cooling and / or refrigeration therein (e.g., in the overhead condenser of the fractionation column of the first fractionation process 50). Vapor effluent 148 constitutes the product from… Figure 2Steam recovered from the cracking process 290 (e.g., cracking zone 205). Three portions 148a, 148b, and 148c of the steam effluent 148 may be fed to the oligomerization process 300, the first fractionation process 50, and / or the second fractionation process 80, any of which may be used as a heat source, for example, as a heat source for one or more fractionation column reboilers. CPG stream 142 and fuel gas stream 144 flow into the second fractionation process 80. A portion of the hydrogen effluent 81 is fed into the hydrogen efflux 87. The first portion 87a of the hydrogen efflux 87 flows into the oligomerization process 300, where it... Figure 3 The hydrogen feed 302 is combined. The second part 87b of the hydrogen effluent 87 flows into the hydrotreating process 70.

[0124] In one respect, the utilization of refrigerant stream 146 and / or vapor effluent 148 provides for a portion of the utility requirements of the integrated conversion system 1800 (e.g., heating and cooling) and advantageously reduces the associated operating costs.

[0125] refer to Figure 13 The integrated conversion system 1900 is described, where the same number represents the same information as... Figure 11 and 12 The same components are described. System 1900 is characterized by having the flexible configuration of integrated conversion system 1500 and a portion of the integration utility of integrated conversion system 1800.

[0126] This document discloses a method for enriching motor fuel streams (i.e., automotive gasoline (mogas)). In one aspect, the automotive gasoline comprises a fuel gas stream 144 from an integrated conversion system 1800 or 1900. In a further aspect, the automotive gasoline is enriched motor fuel. In a specific aspect, the automotive gasoline is enriched by blending one or more effluent streams generated by the integrated conversion system of this disclosure. For example, heavy effluent 56, raffinate stream 88, or combinations thereof may be blended into the automotive gasoline.

[0127] This document describes a limited set of operating conditions (e.g., temperature, pressure) for the processes and systems used in this disclosure. Those skilled in the art will understand that any operating conditions not currently disclosed may have any numerical value, or alternatively, a range of values, suitable for the operation of the processes and systems disclosed herein. In a further aspect, those skilled in the art can, with the aid of this disclosure, implement changes to the operating conditions within any of the processes and systems disclosed herein to maintain the operation of the disclosed processes and systems.

[0128] In one respect, the integrated conversion system of this disclosure offers advantages in one or more areas compared to conventional benzene production methods that utilize non-integrated (i.e., stand-alone) conversion processes. Conventional benzene production methods utilize substances contained in crude oil (e.g., materials obtained via naphtha cracking), thus linking the cost of benzene production to crude oil. This disclosure utilizes ethane contained in natural gas as a starting material (e.g., ethane produced via ethane steam cracking), advantageously decoupling the cost of benzene production from crude oil. With increasing natural gas reserves and declining natural gas prices, other factors contribute to the increasing demand for benzene. For example, in North America, ample ethane reserves for steam cracking make naphtha cracking uneconomical. There is also a perceived possibility of a significant oversupply of ethylene in the future. A further advantage is that the integrated conversion system disclosed herein can be used to convert ethylene to benzene in a manner optimally consistent with relevant financial and / or market conditions, particularly taking into account the significant global price increases associated with benzene (see, for example, https: / / www.statista.com / statistics / 1171072 / price-benzene-forecast-globally / ).

[0129] A further advantage of the integrated conversion system disclosed herein is its ability to produce large quantities of ethylene, 1-hexene, 1-octene, and benzene, and subsequently sell portions of each compound according to relevant global demand. The integrated conversion system of this disclosure features the ability to flexibly modify the production rate of the product streams to accommodate changes in demand and / or price for 1-hexene, 1-octene, and / or benzene. In some respects, up to 1.5 million tons of ethylene can be produced annually. Other products for sale that can be generated using the integrated conversion system of this disclosure include hydrogen (i.e., hydrogen effluent 81), cyclohexane (i.e., cyclohexane effluent 67), and toluene (i.e., toluene effluent 84).

[0130] A further advantage of the integrated conversion system disclosed herein is that 1-hexene can potentially be used as feedstock for the aromatization process. Hydrogenating 1-hexene to n-hexane, as disclosed herein, offers further production advantages, including slower catalyst deactivation, less facility turnaround time, and higher selectivity for aromatic compounds. Because the cracking feedstock is derived from natural gas, plastic or polymer waste, biomass, other natural sources, etc., instead of crude oil, the 1-hexene / n-hexane fed to the aromatization process has a low sulfur content, potentially allowing for removal, recycling, conversion, etc., by conventional staged combustion air pre-processors, as well as subsequent reductions in capital costs.

[0131] A further advantage of the integrated conversion system disclosed herein is the use of light hydrocarbons produced by the cracking process 200 as a cooling and / or refrigeration source in the oligomerization process 300. This approach allows for the elimination of a dedicated refrigeration unit in the oligomerization reaction process 300 and provides subsequent reductions in capital costs. A further advantage is that the cracking process 200 can produce hydrogen and methane (not shown), which can be used as fuel for heating and / or operating other processes within the integrated conversion system. This allows for beneficial design improvements to the facility or system, such as reducing the size of heat exchangers.

[0132] Example Having provided a general description of the subject matter, the following embodiments are given as specific aspects of this disclosure and demonstrate their practice and advantages. It should be understood that the embodiments are given by way of example and are not intended to limit the scope of the appended claims in any way. It should be clearly understood that various other aspects, modifications, and equivalents may be employed, as will occur to those skilled in the art upon reading this description, without departing from the spirit of this disclosure or the scope of the appended claims.

[0133] Figure 14 and 15 Demonstrates the use of Aromax ® The catalyst was used to produce benzene from 1-hexene. Operating conditions were a constant temperature of 950℉ (510℃) and a liquid hourly space velocity of 12 h⁻¹. -1 The pressure was 100 psig (0.68 MPag), and the molar ratio of hydrogen to hydrocarbon was 1.2:1. Figure 14 It is shown that, under specified conditions, the conversion rate of 1-hexene to benzene approaches 100% at approximately 5 hours. Figure 15 It is shown that, under specified conditions, the selectivity for the conversion of 1-hexene to benzene remains at approximately 85% for about 5 hours. After about 1 hour, the selectivity for benzene under the above conditions is approximately 80%.

[0134] The scope of protection of this disclosure is not limited by the foregoing description, but only by the appended claims, which include all equivalent forms of the subject matter of the claims. Each claim is incorporated herein by reference as an embodiment of this disclosure. Therefore, the claims are further descriptions and supplements to the specific description of this disclosure. All disclosures of patents, patent applications, and publications cited herein are hereby incorporated by reference.

[0135] Aspects of the processor regeneration method have been described. The following is a first set of non-limiting specific embodiments according to this disclosure: Although several aspects and embodiments of this disclosure have been shown and described, modifications can be made thereto by those skilled in the art without departing from the spirit and teachings of this disclosure. The aspects, embodiments, and examples described herein are exemplary only and are not intended to be limiting. Many variations and modifications of this disclosure are possible and within the scope of the subject matter.

[0136] Regarding transitional terms or phrases in claims, the transitional term "comprising," synonymous with "including," "containing," "having," or "characterized as," is inclusive or open-ended and does not exclude additional, unrecorded elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not defined in the claim. The transitional phrase "substantially consisting of" limits the scope of the claim to the specified materials or steps and those that do not substantially affect the essential and novel features of the claim. Claims of the "substantially consisting of" form occupy an intermediate zone between closed claims drafted in the "consisting of" format and fully open claims drafted in the "comprising" format. In the absence of an indication to the contrary, describing a compound or composition as "substantially consisting of" should not be interpreted as "comprising," but rather is intended to describe that the recited components include materials that do not significantly alter the composition or method to which the term is applied. For example, a raw material substantially composed of a certain material may include impurities typically present in commercially produced or commercially available samples of the recited compound or composition. When a claim includes different features and / or feature categories (e.g., method steps, raw material features, and / or product features, and other possibilities), transitional terms such as include, substantially consist of, and consist of apply only to the feature category in which they are used, and different transitional terms or phrases may be used for different features in the claim. For example, a method may include several described steps (and other undescribed steps) but utilize a catalyst system consisting of a specific component; alternatively, substantially consist of a specific component; or alternatively, include a catalyst system comprising a specific component and other undescribed components.

[0137] In this disclosure, while systems, processes, and methods are generally described as “comprising” various components, instruments, or steps, unless otherwise stated, systems, processes, and methods may also “consist substantially of” or “comprise” various components, instruments, or steps.

[0138] As used herein, the term "about" means that a quantity, size, formulation, parameter, or other quantity and characteristic is not and does not need to be exact, but may be approximate and / or larger or smaller as required, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, whether explicitly stated or not, quantities, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate." The term "about" also covers quantities that differ due to variations in equilibrium conditions of the composition resulting from specific initial mixtures. Whether modified by the term "about," the claims include equivalent forms of the stated quantities. The term "about" may mean within 10% of a reported value, alternatively within 5% of a reported value.

[0139] Unless otherwise stated, when disclosing or requesting any type of range (e.g., ranges of carbon atom number, molar ratio, temperature, etc.), it is intended to disclose or request each individual possible value that the range may reasonably cover, including any subranges covered therein. For example, when describing a range of carbon atom number, every possible individual integer included in the range, as well as the range of atoms between those integers, is included. Thus, by disclosing C1 to C 10 Alkyl groups or alkyl groups having 1 to 10 carbon atoms or "at most" 10 carbon atoms, the applicant intends to state that said alkyl groups can have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and that these methods of describing such groups are interchangeable. When describing a range of measurement results (such as molar ratios), each possible value that such a range can reasonably cover can, for example, refer to a value within the range that has one more significant digit than those present at the endpoints of the range. In this example, molar ratios between 1.03:1 and 1.12:1 include individual molar ratios of 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, 1.10:1, 1.11:1, and 1.12:1. The applicant intends that these two methods of describing ranges are interchangeable. Furthermore, when disclosing or claiming protection for a range of values, the applicant aims to reflect each individual possible value that such a range can reasonably cover, and the applicant also aims to disclose a range that reflects and is interchangeable with any and all subranges and combinations of subranges covered therein. In this respect, the applicant discloses C1 to C... 10Alkyl is intended to literally encompass C1 to C6 alkyl, C4 to C8 alkyl, C2 to C7 alkyl, combinations of C1 to C3 and C5 to C7 alkyl, and so on. When the endpoints of the described range have different numbers of significant figures (e.g., molar ratios of 1:1 to 1.2:1), each possible value that such a range can reasonably cover can, for example, refer to a value within the range that has one more significant figure than the endpoint with the most significant figures in the range (1.2:1 in this example). In this example, molar ratios from 1:1 to 1.2:1 include individual molar ratios of 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, and 1.20—all relative to 1—and any and all subranges and combinations thereof covered therein. Therefore, the applicant reserves the right to exclude or exclude any individual member of any such group (including any subranges or combinations thereof within said group) if the applicant chooses, for any reason, to claim protection of a measure smaller than the full scope of this disclosure (e.g., considering references unknown to the applicant at the time of filing).

[0140] Unless otherwise specified, the terms “contact,” “combination,” and “in the presence of” refer to any order, sequence, or concentration of addition that brings two or more components into contact or combination in any process disclosed herein. Component combination or contact according to the various methods described herein can be carried out in one or more contact zones under suitable contact conditions (such as temperature, pressure, contact time, etc.). Contact zones may be located in a vessel (e.g., a storage tank, carrying case, container, mixing vessel, reactor, etc.), a section of piping (e.g., a tee, inlet, injection port, or head—used to combine component feed lines into a common line), or any other equipment suitable for bringing the components into contact.

[0141] For the purpose of filing any U.S. national phase application of this application, all publications and patents mentioned in this disclosure are incorporated herein by reference in their entirety for the purpose of describing and disclosing constructions and methods described in those publications that can be used in conjunction with the methods of this disclosure. Any publications and patents discussed herein are provided only for their disclosure prior to the filing date of this application. Nothing herein shall be construed as an admission that the inventor has no prior rights to those disclosures due to their earlier disclosures.

[0142] In any application filed with the United States Patent and Trademark Office, an abstract of this application is provided to satisfy the requirements of 37 CFR § 1.72 and the purpose set forth in 37 CFR § 1.72(b), namely, “to enable the United States Patent and Trademark Office and the public to quickly determine the nature and essence of the technical disclosure by a cursory examination.” Therefore, the abstract of this application is not intended to construe the scope of the claims or limit the scope of the subject matter disclosed herein. Furthermore, any headings that may be used herein are not intended to construe the scope of the claims or limit the scope of the subject matter disclosed herein. Any use of past tenses to describe instances (otherwise indicated as constructive or prophetic) is not intended to reflect instances that have actually been implemented as constructive or prophetic.

[0143] At least one embodiment is disclosed, and variations, combinations, and / or modifications made by those skilled in the art to the embodiment and / or its features are within the scope of this disclosure. Alternative embodiments resulting from combining, integrating, and / or omitting features of the embodiment are also within the scope of this disclosure. When numerical ranges or limitations are explicitly stated, it should be understood that such explicit ranges or limitations include iterative ranges or limitations of similar magnitudes falling within the explicitly stated ranges or limitations (e.g., "about 1 to about 10" includes 2, 3, 4, etc.; "greater than 0.10" includes 0.11, 0.12, 0.13, etc.). For example, whenever a lower limit R is disclosed... l and upper limit R u When specifying the numerical range, any value falling within that range is explicitly disclosed. Specifically, values ​​within the following range are explicitly disclosed: R = R l + k • (R u - R l ), where k is a variable in increments of 1% ranging from 1% to 100%, i.e., k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99%, or 100%. Furthermore, any numerical range defined by the two R values ​​as defined above is explicitly disclosed. The use of the term "optionally" with respect to any element of the claim means that the element is required, or alternatively, that the element is not required, both of which are within the scope of the claim.

[0144] Additional public content The following embodiments listed in this disclosure are provided as non-limiting examples.

[0145] Implementation Scheme 1 is a method comprising: in an oligomerization process, contacting ethylene with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising a C6 hydrocarbon including 1-hexene and a C8 hydrocarbon including 1-octene; recovering 1-hexene and 1-octene from the oligomerization reactor effluent; in a hydrotreating process, contacting the 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrotreating catalyst to produce an aromatized feed comprising hexane, octane, or both; and in an aromatization process, contacting the aromatized feed with an aromatization catalyst to produce a reforming effluent comprising benzene.

[0146] Embodiment 2 is the method as described in Embodiment 1, wherein the C6 hydrocarbon is present in an amount of about 20% to about 99% by weight based on the total weight of the oligomerization reactor effluent, and the C8 hydrocarbon is present in an amount of about 0.1% to about 75% by weight based on the total weight of the oligomerization reactor effluent.

[0147] Implementation scheme 3 is the method as described in implementation scheme 1 or 2, wherein the purity of 1-hexene is from about 60% by weight to about 99.9% by weight based on the total weight of the C6 hydrocarbons in the effluent of the oligomerizing reactor.

[0148] Implementation scheme 4 is the method as described in any one of implementation schemes 1 to 3, wherein the purity of 1-octene is about 95% by weight to about 99.3% by weight based on the total weight of the C8 hydrocarbons in the effluent of the oligomerizing reactor.

[0149] Embodiment 5 is the method as described in any one of Embodiments 1 to 4, wherein the oligomerizing reactor effluent further comprises C 10 Hydrocarbons, C 12 Hydrocarbons, C 14+ Hydrocarbons or combinations thereof.

[0150] Implementation scheme 6 is the method as described in implementation scheme 5, wherein C 10 Hydrocarbons are present in an amount of about 1% to about 4% by weight based on the total weight of the oligomerizing reactor effluent, wherein C 12 Hydrocarbons are present in an amount of about 0.1% to about 3% by weight based on the total weight of the oligomerization reactor effluent, and the C 14+ Hydrocarbons are present in amounts from about 0% to about 3.5% by weight based on the total weight of the oligomerizing reactor effluent.

[0151] Embodiment 7 is the method as described in any one of Embodiments 1 to 6, wherein the selective higher olefin catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PNGuan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh, or combinations thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

[0152] Embodiment 8 is the method as described in any one of Embodiments 1 to 7, wherein the step of contacting ethylene with the selective higher olefin catalyst is carried out in the presence of a diluent selected from isobutane, cyclohexane, methylcyclohexane, isobutene, 1-hexene, or combinations thereof.

[0153] Implementation scheme 9 is a method as described in any one of implementation schemes 1 to 8, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerization reactor comprises: fractionating the effluent of the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein of the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the hydrotreating process.

[0154] Implementation scheme 10 is a method as described in any one of embodiments 1 to 8, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerization reactor comprises: fractionating the effluent of the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein in the first stream, the second stream, and the third stream, only a portion of the second stream and only a portion of the third stream are fed to the hydrotreating process.

[0155] Implementation scheme 11 is a method as described in any one of embodiments 1 to 8, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerization reactor comprises: fractionating the effluent of the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst and a second stream containing hexene and octene, wherein in the first stream and the second stream, only a portion of the second stream is fed to the hydrotreating process.

[0156] Implementation scheme 12 is a method as described in any one of embodiments 1 to 8, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerization reactor comprises: fractionating the effluent of the oligomerization reactor into a first stream containing spent catalyst and a second stream containing hexene, octene and heavy hydrocarbons, wherein in the first stream and the second stream, only a portion of the second stream is fed to the hydrotreating process.

[0157] Implementation scheme 13 is a method as described in any one of embodiments 1 to 8, wherein the recovery of 1-hexene and 1-octene from the effluent of the oligomerization reactor comprises: separating the effluent of the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene; fractionating the third stream to obtain a high-purity 1-hexene stream and a C6 feed stream; and feeding the C6 feed stream into the hydrotreating process.

[0158] Implementation scheme 14 is a method as described in any one of implementation schemes 1 to 13, further comprising: fractionating a refinery stream to recover a naphtha stream; feeding the naphtha stream to the hydrotreating process; and in the hydrotreating process, contacting the naphtha with the hydrotreating catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0159] Implementation scheme 15 is the method as described in any one of implementation schemes 1 to 14, wherein the reformate further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene or a combination thereof, and the method further comprises: fractionating the reformate into a benzene stream, a toluene stream, a xylene stream and a raffinate stream.

[0160] Implementation scheme 16 is the method as described in implementation scheme 15, wherein the 1-hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

[0161] Implementation scheme 17 is the method as described in implementation scheme 15, wherein the 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

[0162] Embodiment 18 is a method as described in any one of Embodiments 1 to 17, wherein the aromatization process is further configured to generate a hydrogen effluent, and the method further comprises: flowing a portion of the benzene stream and a portion of the hydrogen effluent into a hydrogenation process to generate cyclohexane; and recycling the cyclohexane to the oligomerization process.

[0163] Embodiment 19 is a method as described in any one of Embodiments 1 to 18, wherein the oligomerization reactor effluent further comprises cyclohexane and other hexanes, the method further comprising: recovering cyclohexane and the other hexanes from the oligomerization reactor effluent; feeding the recovered other hexanes from the oligomerization reactor effluent into the hydrotreating process; and recycling the recovered cyclohexanes from the oligomerization reactor effluent back into the oligomerization process.

[0164] Implementation scheme 20 is a method as described in any one of embodiments 1 to 19, further comprising: cracking ethane, propane, butane, pentane, naphtha or mixtures thereof in a steam cracker to produce a cracker effluent containing ethylene; and allowing ethylene recovered from the cracker effluent to flow into the oligomerization process.

[0165] Implementation scheme 21 is the method as described in implementation scheme 20, wherein the pyrolysis effluent further comprises light hydrocarbons, and the method further comprises: using the light hydrocarbons recovered from the pyrolysis effluent as a cooling source for an oligomerization reactor in the oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or a combination thereof.

[0166] Implementation scheme 22 is the method as described in any one of implementation schemes 1 to 21, further comprising: recovering steam from the steam pyrolyzer; and using steam as a heating source for the oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or a combination thereof.

[0167] Embodiment 23 is the method as described in any one of Embodiments 1 to 22, wherein the step of contacting ethylene with the selective higher olefin catalyst is carried out in the presence of a diluent recovered from the reforming effluent, wherein the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof.

[0168] Implementation scheme 24 is a method as described in any one of implementation schemes 1 to 23, further comprising: flowing the raffinate recovered from the aromatization process into a steam pyrolyzer; and pyrolyzing the raffinate in the steam pyrolyzer.

[0169] Embodiment 25 is the method as described in any one of Embodiments 1 to 24, wherein the oligomerizing reactor effluent further comprises C 9+ Hydrocarbons, the method further comprising: dissolving the C 9+ Hydrocarbons, raffinate stream obtained from the reformate effluent, or the C 9+ The hydrocarbon and the raffinate stream are both mixed into the motor fuel stream.

[0170] Implementation scheme 26 is a method as described in any one of implementation schemes 1 to 25, further comprising: allowing hydrogen obtained from the reforming effluent to flow into the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process.

[0171] Embodiment 27 is the method as described in any one of Embodiments 1 to 26, wherein the ethylene contacted in the oligomerization process is received in a stream comprising ethylene and ethane.

[0172] Implementation scheme 28 is the method as described in any one of implementation schemes 1 to 27, wherein no sulfur removal system is used between the oligomerization process and the aromatization process.

[0173] Embodiment 29 is a system comprising: an oligomerization reactor configured to contact ethylene with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising a C6 hydrocarbon including 1-hexene and a C8 hydrocarbon including 1-octene; a first separation unit configured to recover 1-hexene and 1-octene from the oligomerization reactor effluent; a hydrogenation reactor configured to contact 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to produce an aromatization feed comprising hexane, octane, or both; and an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce a reforming effluent comprising benzene, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

[0174] Implementation scheme 30 is the system as described in implementation scheme 29, which further includes: a steam pyrolyzer configured to produce a pyrolyzer effluent containing ethylene, wherein ethylene is recovered from the pyrolyzer effluent for oligomerization in the oligomerization reactor.

[0175] Implementation scheme 31 is a system as described in implementation scheme 30, wherein the pyrolysis effluent further comprises light hydrocarbons, wherein the oligomerization reactor, the first separation unit, the second separation unit configured to receive and separate the reforming effluent, or a combination thereof, are configured to use the light hydrocarbons as a cooling source.

[0176] Implementation scheme 32 is a system as described in implementation scheme 30, wherein the steam pyrolyzer is configured to produce a steam effluent, and wherein the oligomerizing reactor, the first separation unit, the second separation unit configured to receive and separate the reformed effluent, or a combination thereof, is configured to use the steam effluent as a heat source.

[0177] Embodiment 33 is a system as described in any one of embodiments 29 to 32, further comprising: a fractionator configured to fractionate a refinery stream to recover a naphtha stream, wherein in the hydrotreating reactor, the naphtha contacts the hydrotreating catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0178] Implementation scheme 34 is a system as described in any one of implementation schemes 29 to 32, wherein the reformate further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene or a combination thereof, and the system further comprises: a second separation unit configured to fractionate the reformate into a benzene stream, a toluene stream, a xylene stream comprising ethylbenzene and xylene, and a raffinate stream.

[0179] Implementation scheme 35 is the system as described in implementation scheme 34, wherein 1-hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

[0180] Implementation scheme 36 is the system as described in implementation scheme 34, wherein 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

[0181] Embodiment 37 is the system as described in Embodiment 34, wherein the aromatization reactor is further configured to produce a hydrogen effluent, wherein the hydrogenation reactor is configured to receive a portion of the benzene stream and a portion of the hydrogen effluent and produce cyclohexane therefrom, and wherein the oligomerization reactor is configured to receive the cyclohexane.

[0182] Embodiment 38 is a system as described in any one of Embodiments 29 to 37, further comprising: a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein in the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the aromatization reactor.

[0183] Embodiment 39 is a system as described in any one of Embodiments 29 to 38, further comprising: a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein in the first stream, the second stream, and the third stream, only a portion of the second stream is fed to the aromatization reactor.

[0184] Implementation scheme 40 is a system as described in any one of embodiments 29 to 38, further comprising: a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein in the first stream, the second stream, and the third stream, only a portion of the second stream and at least a portion of the third stream are fed to the aromatization reactor.

[0185] Implementation scheme 41 is a system as described in any one of embodiments 29 to 38, further comprising: a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing heavy hydrocarbons and spent catalyst and a second stream containing hexene and octene, wherein in the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

[0186] Implementation scheme 42 is a system as described in any one of embodiments 29 to 38, further comprising: a second separation unit configured to fractionate the effluent from the oligomerization reactor into a first stream containing spent catalyst and a second stream containing hexene, octene and heavy hydrocarbons, wherein in the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

[0187] Embodiment 43 is a system as described in any one of Embodiments 29 to 42, wherein the first separation unit is configured to recover a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene and hexane, the system further comprising: a C6 separator configured to separate the third stream into a high-purity 1-hexene stream and a hexane stream; and a cyclohexane recovery tower configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle, wherein the residual C6 feed is fed to the aromatization reactor, and wherein the cyclohexane recycle is fed to the oligomerization reactor.

[0188] Embodiment 44 is a system as described in any one of Embodiments 29 to 43, wherein the selective higher olefin catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PNGuan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh, or combinations thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

Claims

1. A method for producing benzene, comprising: In a cracking process, hydrocarbon feedstock is cracked to produce a cracker effluent containing ethylene; The ethylene recovered from the pyrolysis effluent is then fed into the oligomerization process; In the oligomerization process, ethylene is contacted with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising C6 hydrocarbons including 1-hexene and C8 hydrocarbons including 1-octene. 1-hexene and 1-octene were recovered from the effluent of the oligomerizing reactor. In the hydrotreating process, 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the effluent of the oligomerization reactor are contacted with a hydrotreating catalyst to produce an aromatized feed comprising hexane, octane, or both. as well as In the aromatization process, the aromatization feed is contacted with the aromatization catalyst to produce an aromatization effluent containing benzene. The hydrocarbon feedstock is derived from natural gas, plastic or polymer waste, or biomass.

2. The method of claim 1, wherein the hydrocarbon feedstock comprises ethane derived from natural gas.

3. The method of claim 1, wherein the C6 hydrocarbon is present in an amount of 20% to 99% by weight based on the total weight of the oligomerization reactor effluent, and the C8 hydrocarbon is present in an amount of 0.1% to 75% by weight based on the total weight of the oligomerization reactor effluent.

4. The method of claim 1, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerizing reactor comprises: fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, the heavy hydrocarbons comprising C 9+ hydrocarbons, Of the first stream, the second stream, and the third stream, a portion of the third stream is fed into the hydrogenation process.

5. The method of claim 1, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerizing reactor comprises: fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, the heavy hydrocarbons comprising C 9+ hydrocarbons, In the first stream, the second stream, and the third stream, a portion of the second stream and a portion of the third stream are fed into the hydrogenation process.

6. The method of claim 1, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerizing reactor comprises: fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, the heavy hydrocarbons comprising C 9+ hydrocarbons, In the first stream and the second stream, a portion of the second stream is fed into the hydrogenation process.

7. The method of claim 1, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerizing reactor comprises: The effluent from the oligomerization reactor is fractionated into a first stream containing spent catalyst and a second stream containing hexene, octene, and heavy hydrocarbons, the heavy hydrocarbons comprising C 9+ hydrocarbon, In the first stream and the second stream, a portion of the second stream is fed into the hydrogenation process.

8. The method of claim 1, wherein recovering 1-hexene and 1-octene from the effluent of the oligomerizing reactor comprises: The effluent from the oligomerization reactor is separated into a first stream containing heavy hydrocarbons and spent catalyst, a second stream containing octene, and a third stream containing hexene, wherein the heavy hydrocarbons contain C 9+ hydrocarbon; Fractionating the third stream to produce a 1-hexene stream and a C6 feed stream; and The C6 feed stream is then fed into the hydrogenation process.

9. The method of claim 1, further comprising: Fractionation refinery streams are used to recover naphtha streams; The naphtha stream is fed into the hydrotreating process; as well as In the hydrotreating process, naphtha is contacted with the hydrotreating catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

10. The method of claim 1, wherein the aromatized effluent further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene, or a combination thereof, and the method further comprises: The aromatized effluent is fractionated into a benzene stream, a toluene stream, a xylene stream, and a raffinate stream.

11. The method of claim 10, wherein the aromatization process is further configured to produce a hydrogen effluent, the method further comprising: A portion of the benzene stream and a portion of the hydrogen effluent are fed into a hydrogenation process to produce cyclohexane; as well as The cyclohexane is recycled to the oligomerization process.

12. The method of claim 1, wherein the oligomerization reactor effluent further comprises cyclohexane and other hexanes, the method further comprising: Cyclohexane and the other hexanes are recovered from the effluent of the oligomerization reactor; The other hexane recovered from the effluent of the oligomerization reactor is then fed into the hydrotreating process; as well as The cyclohexane recovered from the effluent of the oligomerization reactor is recycled back to the oligomerization process.

13. The method of claim 1, further comprising: Cracking ethane, propane, butane, pentane, naphtha or mixtures thereof in a steam cracker to produce a cracker effluent containing ethylene; as well as Ethylene recovered from the pyrolysis effluent is fed into the oligomerization process.

14. The method of claim 13, wherein the pyrolysis effluent further comprises light hydrocarbons, the method further comprising: The light hydrocarbons recovered from the pyrolysis effluent are used as a cooling source in the oligomerization reactor of the oligomerization process, in the first fractionation process downstream of the oligomerization process, in the second fractionation process downstream of the aromatization process, or a combination thereof.

15. The method of claim 13, further comprising: Steam is recovered from the steam pyrolysis unit; as well as Steam is used as a heating source for the oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or a combination thereof.

16. The method of claim 13, further comprising: The raffinate recovered from the aromatization process is then fed into a steam pyrolysis unit; and The raffinate is pyrolyzed in the steam pyrolyzer.

17. The method of claim 1, wherein the step of contacting ethylene with the selective higher olefin catalyst is carried out in the presence of a diluent recovered from the aromatization effluent, wherein the diluent is raffinate, benzene, toluene, xylene, branched alkanes, or a combination thereof.

18. The method of claim 1, further comprising: The raffinate recovered from the aromatization process is then fed into a steam pyrolysis unit; and The raffinate is pyrolyzed in the steam pyrolyzer.

19. The method of claim 1, wherein the oligomerizing reactor effluent further comprises C 9+ Hydrocarbons, the method further comprising: C 9+ Hydrocarbons, raffinate stream obtained from the aromatized effluent, or the C 9+ The hydrocarbon and the raffinate stream are both mixed into the motor fuel stream.

20. The method of claim 1, further comprising: Hydrogen obtained from the aromatization effluent is fed into the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process.

21. A method for producing benzene, comprising: In a cracking process, hydrocarbon feedstock is cracked to produce a cracker effluent containing ethylene; The ethylene recovered from the pyrolysis effluent is then fed into the oligomerization process; In the oligomerization process, ethylene is contacted with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising C6 hydrocarbons including 1-hexene and C8 hydrocarbons including 1-octene. 1-hexene and 1-octene were recovered from the effluent of the oligomerizing reactor. In the hydrotreating process, the hydrotreating catalyst is contacted with 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the effluent of the oligomerizing reactor to produce an aromatized feed comprising hexane, octane, or both. as well as In an aromatization process that includes multiple aromatization reactors and furnaces, the aromatization feed is contacted with an aromatization catalyst to produce an aromatization effluent containing benzene. The hydrocarbon feedstock is derived from natural gas, plastic or polymer waste, or biomass.

22. The method of claim 21, wherein the hydrocarbon feedstock comprises ethane derived from natural gas.

23. The method of claim 21, further comprising: Fractionation refinery streams are used to recover naphtha streams; The naphtha stream is fed into the hydrotreating process; as well as In the hydrotreating process, naphtha is contacted with the hydrotreating catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

24. The method of claim 23, wherein the aromatized effluent further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene, or a combination thereof, and the method further comprises: The aromatized effluent is fractionated into a benzene stream, a toluene stream, a xylene stream, and a raffinate stream.

25. The method of claim 24, wherein the aromatization process is further configured to produce a hydrogen effluent, the method further comprising: A portion of the benzene stream and a portion of the hydrogen effluent are fed into a hydrogenation process to produce cyclohexane; as well as The cyclohexane is recycled to the oligomerization process.

26. The method of claim 25, further comprising: A portion of the hydrogen effluent may flow into the oligomerization process, the hydrogenation process, or both the oligomerization process and the hydrogenation process.

27. The method of claim 23, further comprising: The raffinate recovered from the aromatization process is then fed into a steam pyrolysis unit; and The raffinate is pyrolyzed in the steam pyrolyzer to produce pyrolyzer effluent.

28. The method of claim 23, further comprising: Cracking ethane, propane, butane, pentane, naphtha or mixtures thereof in a steam cracker to produce a cracker effluent containing ethylene; as well as Ethylene recovered from the pyrolysis effluent is fed into the oligomerization process.

29. The method of claim 28, wherein the oligomerizing reactor effluent further comprises C 9+ Hydrocarbons, the method further comprising: C 9+ Hydrocarbons, raffinate stream obtained from the aromatized effluent, or the C 9+ The hydrocarbon and the raffinate stream are both mixed into the motor fuel stream.

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