Flexible benzene production via selective higher olefin oligomerization of ethylene

Abstract

The present disclosure relates to the integration of systems and methods related to steam cracking, oligomerization reactions, hydrogenation reactions, and aromatization reactions for producing benzene by hydrogenating oligomers generated from ethylene. In some embodiments, the disclosed systems and methods utilize one or more of an oligomerization process, a hydrotreating process, and an aromatization process to produce an effluent containing benzene. In further embodiments, the systems and methods disclosed herein utilize one or more selective oligomerization catalyst systems.

Description

Technical Field

[0001] The present disclosure relates to the integration of systems and processes related to steam cracking, oligomerization reactions, hydrogenation reactions, and aromatization reactions such that benzene can be produced by hydrogenating oligomers produced from ethylene.

Background Art

[0002] Benzene, also known as benzol, mineral naphtha, phenyl hydride, and annulene, is a commercially important aromatic compound. Benzene is found in crude oil, is a component of gasoline, and is widely used in the manufacture of plastics, resins, synthetic fibers, rubber lubricants, dyes, detergents, pharmaceuticals, pesticides, adhesives, sealants, cleaning products, paint strippers, and other commercially available products. Conventional methods of benzene production starting from materials contained in crude oil are becoming increasingly expensive due to the increasing demand for crude oil. Methods of producing benzene using natural gas as a starting material can provide a lower-cost alternative. Accordingly, additional new and improved systems and methods for producing benzene are desired.

Summary of the Invention

[0003] Accordingly, the present disclosure provides novel and non-obvious methods and systems for producing benzene, including systems and methods for generating reformate effluent(s) containing benzene and additional commercially valuable hydrocarbons. For example, in certain embodiments, the present disclosure provides a method comprising: a) in an oligomerization process, contacting ethylene with a selective higher olefin catalyst to obtain an oligomerization reactor effluent comprising 1) C6 hydrocarbons comprising 1-hexene, and 2) C8 hydrocarbons 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 obtain an aromatization feed comprising hexane, octane, or both; and d) in an aromatization process, contacting the aromatization feed with an aromatization catalyst to obtain a reformate effluent comprising benzene. In related embodiments, the C6 hydrocarbons of the oligomerization reactor effluent comprise from about 20 wt% to about 99 wt% of the total weight of the oligomerization reactor effluent, while the C8 hydrocarbons comprise from about 0.1 wt% to about 75 wt% of the total weight of the oligomerization reactor effluent. In related features, the resulting 1-hexene and 1-octene streams are beneficially characterized by significant levels of purity, including 1) a purity level of from about 60 wt% to about 99.9 wt% for 1-hexene relative to the total weight of the C6 hydrocarbons of the oligomerization reactor effluent, and 2) a purity level of from about 95 wt% to about 99.3 wt% for 1-octene relative to the total weight of the C8 hydrocarbons in the oligomerization reactor effluent.

[0004] In some embodiments, the oligomerization reactor effluent produced according to the present disclosure further comprises one or more (including combinations thereof) of C 10 hydrocarbons, C 12 hydrocarbons, and / or C 14+ hydrocarbons. For example, the oligomerization reactor effluent comprises 1) C 10Hydrocarbon stream, 2) C containing from about 0.1 wt% to about 3 wt% 12 Hydrocarbon stream, and / or 3) C containing from about 0 wt% to about 3.5 wt% 14+ Can be characterized by one or more of the hydrocarbon streams (all based on the total weight of the oligomerization reactor effluent).

[0005] Further features of the disclosed method relate to the use of a catalyst and / or catalyst system capable of producing an oligomerization reactor effluent characterized by the components and component concentrations described herein. For example, catalysts for use in the methods of the present disclosure can include selective oligomerization 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, PNP DPh-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 the selective oligomerization catalysts such as those described above. In a further aspect, the aromaticating catalyst described above can include one or more of a zeolite support, a Group VIII transition metal according to the Periodic Table of the Elements, and one or more halides. The disclosed method, in certain aspects, further can include contacting ethylene with a selective oligomerization catalyst in the presence of a diluent, including combinations thereof, such as isobutane, cyclohexane, methylcyclohexane, isobutene, and / or 1-hexene. Further, the step of contacting ethylene with the selective oligomerization catalyst can be carried out in the presence of a diluent, including but not limited to a diluent recovered from a reformate effluent, the diluent being selected from one or more of raffinate, benzene, toluene, xylene, and one or more branched alkanes, and combinations thereof. In an alternative aspect, the method can further include 1) flowing a raffinate recovered from an aromatization process to a steam cracker, and 2) cracking the raffinate in the steam cracker. The ethylene stream used in the methods of the present disclosure can be pure or essentially pure ethylene, or alternatively, the ethylene stream can include ethylene and one or more additional hydrocarbons. For example, in some aspects, the ethylene contacted in the oligomerization process is received in a stream comprising ethylene and ethane. Further, the method can potentially benefit from the use of one or more removal, purification, and / or separation systems.For example, the sulfur removal system may or may not be used in one or more steps or processes that characterize the methodology. In some embodiments, for example, the use of the sulfur removal system is advantageously avoided between the oligomerization process and the aromatization process.

[0006] A further feature of this methodology may involve recovering one or more target hydrocarbons including, but not limited to, 1 - hexene and 1 - octene from the oligomerization reactor effluent by fractionating 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. In a related feature, only a portion of the third stream (with respect to the first, second, and third streams described above) is utilized as feedstock for the hydrotreating process. Alternatively, the recovery of 1 - hexene and 1 - octene from the oligomerization reactor effluent may involve fractionating 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, and 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, recovering 1-hexene and 1-octene from the oligomerization reactor effluent described herein involves fractionating the oligomerization reactor effluent into 1) a first stream containing heavy hydrocarbons and spent catalyst, and 2) a second stream containing hexene and octene, and only a portion of the second stream is fed to the hydrotreating process. In a further aspect, recovering 1-hexene and 1-octene from the oligomerization reactor effluent described herein involves fractionating the oligomerization reactor effluent 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 the hydrotreating process. Additional features associated with the methodologies described herein further include 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 obtain a high-purity 1-hexene stream and a C6 feed stream, and flowing the C6 feed stream to the hydrotreating process, including recovering 1-hexene and 1-octene from the oligomerization reactor effluent. In certain aspects, the method may further include fractionating the purified stream to recover a naphtha stream, feeding the naphtha stream to the hydrotreating process, and in the hydrotreating process, contacting the naphtha with a hydrogenation catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0008] In one aspect, the reformate effluent produced in accordance with the present disclosure may further include, in addition to benzene, one or more commercially valuable hydrocarbons that can be isolated and / or directed to further processing. For example, the reformate effluent may further include one or more of toluene, ethylbenzene, xylene, 1 - hexene, and 1 - octene (including combinations thereof). According to certain features, the reformate effluent may further be fractionated or separated into individual 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 streams 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 methodology, while 1 - octene may be present in the xylene stream and / or raffinate stream.

[0009] According to an additional feature of the disclosed methodology, the aromatization process may be further configured to beneficially produce a hydrogen effluent, which can be achieved by: 1) flowing a portion of the benzene stream and a portion of the hydrogen effluent to a hydrogenation process to obtain cyclohexane; and 2) recycling the cyclohexane to an oligomerization process.

[0010] As described herein, the oligomerization reactor effluent may be characterized by the presence of various hydrocarbons. In certain aspects, the oligomerization reactor effluent may include, inter alia, hexane species such as cyclohexane, which can be recovered or isolated from the oligomerization reactor effluent as cyclohexane and / or other (non - cyclohexane) hexanes. In additional aspects, non - cyclohexane species may be recovered from the oligomerization reactor effluent upon treatment or fluidly conveyed to the hydrogenation treatment process described herein, while any remaining cyclohexane may be recovered from the oligomerization reactor effluent and recycled or conveyed 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 non-limiting embodiments, the method may further include: 1) cracking one or more of ethane, propane, butane, pentane, and / or naphtha (including mixtures thereof) in a pyrolyzer to obtain a pyrolyzer-derived effluent comprising ethylene; and 2) flowing or otherwise conveying the obtained ethylene recovered or isolated from the pyrolyzer effluent to the oligomerization process described herein. The obtained pyrolyzer effluent may, in certain embodiments, further comprise one or more light hydrocarbons, and the method may advantageously further include: 1) using the light hydrocarbons recovered from the pyrolyzer effluent as a cooling source for the oligomerization reactor in the oligomerization process, which may include use in a first fractionation process located downstream of the oligomerization process, use in a second fractionation process located downstream of the aromatization process, or use in combination with the first and second fractionation processes. In related embodiments, the thermal energy associated with the methodologies of the present disclosure may be beneficially recycled and / or recovered for use in one or more associated steps or processes. For example, the method may further include: 1) recovering steam from the pyrolyzer; and 2) using the recovered steam as a heating source for the oligomerization process described above, for use in a first fractionation process located downstream of the oligomerization process, use in a second fractionation process located downstream of the aromatization process, or use in combination with the first and second fractionation processes further described herein.

[0012] As described herein, the oligomerization reactor effluent produced in accordance with the present disclosure may contain a number of hydrocarbon species and their derivatives. According to certain features, the oligomerization reactor effluent may comprise one or more C 9+It may contain or additionally contain hydrocarbons. Thus, the method can further include steps or processes for utilizing them, which include, but are not limited to, 1) mixing C9+ hydrocarbons into a fuel stream such as a prime mover fuel stream. In an additional aspect, the C9+ hydrocarbon stream may first be mixed with an additional hydrocarbon stream, such as a raffinate stream isolated from a reformate effluent, and the resulting C 9+ The hydrocarbon / raffinate stream is then mixed with a fuel stream, such as a prime mover fuel stream.

[0013] In certain aspects, the disclosed method may further include recycling, reintroducing, or utilizing chemical species or portions generated therein, which includes 1) flowing or recycling hydrogen obtained from a reformate effluent to an oligomerization process, a hydrotreating process, or both (i.e., an oligomerization process and a hydrotreating process).

[0014] The present disclosure further provides a system configured to perform and capable of performing, for example, the methods disclosed herein. According to certain features, 1) an oligomerization reactor configured to contact ethylene with a selective oligomerization catalyst to obtain 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 obtain an aromatization feed comprising one or more of hexane(s), octane(s), and alkylcyclopentane(s), and 4) an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to obtain a reformate effluent comprising benzene, are provided, 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 comprise a steam cracker configured to produce a cracker effluent comprising ethylene, and the ethylene obtained may be recovered from the cracker effluent for use in performing oligomerization in the oligomerization reactor. According to a further feature, the cracker effluent may comprise one or more light hydrocarbons, whereby the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or one or more combinations of two or more of these components may be configured to advantageously utilize the light hydrocarbons as a cooling source.

[0015] The steam cracker may be configured to best implement the methods of the present disclosure, including aspects in which the steam cracker is configured to produce a steam effluent, and aspects in which the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or combinations thereof are configured to beneficially utilize the steam effluent as a heat source derived internally.

[0016] The disclosed system may further include a fractionator configured to fractionate a purification stream to recover a naphtha stream such that, among other things, naphtha can effectively contact a hydrogenation catalyst to produce one or more of n - hexane and n - octane in an aromatization feed.

[0017] In an additional aspect, the reformate effluent produced by the disclosed system may further include 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 reformate effluent, for example, a second separation unit configured to fractionate the reformate effluent into a benzene stream, a toluene stream, a xylene stream including ethylbenzene and xylene, and a raffinate stream. In related aspects, 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 may be additionally arranged or customized such that, according to certain characteristics, 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 cyclohexane production, and the oligomerization reactor is configured to receive the cyclohexane produced by the hydrogenation reactor. In an alternative aspect, 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, and only a portion of the third stream (containing hexene) is fed to the aromatization reactor.

[0019] According to a further feature, the system may further include a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octene, and a third stream comprising hexene, and only a portion of the second stream (comprising octene) is fed to the aromatization reactor. In certain features, the system may further include a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octene, and a third stream comprising hexene, and only a portion of the second stream (comprising octene) and at least a portion of the third stream (comprising hexene) are fed to the aromatization reactor. In one aspect, the system further includes a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, and a second stream comprising hexene and octene, and only a portion of the second stream (comprising 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 oligomerization reactor effluent into a first stream comprising spent catalyst, and a second stream comprising hexene, octene, and heavy hydrocarbons, and only a portion of the second stream (comprising 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. The system further includes: 1) a C6 separator configured to divide the third stream into a) a high-purity 1-hexene stream and b) a hexane stream, and 2) a cyclohexane recovery column configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle stream. 1) The residual C6 feed is supplied to an aromatization reactor, and 2) the cyclohexane recycle stream is supplied 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. The aromatization catalyst includes a zeolite support, a Group VIII metal, and one or more halides, as further described herein.

Brief Description of the Drawings

[0021]

Figure 1

[0022]

Figure 2

[0023]

Figure 3

[0024]

Figure 4

[0025]

Figure 5

[0026]

Figure 6

[0027]

Figure 7

[0028]

Figure 8

[0029]

Figure 9

[0030]

Figure 10

[0031]

Figure 11

[0032]

Figure 12

[0033]

Figure 13

[0034]

Figure 14

[0035]

Figure 15

Mode for Carrying Out the Invention

[0036] Exemplary forms of one or more aspects are provided below, but it should first be understood that the disclosed systems, processes, and / or methods can be implemented using any number of techniques, whether currently known or existing. The present disclosure should in no way be limited to the exemplary forms, drawings, and techniques shown below, including the exemplary designs and forms illustrated and described herein, but can be modified within the scope of the appended claims and within the full scope of their equivalents.

[0037] Disclosed herein are systems, processes, apparatuses, and methods for multi-step chemical conversion, where several chemical conversions that were conventionally performed in separate processes are integrated into a single continuous flow system. The integrated conversion systems, as well as the processes, apparatuses, and methods related thereto, generally relate to a continuous flow system that integrates the conversion of hydrocarbons (e.g., ethane) derived from natural gas to oligomer intermediates (e.g., 1-hexene and / or 1-octene), which are further converted to arenes (e.g., benzene). 4- It is related to a continuous flow system that integrates the conversion of hydrocarbons to oligomer intermediates (e.g., 1-hexene and / or 1-octene), which are further converted to arenes (e.g., benzene).

[0038] As disclosed herein, a method of using an integrated conversion system generally includes (a) decomposing a hydrocarbon feedstock in a cracking process to obtain a cracker effluent comprising monomers, (b) flowing the monomers recovered from the cracker effluent to an oligomerization process, (c) contacting the monomers with an oligomerization catalyst in the oligomerization process to obtain an oligomerization reactor effluent comprising an oligomer product, (d) flowing the oligomer product recovered from the oligomerization reactor effluent to a hydrotreating process, (e) contacting the oligomer product with a hydrotreating catalyst in the hydrotreating process to obtain an aromatization feed comprising hexane, octane, or both, (f) flowing the aromatization feed to an aromatization process, and (g) contacting the aromatization feed with an aromatization catalyst in the aromatization process to obtain a reformate effluent comprising arenes, and includes one or more of the foregoing. In one aspect, the disclosed integrated conversion system is a continuous series flow system, for example, the cracking process is connected to the oligomerization process, the oligomerization process is connected to the hydrotreating process, and the hydrotreating process is connected to the aromatization process.

[0039] Through the systems, processes, and methods disclosed herein, numerous streams and products (e.g., ethylene, 1-hexene, 1-octene, benzene) are recovered from reactors and / or process streams. One of ordinary skill in the art will recognize that a stream or product can be recovered directly from the reactor or process in which it is formed, or that a stream or product can be recovered from another process and / or stream located downstream of where it was formed.

[0040] The following definitions are provided to assist one of ordinary skill in the art in understanding the detailed description of the present disclosure. Unless otherwise defined herein, scientific and technical terms used in connection with the present disclosure shall have the meanings commonly understood by one of ordinary skill in the art to which this disclosure pertains. Further, unless the context otherwise requires, singular terms shall include pluralities and plural terms shall include singulars.

[0041] Furthermore, for clarity, certain features of the present disclosure described herein in the context of separate aspects may also be provided in combination in a single aspect. Conversely, various features of the present disclosure described in the context of a single aspect for brevity 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 indicated, the following definitions apply to the present disclosure. Where a term is used in the present disclosure but not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2 nd ed (1997) may apply, 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 indefinite or invalid. To the extent that any definition or usage set forth in any document incorporated herein by reference conflicts with the definition or usage set forth herein, the definition or usage set forth herein shall control.

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

[0044] General formula C A+ and C A- represent the number of carbon atoms in the molecular formula of an organic molecule (e.g., a hydrocarbon), where A is an integer or a positive integer. For example, C 3+represents a compound having 3 or more carbon atoms per molecule, C 5- represents a compound having 5 or fewer carbon atoms per molecule.

[0045] Unless expressly stated otherwise in the defined context, all percentages, parts, ratios, and like amounts used herein are defined by weight.

[0046] The term "olefin" as used herein and in the claims always refers to a compound having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. The term "olefin" includes, unless otherwise specified, aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched-chain compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Unless expressly indicated, the term "olefin" by itself does not imply the presence or absence of heteroatoms and / or the presence or absence of other carbon-carbon double bonds. Olefins having only one, only two, only three, etc. carbon-carbon double bonds can be identified by using terms such as "mono", "di", "tri", etc. in the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bond(s).

[0047] The term "reactor effluent" and its derivatives (e.g., oligomerization reactor effluent) generally refer to all substances exiting the reactor. The term "reactor effluent" and its derivatives can also be preceded by other descriptors that limit the portion of the reactor effluent being referred to. For example, the term "reactor effluent" refers to all substances exiting the reactor (e.g., among other things, products and solvents or diluents), while the term "olefin reactor effluent" refers to the effluent of a reactor that contains an olefin (i.e., carbon-carbon) double bond.

[0048] The term "oligomerization" and its derivatives refer to a process that produces a mixture of products containing at least 70 weight percent (70 wt%) of a product containing from 2 to 30 monomer units. Similarly, an "oligomer" is a product containing from 2 to 30 monomer units, while an "oligomerization product" includes all products made by an "oligomerization" process that includes "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 "oligomerization product" need not be the same. For example, an "oligomer" or "oligomerization product" of an "oligomerization" process using ethylene and propylene as monomers may include both ethylene units and / or propylene units.

[0049] The term "trimerization" and its derivatives refer to a process that produces a mixture of products containing at least 70 weight percent of a product containing 3 or only 3 monomer units. A "trimer" is a product containing 3 or only 3 monomer units, while a "trimerization product" includes all products made by a trimerization process that includes trimers and products that are not trimers (e.g., dimers and / or tetramers). Generally, the trimerization of an olefin reduces the number of olefin bonds, i.e., carbon-carbon double bonds, by 2 when considering the number of olefin bonds in the monomer unit and the number of olefin bonds in the trimer. It should be noted that the monomer units in a "trimer" or "trimerization product" need not be the same. For example, a "trimer" of a "trimerization" process using ethylene and butene as monomers can include monomer units of ethylene and / or butene, i.e., the "trimer" can include C6, C8, C 10 , and C 12 products. In another example, a "trimer" of a "trimerization" process using ethylene as a monomer can include ethylene monomer units. It should also be noted that a single molecule can contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomer units in one molecule.

[0050] The term "tetramerization" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing 4 or only 4 monomer units. A "tetramer" is a product containing 4 or only 4 monomer units, while a "tetramerization product" includes all products made by a tetramerization process that includes tetramers and products that are not tetramers (e.g., dimers or trimers). Generally, the tetramerization of an olefin reduces the number of olefin bonds, i.e., carbon-carbon double bonds, by 3 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 "tetramerization product" do not have to be the same. For example, the "tetramer" of a "tetramerization" process using ethylene and butene as monomers can include monomer units of ethylene and / or butene. In one example, the "tetramer" of a "tetramerization" process using ethylene as a monomer can include ethylene monomer units. It should also be noted that a single molecule can contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomer units within one molecule.

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

[0052] The term "oligomer" refers to a C 6+ hydrocarbon having a molecular structure containing at least one carbon-carbon double bond. For example, an oligomer can be a C6 monoolefin.

[0053] The term "arene" refers to a monocyclic C6 - C 14 aromatic compound.

[0054] The term "cetane number" refers to cetane (C 16 H 34) is a measure of the ignition characteristics of diesel fuel.

[0055] The term "smoke point", as used for oils or fats, is the temperature at which, under certain defined conditions, the oil or fat begins to produce a continuous bluish smoke that is clearly visible.

[0056] A further understanding of aspects of the present disclosure can be found by reference to the accompanying schematic flow diagrams in combination with the following description. Various additional pumps, valves, heaters, coolers, and other conventional equipment necessary for the practice of the present disclosure herein are well known to those skilled in the art. The above additional equipment has been omitted from the drawings for clarity. The description of the drawings provides one way of operating the process. However, it should be understood that although these drawings are a general representation of the process, minor modifications can be made when adapting these drawings to various conditions within the scope of the present disclosure. Also, it is understood that the reference to drawing numbers is consistent throughout the drawings. For example, the inlet stream 10 containing the hydrocarbon feedstock is the hydrocarbon feedstock inlet stream in all of the drawings. Unless otherwise explicitly disclosed, the functions and components of a process in one integrated conversion system are substantially the same within another integrated conversion system containing that process. In other words, unless otherwise explicitly disclosed, the functions and components of the cracking process 200 within the integrated conversion system 1000 are substantially the same as the functions and components of the cracking process 200 within the integrated conversion system 1100, or the functions and components of the cracking process 200 within the integrated conversion system 1200, etc.

[0057] With reference to FIG. 1, an 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 in fluid communication via one or more conduits (e.g., pipes, tubes, flowlines, etc.) suitable for conveying a particular stream, as shown in detail in the numbered streams of FIG. 1, for example.

[0059] The hydrocarbon feedstock 10 flows into a cracking process 200 where the hydrocarbons are converted (i.e., cracked) into monomers. In certain embodiments, the monomers include ethylene. The cracking process 200 can include any cracking process suitable for producing ethylene as disclosed herein. The method of converting hydrocarbons to ethylene is disclosed in U.S. Patent No. 6,790,342, which is hereby incorporated by reference in its entirety. Any method of producing ethylene disclosed in U.S. Patent No. 6,790,342 can be utilized herein. The hydrocarbon feedstock 10 includes any one or more hydrocarbons suitable for the uses disclosed herein. For example, the hydrocarbons can include non-aromatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. The hydrocarbons can be derived from natural gas, gas condensate, light oil, or combinations thereof. In certain embodiments, the hydrocarbons include ethane, propane, butane, pentane, naphtha, or combinations thereof. In a further embodiment, the hydrocarbon feedstock 10 includes ethane, which can be derived from a natural gas source.

[0060] In certain embodiments, the amount of ethane in the hydrocarbon feedstock 10 ranges from about 10 wt% to about 95 wt%, alternatively from about 20 wt% to about 80 wt%, or alternatively from about 40 wt% to about 60 wt% based on the total weight of the hydrocarbon feedstock 10.

[0061] Referring to FIG. 2, an embodiment of the cracking process 200 is described. The hydrocarbon feedstock 10 is combined with a 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 is the C 3+ stream 262 and / or an alternative C 3+Stream 282, and / or alternatively, the heavy recycle 180 of FIGS. 12 and 13, and alternatively, as further described herein, may be combined (not shown). It is contemplated that some aspects of the cracking process 200 may operate without hydrocarbon recycle 201.

[0062] The hydrocarbon feedstock 10 flows into a cracking zone 205 that includes a steam cracker, where cracker effluent 210 is produced by contact with high temperatures. The cracking zone 205 comprises one or more radiant furnace reactors capable of producing cracker effluent 210. In certain aspects, the cracking zone 205 may have a temperature in the range of about 600 °C to about 1500 °C, alternatively, about 750 °C to about 900 °C. In a further aspect, the cracking 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). The radiant 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 certain aspects, the cracker effluent 210 includes one or more monomers, hydrogen, methane, acetylene, ethane, C 3+ saturated hydrocarbons, and combinations thereof. In a further aspect, the monomer(s) may include ethylene, propylene, butene, or combinations thereof, or alternatively, may include ethylene.

[0063] The amount of ethylene in the cracker effluent 210 can range from about 10 wt% to about 95 wt%, alternatively from about 20 wt% to about 80 wt%, or alternatively from about 40 wt% to about 70 wt% based on the total weight of the cracker effluent 210. In a further aspect, the cracker effluent 210 can contain about 1 wt% to about 20 wt% hydrogen, about 1 wt% to about 30 wt% methane, about 1 wt% to about 30 wt% acetylene, about 3 wt% to about 45 wt% ethane, and about 0 wt% to about 25 wt% C 3+ hydrocarbons.

[0064] The cracker effluent 210 flows into a cooling zone 215 to produce a cooled gas stream 220. In one aspect, the operating temperature of the cooling zone 215 can be below the temperature required to maintain the cracking reactions occurring within the cracker effluent 210. In one aspect, the cracker effluent 210 is cooled to a temperature below about 595 °C, alternatively to a temperature in the range of about 30 °C to about 110 °C to form the cooled gas stream 220. Cooling can be effected by any means suitable to those skilled in the art. For example, the cracker effluent 210 can be passed through a cooling boiler and a cooling tower where fuel oil and dilution streams can be removed. Methods for cooling the cracker effluent 210 are disclosed in U.S. Patent Nos. 3,407,798, 5,427,655, 3,392,211, 4,351,275, and 3,403,722, all of which are incorporated herein by reference in their entirety. The cooled gas stream 220 flows into a first compression zone 225 to produce a pressurized gas stream 230. In one aspect, the pressurized gas stream 230 can contain a pressure in the range of 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, and the gas compressors can be any gas compressor suitable for the uses disclosed herein.

[0065] The pressurized gas stream 230 flows into the deacidification zone 235 where hydrogen sulfide (H2S) and carbon dioxide (CO2) are removed and a wet gas stream 240 is produced. In certain embodiments, the deacidification zone 235 removes some of the H2S and CO2 in the pressurized gas stream 230. In further embodiments, the wet gas stream 240 may have an H2S concentration of less than about 0.1 weight ppm, alternatively in the range of about 25 weight ppb to about 100 weight ppb. In yet another embodiment, the wet gas stream 240 may have a CO2 concentration of less than about 5 weight ppm. The removal of H2S and CO2 can be effected by any suitable means determined by those skilled in the art and using the present disclosure. In yet another embodiment, diethanolamine or a caustic contactor can be used to remove at least a portion of the H2S and CO2 comprising the pressurized gas stream 230. The wet gas stream 240 flows into a drying zone 245 to produce a cracked gas stream 250. In certain embodiments, the water content of the cracked gas stream 250 is less than the amount necessary to cause problems in downstream operations. In further embodiments, the water content of the cracked gas stream 250 is less than about 10 weight ppm. Drying in the drying zone 245 can be effected by any suitable means determined by those skilled in the art and using the present disclosure. In certain embodiments, a molecular sieve bed can be utilized to remove water from the wet gas stream 240.

[0066] The cracked gas stream 250 flows into a deethanizer zone 255 to produce a C 2- stream 260 and a C 3+ stream 262. The deethanizer zone 255 includes a fractionator capable of producing the C 2- stream 260 and the C 3+ stream 262. The C 2- stream 260 can include hydrogen, methane, ethane, acetylene, ethylene, or combinations thereof. The C 3+ stream 262 includes C3 hydrocarbons and heavier components and in certain embodiments can be combined with a hydrocarbon recycle stream 201 (not shown). The C 2- stream 260 flows into a hydrogenation zone 265 where some of the acetylene in the C 2- stream 260 can be removed. An ethylene stream 270 is recovered from the hydrogenation zone 265.2- The hydrogenation of stream 260 can be carried out by those skilled in the art and by any suitable means determined using the present disclosure. For example, an acetylene reactor containing a catalyst can be utilized to hydrogenate a portion of the acetylene in C 2- stream 260. Generally, Group VIII metal hydrogenation catalysts are utilized. The 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 hereby incorporated by reference in its entirety. The operating conditions within the hydrogenation zone 265 can include any combination of suitable conditions determined by those skilled in the art and using the present disclosure. In one aspect, the temperature and pressure within the hydrogenation zone 265 can be at a level capable of hydrogenating a portion of the acetylene in C 2- stream 260. In a further aspect, the hydrogenation zone 265 can have a temperature in the range of about 10°C to about 205°C. In a further aspect, the hydrogenation zone 265 can have a pressure in the range of about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag). In some aspects, the amount of acetylene remaining in the ethylene stream 270 can be less than about 5 weight ppm, alternatively, in the range of about 0.5 weight ppm to about 3 weight ppm.

[0067] Alternatively, C 2- stream 260 flows through line 266, has valves in lines 260 and 268, and flows into a second compression zone 267 to produce a pressurized C 2- stream 268. Pressurized C 2-Stream 268 may have a pressure in the range of 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 comprises one or more gas compressors, which may be any gas compressor suitable for the uses disclosed herein. Pressurized C 2- Stream 268 flows into the hydrogenation zone 265, where Pressurized C 2- A portion of the acetylene that makes up stream 268 is removed. Ethylene stream 270 may be recovered from the hydrogenation zone 265 as described herein. In another alternative, the effluent of the drying zone 245 is alternative gas stream 272. Alternative gas stream 272 flows into alternative hydrogenation zone 275, where a portion of the acetylene that makes up alternative gas stream 272 is removed and reduced gas stream 276 is produced. In one aspect, alternative hydrogenation zone 275 operates equivalently to hydrogenation zone 265. Reduced gas stream 276 flows into alternative deethanizer zone 277, where alternative ethylene stream 280 is recovered and alternative C 3+ Stream 282 is produced. In one aspect, alternative deethanizer zone 277 operates equivalently to deethanizer zone 255. In a further aspect, the compositions of alternative ethylene stream 280 and alternative C 3+ Stream 282 correspond to the compositions of ethylene stream 270 and C 3+ Stream 262, respectively. In one aspect, alternative C 3+ Stream 282 may be mixed with hydrocarbon recycle stream 201 (not shown). Ethylene stream 270 and / or alternative ethylene stream 280 flow into the cracking process effluent 25.

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

[0069] According to the embodiment of FIG. 1, the cracking process effluent 25 flows into the oligomerization process 300. In some embodiments, the cracking process effluent 25 continuously flows from the cracking process 200 into the oligomerization process 300. Those skilled in the art will understand that, as described herein for the cracking process effluent 25, each stream described throughout the present disclosure continuously flows from one process to the next. The continuous flow of each stream is a characteristic of each stream, although not explicitly stated for simplicity. The ethylene effluent 29 results from the cracking process effluent 25. In some embodiments, the ethylene effluent 29 contains ethylene and can be sent for storage and / or provided for sale. Within the oligomerization process 300, monomers can be contacted with an oligomerization catalyst in an oligomerization reactor to produce one or more oligomer products. In some embodiments, the monomers can be alpha-olefins, alternatively linear alpha-olefins, or alternatively normal alpha-olefins. In further embodiments, the monomers can include ethylene, propylene, or combinations thereof. When the monomer includes ethylene, the oligomerization process 300 can be an ethylene oligomerization process. In some embodiments, 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 an ethylene trimerization and tetramerization process, the olefin product can include hexene, octene, 1-hexene, 1-octene, or any combination thereof. In further embodiments, the oligomerization process 300 includes an oligomerization reaction, which can be a trimerization reaction, a tetramerization reaction, or a combination thereof. A method for oligomerizing ethylene using an oligomerization catalyst is disclosed in U.S. Patent No. 8,680,003, which is hereby incorporated by reference in its entirety.

[0070] Referring to FIG. 3, an aspect of the oligomerization process 300 is described. The cracked process effluent 25 can be combined with the ethylene recycle stream 306 to form the oligomerization feed 301. In some aspects, the ethylene recycle stream 306 can be combined with the ethylene recovery stream 335, as further described herein (not shown). Alternatively, the ethylene recycle stream 306 is combined with an ethylene source discharged from outside the integrated conversion process 1000. In a further aspect, the ethylene recycle stream 306 includes the light effluent of the polyethylene polymerization process. It is contemplated that some aspects of the oligomerization process 300 may operate without the ethylene recycle stream 306. The oligomerization feed 301 flows into the oligomerization reactor 305. In some aspects, the oligomerization feed 301 includes ethane, ethylene, or a combination thereof. The hydrogen feed 302 flows into the oligomerization reactor 305. In some aspects, the hydrogen feed 302 can be combined with a stream from another section of the disclosed integrated reforming system. For example, as further described herein, the hydrogen feed 302 may be combined with the hydrogen effluent 81 of FIG. 1. Without wishing to be bound by theory, performing the oligomerization reaction in the presence of hydrogen can increase the product selectivity, reduce the formation of polymer products, or both. It is contemplated that some aspects of the oligomerization process 300 may operate without the hydrogen feed 302. The oligomerization catalyst stream 304 flows into the oligomerization reactor 305. In some aspects, ethylene is contacted with the oligomerization catalyst in the presence of a solvent within the oligomerization reactor 305. In such aspects, the solvent feed 308 is combined with the oligomerization catalyst stream 304. For the purposes of the present disclosure, "solvent" refers to a diluent or medium in which the oligomerization reaction occurs. The solvent can be any inert solvent suitable for use in the oligomerization reactions disclosed herein. In some aspects, the solvent can be a hydrocarbon solvent, a halogenated hydrocarbon solvent, an aliphatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aromatic solvent, or any combination thereof.In a further aspect, the solvent can be isobutane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, or combinations thereof. In certain aspects, the solvent feed 308 can be combined with the solvent recycle 345 and / or the cyclohexane effluent 67 (e.g., see FIGS. 10 or 11), or alternatively, the raffinate stream 88 (e.g., see any of FIGS. 1 or 5-11), as further disclosed herein (not shown). It is contemplated that some aspects of the oligomerization process 300 can operate without the solvent feed 308.

[0071] In one aspect, the oligomerization catalyst comprises a selective oligomerization catalyst system. Suitable selective oligomerization catalyst systems for use herein include N-phosphinyl amidine compounds, metal salts, and metal alkyls, alternatively, N-phosphinyl amidine compounds, metal salts, and aluminoxanes, alternatively, N-phosphinyl amidine metal salt complexes and metal alkyls, or alternatively, N-phosphinyl amidine metal salt complexes and aluminoxanes. In a further aspect, the selective oligomerization catalyst system may include one or more neutral ligands. Suitable selective oligomerization catalyst systems for use herein are described in U.S. Patent No. 8,680,003, as previously disclosed, and include all components comprising the selective oligomerization catalyst system, the ratios of those components, and methods of combining the components to produce the selective oligomerization catalyst system.In one aspect, the selective oligomerization catalyst system can include [4-tert-butyl-N1-(2,4,6-trimethylphenyl)-N2(diisopropylphosphino)benzamidine](THF)CrCl3 (i.e., PN Mes-tBuPh-DIP), [4-methoxy-N1-(2,4,6-trimethylphenyl)-N2(diisopropylphosphino)benzamidine](THF)CrCl3 (i.e., PN Mes-MeOPh-DIP), N1-(2,6-dimethylphenyl)-N2-(di-n-butylphosphino)-2-p-tolylacetamidine](THF)CrCl3 (i.e., PN Xyl-Bz-DnB), [N1-(2,6-dimethylphenyl)-N2-(diphenylphosphino)-2-p-tolylacetamidine](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-pyrimido[1,2-a]pyrimidine-κN9]trichloro(tetrahydrofuran)-chromium (i.e., PN Guan-DIP), [N1-(2,4,6-trimethylphenyl)-N2-(diisopropylphosphino)benzamidine](THF)CrCl3 (i.e., PN Mes Ph-DIP), [N1-(2,6-dimethylphenyl)-N2-(diethylphosphino)benzamidine](THF)CrCl3 (i.e., PN Xyl-Ph-Det), [bis(diphenylphosphino)(n-hexyl)amine]trichlorochromium trichloro[N-(diphenylphosphino)-κP)-N-(hexyl)-P,P-diphenylphosphinic acid amide-κP]-chromium (i.e., PNP DPh-Hex-DPh), [bis(diphenyl-phosphino)(cyclohexyl)amine]trichlorochromium, PNP trichloro[N-cyclohexyl-N-(diphenylphosphino-κP)-P,P-diphenylphosphinamide-κP]-chromium (i.e., PNP DPh-Cy-DPh), PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR -DPh, or combinations thereof.

[0072] The contact between the selective oligomerization catalyst system and ethylene in the oligomerization reactor 305 can be carried out in any suitable manner and using the present disclosure. In some embodiments, the oligomerization reactor 305 can include a loop reactor, a tubular reactor, a continuous stirred tank reactor (CSTR), or a combination thereof. In certain embodiments, the suspension formed between the selective oligomerization catalyst system and the solvent can be stirred to maintain a uniform selective oligomerization catalyst system concentration throughout the suspension, or alternatively, the solution formed between the selective oligomerization catalyst system and the solvent can be stirred to maintain the selective oligomerization catalyst system in solution throughout the oligomerization process. In one embodiment, the oligomerization reaction can be carried out in one or more oligomerization reactors. In one embodiment, the oligomerization reaction can be carried out under suitable reaction conditions including one or more of catalyst concentration, reaction temperature, reaction pressure, and / or reaction time(s). In one embodiment, the concentration of the selective oligomerization catalyst system can be at least 1×10 equivalents / liter, alternatively, at least 2×10 equivalents / liter, or alternatively, at least 5×10 equivalents / liter. The temperature in the oligomerization reactor 305 can be any temperature suitable for the oligomerization reaction of ethylene. In one embodiment, 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 the polymer product. In a further embodiment, the temperature in the oligomerization reactor 305 can be at least 0°C, alternatively, at least 10°C, alternatively, at least 20°C, or alternatively, at least 30°C. In some embodiments, the temperature in the oligomerization reactor 305 can 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 in the oligomerization reactor 305 can be any pressure suitable for the oligomerization reaction of ethylene. In one embodiment, 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 be in the range of from approximately 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). In certain aspects, the oligomerization reaction can have a single pass conversion of ethylene of at least about 30 wt%, alternatively at least about 35 wt%, alternatively at least about 40 wt%, or alternatively at least about 45 wt%.

[0073] As shown in FIG. 3, the oligomerization reactor effluent 310 flowing from the oligomerization reactor 305 includes all components that can be present in and removed from the oligomerization reactor. The oligomerization reactor effluent 310 can include oligomer product(s), by-product(s), co-product(s), side-product(s), light hydrocarbons, heavy hydrocarbons, unreacted monomer(s), a selective oligomerization catalyst system, solvent(s), and other reactor components. In one aspect, the oligomerization reactor effluent 310 includes hexene, octene, 1 - hexene, 1 - octene, alkylcyclopentane(s), solvent(s), cyclohexane, unreacted ethylene, and combinations thereof. In a further aspect, the oligomerization reactor effluent 310 includes C 10 hydrocarbons, C 12 hydrocarbons, C 14+It contains hydrocarbons or combinations thereof. Streams 301, 302, 304, and 310 may be located anywhere on the oligomerization reactor 305 suitable to allow ethylene to come into complete contact with the selective oligomerization catalyst system within the oligomerization reactor 305, which will be understood by those skilled in the art. The catalyst neutralization stream 312 can be combined with the oligomerization reactor effluent 310. The catalyst neutralization stream 312 contains a catalyst deactivation composition that can partially or completely deactivate the selective oligomerization catalyst system. In some embodiments of the oligomerization process 300, it is contemplated that the catalyst neutralization stream 312 may not be utilized. The filter 315 can remove particulates (e.g., catalyst particulates and unwanted polymer products) from the oligomerization reactor effluent 310. Without wishing to be bound by theory, it is believed that higher reactor and stream temperatures may suppress the solidification of unwanted polymer particles. If the oligomerization reactor effluent 310 is maintained at a high temperature, fewer particulates may be formed and the filter 315 may not be necessary. In embodiments where the process conditions favor particulate formation (e.g., cooling of the oligomerization reactor effluent 310), the filter 315 can be used. In some embodiments of the oligomerization process 300, it is contemplated that the filter 315 may not be utilized.

[0074] Process stream 320 includes the effluent of filter 315 or an extension of oligomerization reactor effluent 310, and process stream 320 contains little or no particulate matter. Process stream 320 flows into a first separator 330 to produce an ethylene recovery stream 335 and an oligomer effluent 338. The ethylene recovery stream 335 can include methane, ethane, ethylene, propane, propylene, butane, or combinations thereof. In certain embodiments, the ethylene recovery stream 335 can be further processed (not shown) to recover a high-purity ethylene concentration. The ethylene recovery stream 335 can be combined with the ethylene recycle stream 306 as disclosed herein (not shown). In certain embodiments, the heavy feed 322 is optionally combined with process stream 320 to form an inlet to the first separator 330. The heavy feed 322 can contain the desired oligomer product and heavy hydrocarbons as further described herein. In certain embodiments, the heavy feed 322 can be the effluent of a polyethylene production plant. The oligomer effluent 338 flows into a second separator 340 to produce a solvent recycle 345 and an oligomerization process effluent 36. The solvent recycle 345 can be combined with the solvent feed 308 disclosed herein (not shown). In certain embodiments, the solvent recycle 345 can contain cyclohexane. The first separator 330 and the second separator 340 can operate in any manner suitable for producing their respective effluents. In a further embodiment, each of the first separator 330 and the second separator 340 includes at least one fractionator. III.B.5. Effluent Composition

[0075] In certain embodiments, the oligomerization process effluent 36 contains an oligomer product comprising C6 and C8 olefins. In certain embodiments, the C6 olefins include hexene, 1-hexene, or combinations thereof, and the C8 olefins include octene, 1-octene, or combinations thereof. In certain embodiments, the oligomerization process effluent 36 contains an oligomer product comprising at least 60 wt% C6 and C8 olefins, alternatively at least 70 wt% C6 and C8 olefins, alternatively at least 80 wt% C6 and C8 olefins, alternatively at least 85 wt% C6 and C8 olefins, or alternatively at least 90 wt% C6 and C8 olefins.

[0076] In certain embodiments, the oligomerization process effluent 36 can contain C6 olefins, and the amount of C6 olefins can 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% based on the total weight of the oligomerization process effluent 36. In a further embodiment, the oligomerization process effluent 36 can contain 1-hexene, and the amount of 1-hexene can 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 certain embodiments, the amount of 1-hexene in the oligomerization process effluent 36 can 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, and 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% based on the total weight of the oligomerization process effluent 36. In a further aspect, the oligomerization process effluent 36 may contain 1-octene, and 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] With respect to FIG. 1, the oligomerization process effluent 36 flows into a first fractionation process 50, where a hexene effluent 52 and an octene effluent 54 are recovered. The first fractionation process 50 produces a heavy effluent 56 that may contain heavy hydrocarbons and spent selective oligomerization catalyst system. Heavy hydrocarbons may include C 9+ hydrocarbons, C 9+ oligomers formed by the oligomerization reaction, polymer products formed by the oligomerization reaction, or combinations thereof. In one aspect, the C 9+ oligomers include decene, dodecene, tetradecene, and combinations thereof. Those skilled in the art will understand that the first fractionation process 50 may operate in any suitable manner to produce the disclosed effluents. For example, the first fractionation process 50 may include a series of separation units, such as flash distillation columns, fractional distillation columns, liquid-liquid extraction units.

[0079] In one aspect, a first portion of the hexene effluent 52 is used as the hexene feed 53. The remaining portions of the hexene effluent 52 and the octene effluent 54 may be sent to storage or provided for sale. In one aspect, the hexene feed 53 is optionally combined with the naphtha feed 60 to form the processor feed 65. The naphtha feed 60 may include non-aromatic hydrocarbons containing at least 6 carbon atoms. In a further aspect, the naphtha feed 60 contains up to about 15 wt% C 5- hydrocarbons and up to about 10 wt% C 9+ hydrocarbons and may include a mixture of hydrocarbons including C6 - C8 hydrocarbons, with the weight percentages based on the total weight of the naphtha feed 60. In certain aspects, the naphtha feed 60 may be a light naphtha having a boiling range of from about 20 °C to about 235 °C, and the naphtha feed may include one or more of aliphatic, naphthenic, and / or paraffinic hydrocarbons. It is contemplated that some aspects of the integrated conversion system 1000 may operate without the naphtha feed 60. III.D. Hydrotreating Process 70

[0080] As further shown in FIG. 1, the processor feed 65 flows into the hydrotreating process 70. In certain embodiments, the hydrotreating process 70 includes at least one hydrotreating reactor. At least a portion of the oligomer product within the processor feed 65 may flow into the hydrotreating reactor and may contact a hydrotreating catalyst to produce a hydrotreated effluent (not shown). In embodiments where the oligomer product includes hexene, the hydrotreated effluent includes hexane. In embodiments where the oligomer product includes octene, the hydrotreated effluent includes octane. In such embodiments, the oligomer product may be contacted with the hydrotreating catalyst in any manner suitable for the formation of hexane. In certain embodiments, the hydrotreating catalyst includes one or more of hydrotreating catalysts (plural possible) including nickel (Ni), palladium (Pd), platinum (Pt), iridium (Ir), and / or ruthenium (Ru). Within the hydrotreating process 70, the hydrotreated effluent passes through a purification stage, whereby an aromatization feed 75 including hexane (e.g., n - hexane) is recovered. Further processes (e.g., fractionation) within the hydrotreating process 70 may 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 certain embodiments, the hydrotreating process 70 includes a sulfur removal system. Without wishing to be bound by theory, when the amount of sulfur, nitrogen, and / or aromatic compounds in the feed to the aromatization process 400 is low, the deterioration and deactivation of the aromatization catalyst therein is slower, and advantageously, the plant maintenance is reduced and the aromatic selectivity is improved. In further embodiments, the processes within the hydrotreating process 70 may improve the cetane number, density, and / or smoke point of the components of the aromatization feed 75.

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

[0082] With reference to FIG. 1, the aromatization feed 75 flows into an aromatization process 400. The aromatization process 400 includes an aromatization reactor system where the acyclic oligomers are subjected to an aromatization reaction in contact with an aromatization catalyst to produce arenes. In a further embodiment, the aromatization reaction converts 1 - hexene to benzene. A method for converting 1 - hexene to benzene is disclosed, for example, in U.S. Patent No. 7,932,425, which is hereby incorporated 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 contemplated that the aromatization process 400 may be utilized with acyclic hydrocarbons other than 1 - hexene to produce arenes other than benzene.

[0083] Referring to FIG. 4, an embodiment of an aromatization process 400 is described. In the illustrated embodiment, the aromatization reactor system includes a catalytic reactor system in which four aromatization reactors, namely reactors 410, 420, 430, and 440, are connected in series. However, the catalytic reactor system may include aromatization reactors in any suitable number and / or configuration, for example, one, two, three, five, six, or more reactors arranged in series or in parallel. Since the aromatization reaction is highly endothermic, a large temperature drop can occur across reactors 410, 420, 430, and 440. Thus, to reheat the components to the desired temperature to maintain the desired reaction rate, each of the reactors 410, 420, 430, and 440 in series may each include a corresponding furnace 411, 421, 431, and 441. Alternatively, one or more of the reactors 410, 420, 430, and 440 may share a common furnace, if feasible. All of reactors 410, 420, 430, and 440, furnaces 411, 421, 431, and 441, and the associated piping may be referred to herein as the aromatization zone.

[0084] In one aspect, the aromatization feed 75 and optional raffinate recycle 90 are combined to form a mixed feed 402, as further disclosed herein, which flows into a purification process 480. The purification process 480 employs a process known for purifying the mixed feed 402, which may include fractionation and removing impurities such as oxides, sulfur, and / or metals. In one aspect, the purification process 480 includes a sulfur removal system. In a further aspect, the sulfur removal system includes a staged combustion air (SCA) pretreater, an SCF / SCG sulfur guard, or both. What results from the purification process 480 is a purified feed 403. The purified feed 403 can be combined with a dry hydrogen recycle stream 465 to produce a hydrogen-rich purified feed 404. An oxides and / or nitrogen-containing stream 405 (i.e., an O / N stream) may be combined with the hydrogen-rich purified feed 404 to produce an aromatization reactor feed 406. As further described in detail herein, oxides and / or nitride compound(s) may be fed to the catalytic reactor system at one or more locations in addition to, or in place of, the O / N stream 405. It is contemplated that some aspects of the aromatization process 400 may operate without the purification process 480, and the mixed feed 402 directly follows the stream 403.

[0085] In one aspect, the aromatization reactor feed 406 is preheated in a first furnace 411, which heats the contents of the 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 arene content. A first aromatization reactor effluent 415, which includes arenes (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or by-products, is recovered from the first aromatization reactor 410.

[0086] Subsequently, the first aromatization reactor effluent 415 is preheated in a second furnace 421 to heat the contents of stream 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 to aromatize one or more components in the feed and increase its aromatic content. A second aromatization reactor effluent 425 containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or by-products is recovered from the second aromatization reactor 420.

[0087] Subsequently, the second aromatization reactor effluent 425 is preheated in a third furnace 431 to heat the contents of stream 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 to aromatize one or more components in the feed and increase its aromatic content. A third aromatization reactor effluent 435 containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or by-products is recovered from the third aromatization reactor 430.

[0088] Subsequently, the third aromatization reactor effluent 435 is preheated in a fourth furnace 441 to heat the contents of stream 435 to a desired temperature, thereby producing a fourth aromatization reactor feed 442. Subsequently, the fourth aromatization reactor feed 442 is sent to a fourth aromatization reactor 440 where it is contacted with an aromatization catalyst under suitable reaction conditions to aromatize one or more components in the feed and increase its aromatic content. A fourth aromatization reactor effluent 445 containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or by-products is recovered from the fourth aromatization reactor 440.

[0089] The fourth aromatization reactor effluent 445 flows into a hydrogen separation process 450 where a recovered hydrogen stream 455 is separated from the reformate effluent 45. The reformate effluent 45 includes the aromatization reaction products from reactors 410, 420, 430, and 440, and optionally, aromatization reaction by-products and / or co-products, unreacted feed, other hydrocarbons, or combinations thereof. In certain embodiments, the aromatization reaction by-products include toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, hexamethylbenzene, or combinations thereof. The recovered hydrogen stream 455 is dried in a dryer 460, thereby forming a dry hydrogen recycle stream 465 which can be recycled to the purified feed 403 as disclosed herein. Hydrogen separation processes are known in the art and are 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 does not show the by-product streams removed from the system at various points throughout the catalytic reactor system. However, those skilled in the art will recognize the composition and location of such by-product streams. Also, while Figure 4 shows an O / N stream 405 being added to the hydrogen-rich purified feed 404, those skilled in the art will understand that oxides and / or nitrides may 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 embodiments of the aromatization process can operate in the absence of the hydrogen separation process 450 and the dryer 460, where the recovered hydrogen stream 455 and the dry hydrogen recycle stream 465 do not exist. In such embodiments, the fourth aromatization reactor effluent 445 flows directly into the reformate effluent 45 and includes its components.

[0090] In various aspects, the catalytic reactor system described herein may include a fixed catalyst bed system, a moving catalyst bed system, a fluidized catalyst bed system, or combinations thereof. Such a reactor system may be a batch or continuous system. In one aspect, the catalytic reactor system is a fixed bed system that includes one or more fixed bed reactors. In a fixed bed system, the aromatization reactor feed may be preheated in furnace tubes and passed through at least one reactor that includes a fixed bed of the catalyst. The aromatization reactor feed stream may pass through the reactor upwardly, downwardly, or radially. In various aspects, the catalytic reactor system described herein may operate as an adiabatic catalytic reactor system or an isothermal catalytic reactor system. As used herein, the terms "catalytic reactor" and "reactor" are used synonymously to refer to a reaction vessel, the interior of the reactor, and associated processing equipment, including, but not limited to, catalysts, inert packing materials, scallops, diverters, center pipes, reactor ports, catalyst transfer and distribution systems, furnaces, as well as other heating, heat transfer, and piping equipment.

[0091] In one aspect, the catalytic reactor system is an aromatization reactor system that includes at least one aromatization reactor and a corresponding processing unit. As used herein, the terms "aromatization," "aromatizing," and "reforming" refer to the treatment of a feed to obtain an aromatic-rich product, where the aromatic content of the product is greater than the aromatic content of the feed. Typically, one or more components of the feed undergo one or more reforming reactions to produce aromatics. Some of the reforming reactions that occur within the aromatization reactor system include the dehydrogenative cyclization of acyclic hydrocarbons to aromatics (e.g., from 1-hexene to benzene), the dehydrogenation of cyclohexane to aromatics, the dehydrogenative isomerization of alkylcyclopentanes to aromatics, or combinations thereof. Depending on the composition of the feed, additional reactions may also occur, including the dealkylation of alkylbenzenes, the isomerization of paraffins, the hydrocracking reactions that produce light gaseous hydrocarbons such as methane, ethane, ethylene, propane, propylene, and butane, or combinations thereof. Certain aspects of the integrated reforming system described herein utilize the dehydrogenative cyclization of 1-hexene, n-hexane, or combinations thereof to produce benzene. In a further aspect, the integrated reforming system utilizes the dehydrogenation of cyclohexane to produce benzene.

[0092] In one aspect, the aromatization reaction is carried out under process conditions that are thermodynamically favorable for the dehydrogenative cyclization reaction and that limit undesirable hydrocracking reactions. The pressure within the reactor(s) can range from about 0 psig to about 500 psig (about 0 MPag to about 3.45 MPag), for example, from about 25 psig to about 300 psig (about 0.17 MPag to about 2.07 MPag). The operating temperature includes a reactor inlet temperature in the range of about 370 °C to about 565 °C, for example, about 480 °C to about 540 °C. The molar ratio of hydrogen to hydrocarbon (e.g., 1-hexene) in the aromatization reactor feed can range from about 0.1:1 to about 20:1, for example, from about 1:1 to about 6:1.

[0093] In some embodiments, the aromatization reaction of the present disclosure can be characterized by the conversion of some or all of the C6 stream (including but not limited to 1 - hexene) to benzene, based on the total weight of the C6 stream feed containing 1 - hexene supplied to the aromatization reactor. In one embodiment, the conversion of C6 species such as 1 - hexene to benzene is greater than about 40 wt%, alternatively greater than about 50 wt%, alternatively greater than about 60 wt%, or alternatively greater than about 70 wt%.

[0094] The aromatization reaction of the present disclosure can be characterized by the selectivity of the C6 feed stream species, such as 1 - hexene, to benzene, based on the total weight of 1 - hexene converted in the aromatization reactor. In one embodiment, the selectivity of 1 - hexene to benzene is greater than about 50 wt%, alternatively greater than about 60 wt%, alternatively greater than about 70 wt%, or alternatively greater than about 75 wt%.

[0095] Various types of aromatization catalysts can be used with the catalytic reactor systems disclosed herein. In one embodiment, 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, and platinum, and combinations thereof. Examples of catalysts suitable for use with the catalytic reactor systems described herein include the AROMAX® (registered trademark) (Chevron Phillips Chemical Company LLC, The Woodlands, TX, USA) brand of catalysts, including the catalysts discussed in U.S. Pat. Nos. 6,812,180, 7,153,801, and 7,932,425, which are hereby incorporated by reference in their entireties.

[0096] The inorganic carrier for the aromatization catalyst of the present disclosure can generally include any inorganic oxide. These inorganic oxides include bonded macroporous aluminosilicates (zeolite carriers), amorphous inorganic oxides, and mixtures thereof. Examples of macroporous aluminosilicates include, but are not limited to, L-zeolite, Y-zeolite, mordenite, omega zeolite, beta zeolite, etc. Examples of amorphous inorganic oxides include, but are not limited to, aluminum oxide, silicon oxide, and titania. Examples of binders suitable for inorganic oxides include, but are not limited to, silica, alumina, clay(s), titania, and magnesium oxide.

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

[0098] In one aspect, the Group VIII metal may be platinum. Platinum and optionally one or more halides can be added to the zeolite carrier by any suitable method, such as by impregnating 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, diamineplatinum(II) nitrate, bis(ethylenediamine)platinum(II) chloride, platinum(II) acetylacetonate, dichlorodiamineplatinum, platinum(II) chloride, tetraamineplatinum(II) hydroxide, tetraamineplatinum chloride, and tetraamineplatinum(II) nitrate.

[0099] In a further aspect, the catalyst can be a large pore zeolite support having a platinum-containing compound and at least one organic ammonium halide compound. The organic ammonium halide compound may include one or more compounds represented by the formula N(R)4X, where X is a halide and R represents hydrogen or a substituted or unsubstituted carbon chain molecule having 1 to 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, and more specifically is methyl. Examples of suitable organic ammonium compounds are represented by the formula N(R)4X and 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 the present disclosure, oxides, nitrides, or both can be added to one or more process streams and / or components within a catalytic reactor system. Without being bound by theory, oxides and / or nitrides (e.g., water) can be beneficial, for example, in activating, maintaining, and / or improving the productivity of certain types of aromatization catalysts as described 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 harmful substances to the aromatization catalyst and are initially substantially free of oxides and nitrides. If present, such harmful substances 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 using conventional hydrotreating techniques and then using adsorbents to remove residual harmful substances. Such hydrotreating techniques and adsorbents are included in the purification processes related to the oxides and / or nitrides described below.

[0101] As used herein, the term "oxide" refers to water or any 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 oxide. In another aspect, oxygen can be used as the oxide, and such oxygen is converted in situ to water under typical aromatization conditions within one or more aromatization reactors or under normal hydrotreating conditions within one or more hydrotreating catalysts or adsorbent beds. Further, the oxide can be any alcohol-containing compound. Specific examples of suitable alcohol-containing compounds are methanol, ethanol, propanol, isopropanol, butanol, t-butanol, pentanol, amyl alcohol, hexanol, cyclohexanol, phenol, or combinations thereof.

[0102] As used herein, the term "nitride" refers to ammonia or any compound that forms ammonia under catalytic aromatization conditions, such as nitrogen, nitrogen-containing compounds, alkylamines, aromatic amines, pyridine, pyridazine, pyrimidine, pyrazine, triazine, heterocyclic N-oxides, pyrrole, pyrazole, imidazole, triazole, nitrile, amide, urea, imide, nitro compounds, and nitroso compounds (including combinations thereof). Without wishing to be bound by theory, ammonia is thought to enhance catalytic activity in much the same way as water. Further, all methods of addition and control of oxides described herein can be fully applied additionally or alternatively to methods of addition and control of nitrides.

[0103] One of ordinary skill in the art will understand that any of the oxides, nitrides, or mixtures thereof described herein may be used alone, in combination, or even further combined to produce other suitable oxides or nitrides. In some embodiments, the oxides and nitrides may be included within a single bifunctional compound. The oxides and / or nitrides can be added in any suitable physical phase, such as a gas, liquid, or a combination thereof. The oxides and / or nitrides may be added to one or more process streams and / or components via any suitable means for their addition, such as pumps, injectors, spargers, bubblers, etc. The oxides and / or nitrides may be introduced as a mixture with a carrier. In some embodiments, the carrier is selected from hydrogen, hydrocarbons, nitrogen, noble gases, or mixtures thereof. In one embodiment, the carrier is hydrogen. In a further embodiment, the oxides and / or nitrides can be added in any suitable manner at various locations within the aromatization process, at any point during the useful life of the aromatization catalyst. In yet a further embodiment, the addition of the oxides and / or nitrides functions to activate the aromatization catalyst, increase the useful life of the aromatization catalyst, increase the selectivity and / or productivity of the aromatization catalyst, and combinations thereof.

[0104] In one aspect, prior to adding an oxide and / or a nitride, the content of existing oxides and / or nitrides in the stream to which the oxide and / or nitride is added is measured and / or adjusted. For example, referring to FIG. 4, one or more feed streams such as aromatization feed 75, raffinate recycle 90, mixed feed stream 402, or dry hydrogen recycle stream 465 may be measured for the content of oxides and / or nitrides prior to the addition of the oxide and / or nitride, and the content of the oxide and / or nitride may be adjusted. Similarly, the same stream may be measured for the content of nitrides prior to the addition of the nitride and / or the content of the nitride may be adjusted. Generally, raw or untreated feed streams such as aromatization feed 75 may contain some amount of oxides or nitrides when flowing into the catalytic reaction system described herein. Further, depending on one or more of the plant configuration, feed storage period, and / or weather / storage conditions, the feed may absorb oxides or nitrides in the air. To accurately control the amount of oxide(s) and / or nitride(s) flowing into one or more of the aromatization reactors (e.g., reactors 410, 420, 430, 440), the amount of oxides and / or nitrides in one or more feed streams may be measured, adjusted, or both.

[0105] In one aspect, the oxide and / or nitride content of a given stream, such as a feed stream, may be measured, for example, by a real-time in-line analyzer (not shown). Depending on such measurement value(s), the content of oxides and / or nitrides in the stream may be adjusted by treating and / or adding oxides and / or nitrides to the stream to obtain a desired amount of oxides and / or nitrides therein. In one aspect, a control loop couples the analyzer to a processor and an oxide and / or nitride injector such that the amount of oxides and / or nitrides in one or more streams is controlled in response to the setpoint for oxides and / or nitrides for those streams. In some aspects, the measurement and / or adjustment of the oxide and / or nitride content, as well as associated equipment such as a processor and / or a chemical injector, are included as part of the purification process 480. Oxide and / or nitride processors vary based on the type and amount of oxides and / or nitrides. In aspects where the oxide contains water, a bed of adsorbent material may be used. These adsorption beds are generally known as dryers. In aspects where the oxide contains oxygen, the use of a processor that converts oxygen to water may be used in combination with a dryer. In a further aspect where the nitride contains a basic chemical, one or more beds of adsorbent material may 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 prior to adding oxides and / or nitrides. In such aspects, the measurement of the oxide and / or nitride content of the stream prior to such treatment may optionally be omitted. If there is no device for easily measuring the oxide and / or nitride content of the feed, it may be difficult to ensure that the desired level is maintained in the aromatization reactor.

[0107] Treating one or more streams prior to the addition of oxides and / or nitrides can assist in the overall control of the amount of water and / or ammonia in one or more streams flowing into the aromatization reactor by removing variations in the oxide and / or nitride content of such streams. By treating such streams, a consistent baseline amount of oxides and / or nitrides is provided to such streams in order to add oxides and / or nitrides to form an oxygenated stream such as aromatization reactor feed 406. If the reactor feed does not sufficiently contain oxides and / or nitrides, the exact amount of oxides and / or nitrides can be added to the reactor feed to ensure the amount of oxides and / or nitrides in the reactor is maintained. In one aspect, purification process 480 can include a hydrocarbon dryer that dries a feed stream (e.g., aromatization feed 75) to an appropriate water content. In another aspect, purification process 480 can include a bed of reduced copper or a bed of triethylaluminum on silica for use in removing oxides. In a further aspect, the bed of reduced copper or the bed of triethylaluminum on silica is used in combination with a hydrocarbon dryer. Similarly, dryer 460 can be used to dry recycle hydrogen stream 455 and / or other process streams (e.g., aromatization feed 75) to an appropriate water content. In one aspect, suitable oxide levels in one or more streams such as aromatization feed 75, raffinate recycle 90, mixed feed 402, or dry hydrogen recycle stream 465 are levels such that their combination results in a water concentration of less than about 1 part per million by volume (ppmv), alternatively less than about 0.5 ppmv, or alternatively less than about 0.1 ppmv in the untreated recycle hydrogen stream 455. In one aspect, one or more streams supplied to the aromatization reactor, aromatization feed 75, raffinate recycle 90, mixed feed 402, or dry hydrogen recycle stream 465 are substantially free of water after being dried. In one aspect, the exact amount of oxides and / or nitrides may be added by bypassing such treatment processes partially or completely.Alternatively, an exact amount of oxide and / or nitride can be added by passing at least a portion of the hydrogen recovery stream 455 through a wet (e.g., used) molecular sieve bed, or completely passing it through.

[0108] The reformate effluent 45 can contain C6 arenes. In certain embodiments, the concentration of C6 arenes in the reformate effluent 45 can 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% based on the total weight of the reformate effluent 45. In further embodiments, the concentration of C6 arenes in the reformate effluent 45 can range from about 60 wt% to about 99.9 wt%, alternatively from about 70 wt% to about 99.8 wt%, alternatively from about 75 wt% to about 99.7 wt%, or alternatively from about 80 wt% to about 99.6 wt%, or alternatively from about 85 wt% to about 99.5 wt%. In further embodiments, the concentration of benzene in the reformate effluent 45 can 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 certain embodiments, the concentration of benzene in the reformate effluent 45 can 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%.

[0109] Returning to FIG. 1, the reformate effluent 45 flows into a second fractionation process 80 where a benzene stream 82, a toluene stream 84, a xylene stream 86, and a raffinate stream 88 are recovered. The benzene stream 82, the toluene stream 84, and the xylene stream 86 may be sent to storage and / or provided for sale. In certain embodiments, the xylene stream 86 comprises xylene(s). In further embodiments, the xylene stream 86 further comprises ethylbenzene, for example, in embodiments where 1-octene is recovered from the oligomerization reactor effluent 36 and / or the naphtha feed 60 is received in the hydrotreating process 70. In certain embodiments, the raffinate stream 88 comprises C 9+ arenes, non-aromatic C 9+ hydrocarbons, or combinations thereof. In further embodiments, the raffinate stream 88 comprises benzene, toluene, xylene, or combinations thereof. In further embodiments, the raffinate stream 88 comprises ethylbenzene, for example, in embodiments where 1-octene is recovered from the oligomerization reactor effluent 36 and / or the naphtha feed 60 is received in the hydrotreating process 70. The raffinate stream 88 may be sent to the hydrocarbon recycle 201 of the cracking process 200 as disclosed herein, or alternatively, may be sent to storage and / or provided for sale. In certain embodiments, a portion of the raffinate stream 88 is optionally sent to a raffinate recycle 90 as disclosed herein. In some embodiments, the raffinate recycle 90 flows into an aromatization process 400 as disclosed herein.

[0110] One of ordinary skill in the art will understand that the second fractionation process 80 can operate in any manner suitable for producing its effluent. For example, the second fractionation process 80 can include a series of separation units, such as flash distillation columns, fractionation distillation columns, liquid-liquid extraction units, and the like. Some embodiments of the second fractionation process 80 can include a hydrogen separation process substantially similar to the hydrogen separation process 450 of FIG. 4. In such embodiments, a hydrogen effluent 81 is recovered from the second fractionation process 80. The hydrogen effluent 81 may be combined with the hydrogen feed 302 of FIG. 3, as disclosed herein. In further embodiments, the hydrogen effluent 81 may be sent for storage and / or provided for sale.

[0111] Referring to FIG. 5, an integrated conversion system 1100 is described, with like numbers representing like components as described in connection with FIG. 1. In contrast to FIG. 1, a first portion of the octene effluent 54 is used as an octene feed 55. The remaining portions of the octene effluent 54 and the hexene effluent 52 may be sent for storage and / or provided for sale. In one embodiment, the octene feed 55 is optionally combined with a naphtha feed 60 to form a processor feed 65, which is sent to an aromatization process 400. In embodiments where the oligomer product in the processor feed 65 contains octene, the hydrotreated effluent (not shown) produced in the hydrotreating process 70 contains octane. In such embodiments, the oligomer product may be contacted with a hydrotreating catalyst in any manner suitable for the formation of octane. Within the hydrotreating process 70, the hydrotreated effluent passes through a purification stage, whereby an aromatization feed 75 containing octane (e.g., n-octane) is recovered.

[0112] Referring to FIG. 6, an integrated conversion system 1200 is illustrated, and like numbers represent like components as described in connection with FIG. 1. A first portion of the hexene effluent 52 is used as the hexene feed 53, and a first portion of the octene effluent 54 is used as the octene feed 55. The remaining portions of the hexene effluent 52 and the octene effluent 54 may be sent to storage and / or provided for sale. In one aspect, the hexene feed 53 and the octene feed 55 are optionally combined with the naphtha feed 60 to form a processor feed 65, which is sent to a hydrotreating process 70. Within the hydrotreating process 70, the hydrotreated effluent passes through a purification stage, whereby an aromatization feed 75 is recovered that includes hexane (e.g., n - hexane), octane (e.g., n - octane), or a combination thereof.

[0113] Referring to FIG. 7, an integrated conversion system 1300 is illustrated, and like numbers represent like components as described in connection with FIG. 1. The middle cut feed 57 exits from the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form a processor feed 65, which is sent to a hydrotreating process 70. In one aspect, the middle cut feed 57 includes C6 - C8 hydrocarbons. In a further aspect, the middle cut feed 57 includes C6 and C8 olefins, and the C6 and C8 olefins include hexene, octene, or a combination thereof. In a particular aspect, the middle cut feed 57 includes 1 - hexene and 1 - octene.

[0114] Referring to FIG. 8, an integrated conversion system 1400 is described, and like numbers represent like components as described in connection with FIG. 7. The heavy cut feed 59 exits from the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form a processor feed 65, which is sent to a hydrotreating process 70. In one aspect, the heavy cut feed 59 includes C6 - C 12 hydrocarbons. In a further aspect, the heavy cut feed 59 includes C6 and C 12 olefins, and C6 and C12 The olefins include hexene, octene, decene, dodecene, or combinations thereof. In certain embodiments, the heavy cut feed 59 includes 1-hexene and 1-octene.

[0115] The integrated conversion systems 1300 and 1400 do not have hexene effluent 52 and octene effluent 54. The integrated conversion systems 1300 and 1400 integrate all of the hexene and octene produced in the oligomerization process 300 into the hydrogenation process 70.

[0116] Referring to FIG. 9, an integrated conversion system 1500 is described, with like numbers representing like components as described in connection with FIG. 1. The cyclohexane recycle 62 flows into the oligomerization process 300, where the cyclohexane functions as a solvent (i.e., diluent). In some embodiments, the cyclohexane recycle 62 is combined with the solvent feed 308 of FIG. 3 as disclosed herein. The C6 cut feed 58 exits the first fractionation process 50 and enters the C6 separator 151. In certain embodiments, the C6 cut feed 58 includes C6 hydrocarbons. In the C6 separator 151, the hexene effluent 52 and the depleted C6 cut 61 are recovered from the C6 cut feed 58. In some embodiments, the composition and properties of the hexene effluent 52 are the same as those disclosed herein for FIG. 1. The depleted C6 cut 61 exits the C6 separator 151 and enters the cyclohexane recovery (CHR) column 153, where the residual C6 feed 63 and the cyclohexane recycle 62 are recovered from the depleted C6 cut 61. The residual C6 feed 63 is optionally combined with the naphtha feed 60 to form a processor feed 65, which is sent to the aromatization process 400. In certain embodiments, the residual C6 feed 63 includes C6 hydrocarbons (e.g., hexane). The C6 separator 151 and the CHR column 153 can operate in any suitable manner to produce their effluents. In some embodiments, each of the C6 separator 151 and the CHR column 153 includes at least one fractionator.

[0117] As disclosed herein, the entirety of the C6 cut feed 58 enters the C6 separator 151. Such a configuration of the integrated conversion system 1500 advantageously produces the hexene effluent 52 at full capacity. Some embodiments of the integrated conversion system 1500 are configured to operate without the C6 separator 151 and the hexene effluent 52 is not produced. In such embodiments, an optional bypass line 51 sends the entirety of the C6 cut feed 58 to the CHR column 153 and the C6 cut feed 58 enters the CHR column 153 via line 61. Such a configuration of the integrated conversion system 1500 can be utilized, for example, when the demand for C6 olefins (e.g., 1 - hexene) is low and / or when the supply from the source for the naphtha feed 60 is low, or alternatively, to avoid the costs associated with the source for the naphtha feed 60. In a further embodiment, the flow of the C6 cut feed 58 is split between the C6 separator 151 and the CHR column 153 by metering the flow of the optional bypass line 51.

[0118] In one embodiment, the flexible configuration of the integrated conversion system 1500 advantageously enables an operator to quickly respond to, for example, commercial (market), weather, and / or production factors.

[0119] Referring to FIG. 10, an integrated conversion system 1500 is described, where like numbers represent like components as described in connection with FIG. 9. The cyclohexane feed 64 flows into the oligomerization process 300, where cyclohexane functions as a solvent (i.e., diluent). In certain embodiments, the cyclohexane feed 64 is combined with the solvent feed 308 of FIG. 3 as disclosed herein. The C6 cut feed 58 exits the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form a treater feed 65, which is sent to the hydrotreating process 70. Referring to the second fractionation process 80, a portion of the benzene stream 82 is sent via the benzene feed 83, and a portion of the hydrogen effluent 81 is sent via the recycle feed 85. The benzene feed 83 and the recycle feed 85 flow into the benzene hydrogenation process 160, and the hydrogenation of benzene produces a cyclohexane effluent 67. In certain embodiments, the cyclohexane effluent 67 contains cyclohexane and can be sent for storage or sale. A portion of the cyclohexane effluent 67 can be sent to the cyclohexane feed 64 as disclosed herein. The hydrogenation of benzene can be carried out by any suitable means determined by those skilled in the art and using this disclosure. For example, in a non-limiting embodiment, a hydrogenation catalyst can be utilized. The operating conditions within the hydrogenation process 160 can include any combination of suitable conditions determined by those skilled in the art and using this disclosure. In certain embodiments, the temperature and pressure within the hydrogenation process 160 can be at levels that can hydrogenate benzene. The temperature within the hydrogenation process 160 can range from about 10°C to about 205°C. The pressure within the hydrogenation process 160 can range from about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag).

[0120] In one aspect, the concentration of cyclohexane in the cyclohexane effluent 67 can 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%, based on the total weight of the cyclohexane effluent 67. In a further aspect, the concentration of cyclohexane in the cyclohexane effluent 67 can 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%.

[0121] Referring to FIG. 11, an integrated conversion system 1700 is described, where like numbers represent like components as described in connection with FIGS. 9 and 10. A second solvent recycle 68 flows into the oligomerization process 300, where cyclohexane functions as a solvent (i.e., diluent). In one aspect, the second solvent recycle 68 is combined with the solvent feed 308 of FIG. 3, as disclosed herein. The second solvent recycle 68 can be formed by a combination of the cyclohexane recycle 62 and the cyclohexane feed 64, as described herein.

[0122] Referring to FIG. 12, an integrated conversion system 1800 is described, with like numbers representing like components as described in connection with FIG. 1. In contrast to FIG. 1, hydrocarbon feedstock 10 flows into cracking process 290, which operates in a manner similar to cracking process 200 of FIG. 2 unless otherwise explicitly disclosed. Raffinate recycle 90 flows in from the second fractionation process 80 as disclosed earlier herein, and heavy recycle 180 flows into cracking process 290. In one aspect, raffinate recycle 90 and heavy recycle 180 are combined with hydrocarbon recycle 201 of FIG. 2. Heavy recycle 180 can be obtained from the first fractionation process 50. Heavy recycle 180 contains C 9+ hydrocarbons, C formed by an oligomerization reaction 9+ oligomers, polymer products formed by an oligomerization reaction, or heavy hydrocarbons including combinations thereof. In one aspect, C 9+ oligomers include decene, dodecene, tetradecene, and combinations thereof.

[0123] Flowing out of cracking process 290 are the cracking process effluent 25, refrigerant stream 146, crude pyrolysis gasoline (CPG) stream 142, fuel gas stream 144, and steam effluent 148 as disclosed earlier herein. Refrigerant stream 146 is the cracker effluent 210 of FIG. 2, C 3+ stream 262, and / or alternative C 3+It can be recovered from stream 282. In certain embodiments, refrigerant stream 146 includes light hydrocarbons produced in the cracking process 290, which includes methane, ethane, ethylene, propane, propylene, butane, and combinations thereof. Three portions 146a, 146b, and 146c of refrigerant stream 146 may be sent to the oligomerization process 300 and / or the aromatization process 400, where they are used for cooling and / or refrigeration (e.g., in the overhead condenser of the fractionation column of the first fractionation process 50). The vapor effluent 148 includes vapor recovered from the cracking process 290 of FIG. 2 (e.g., cracking zone 205). Three portions 148a, 148b, and 148c of the vapor effluent 148 may be sent to the oligomerization process 300, the first fractionation process 50, and / or the second fractionation process 80, any of which may be utilized there as a heat source, e.g., as a heat source for one or more fractionation column reboilers. The CPG stream 142 and the fuel gas stream 144 flow into the second fractionation process 80. A portion of the hydrogen effluent 81 is sent to the hydrogen vent 87. The first portion 87a of the hydrogen vent 87 flows into the oligomerization process 300 and is combined with the hydrogen feed 302 of FIG. 3. The second portion 87b of the hydrogen vent 87 flows into the hydrotreating process 70.

[0124] In certain embodiments, the utilization of refrigerant stream 146 and / or vapor effluent 148 provides for some of the service needs (e.g., heating and cooling) of the integrated conversion system 1800 and advantageously reduces the associated operating cost(s).

[0125] Referring to FIG. 13, an integrated conversion system 1900 is described, with like numbers representing like components as described in connection with FIGS. 11 and 12. System 1900 features the flexible configuration of the integrated conversion system 1500 and some of the integrated services of the integrated conversion system 1800.

[0126] This specification discloses a method for enriching a prime mover fuel stream (i.e., mogas). In one aspect, the mogas includes the fuel gas stream 144 of the integrated conversion system 1800 or the integrated conversion system 1900. In a further aspect, the mogas is an enriched prime mover fuel. In a particular aspect, the mogas is enriched by mixing into one or more effluent streams produced by the disclosed integrated conversion system. For example, the heavy effluent 56, the raffinate stream 88, or a combination thereof can be mixed into the mogas.

[0127] This specification describes a limited set of operating conditions (e.g., temperature, pressure) for the processes and systems of the present disclosure. One of ordinary skill in the art will understand that any operating conditions not disclosed herein may have any value, or range of values, suitable for the operation of the processes and systems disclosed herein. In a further aspect, changes to the operating conditions within any of the processes and systems disclosed herein may be implemented by one of ordinary skill in the art using the present disclosure to maintain the operation of the disclosed processes and systems.

[0128] In one aspect, the production of benzene by the integrated conversion system of the present disclosure can be advantageous in one or more areas when compared to conventional benzene production methods that utilize non-integrated (i.e., standalone) conversion processes. Conventional methods of producing benzene utilize materials contained in crude oil (e.g., materials obtained from the cracking of naphtha), and the cost of benzene production is linked to crude oil. The present disclosure utilizes ethane contained in natural gas (e.g., ethane produced by steam cracking of ethane) as a starting material so that the cost of benzene production is advantageously decoupled from crude oil. As more natural gas becomes available, the price of natural gas is decreasing while other factors are increasing the demand for benzene. For example, in North America, ethane for steam cracking is abundant, making naphtha cracking uneconomical. Also, there appears to be a potential significant oversupply of ethylene in the future. A further advantage is that the integrated conversion system of the present disclosure can convert ethylene to benzene so as to best match the associated financial and / or market conditions, particularly considering the significant increase in the global price related to benzene (see, for example, https: / / www.statista.com / statistics / 1171072 / price-benzene-forecast-globally / ).

[0129] A further advantage of the integrated conversion system of the present disclosure is the ability to produce large quantities of ethylene, 1-hexene, 1-octene, and benzene and then sell a portion of each compound according to the associated global demand. The integrated conversion system according to the present disclosure is characterized by flexibly changing the production rate of the product stream so as to respond to changes in the demand and / or price(s) of 1-hexene, 1-octene, and / or benzene. In some aspects, up to 1.5 million tons per year of ethylene can be produced. Other products that can be produced for sale by utilizing the integrated conversion system of the present disclosure include hydrogen (i.e., hydrogen effluent 81), cyclohexane (i.e., cyclohexane effluent 67), and toluene (i.e., toluene stream 84).

[0130] A further advantage of the integrated conversion system of the present disclosure is that 1 - hexene can potentially be used as a feed for the aromatization process. Hydrogenation of 1 - hexene to n - hexane, as disclosed herein, can provide further production advantages including slower catalyst deactivation, less plant maintenance, and higher aromatic selectivity. Since 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 will potentially have a low sulfur content, which can potentially enable the removal, recycling, conversion, etc. of conventional staged combustion air pre - treatment units, followed by a reduction in capital costs.

[0131] A further advantage of the integrated conversion system of the present disclosure is by using the light hydrocarbons produced in the cracking process 200 as a cooling and / or refrigeration source in the oligomerization process 300. This approach will enable the removal of dedicated refrigeration units within the oligomerization process 300, resulting in a subsequent reduction in capital costs. A further advantage is that the cracking process 200 can produce hydrogen and methane (not shown) that can be used as fuel for heating and / or operating other processes within the integrated conversion system. This can enable beneficial design improvements to the plant or system, such as miniaturization of heat exchangers.

Examples

[0132] Although the subject matter has been generally described, the following examples are provided as specific aspects of the present disclosure and to demonstrate its implementation and advantages. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims in any way. It will be clearly understood that various other aspects, modifications, and their equivalents can be relied upon, and such means can be suggested to those skilled in the art without departing from the spirit of the present disclosure or the scope of the appended claims after reading the description herein.

[0133] Figures 14 and 15 show the results regarding the use of the Aromax® catalyst for generating benzene from 1 - hexene. The operating conditions were a constant temperature of 950 o °F (510°C), a liquid hourly space velocity of 12 h -1 , a pressure of 100 psig (0.68 MPag), and a molar ratio of hydrogen to hydrocarbon of 1.2:1. Figure 14 shows that under the specified conditions, the conversion of 1 - hexene to benzene approaches nearly 100% in about 5 hours. Figure 15 shows that under the specified conditions, the selectivity for converting 1 - hexene to benzene remains at about 85% at about the 5 - hour mark. After about 1 hour, the selectivity for benzene under the above conditions is about 80%.

[0134] The scope of protection of the present disclosure is not limited by the above description, but is limited only by the following appended claims, and the scope includes all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present disclosure. Thus, the claims are a further description and an addition to the detailed description of the present disclosure. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference into this specification.

[0135] Aspects of a method for the regeneration of a processor have been described. The following is a first set of non - limiting specific embodiments according to the present disclosure.

[0136] Although some aspects and embodiments of the present disclosure have been shown and described, modifications can be made by those skilled in the art without departing from the spirit and teachings of the present disclosure. The aspects, embodiments, and examples described herein are merely illustrative and not intended to be limiting. Many variations and modifications of the present disclosure are possible and are within the scope of the subject matter.

[0137] Regarding transitional terms or phrases in the claims, the transitional term "comprising", which is synonymous with "including", "containing", "having", or "characterized by", is inclusive or open-ended and does not exclude additional unrecited elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claims. The transitional phrase "consisting essentially of" limits the claims to the specified materials or steps and those that do not substantially affect the basic and novel characteristics (s) of the claim. Claims in the form of "consisting essentially of" occupy a middle ground between closed claims in the form of "consisting of" and fully open claims in the form of "comprising". Unless otherwise indicated, the description of a "consisting essentially of" compound or composition should not be construed as "comprising", but is intended to describe the recited ingredients including substances that do not materially alter the composition or method to which the term applies. For example, a feedstock consisting essentially of a substance may contain impurities normally present in samples of the recited compound or composition that are commercially produced or commercially available. When the claims include different features and / or feature classes (e.g., among others, method steps, feedstock features, and / or product features), the transitional terms of "comprising", "consisting essentially of", and "consisting of" apply only to the feature class in which they are used and may have different transitional terms or phrases used with different features within the claims. For example, a method may include some recited steps (and other unrecited steps), but uses a catalyst system consisting of certain components, alternatively consisting essentially of certain components, or alternatively comprising certain components and other unrecited components.

[0138] In the present disclosure, systems, processes, and methods are described in terms of "including" various components, devices, or steps, but the systems, processes, and methods can also "consist essentially of" or "consist of" those various components, devices, or steps, unless otherwise stated.

[0139] As used herein, the term "about" means that the quantity, size, formulation, parameter, and other quantities and characteristics are not exact and need not be exact, but optionally reflect tolerances, conversion factors, rounding, measurement errors, etc., and other elements known to those skilled in the art, and that the quantity can be an approximation and / or can be larger or smaller. Generally, a quantity, size, formulation, parameter, or other quantity or characteristic is "about" or "approximately", whether or not it is stated explicitly as such. The term "about" also encompasses different amounts resulting from different equilibrium states of a composition brought about by a particular initial mixture. Whether or not modified by the term "about", a claim includes equivalents of that quantity. The term "about" can mean within 10% of the reported numerical value, or within 5% of the reported numerical value.

[0140] Unless otherwise indicated, when any kind of range, for example, a range of the number of carbon atoms, molar ratio, temperature, etc., is disclosed or claimed, each possible numerical value that such a range can reasonably encompass, including sub-ranges subsumed therein, is intended to be individually disclosed or claimed. For example, when describing a range of the number of carbon atoms, each possible individual integer, and the ranges between the integers of the atoms included in that range are subsumed therein. Thus, C1 to C 10By disclosing an alkyl group, or an alkyl group having from 1 to 10 carbon atoms or "up to" 10 carbon atoms, Applicant intends that the alkyl group can have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and these methods of describing such groups are compatible. When describing a range of measured values such as a molar ratio, all possible numerical values that such a range could reasonably encompass can refer to values within a range having one more significant digit than exists at the endpoints of the range, for example. In this example, a molar ratio of 1.03:1 to 1.12:1 individually includes 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. Applicant intends that these two methods of describing a range are compatible. Further, when a range of values is disclosed or claimed and Applicant intends to individually reflect each of the possible numbers that such a range could reasonably encompass, Applicant also intends to reflect and be compatible with the disclosure of every subrange and combination of subranges encompassed thereby. In this regard, C1 to C 10The applicant's disclosure of an alkyl group is intended to literally encompass C1-C6 alkyl, C4-C8 alkyl, C2-C7 alkyl, a combination of C1-C3 and C5-C7 alkyl, and the like. When describing ranges with different significant digits at the endpoints, for example, when describing a molar ratio of 1:1 to 1.2:1, all possible numbers that such a range could reasonably encompass can refer to values within a range that is one digit more than the significant digits present at the endpoints of the range with the largest number of digits (in this case 1.2:1). In this example, the molar ratio of 1:1 to 1.2:1 individually includes 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), as well as all molar ratios of any and all sub-ranges and combinations of sub-ranges included therein. Thus, for any reason, if the applicant, for example, to account for reference documents not recognized at the time of filing, chooses to claim means that are less than a complete means of the present disclosure, the applicant reserves the right to exclude any of the individual components of any such group (including any sub-range or combination of sub-ranges within that group).

[0141] Unless otherwise specified, the terms contacting, combining, and "in the presence of" refer to any additional order, sequence, or concentration when contacting or combining two or more components of any process disclosed herein. The combination or contact of components by the various methods described herein can occur in one or more contact zones under suitable contact conditions such as temperature, pressure, contact time, etc. The contact zone can be located within a vessel (e.g., storage tank, tote, container, mixing vessel, reactor, etc.), a length of pipe (e.g., tee, inlet, injection port, or header for combining component supply lines into a common line), or any other suitable device for contacting the components.

[0142] For purposes of all domestic stage applications in the United States from this application, all publications and patents mentioned in this disclosure are hereby incorporated by reference in their entirety for the purpose of disclosing and describing any constructs and methodologies described in those publications that may be used in connection with the methods of this disclosure. All publications and patents discussed herein are provided solely for their disclosure prior to the filing date of this application. Nothing in this specification should be construed as an admission by the inventors that they are not entitled to antedate such disclosure by virtue of prior disclosure.

[0143] In any application to the United States Patent and Trademark Office, the abstract of this application is provided for the purpose of complying with the requirements of 37 C.F.R. § 1.72 and for the purpose of enabling the United States Patent and Trademark Office and the public generally to determine quickly from a cursory inspection the nature and gist of the technical disclosure. Accordingly, the abstract of this application is not intended to be used for interpreting the claims or limiting the scope of the subject matter disclosed herein. Further, any headings used herein are not intended to be used for interpreting the claims or limiting the scope of the subject matter disclosed herein. Any use of the past tense, whether or not separately indicated for interpretive or hypothetical examples, is not intended to reflect actual acts in carrying out any interpretive or hypothetical examples.

[0144] At least one embodiment is disclosed, and variations, combinations, and / or modifications of the embodiment(s) and / or features thereof made by those skilled in the art are within the scope of this disclosure. Alternative embodiments resulting from combinations, integrations, and / or omissions of features of the embodiment(s) are also within the scope of this disclosure. When a numerical range or limitation is explicitly stated, such explicit range or limitation should be understood to include iterative ranges or limitations of the same magnitude that fall within the explicitly stated range or limitation (e.g., about 1 to about 10 includes 2, 3, 4, etc., and greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, if the lower limit value is R l and the upper limit value is R u are disclosed, then any number within that range is always specifically disclosed. Specifically, the following numbers within the range are clearly disclosed: R = R l + k·(R u - R l ), where k is a variable in the range of 1 percent to 100 percent, changing in 1 percent increments, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,.....50 percent, 51 percent, 52 percent...95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Further, any numerical range defined by the two R numbers defined above is also clearly disclosed. The use of the term "optionally" with respect to any element of a claim means that the element is either required or, alternatively, the element is not required, and both alternatives are included in the claim scope. Additional Disclosure

[0145] The following listed embodiments of this disclosure are provided as non-limiting examples.

[0146] In the oligomerization process, ethylene is contacted with a selective higher olefin catalyst to obtain an oligomerization reactor effluent containing C6 hydrocarbons including 1-hexene and C8 hydrocarbons including 1-octene; recovering 1-hexene and 1-octene from the oligomerization reactor effluent; in the hydrotreating process, contacting 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to obtain an aromatization feed containing hexane, octane, or both; and, in the aromatization process, contacting the aromatization feed with an aromatization catalyst to obtain a reformate effluent containing benzene. A first embodiment, which is a method including these steps.

[0147] The method according to the first embodiment, wherein the C6 hydrocarbons are present in an amount of about 20 wt% to about 99 wt% based on the total weight of the oligomerization reactor effluent, and the C8 hydrocarbons are present in an amount of about 0.1 wt% to about 75 wt% based on the total weight of the oligomerization reactor effluent. A second embodiment.

[0148] The method according to the first or second embodiment, wherein the purity of 1-hexene is about 60 wt% to about 99.9 wt% based on the total weight of the C6 hydrocarbons in the oligomerization reactor effluent. A third embodiment.

[0149] The method according to any one of the first to third embodiments, wherein the purity of 1-octene is about 95 wt% to about 99.3 wt% based on the total weight of the C8 hydrocarbons in the oligomerization reactor effluent. A fourth embodiment.

[0150] The method according to any one of the first to fourth embodiments, wherein the oligomerization reactor effluent further comprises C 10 hydrocarbons, C 12 hydrocarbons, C 14+ hydrocarbons, or a combination thereof. A fifth embodiment.

[0151] The method according to the fifth embodiment, wherein the C 10The hydrocarbon is present in an amount of about 1 wt% to about 4 wt% based on the total weight of the oligomerization reactor effluent, and the C 12 The hydrocarbon is present in an amount of about 0.1 wt% to about 3 wt% based on the total weight of the oligomerization reactor effluent, and the C 14+ A sixth embodiment, wherein the hydrocarbon is present in an amount of about 0 wt% to about 3.5 wt% based on the total weight of the oligomerization reactor effluent.

[0152] A method according to any one of the first to sixth embodiments, 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, 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. A seventh embodiment.

[0153] A method according to any one of the first to seventh embodiments, 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. An eighth embodiment.

[0154] A method according to any one of the first to eighth embodiments, wherein the recovery of 1-hexene and 1-octene from the oligomerization reactor effluent comprises fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octene, and a third stream comprising hexene, and only a portion of the third stream is fed to the hydrotreating process among the first stream, the second stream, and the third stream. A ninth embodiment.

[0155] A method according to any one of Embodiments 1 to 8, wherein the recovery of 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises fractionating 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, and only a part of the second stream and only a part of the third stream among the first stream, the second stream, and the third stream are supplied to the hydrogenation process, Embodiment 10.

[0156] A method according to any one of Embodiments 1 to 8, wherein the recovery of 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises fractionating the oligomerization reactor effluent into a first stream containing heavy hydrocarbons and spent catalyst, and a second stream containing hexene and octene, and only a part of the second stream among the first stream and the second stream is supplied to the hydrogenation process, Embodiment 11.

[0157] A method according to any one of Embodiments 1 to 8, wherein the recovery of 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises fractionating the oligomerization reactor effluent into a first stream containing spent catalyst, and a second stream containing hexene, octene, and heavy hydrocarbons, and only a part of the second stream among the first stream and the second stream is supplied to the hydrogenation process, Embodiment 12.

[0158] A method according to any one of Embodiments 1 to 8, wherein the recovery of 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises separating 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, fractionating the third stream to obtain a high - purity 1 - hexene stream and a C6 feed stream, and flowing the C6 feed stream to the hydrogenation process, Embodiment 13.

[0159] A method according to any one of Embodiments 1 to 13, further comprising fractionating a purification stream to recover a naphtha stream, feeding the naphtha stream to the hydrotreating process, and in the hydrotreating process, contacting naphtha with the hydrotreating catalyst to produce one or more of n-hexane and n-octane in the aromatization feed, a 14th embodiment.

[0160] A method according to any one of Embodiments 1 to 14, wherein the reformate effluent further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene, or a combination thereof, and the method further comprises fractionating the reformate effluent into a benzene stream, a toluene stream, a xylene stream, and a raffinate stream, a 15th embodiment.

[0161] A method according to the 15th embodiment, wherein the 1-hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream, a 16th embodiment.

[0162] A method according to the 15th embodiment, wherein the 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream, a 17th embodiment.

[0163] A method according to any one of Embodiments 1 to 17, wherein the aromatization process is further configured to produce a hydrogen effluent, and the method further comprises flowing a portion of the benzene stream and a portion of the hydrogen effluent to a hydrogenation process to obtain cyclohexane, and recycling the cyclohexane to the oligomerization process, a 18th embodiment.

[0164] A method according to any one of Embodiments 1 to 18, wherein the oligomerization reactor effluent further comprises cyclohexane and other hexanes, and the method further comprises recovering cyclohexane and the other hexanes from the oligomerization reactor effluent, flowing the other hexanes recovered from the oligomerization reactor effluent to the hydrotreating process, and recycling the cyclohexane recovered from the oligomerization reactor effluent to the oligomerization process. A 19th embodiment.

[0165] A method according to any one of Embodiments 1 to 19, further comprising decomposing ethane, propane, butane, pentane, naphtha, or a mixture thereof in a steam cracker to obtain a cracker effluent containing ethylene, and flowing the ethylene recovered from the cracker effluent to the oligomerization process. A 20th embodiment.

[0166] A method according to the 20th embodiment, wherein the cracker effluent further comprises light hydrocarbons, and the method further comprises using the light hydrocarbons recovered from the cracker effluent as a cooling source for the oligomerization reactor in the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof. A 21st embodiment.

[0167] A method according to any one of Embodiments 1 to 21, further comprising recovering steam from the steam cracker and using the steam as a heat source for the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof. A 22nd embodiment.

[0168] A method according to any one of Embodiments 1 to 22, wherein the step of contacting ethylene with a selective higher olefin catalyst is carried out in the presence of a diluent recovered from the reformate effluent, and the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof, Embodiment 23.

[0169] A method according to any one of Embodiments 1 to 23, further comprising flowing the raffinate recovered from the aromatization process to a steam cracker and cracking the raffinate in the steam cracker, Embodiment 24.

[0170] A method according to any one of Embodiments 1 to 24, wherein the oligomerization reactor effluent further contains C 9+ hydrocarbons, and the method further comprises mixing the C 9+ hydrocarbons, a raffinate stream obtained from the reformate effluent, or both the C 9+ hydrocarbons and the raffinate stream into a prime mover fuel stream, Embodiment 25.

[0171] A method according to any one of Embodiments 1 to 25, further comprising flowing hydrogen obtained from the reformate effluent to the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process, Embodiment 26.

[0172] A method according to any one of Embodiments 1 to 26, wherein the ethylene contacted in the oligomerization process is received in a stream containing ethylene and ethane, Embodiment 27.

[0173] A method according to any one of Embodiments 1 to 27, wherein a sulfur removal system is not used between the oligomerization process and the aromatization process, Embodiment 28.

[0174] An oligomerization reactor configured to contact ethylene with a selective higher olefin catalyst to obtain an oligomerization reactor effluent comprising C6 hydrocarbons including 1-hexene and C8 hydrocarbons 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 the 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to obtain an aromatization feed comprising hexane, octane, or both, and an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to obtain a reformate effluent comprising benzene, a system comprising, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides, a 29th embodiment.

[0175] The system according to the 29th embodiment, further comprising a steam cracker configured to obtain a cracker effluent comprising ethylene, wherein ethylene is recovered from the cracker effluent for oligomerization in the oligomerization reactor, a 30th embodiment.

[0176] The system according to the 30th embodiment, wherein the cracker effluent further comprises light hydrocarbons, and the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or a combination thereof is configured to use the light hydrocarbons as a cooling source, a 31st embodiment.

[0177] The system according to the 30th embodiment, wherein the steam cracker is further configured to generate a steam effluent, and the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or a combination thereof is configured to use the steam effluent as a heat source, a 32nd embodiment.

[0178] A system according to any one of Embodiments 29 to 32, further comprising a fractionator configured to fractionate a purification stream to recover a naphtha stream, wherein in the hydrogenation reactor, naphtha contacts the hydrogenation catalyst to produce one or more of n - hexane and n - octane in the aromatization feed, a 33rd embodiment.

[0179] A system according to any one of Embodiments 29 to 32, wherein the reformate effluent 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 effluent into a benzene stream, a toluene stream, a xylene stream comprising ethylbenzene and xylene, and a raffinate stream, a 34th embodiment.

[0180] A system according to the 34th embodiment, wherein 1 - hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream, a 35th embodiment.

[0181] A system according to the 34th embodiment, wherein 1 - octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream, a 36th embodiment.

[0182] A system according to the 34th embodiment, wherein the aromatization reactor is further 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 and produce cyclohexane therefrom, and the oligomerization reactor is configured to receive the cyclohexane, a 37th embodiment.

[0183] A system according to any one of Embodiments 29 to 37, further comprising 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, and only a part of the third stream is supplied to the aromatization reactor, according to Embodiment 38.

[0184] A system according to any one of Embodiments 29 to 38, further comprising 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, and only a part of the second stream is supplied to the aromatization reactor, according to Embodiment 39.

[0185] A system according to any one of Embodiments 29 to 38, further comprising 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, and at least a part of the second stream and at least a part of the third stream are supplied to the aromatization reactor, according to Embodiment 40.

[0186] A system according to any one of Embodiments 29 to 38, further comprising 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, and only a part of the second stream is supplied to the aromatization reactor, according to Embodiment 41.

[0187] The system according to any one of Embodiments 29 to 38, further comprising a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream containing spent catalyst and a second stream containing hexene, octene, and heavy hydrocarbons, wherein only a part of the second stream among the first stream and the second stream is supplied to the aromatization reactor. Embodiment 42.

[0188] The system according to 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 comprising a C6 separator configured to split the third stream into a high-purity 1-hexene stream and a hexane stream, and a cyclohexane recovery column configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle, the residual C6 feed being supplied to the aromatization reactor and the cyclohexane recycle being supplied to the oligomerization reactor. Embodiment 43.

[0189] The system according to 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, 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 a combination thereof, and the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides. Embodiment 44.

Claims

1. In the oligomerization process, ethylene is contacted with a selective higher olefin catalyst to produce an oligomerization reactor effluent containing C hydrocarbons including 1-hexene and C hydrocarbons including 1-octene. ６ ８ ​ Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent, in a hydrotreating process, contacting 1 - hexene, 1 - octene, or both 1 - hexene and 1 - octene recovered from the oligomerization reactor effluent with a hydrotreating catalyst to obtain an aromatization feed containing hexane, octane, or both, and in an aromatization process, contacting the aromatization feed with an aromatization catalyst to obtain a reformate effluent containing benzene, A method comprising.

2. Said C ６ The hydrocarbon is present in an amount of about 20 wt% to about 99 wt% based on the total weight of the oligomerization reactor effluent, and said C ８ The method according to claim 1, wherein the hydrocarbon is present in an amount of about 0.1 wt% to about 75 wt% based on the total weight of the oligomerization reactor effluent.

3. The purity of 1-hexene is the C in the oligomerization reactor effluent ６ The method according to claim 2, wherein the purity is from about 60 wt% to about 99.9 wt% based on the total weight of the hydrocarbons.

4. The purity of 1-octene is the C in the oligomerization reactor effluent ８ The method according to claim 2, wherein the purity is from about 95 wt% to about 99.3 wt% based on the total weight of the hydrocarbons.

5. The oligomerization reactor effluent further comprises C １０ hydrocarbons, C １２ hydrocarbons, C １４＋ hydrocarbons, or combinations thereof, according to claim 1.

6. Said C １０ hydrocarbons are present in an amount of from about 1 wt% to about 4 wt% based on the total weight of the oligomerization reactor effluent, and said C １２ hydrocarbons are present in an amount of from about 0.1 wt% to about 3 wt% based on the total weight of the oligomerization reactor effluent, and said C １４＋ The method according to claim 5, wherein the hydrocarbons are present in an amount of from about 0 wt% to about 3.5 wt% based on the total weight of the oligomerization reactor effluent.

7. The method according to claim 1, wherein the selective higher olefin catalyst is selected from PN Mes - tBuPh - DIP, PN Mes - MeOPPh - 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.

8. The method according to claim 1, 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.

9. Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises fractionating 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 third stream is fed to the hydrotreating process among the first stream, the second stream, and the third stream. The method according to claim 1.

10. Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent comprises fractionating 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, The method according to claim 1, wherein only a part of the second stream and only a part of the third stream among the first stream, the second stream, and the third stream are supplied to the hydrogenation process.

11. Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent, including fractionating the oligomerization reactor effluent into a first stream containing heavy hydrocarbons and spent catalyst, and a second stream containing hexene and octene, The method according to claim 1, wherein only a part of the second stream among the first stream and the second stream is supplied to the hydrogenation process.

12. Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent, including fractionating the oligomerization reactor effluent into a first stream containing spent catalyst, and a second stream containing hexene, octene and heavy hydrocarbons, The method according to claim 1, wherein only a part of the second stream among the first stream and the second stream is supplied to the hydrogenation process.

13. Recovering 1 - hexene and 1 - octene from the oligomerization reactor effluent, separating 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, Fractionating the third stream to obtain a high-purity 1-hexene stream and a C ６ feed stream, and said C ６ The method according to claim 1, comprising flowing a feed stream into the hydrogenation process.

14. fractionating a purified stream to recover a naphtha stream, supplying the naphtha stream to the hydrogenation process, and in the hydrogenation process, contacting naphtha with the hydrogenation catalyst to obtain one or more of n - hexane and n - octane in the aromatization feed. The method according to claim 1 further includes this.

15. The reformate effluent further includes toluene, ethylbenzene, xylene, 1 - hexene, 1 - octene, or a combination thereof, and the method The method according to claim 1 further includes fractionating the reformate effluent into a benzene stream, a toluene stream, a xylene stream, and a raffinate stream.

16. The method according to claim 15, wherein the 1 - hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

17. The method according to claim 15, wherein the 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

18. The aromatization process is further configured to produce a hydrogen effluent, and the method flows a portion of the benzene stream and a portion of the hydrogen effluent to a hydrogenation process to produce cyclohexane, and further comprises recycling the cyclohexane to the oligomerization process, the method according to claim 1.

19. The oligomerization reactor effluent further comprises cyclohexane and other hexanes, and the method recovers cyclohexane and the other hexanes from the oligomerization reactor effluent, flows the other hexanes recovered from the oligomerization reactor effluent to the hydrotreating process, and recycles the cyclohexane recovered from the oligomerization reactor effluent to the oligomerization process, the method according to claim 1.

20. decomposing ethane, propane, butane, pentane, naphtha, or a mixture thereof in a steam cracker to obtain a cracker effluent containing ethylene, and flowing the ethylene recovered from the cracker effluent to the oligomerization process, the method according to claim 1.

21. The cracker effluent further comprises light hydrocarbons, and the method further comprises using the light hydrocarbons recovered from the cracker effluent as a cooling source for the oligomerization reactor in the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof, the method according to claim 20.

22. recovering steam from the steam cracker, and using the steam as a heat source for the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof, the method according to claim 1.

23. The step of contacting ethylene with the selective higher olefin catalyst is carried out in the presence of a diluent recovered from the reformate effluent, and the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof, according to the method of claim 1.

24. Flowing the raffinate recovered from the aromatization process to a steam cracker, and decomposing the raffinate in the steam cracker, further comprising the method of claim 1.

25. The oligomerization reactor effluent further comprises C ９＋ hydrocarbons, and the method comprises said C ９＋ hydrocarbon, a raffinate stream obtained from said reformate effluent, or said C ９＋ mixing both said hydrocarbon and said raffinate stream into a prime mover fuel stream, further comprising the method according to claim 1.

26. Flowing the hydrogen obtained from the reformate effluent to the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process, further comprising the method of claim 1.

27. The ethylene contacted in the oligomerization process is received in a stream containing ethylene and ethane, according to the method of claim 1.

28. A sulfur removal system is not used between the oligomerization process and the aromatization process, according to the method of claim 1.

29. Ethylene is contacted with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising hydrocarbons containing 1-hexene and hydrocarbons containing 1-octene, ６ configured to produce an oligomerization reactor effluent comprising hydrocarbons containing 1-hexene and hydrocarbons containing 1-octene, ８ an oligomerization reactor, 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 containing hexane, octane, or both, and An aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce a reformate effluent containing benzene, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides, the aromatization reactor, comprising a system.

30. A steam cracker configured to produce a cracker effluent containing ethylene, wherein ethylene is recovered from the cracker effluent for oligomerization in the oligomerization reactor, further comprising the steam cracker of claim 29.

31. The system of claim 30, wherein the cracker effluent further comprises light hydrocarbons, and the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or a combination thereof, is configured to use the light hydrocarbons as a cooling source.

32. The system of claim 30, wherein the steam cracker is further configured to produce a steam effluent, and the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reformate effluent, or a combination thereof, is configured to use the steam effluent as a heat source.

33. Further comprising a fractionator configured to fractionate a purification stream to recover a naphtha stream, The system of claim 29, wherein in the hydrogenation reactor, naphtha contacts the hydrogenation catalyst to produce one or more of n - hexane and n - octane in the aromatization feed.

34. The reformate effluent further comprises toluene, ethylbenzene, xylene, 1 - hexene, 1 - octene, or a combination thereof, and the system The system of claim 29, further comprising a second separation unit configured to fractionate the reformate effluent into a benzene stream, a toluene stream, a xylene stream containing ethylbenzene and xylene, and a raffinate stream.

35. The system of claim 34, wherein 1 - hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

36. The system of claim 34, wherein 1 - octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

37. The system of claim 34, wherein the aromatization reactor is further 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 and produce cyclohexane therefrom, and the oligomerization reactor is configured to receive the cyclohexane.

38. 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. The system according to claim 29, wherein only a portion of the third stream among the first stream, the second stream, and the third stream is supplied to the aromatization reactor. **Claim 39** 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. The system according to claim 29, wherein only a portion of the second stream among the first stream, the second stream, and the third stream is supplied to the aromatization reactor. **Claim 40** 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. The system according to claim 29, wherein at least a portion of the second stream and at least a portion of the third stream among the first stream, the second stream, and the third stream are supplied to the aromatization reactor. **Claim 41** 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. The system according to claim 29, wherein only a portion of the second stream among the first stream and the second stream is supplied to the aromatization reactor. **Claim 42** A second separation unit configured to fractionate the oligomerization reactor effluent into a first stream containing spent catalyst, and a second stream containing hexene, octene, and heavy hydrocarbons. The system according to claim 29, wherein only a portion of the second stream among the first stream and the second stream is supplied to the aromatization reactor. **Claim 43** 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 C configured to divide the third stream into a high-purity 1-hexene stream and a hexane stream ６ separator, and The hexane stream to residual C ６ further includes a cyclohexane recovery column configured to separate the feed and the cyclohexane recycle into a cyclohexane recycle, The residual C ６ The system according to claim 29, wherein the feed is supplied to the aromatization reactor and the cyclohexane recycle is supplied to the oligomerization reactor. **Claim 44** The system according to claim 29, wherein the selective advanced olefin catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPPh-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 a combination thereof, and the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

Images