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

Description

Technical Field

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

[0002] Benzene, also known as crude benzene, mineral naphtha, benzene hydride and annulene, is an aromatic compound with important commercial significance. Benzene is present in crude oil, is a component of gasoline, and is widely used in the manufacture of plastics, resins, synthetic fibers, rubber lubricants, dyes, detergents, medicines, pesticides, glues, adhesives, cleaning products, paint strippers and other commercial products. Due to the increase in crude oil demand, the cost of conventional methods for producing benzene from materials contained in crude oil is increasing. The method of using natural gas as a starting raw material to produce benzene can provide a lower cost alternative. Therefore, it is desirable to use additional novel and improved systems and methods for the production of benzene. Summary of the invention

[0003] Thus, the present disclosure provides novel and non-obvious methods and systems for benzene production, including systems and methods for producing a reforming effluent comprising benzene and additional commercially valuable hydrocarbons. For example, in certain aspects, the present disclosure provides a method comprising: a) contacting ethylene with a selective higher olefin catalyst in an oligomerization process to produce an oligomerization reactor effluent, the oligomerization reactor effluent comprising 1) C6 hydrocarbons including 1-hexene and 2) C8 hydrocarbons including 1-octene; b) recovering 1-hexene and 1-octene from the oligomerization reactor effluent; c) contacting 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst in a hydrotreating process to produce an aromatization feed comprising hexane, octane, or both; and d) contacting the aromatization feed with an aromatization catalyst in an aromatization process to produce a reforming effluent comprising benzene. In a related aspect, 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, and the C8 hydrocarbons comprise from about 0.1 wt% to about 75 wt% of the total weight of the oligomerization reactor effluent. In a related feature, the resulting 1-hexene and 1-octene streams are advantageously characterized by significant purity levels, including 1) a purity level of about 60 wt% to about 99.9 wt% for 1-hexene relative to the total weight of the C6 hydrocarbons in the oligomerization reactor effluent, and 2) a purity level of 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 aspects, in addition to C6 hydrocarbons and C8 hydrocarbons, the oligomerization reactor effluent produced according to the present disclosure may further comprise C 10 Hydrocarbon, C 12Hydrocarbons and / or C 14+ hydrocarbons, including combinations of the foregoing. For example, the oligomerization reactor effluent may be characterized by one or more of the following: 1) about 1% by weight (wt%) to about 4% by weight of C 10 2) about 0.1 wt % to about 3 wt % of C 12 and / or 3) from about 0 wt % to about 3.5 wt % of C 14+ hydrocarbon streams, all based on the total weight of the oligomerization reactor effluent.

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

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

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

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

[0009] According to additional features of the disclosed methods, the aromatization process can be further configured to beneficially produce a hydrogen effluent by: 1) passing a portion of the benzene stream and a portion of the hydrogen effluent to a hydrogenation process to produce cyclohexane; and 2) recycling the cyclohexane to the oligomerization process.

[0010] As described herein, the feature of oligomerization reactor effluent can be the presence of various hydrocarbons.In some aspects, oligomerization reactor effluent can especially comprise hexane material, such as hexanaphthene, which can be recovered or separated into hexanaphthene and / or other (non-hexanaphthene) hexanes from oligomerization reactor effluent.In additional aspect, non-hexanaphthene material can be recovered from oligomerization reactor effluent---when processing or when fluid is transported to hydrotreating process as described herein, and any residual hexanaphthene can be recovered from oligomerization reactor effluent and recycled or transported to 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 aspects, the method may further include 1) cracking one or more of ethane, propane, butane, pentane and / or naphtha (including mixtures thereof) in a steam cracker to produce a cracker-derived effluent containing ethylene; and 2) causing the resulting ethylene recovered or separated from the cracker effluent to flow into or otherwise transport it to the oligomerization process described herein. In some aspects, the resulting cracker effluent may further include one or more light hydrocarbons, wherein the method may advantageously further include 1) using the light hydrocarbons recovered from the cracker effluent as a cooling source for the oligomerization reactor in the oligomerization process, including a first fractionation process located downstream of the oligomerization process, a second fractionation process located downstream of the aromatization process, or for use in combination with the first fractionation process and the second fractionation process. In related aspects, the heat energy associated with the method of the present disclosure may be beneficially recycled and / or recovered for one or more steps or processes associated therewith. For example, the method can further include 1) recovering steam from the steam cracker; and 2) utilizing the recovered steam as a heat source for the aforementioned oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or for a combination of the first and second fractionation processes, as further described herein.

[0012] As described herein, the oligomerization reactor effluent produced according to the present disclosure may include a variety of hydrocarbon species and their derivatives. According to certain features, the oligomerization reactor effluent may include or additionally include one or more C 9+ Thus, the method may further include steps or processes for utilizing the C9+ hydrocarbons, including but not limited to 1) blending the C9+ hydrocarbons into a fuel stream (such as a motor fuel stream). In additional aspects, the C9+ hydrocarbon stream may first be blended with an additional hydrocarbon stream (such as a raffinate stream separated from a reforming effluent), and then the resulting C9+ hydrocarbon stream may be blended with the raffinate stream. 9+ The hydrocarbon / raffinate stream is blended into a fuel stream (eg, a motor fuel stream).

[0013] In certain aspects, the disclosed methods may further include recycling, reintroducing, or utilizing chemicals or moieties produced therein, including 1) passing or recycling hydrogen obtained from the reforming effluent to the oligomerization process, the hydrotreating process, or both (i.e., the oligomerization process and the hydrotreating process).

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

[0015] The steam cracker can be configured for optimally performing the disclosed methods, including aspects wherein the steam cracker is configured to produce a steam effluent, and wherein the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reforming effluent, or a combination thereof are configured to advantageously utilize the steam effluent as an internally derived heat source.

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

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

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

[0019] According to further features, the system may additionally include a second separation unit, which is 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, wherein only a portion of the second stream (comprising octene) is fed to the aromatization reactor. In certain aspects, the system may further include a second separation unit, which is 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, wherein 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 some aspects, the system further includes a second separation unit, which is 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, wherein only a portion of the second stream (comprising hexene and octene) is fed to the aromatization reactor. In an additional aspect, the system further comprises 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, wherein 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, a first separation unit of the system is configured to recover a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes and hexanes, wherein the system further comprises 1) a C6 splitter configured to separate the third stream into a) a high purity 1-hexene stream; and b) a hexane stream; and 2) a cyclohexane recovery tower configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle stream, wherein 1) the residual C6 feed is fed to an aromatization reactor, and 2) the cyclohexane recycle stream is fed to an oligomerization reactor. In a further aspect, the selective oligomerization catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PN Guan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh or a combination thereof; and the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides, as further described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the integrated transformation system is illustrated.

[0022] Figure 2 A schematic diagram of the cracking process is illustrated.

[0023] Figure 3 Schematic diagram of the oligomerization process is illustrated.

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

[0025] Figure 5 A schematic diagram of another integrated transformation system is illustrated.

[0026] Figure 6 Schematic diagrams of additional integrated transformation systems are illustrated.

[0027] Figure 7 Schematic diagram of the integrated transformation system is illustrated.

[0028] Figure 8 A schematic diagram of another integrated transformation system is illustrated.

[0029] Fig. 9 Schematic diagrams of additional integrated transformation systems are illustrated.

[0030] Fig.10 Schematic diagram of the integrated transformation system is illustrated.

[0031] Fig.11 A schematic diagram of another integrated transformation system is illustrated.

[0032] Fig.12 Schematic diagrams of additional integrated transformation systems are illustrated.

[0033] Fig.13 Schematic diagram of the integrated transformation system is illustrated.

[0034] Fig.14 A graph showing the conversion of 1-hexene to benzene.

[0035] Fig.15 A graph showing the selectivity of 1-hexene to benzene. DETAILED DESCRIPTION

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

[0037] Disclosed herein are systems, processes, apparatus and methods for multi-step chemical conversions in which several chemical conversions that are each conventionally performed in discrete processes are integrated into a single continuous flow system. The integrated conversion system and processes, apparatus and methods associated therewith generally relate to a continuous flow system that integrates the conversion of C4 hydrocarbons, such as hydrocarbons derived from natural gas (e.g., ethane), into oligomer intermediates (e.g., 1-hexene and / or 1-octene), which are further converted into aromatic hydrocarbons (e.g., benzene).

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

[0039] In the systems, processes and methods disclosed herein, various 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 the stream or product is formed; alternatively, the stream or product can be recovered from another process and / or stream located downstream of where it is formed.

[0040] The following definitions are provided to help those skilled in the art understand the detailed description of the present disclosure. Unless otherwise defined herein, the scientific and technical terms used in conjunction with the present disclosure should have the meanings commonly understood by those of ordinary skill in the art to which the present disclosure belongs. In addition, unless the context requires otherwise, singular terms should include plural (forms) and plural terms should include singular (forms).

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

[0042] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If a term is used in the present disclosure, but is not clearly defined in this article, the definition in IUPAC Compendium of Chemical Terminology, 2nd edition (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition applied herein, or does not make any claim to which the definition is applied unclear or unimplementable. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

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

[0044] Formula C A+ and C A- A represents the number of carbon atoms in the molecular formula of an organic molecule (e.g., a hydrocarbon), where A is an integer or whole number. 3+ It refers to compounds containing 3 or more carbon atoms per molecule. 5- Denotes a compound containing 5 or fewer carbon atoms per molecule.

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

[0046] Whenever used in this specification and claims, the term "alkene" refers to a compound with at least one carbon-carbon double bond, which is not a part of an aromatic ring or ring system. Unless otherwise expressly stated, the term "alkene" includes aliphatic and aromatic, acyclic and cyclic, and / or straight and branched compounds with at least one carbon-carbon double bond, which is not a part of an aromatic ring or ring system. Unless expressly indicated, the term "alkene" itself does not indicate whether there are heteroatoms and / or whether there are other carbon-carbon double bonds. Alkenes with only one, only two, only three, etc. carbon-carbon double bonds can be identified by using the terms "single", "two", "three", etc. in the name of the alkene. Alkenes can be further identified by the position of the carbon-carbon double bond (one or more).

[0047] The term "reactor effluent" and its derivatives (e.g., oligomerization reactor effluent) generally refer to all materials leaving the reactor. The term "reactor effluent" and its derivatives may also be preceded by other descriptors that limit the portion of the reactor effluent. For example, while the term "reactor effluent" refers to all materials leaving the reactor (e.g., product and solvent or diluent, etc.), the term "olefin reactor effluent" refers to the reactor effluent containing olefin (i.e., carbon-carbon) double bonds.

[0048] The term "oligomerization" and its derivatives refer to a process for producing a product mixture containing at least 70 weight percent (70 wt%) of a product containing 2 to 30 monomer units. Similarly, an "oligomer" is a product containing 2 to 30 monomer units, and an "oligomerization product" includes all products made by the "oligomerization" process, including "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" do not have to be the same. For example, an "oligomer" or "oligomerization product" of an "oligomerization" process using ethylene and propylene as monomers can contain ethylene and / or propylene units at the same time.

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

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

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

[0052] The term "oligomer" refers to a C-carbon double bond in the molecular structure. 6+ Hydrocarbons. For example, the oligomer may be a C6 monoolefin.

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

[0054] The cetane number is the relative value of diesel fuel to cetane (C 16 H 34 ) as a measure of the ignition properties of a standard.

[0055] The term "smoke point" as applied to an oil or fat refers to the temperature at which, under specific and defined conditions, the oil or fat begins to produce a continuous blue smoke that becomes clearly visible.

[0056] By referring to the attached flow diagram and in combination with the following description, the aspects of the present disclosure can be further understood. Those skilled in the art will be familiar with various additional pumps, valves, heaters, coolers and other conventional devices required for implementing the present disclosure. For the sake of clarity, the additional devices have been omitted from the figure. The description of the accompanying drawings provides a method for operating the process. However, it should be understood that although these drawings are general representations of the process, minor changes can be made to adapt the drawings to various conditions within the scope of the present disclosure. It should also be understood that the number references in the drawings are consistent in all drawings. For example, the inlet stream 10 containing hydrocarbon feed is the hydrocarbon feed inlet stream in all drawings. Unless otherwise clearly disclosed, the functions and components of the process in one integrated conversion system are substantially the same as those in another integrated conversion system including the process. In other words, unless otherwise clearly disclosed, the functions and components of the cracking process 200 in the integrated conversion system 1000 are substantially the same as the functions and components of the cracking process 200 in the integrated conversion system 1100, or the functions and components of the cracking process 200 in the integrated conversion system 1200, etc.

[0057] refer to Figure 1 , describes an integrated conversion system 1000. 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 hydrotreatment process 70, and a second fractionation process 80.

[0058] In the integrated conversion systems disclosed herein, the various system components may be in fluid communication via one or more conduits (e.g., pipes, tubes, flow lines, etc.) suitable for conveying a particular flow, e.g., Figure 1 The numbered streams in the detail display.

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

[0060] In a specific aspect, the amount of ethane in the hydrocarbon feed 10 is in the range of about 10 wt % to about 95 wt % based on the total weight of the hydrocarbon feedstock 10; alternatively, about 20 wt % to about 80 wt %, or alternatively, about 40 wt % to about 60 wt %.

[0061] refer to Figure 2 , describing aspects of a cracking process 200. The hydrocarbon feed 10 is combined with a hydrocarbon recycle stream 201. The hydrocarbon recycle stream 201 may be combined with other streams of the integrated reforming system disclosed herein. For example, the hydrocarbon recycle stream 201 may be combined with the C 3+ STREAM 262 and / or Alternative C 3+ 282 (not shown); or alternatively, with Fig.12 and Fig.13 Alternatively, as further described herein. It is contemplated that some aspects of the cracking process 200 may be operated in the absence of the hydrocarbon recycle 201.

[0062] The hydrocarbon feed 10 flows into a cracking zone 205 including a steam cracker, where it is contacted with a high temperature to produce a cracker effluent 210. The cracking zone 205 includes one or more radiant furnace reactors capable of producing the cracker effluent 210. In one aspect, the temperature of the cracking zone 205 can be 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 can 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). 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 one aspect, the cracker effluent 210 comprises one or more monomers, hydrogen, methane, acetylene, ethane, C 3+ Saturated hydrocarbons and combinations thereof. In a further aspect, the monomer comprises ethylene, propylene, butene, or a combination thereof; or alternatively, ethylene.

[0063] The amount of ethylene in the cracker effluent 210 may be in the range of about 10 wt % to about 95 wt % based on the total weight of the cracker effluent 210; alternatively, about 20 wt % to about 80 wt %; or alternatively, about 40 wt % to about 70 wt %. In a further aspect, the cracker effluent 210 may include 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+ hydrocarbon.

[0064] The cracker effluent 210 flows into the quench zone 215 to produce a quench gas stream 220. In one aspect, the operating temperature of the quench zone 215 may be lower than the temperature required to maintain the cracking reaction occurring in the cracker effluent 210. In one aspect, the cracker effluent 210 is cooled to a temperature below about 595°C; alternatively, cooled to a temperature in the range of about 30°C to about 110°C to form a quench gas stream 220. Quenching can be performed by any means suitable to one of ordinary skill in the art. For example, the cracker effluent 210 can be conveyed to a quench boiler and a quench tower, where fuel oil and dilution streams can be removed. U.S. Patent Nos. 3,407,798; 5,427,655; 3,392,211; 4,351,275; and 3,403,722 disclose methods for cooling the cracker effluent 210, all of which are incorporated herein by reference in their entirety. The quench gas stream 220 flows into the first compression zone 225 to produce a pressurized gas stream 230. In one aspect, the pressurized gas stream 230 may include 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, wherein the gas compressors may be any suitable gas compressor as disclosed herein.

[0065] The pressurized gas stream 230 flows into the deacidification zone 235, where hydrogen sulfide (H2S) and carbon dioxide (CO2) are removed to produce a wet gas stream 240. In one aspect, the deacidification zone 235 removes a portion of the H2S and CO2 in the pressurized gas stream 230. In a further aspect, the H2S concentration of the wet gas stream 240 may be less than about 0.1 ppm by weight; alternatively, in the range of about 25 ppb to about 100 ppb by weight. In a further aspect, the CO2 concentration of the wet gas stream 240 may be less than about 5 ppm by weight. The removal of H2S and CO2 may be achieved by any suitable means as determined by one of ordinary skill in the art and with the aid of the present disclosure. In a further aspect, diethanolamine or a caustic contactor may be used to remove at least a portion of the H2S and CO2 that make up the pressurized gas stream 230. The wet gas stream 240 flows into the drying zone 245, producing a cracked gas stream 250. In one aspect, the water content of the cracked gas stream 250 is below the amount required to cause downstream operating problems. In a further aspect, the water content of the cleaved gas stream 250 is less than about 10 ppm by weight. Drying in drying zone 245 can be accomplished by any suitable means as determined by one of ordinary skill in the art and with the benefit of the present disclosure. In one aspect, water can be removed from wet gas stream 240 using a molecular sieve bed.

[0066] The cracked gas stream 250 flows into a de-ethanizer zone 255 to produce C 2- Stream 260 and C 3+ Stream 262. Deethanizer section 255 includes a deethanizer section capable of producing C 2- Stream 260 and C 3+ Fractionator for stream 262. C 2- Stream 260 may comprise hydrogen, methane, ethane, acetylene, ethylene, or combinations thereof. 3+ Stream 262 comprises C3 hydrocarbons and heavier components and, in one aspect, may be combined with hydrocarbon recycle stream 201 (not shown). 2- Stream 260 flows into hydrogenation zone 265, where C 2- A portion of the acetylene in stream 260 is recovered from hydrogenation zone 265 as ethylene stream 270. The C 2- Hydrogenation of stream 260. For example, an acetylene reactor containing a catalyst may be used to hydrogenate C 2-A portion of the acetylene in stream 260 is hydrogenated. Typically, a Group VIII metal hydrogenation catalyst is utilized. Hydrogenation catalysts are disclosed in U.S. Pat. Nos. 3,679,762; 4,571,442; 4,347,392; 4,128,595; 5,059,732; 5,488,024; 5,489,565; 5,520,550; 5,583,274; 5,698,752; 5,585,318; 5,587,348; 6,127,310 and 4,762,956, each of which is incorporated herein by reference in its entirety. The operating conditions in hydrogenation zone 265 may encompass any combination of suitable conditions as determined by one of ordinary skill in the art with the aid of this disclosure. In one aspect, the temperature and pressure in hydrogenation zone 265 may be at a temperature that is capable of reacting C 2- In some aspects, the amount of acetylene remaining in ethylene stream 270 may be less than about 5 ppm by weight; alternatively, in the range of about 0.5 ppm to about 3 ppm by weight.

[0067] Alternatively, C 2- Stream 260 passes through line 266 (valves are provided in line 260 and line 268) and flows into second compression zone 267 to produce pressurized C 2- Stream 268. Pressurized C 2- The pressure of stream 268 may be in the range of about 100 psig to about 750 psig (about 0.68 MPag to about 5.17 MPag); alternatively, about 200 psig to about 650 psig (about 1.37 MPag to about 4.48 MPag). Second compression zone 267 includes one or more gas compressors, wherein the gas compressors may be any suitable gas compressor as disclosed herein. Pressurization C 2- Stream 268 flows into hydrogenation zone 265, wherein the 2- As described herein, ethylene stream 270 may be recovered from hydrogenation zone 265. In another alternative, the effluent of drying zone 245 is an 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 to produce reducing gas stream 276. In one aspect, alternative hydrogenation zone 275 operates comparable to hydrogenation zone 265. Reducing gas stream 276 flows into alternative deethanization zone 277, where alternative ethylene stream 280 is recovered and an alternative C 3+In one aspect, alternative deethanization zone 277 operates comparable to deethanization zone 255. In a further aspect, alternative ethylene stream 280 and alternative C 3+ The composition of stream 282 is similar to that of ethylene stream 270 and C 3+ The composition of stream 262 is comparable. In one aspect, replacing C 3+ Stream 282 may be combined with hydrocarbon recycle stream 201 (not shown). Ethylene stream 270 and / or alternative ethylene stream 280 flow into cracking process effluent 25.

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

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

[0070] refer to Figure 3, describing aspects of the oligomerization process 300. The cracking process effluent 25 can be combined with an ethylene recycle stream 306 to form an oligomerization feed 301. In one aspect, the ethylene recycle stream 306 can be combined with an ethylene recovery stream 335 (not shown), as further described herein. Alternatively, the ethylene recycle stream 306 is combined with an ethylene source from outside the integrated conversion process 1000. In a further aspect, the ethylene recycle stream 306 comprises a light effluent from a polyethylene polymerization process. It is contemplated that some aspects of the oligomerization process 300 may be operated in the absence of an ethylene recycle stream 306. The oligomerization feed 301 flows into the oligomerization reactor 305. In one aspect, the oligomerization feed 301 comprises ethane, ethylene, or a combination thereof. The hydrogen feed 302 flows into the oligomerization reactor 305. In one aspect, the hydrogen feed 302 can be combined with a stream from another part of the integrated reforming system of the present disclosure. For example, the hydrogen feed 302 can be combined with Figure 1 The oligomerization process 300 is combined with the hydrogen effluent 81 as further described herein. Without wishing to be limited by theory, carrying out the oligomerization reaction in the presence of hydrogen can enhance product selectivity, reduce the formation of polymer products (polymeric products), or both. It is contemplated that some aspects of the oligomerization process 300 can be operated in the absence of hydrogen feed 302. The oligomerization catalyst stream 304 flows into the oligomerization reactor 305. In one aspect, ethylene is contacted with the oligomerization catalyst in the oligomerization reactor 305 in the presence of a solvent. In such aspects, the solvent feed 308 is combined with the oligomerization catalyst stream 304. For the purposes of this disclosure, "solvent" refers to a diluent or medium in which the oligomerization reaction occurs. The solvent can be any inert solvent suitable for the oligomerization reaction as disclosed herein. In one aspect, 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 further aspects, the solvent can be isobutane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, or a combination thereof. In one aspect, solvent feed 308 can be combined with solvent recycle 345 (not shown), as further disclosed herein; alternatively, combined with cyclohexane effluent 67 (e.g., see Fig.10 or Fig.11 ); or alternatively, combined with the raffinate stream 88 (see, e.g., Figure 1 or Figure 5-Figure 11 It is contemplated that some aspects of the oligomerization process 300 may be operated in the absence of a solvent feed 308.

[0071] In one aspect, the oligomerization catalyst includes a selective oligomerization catalyst system. The selective oligomerization catalyst system suitable for use herein may include an N-phosphinyl amidine compound, a metal salt and an alkyl metal; alternatively, an N-phosphinyl amidine compound, a metal salt and an aluminoxane; alternatively, an N-phosphinyl amidine metal salt complex and an alkyl metal; or alternatively, an N-phosphinyl amidine metal salt complex and an aluminoxane. In a further aspect, the selective oligomerization catalyst system may include one or more neutral ligands. As previously disclosed, a selective oligomerization catalyst system suitable for use herein is described in U.S. Patent No. 8,680,003; wherein all components constituting the selective oligomerization catalyst system, the ratio of these components, and a method for combining these components to produce a selective oligomerization catalyst system are listed.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]pyrimidin-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-diphenylphosphinamide-κP]-chromium (i.e., PNP DPh-Hex-DPh), [bis(diphenylphosphino)(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 a combination thereof.

[0072] The contact of ethylene with the selective oligomerization catalyst system within the oligomerization reactor 305 can be carried out in any suitable manner and with the aid of the present disclosure. In some aspects, the oligomerization reactor 305 may include a loop reactor, a tubular reactor, a continuous stirred tank reactor (CSTR), or a combination thereof. In a specific aspect, the suspension formed between the selective oligomerization catalyst system and the solvent can be stirred to maintain a uniform concentration of the selective oligomerization catalyst system throughout the suspension; or alternatively, the solution formed between the selective oligomerization catalyst system and the solvent can be stirred to maintain the selective oligomerization catalyst system in the solution throughout the oligomerization process. In one aspect, the oligomerization reaction can be carried out in one or more oligomerization reactors. In one aspect, the oligomerization reaction can be carried out under suitable reaction conditions, which include one or more of catalyst concentration, reaction temperature, reaction pressure, and / or reaction time. In one aspect, the concentration of the selective oligomerization catalyst system 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 within the oligomerization reactor 305 can be any temperature suitable for the ethylene oligomerization reaction. In one aspect, the temperature is in a range that is low enough to minimize or avoid a reduction in the activity of the selective oligomerization catalyst system, and high enough to minimize or avoid the formation and / or precipitation of polymer products. In a further aspect, the temperature within the oligomerization reactor 305 may be at least 0°C; alternatively, at least 10°C; alternatively, at least 20°C; or alternatively, at least 30°C. In some aspects, the temperature within the oligomerization reactor 305 may be in a range of about 0°C to about 200°C; alternatively, about 10°C to about 160°C; alternatively, about 20°C to about 140°C; or alternatively, about 30°C to about 120°C. The pressure within the oligomerization reactor 305 may be any pressure suitable for the ethylene oligomerization reaction. In one aspect, the pressure is in a range that is high enough to avoid a reduction in the activity of the selective oligomerization catalyst system. In further aspects, the pressure within the oligomerization reactor 305 can be in the range of about atmospheric pressure (about 0 psig) to about 5000 psig (about 0.101 MPag to about 34.5 MPag); alternatively, about 50 psig to about 4000 psig (about 0.345 MPag to about 27.6 MPag); alternatively, about 100 psig to about 3600 psig (about 0.68 MPag to about 24.8 MPag); or alternatively, about 150 psig to about 2000 psig (about 1.03 MPag to about 13.8 MPag). In specific aspects, the oligomerization reaction can have a single-pass ethylene conversion 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] like Figure 3 As shown, the oligomerization reactor effluent 310 flowing out of the oligomerization reactor 305 comprises all components that may be present in the oligomerization reactor and may be removed from the oligomerization reactor. The oligomerization reactor effluent 310 may comprise oligomer products, by-products (by-product(s)), co-products, by-products (side-product(s)), light hydrocarbons, heavy hydrocarbons, unreacted monomers, selective oligomerization catalyst systems, solvents, and other reactor components. In one aspect, the oligomerization reactor effluent 310 comprises hexene, octene, 1-hexene, 1-octene, alkylcyclopentanes, solvents, cyclohexane, unreacted ethylene, and combinations thereof. In a further aspect, the oligomerization reactor effluent 310 comprises C 10 Hydrocarbon, C 12 Hydrocarbon, C 14+ Hydrocarbon or its combination. It will be appreciated by those skilled in the art that stream 301, stream 302, stream 304 and stream 310 may be located at any position on the oligomerization reactor 305 suitable for allowing ethylene to fully contact the selective oligomerization catalyst system in the oligomerization reactor 305. Catalyst kill stream 312 may be combined with the oligomerization reactor effluent 310. Catalyst kill stream 312 comprises a catalyst deactivation (deactivation, deactivation) composition, which may partially or completely deactivate the selective oligomerization catalyst system. It is contemplated that some aspects of the oligomerization process 300 may not utilize catalyst kill stream 312. Filter 315 may remove particulate matter (e.g., catalyst fines and undesirable polymer products) from the oligomerization reactor effluent 310. Although it is not desired to be bound by theory, it is believed that higher reactor and stream temperatures may inhibit the solidification of undesirable polymer particles. When the oligomerization reactor effluent 310 is maintained at high temperatures, less particulate matter may be formed, and filter 315 may not be required. In aspects where process conditions favor particulate formation (eg, cooling of the oligomerization reactor effluent 310), the filter 315 may be used. It is contemplated that some aspects of the oligomerization process 300 may not utilize the filter 315.

[0074] Process stream 320 comprises the effluent of filter 315 or the continuation of oligomerization reactor effluent 310, wherein process stream 320 comprises very little particulate matter or does not comprise particulate matter. Process stream 320 flows into first separator 330 to produce ethylene recovery stream 335 and oligomer effluent 338. Ethylene recovery stream 335 may comprise methane, ethane, ethylene, propane, propylene, butane or a combination thereof. In one aspect, ethylene recovery stream 335 may be further processed (not shown) to recover its ethylene concentrate (material) with higher purity. Ethylene recovery stream 335 may be combined (not shown) with ethylene recycle stream 306 as disclosed herein. In one aspect, heavy feed 322 is optionally combined with process stream 320 to form an inlet into first separator 330. Heavy feed 322 may comprise desired oligomer products and heavy hydrocarbons, as further described herein. In one aspect, heavy feed 322 may be the effluent of a polyethylene production facility. The oligomer effluent 338 flows into the 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 one aspect, the solvent recycle 345 can include cyclohexane. The first separator 330 and the second separator 340 can be operated in any manner suitable for producing their effluents. In a further aspect, the first separator 330 and the second separator 340 each include at least one fractionator.

[0075] III.B.5. Effluent composition

[0076] In one aspect, the oligomerization process effluent 36 contains an oligomer product comprising C6 and C8 olefins. In one aspect, the C6 olefins comprise hexene, 1-hexene, or a combination thereof, and the C8 olefins comprise octenes, 1-octene, or a combination thereof. In one aspect, 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.

[0077] In one aspect, the oligomerization process effluent 36 may comprise C6 olefins, wherein the amount of C6 olefins may be at least 60 wt %; alternatively, at least 70 wt %; alternatively, at least 75 wt %; alternatively, at least 80 wt %; alternatively, at least 85 wt %; or alternatively, at least 90 wt % based on the total weight of the oligomerization process effluent 36. In a further aspect, the oligomerization process effluent 36 may comprise 1-hexene, wherein the amount of 1-hexene may be at least 85 wt %; alternatively, at least 87.5 wt %; alternatively, at least 90 wt %; alternatively, at least 92.5 wt %; alternatively, at least 95 wt %; alternatively, at least 97 wt %; or alternatively, at least 98 wt %. In one aspect, the amount of 1-hexene in the oligomerization process effluent 36 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 %.

[0078] In a further aspect, the oligomerization process effluent 36 may comprise C8 olefins, wherein 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 comprise 1-octene, wherein the amount of 1-octene may be at least 85 wt %; alternatively, at least 87.5 wt %; alternatively, at least 90 wt %; alternatively, at least 92.5 wt %; alternatively, at least 95 wt %; alternatively, at least 97 wt %; or alternatively, at least 98 wt %. In one aspect, the amount of 1-octene in the oligomerization process effluent 36 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 %.

[0079] for Figure 1, the oligomerization process effluent 36 flows into the first fractionation process 50, wherein the hexene effluent 52 and the octene effluent 54 are recovered. The first fractionation process 50 produces a heavy effluent 56, which may include heavy hydrocarbons and spent selective oligomerization catalyst system. The heavy hydrocarbons may include C 9+ Hydrocarbons, C formed by oligomerization 9+ oligomers, polymer products formed by oligomerization, or combinations thereof. 9+ Oligomers include decene, dodecene, tetradecene, and combinations thereof. It will be appreciated by those skilled in the art that the first fractionation process 50 can be operated in any manner suitable for producing the disclosed effluent. For example, the first fractionation process 50 can include a series of separation units, such as a flash tower, a fractionating distillation column, a liquid-liquid extraction unit.

[0080] In one aspect, a first portion of the hexene effluent 52 is used as a hexene feed 53. The remaining portions of the hexene effluent 52 and the octene effluent 54 may be sent to storage or for sale. In one aspect, the hexene feed 53 is optionally combined with a naphtha feed 60 to form a treater feed 65. In one aspect, the naphtha feed 60 may contain non-aromatic hydrocarbons containing at least six carbon atoms. In a further aspect, the naphtha feed 60 may contain a hydrocarbon mixture containing C6 to C8 hydrocarbons, the hydrocarbon mixture containing up to about 15 wt % of C 5- hydrocarbons and up to about 10 wt. % C 9+ The weight percentages are based on the total weight of the naphtha feed 60. In a specific aspect, the naphtha feed 60 can be a light naphtha having a boiling range of about 20° C. to about 235° C., wherein the naphtha feed can contain one or more of aliphatic, cycloparaffinic, and / or paraffinic hydrocarbons. It is contemplated that some aspects of the integrated conversion system 1000 can operate in the absence of the naphtha feed 60.

[0081] III.D. Hydrotreating Process 70

[0082] like Figure 1 As further shown, the processor feed 65 flows into the hydroprocessing process 70. In one aspect, the hydroprocessing process 70 includes at least one hydrogenation reactor. At least a portion of the oligomer product in the processor feed 65 can flow into the hydrogenation reactor and contact the hydrogenation catalyst to produce a hydrogenation effluent (not shown). In aspects where the oligomer product comprises hexene, the hydrogenation effluent comprises hexane. In aspects where the oligomer product comprises octene, the hydrogenation effluent comprises octane. In such aspects, the oligomer product can be contacted with the hydrogenation catalyst in any manner suitable for forming hexane. In one aspect, the hydrogenation catalyst comprises One or more of a hydrogenation catalyst comprising nickel (Ni), palladium (Pd), platinum (Pt), iridium (Ir) and / or ruthenium (Ru). In the hydroprocessing process 70, the hydrogenation effluent is subjected to a purification stage to recover an aromatization feed 75 comprising hexane (e.g., n-hexane). Further processes (e.g., fractionation) in the hydroprocessing process 70 may affect the amount or concentration of sulfur, nitrogen, and / or aromatic compounds entering the hydroprocessing process 70, thereby reducing the amount of sulfur, nitrogen, and / or aromatic compounds of the aromatization feed 75. In one aspect, the hydroprocessing process 70 includes a sulfur removal system. Without wishing to be bound by theory, lower amounts of sulfur, nitrogen, and / or aromatic compounds in the feedstock of the aromatization process 400 may result in slower degradation and deactivation of the aromatization catalyst in the aromatization process, thereby beneficially resulting in fewer facility turnovers and higher aromatic selectivities. In a further aspect, the processes in the hydroprocessing process 70 may enhance the cetane number, density, and / or smoke point of the components of the aromatization feed 75.

[0083] In one aspect, the amount of sulfur in the aromatization feed 75 may be in the range of about 0.01 ppm to about 5 ppm; or alternatively, in the range of about 0.05 ppm to about 0.5 ppm. In one aspect, the amount of nitrogen in the aromatization feed 75 may be in the range of about 0.01 ppm to about 5 ppm; or alternatively, in the range of about 0.05 ppm to about 0.5 ppm. In one aspect, the amount of aromatic components in the aromatization feed 75 may be in the range of about 0.01 ppm to about 1 ppm; or alternatively, in the range of about 0.02 ppm to about 0.2 ppm. The ppm values ​​are weight-weight values ​​based on the total weight of the aromatization feed 75.

[0084] refer to Figure 1 , the aromatization feed 75 flows into the aromatization process 400. The aromatization process 400 includes an aromatization reactor system, wherein the non-cyclic oligomers contact with the aromatization catalyst and undergo an aromatization reaction to produce aromatic hydrocarbons. In a further aspect, the aromatization reaction converts 1-hexene into benzene. For example, U.S. Patent No. 7,932,425 discloses a method for converting 1-hexene into benzene, and the patent is incorporated herein by reference in its entirety. Any suitable method for producing benzene disclosed in U.S. Patent No. 7,932,425 may be utilized herein. It is contemplated that the aromatization process 400 may be used in conjunction with non-cyclic hydrocarbons other than 1-hexene to produce aromatic hydrocarbons other than benzene.

[0085] refer to Figure 4, describing aspects of an aromatization process 400. In the illustrated aspect, the aromatization reactor system includes a catalytic reactor system in which four aromatization reactors are connected in series (i.e., reactor 410, reactor 420, reactor 430, and reactor 440). However, the catalytic reactor system may include any suitable number and / or configuration of aromatization reactors, including one, two, three, five, six or more reactors, which may be arranged in series or in parallel. Since the aromatization reaction is highly endothermic, a substantial temperature drop may occur across reactors 410, 420, 430, and 440. Therefore, each reactor 410, 420, 430, and 440 in series may include a corresponding furnace 411, furnace 421, furnace 431, and furnace 441, respectively, for reheating the components back to the desired temperature to maintain the desired reaction rate. Alternatively, where feasible, one or more reactors 410, 420, 430, and 440 may share a common furnace. Reactors 410, 420, 430, and 440, furnaces 411, 421, 431, and 441, and associated piping may collectively be referred to herein as an aromatization zone.

[0086] In one aspect, as further disclosed herein, the aromatization feed 75 and the optional raffinate recycle 90 are combined to form a mixed feed 402 that flows into the purification process 480. The purification process 480 uses a known process (which may include fractionation) to purify the mixed feed 402 to remove impurities, such as oxygenates, 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) pre-treater, an SCF / SCG sulfur guard, or both. The purified feed 403 comes from the purification process 480. The purified feed 403 can be combined with the dry hydrogen recycle stream 465 to produce a hydrogen-rich purified feed 404. The oxygenate and / or nitrogen-containing stream 405 (i.e., O / N stream) can be combined with the hydrogen-rich purified feed 404 to produce an aromatization reactor feed 406. In addition to O / N stream 405, or in lieu of O / N stream 405, oxygenates and / or nitrogenates may also be fed to one or more locations of the catalytic reactor system, as described in greater detail herein. It is contemplated that some aspects of aromatization process 400 may be operated in the absence of purification process 480, wherein mixed feed 402 continues directly into stream 403.

[0087] In some aspects, the aromatization reactor feed 406 is preheated in the 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 the first aromatization reactor 410, wherein the first aromatization reactor feed 412 is contacted with an aromatization catalyst under suitable reaction conditions (e.g., suitable temperature and pressure) to aromatize one or more components in the feed, thereby increasing its aromatic content. A first aromatization reactor effluent 415 is recovered from the first aromatization reactor 410, which contains aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts.

[0088] The first aromatization reactor effluent 415 is then preheated in a second furnace 421, which heats 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 the second aromatization reactor 420, wherein the second aromatization reactor feed 422 contacts an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. A second aromatization reactor effluent 425 is recovered from the second aromatization reactor 420, which contains aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts.

[0089] The second aromatization reactor effluent 425 is then preheated in a third furnace 431, which heats 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, wherein the third aromatization reactor feed 432 contacts an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. A third aromatization reactor effluent 435 is recovered from the third aromatization reactor 430, which contains aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts.

[0090] The third aromatization reactor effluent 435 is then preheated in a fourth furnace 441, which heats the contents of stream 435 to a desired temperature, thereby producing a fourth aromatization reactor feed 442. The fourth aromatization reactor feed 442 is then fed to a fourth aromatization reactor 440, wherein the fourth aromatization reactor feed 442 is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed to increase its aromatic content. A fourth aromatization reactor effluent 445 is recovered from the fourth aromatization reactor 440, which contains aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts.

[0091] The fourth aromatization reactor effluent 445 flows into the hydrogen separation process 450, where the recovered hydrogen gas stream 455 is separated from the reforming effluent 45. The reforming effluent 45 comprises aromatization reaction products from the reactor 410, the reactor 420, the reactor 430, and the reactor 440, and optionally aromatization reaction byproducts and / or byproducts, unreacted feed, other hydrocarbons, or a combination thereof. In one aspect, the aromatization reaction byproducts include toluene, xylenes, ethylbenzene, diethylbenzene, mesitylene, hexamethylbenzene, or a combination thereof. The recovered hydrogen gas stream 455 is dried in the dryer 460 to form 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 in, for example, 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 The byproduct streams removed from the catalytic reactor system at various points throughout the system are not illustrated. However, one of ordinary skill in the art would know the composition and location of such byproduct streams. Figure 4 O / N stream 405 is shown added to the hydrogen-rich purified feed 404, but one of ordinary skill in the art will appreciate that oxygenates and / or nitrogenates 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 aspects of the aromatization process may operate in the absence of hydrogen separation process 450 and dryer 460, wherein there is no recovered hydrogen stream 455 and dry hydrogen recycle stream 465. In such aspects, the fourth aromatization reactor effluent 445 flows directly into the reforming effluent 45 and constitutes the composition of the reforming effluent 45.

[0092] 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 a combination thereof. Such a reactor system may be a batch or continuous system. In one aspect, the catalytic reactor system is a fixed bed system comprising one or more fixed bed reactors. In a fixed bed system, the aromatization reactor feed can be preheated in a furnace tube and enter at least one reactor containing a catalyst fixed bed. The aromatization reactor feed stream can pass through the reactor upward, downward, or radially. In various aspects, the catalytic reactor system described herein can be operated as an adiabatic catalytic reactor system or an isothermal catalytic reactor system. As used herein, the terms "catalytic reactor" and "reactor" refer interchangeably to reactor vessels, reactor interiors, and related process units, including but not limited to catalysts, inert fillers, pits, flow distributors, center tubes, reactor ports, catalyst transmission and distribution systems, furnaces and other heating devices, heat transfer devices, and pipelines.

[0093] In one aspect, the catalytic reactor system is an aromatization reactor system including at least one aromatization reactor and its corresponding process unit. As used herein, the terms "aromatization / aromatizing" and "reforming" refer to processing a feed to provide a product rich in aromatics, wherein the aromatic content of the product is higher 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 reforming reactions occurring in the aromatization reactor system include dehydrogenation cyclization reactions of non-cyclic hydrocarbons to aromatics (e.g., 1-hexene to benzene), dehydrogenation reactions of cyclohexane to aromatics, dehydrogenation isomerization reactions of alkylcyclopentane to aromatics, or combinations thereof. Depending on the composition of the feed, additional reactions may also occur, including dealkylation reactions of alkylbenzenes, isomerization reactions of paraffins, hydrocracking reactions producing light gaseous hydrocarbons (e.g., methane, ethane, ethylene, propane, propylene and butanes), or combinations thereof. Specific aspects of the integrated reforming system described herein utilize the dehydrogenation cyclization reaction of 1-hexene, n-hexane, or a combination thereof to produce benzene. In a further aspect, the integrated reforming system utilizes the dehydrogenation reaction of cyclohexane to produce benzene.

[0094] In one aspect, the aromatization reaction occurs under process conditions that thermodynamically favor dehydrogenation cyclization reaction and limit undesirable hydrocracking reaction. The pressure in the reactor can be in the range of about 0psig to about 500psig (about 0MPag to about 3.45MPag), such as about 25psig to about 300psig (about 0.17MPag to about 2.07MPag). The operating temperature includes a reactor inlet temperature in the range of about 370°C to about 565°C, including about 480°C to about 540°C. The molar ratio of hydrogen to hydrocarbon (e.g., 1-hexene) in the aromatization reactor feed can be in the range of about 0.1:1 to about 20:1, such as about 1:1 to about 6:1.

[0095] In some aspects, the aromatization reaction of the present disclosure may be characterized in that, based on the total amount by weight of the C6 stream feed (including 1-hexene) fed to the aromatization reactor, part or all of the C6 stream (including but not limited to 1-hexene) is converted to benzene. In one aspect, the conversion rate of C6 materials (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%.

[0096] The aromatization reaction of the present disclosure can be characterized by the selectivity of the C6 feed stream material (e.g., 1-hexene) to benzene based on the total amount of 1-hexene converted by weight in the aromatization reactor. In one aspect, 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 %.

[0097] Various types of aromatization catalysts can be used with the catalytic reactor systems disclosed herein. In one aspect, the aromatization catalyst is a non-acidic catalyst comprising an inorganic support, a Group VIII metal, and one or more halides. Suitable halides include chlorides, fluorides, bromides, iodides, or combinations thereof. Suitable Group VIII metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, and combinations thereof. Examples of catalysts suitable for use in the catalytic reactor systems described herein are HYDRA® brand catalysts (Chevron Phillips Chemical Company LLC, The Woodlands, TX, USA), including the catalysts discussed in US Pat. Nos. 6,812,180; 7,153,801; and 7,932,425, each of which is incorporated herein by reference in its entirety.

[0098] The inorganic support for the aromatization catalyst of the present disclosure may generally include any inorganic oxide. These inorganic oxides include combined macroporous aluminosilicates (zeolite supports), amorphous inorganic oxides and mixtures thereof. Macroporous aluminosilicates include, but are not limited to, L-type zeolites, Y-type zeolites, mordenite, ω zeolite, beta zeolite, etc. Amorphous inorganic oxides include, but are not limited to, aluminum oxide, silicon oxide, and titanium dioxide. Suitable binders for inorganic oxides include, but are not limited to, silicon dioxide, aluminum oxide, clay, titanium dioxide, and magnesium oxide.

[0099] In one aspect, the support is a bound potassium (K) L-type zeolite or KL zeolite. As used herein, the term "KL zeolite" refers to an L-type zeolite in which the major cation "M" incorporated into the zeolite is potassium. The KL zeolite can be cation exchanged or impregnated with another metal and one or more halides to produce, for example, a platinum (Pt) impregnated halide-containing zeolite or a KL supported Pt halide zeolite catalyst.

[0100] In one aspect, the Group VIII metal can be platinum. Platinum and optionally one or more halides can be added to the zeolite carrier by any suitable method, for example, by impregnation with a solution of a platinum-containing compound and one or more halide-containing compounds. For example, the platinum-containing compound can be any decomposable platinum-containing compound. Examples of such compounds include, but are not limited to, ammonium tetrachloroplatinate, chloroplatinic acid, diammine platinum (II) nitrite, bis (ethylenediamine) platinum (II) chloride, platinum (II) acetylacetonate, diammine platinum dichloride, platinum (II) chloride, tetraammine platinum (II) hydroxide, tetraammine platinum chloride, and tetraammine platinum (II) nitrate.

[0101] In a further aspect, the catalyst can be a macroporous zeolite carrier with a platinum-containing compound and at least one organic ammonium halide compound. The organic ammonium halide compound can include one or more compounds represented by formula N (R) 4X, wherein X is a halogen, R represents hydrogen or a substituted or unsubstituted carbon chain molecule with 1-20 carbons, and each R can be the same or different. In one aspect, R is selected from the group consisting of: methyl, ethyl, propyl, butyl and combinations thereof, more specifically methyl. The example of a suitable organic ammonium compound is represented by formula N (R) 4X, and can include ammonium chloride, ammonium fluoride and tetraalkyl ammonium 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.

[0102] In certain aspects of the present disclosure, oxygenates, nitrogenates, or both may be added to one or more process streams and / or components in a catalytic reactor system. Although not bound by theory, oxygenates and / or nitrogenates (e.g., water) may be beneficial for activating, preserving, and / or increasing the productivity of certain types of aromatization catalysts, as described, for example, in U.S. Pat. No. 7,932,425. In one aspect, the aromatization feed 75 and the optional raffinate recycle 90 are substantially free of sulfur, metals, and other known aromatization catalyst poisons, and are initially substantially free of oxygenates and nitrogenates. If present, such poisons may be removed using methods known to those skilled in the art. In some aspects, the aromatization feed 75 and the optional raffinate recycle 90 may be purified by first utilizing conventional hydrofining techniques and then utilizing an adsorbent to remove the remaining poisons. Such hydrofining techniques and adsorbents are included in the purification processes described below related to oxygenates and / or nitrogenates.

[0103] As used herein, the term "oxygenate" refers to any chemical compound that forms water or water under catalytic aromatization conditions, such as oxygen, oxygenated 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 oxygenates. In another aspect, oxygen can be used as oxygenates, wherein this oxygen is converted into water in situ in one or more aromatization reactors under general aromatization conditions, or in one or more hydrorefining catalysts or adsorbent beds under normal hydrorefining conditions. In addition, oxygenates can be any alcohol-containing compounds. Specific examples of suitable alcohol-containing compounds are methanol, ethanol, propanol, isopropanol, butanol, tert-butyl alcohol, pentanol, amyl alcohol, hexanol, cyclohexanol, phenol or a combination thereof.

[0104] As used herein, the term "nitrogen-containing (compound)" refers to ammonia or any chemical compound that forms ammonia under catalytic aromatization conditions, such as nitrogen (gas), nitrogen-containing compounds, alkylamines, aromatic amines, pyridines, pyridazines, pyrimidines, pyrazines, triazines, heterocyclic N-oxides, pyrroles, pyrazoles, imidazoles, triazoles, nitriles, amides, ureas, imides, nitro compounds, and nitroso compounds, including combinations thereof. Although not wanting to be limited by theory, it is believed that ammonia increases catalyst activity in much the same manner as water. In addition, all methods of adding and controlling oxygen-containing (compounds) described herein are also fully applicable to methods of adding and controlling nitrogen-containing (compounds) in addition or alternatively.

[0105] Those of ordinary skill in the art will appreciate that any oxygen-containing (compound) described herein, nitrogen-containing (compound) or its mixture can be used alone, in combination or further combined to produce other suitable oxygen-containing (compound) or nitrogen-containing (compound). In some aspects, oxygen-containing (compound) and nitrogen-containing (compound) can be included in a single bifunctional compound. Oxygen-containing (compound) and / or nitrogen-containing (compound) can be added with any suitable physical phase, such as gas, liquid or its combination. Oxygen-containing (compound) and / or nitrogen-containing (compound) can be added to one or more process streams and / or components via any suitable addition means, such as pumps, syringes, distributors, bubblers, etc. Oxygen-containing (compound) and / or nitrogen-containing (compound) can be introduced as a blend with a carrier. In some aspects, the carrier is selected from hydrogen (gas), hydrocarbons, nitrogen (gas), rare gases or their mixtures. In one aspect, the carrier is hydrogen (gas). In a further aspect, the oxygenate and / or nitrogenate may be added at various locations within the aromatization process, at any time during the useful life of the aromatization catalyst, and in any suitable manner. In a still further aspect, the addition of oxygenate and / or nitrogenate serves 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.

[0106] In one aspect, prior to adding oxygenates and / or nitrogenates, the existing oxygenate and / or nitrogenate content of the stream to which the oxygenates and / or nitrogenates are to be added is measured and / or adjusted. Figure 4 , before adding oxygenates and / or nitrogenates, the oxygenate and / or nitrogenate content of one or more feed streams (such as aromatization feed 75, raffinate recycle 90, mixed feed stream 402, or dry hydrogen recycle stream 465) can be measured and adjusted. Similarly, before adding nitrogenates, the nitrogenate content of the above streams can be measured and / or adjusted. In general, the original or untreated feed stream (such as aromatization feed 75) may contain a certain amount of oxygenates or nitrogenates when flowing into the catalytic reaction system described herein. In addition, depending on one or more of the facility configuration, feed storage time, and / or weather / storage conditions, the feed may absorb oxygenates or nitrogenates from the air. In order to accurately control the amount of oxygenate or nitrogenate flowing into one or more of the aromatization reactors (e.g., reactor 410, reactor 420, reactor 430, reactor 440), the amount of oxygenate and / or nitrogenate in one or more feed streams to the reactors may be measured, adjusted, or both.

[0107] In one aspect, the oxygenate and / or nitrogenate content of a given stream (such as a feed stream) can be measured, for example, using a real-time online analyzer (not shown). In response to such measurements, the oxygenate and / or nitrogenate content of the stream can be adjusted by treating and / or adding oxygenates and / or nitrogenates to the stream to obtain a desired amount of oxygenates and / or nitrogenates therein. In one aspect, a control loop connects the analyzer to a processor and oxygenate and / or nitrogenate injectors so that the amount of oxygenates and / or nitrogenates in one or more streams is controlled in response to oxygenate and / or nitrogenate set points for such streams. In some aspects, the measurement and / or regulation of oxygen-containing (compounds) and / or nitrogen-containing (compounds) content and related equipment (such as processors and / or chemical agent injectors) are included as part of the purification process 480. The oxygen-containing (compounds) and / or nitrogen-containing (compounds) processors vary according to the type and amount of oxygen-containing (compounds) and / or nitrogen-containing (compounds). In the aspect that the oxygen-containing (compounds) contain water, an adsorbent material bed can be used. These adsorbent beds are often referred to as dryers. In the aspect that the oxygen-containing (compounds) contain oxygen, the use of a processor that converts oxygen into water can be used in combination with a dryer. In the further aspect that the nitrogen-containing (compounds) contain alkaline chemicals, one or more adsorbent material beds can be used.

[0108] In one aspect, one or more streams such as the aromatization feed 75, the raffinate recycle 90, the mixed feed 402, and / or the dry hydrogen recycle stream 465 are treated prior to the addition of oxygenates and / or nitrogenates. In such aspects, the oxygenate and / or nitrogenate content of the streams is measured prior to such treatment, which may optionally be omitted. Without an apparatus to easily measure the oxygenate and / or nitrogenate content in the feed, it may be difficult to reliably maintain the desired levels in the aromatization reactor.

[0109] Treating one or more streams prior to adding oxygenates and / or nitrogenates can help to overall control the amount of water and / or ammonia in one or more streams flowing into the aromatization reactor by removing variations in the oxygenate and / or nitrogenate content in such streams. Treating such streams provides a consistent, baseline amount of oxygenates and / or nitrogenates in such streams for adding oxygenates and / or nitrogenates to form an oxygenated stream, such as the aromatization reactor feed 406. When the reactor feed is substantially free of oxygenates and / or nitrogenates, a precise amount of oxygenates and / or nitrogenates can be added to the reactor feed so that the amount of oxygenates and / or nitrogenates in the reactor can be reliably maintained. In one aspect, the purification process 480 can include a hydrocarbon dryer that dries the feed stream (e.g., the aromatization feed 75) to a suitable moisture content. In other aspects, purification process 480 may include a triethylaluminum bed on a reduced copper bed or silica for removing oxygenates. In yet further aspects, a triethylaluminum bed on a reduced copper bed or silica is used in combination with a hydrocarbon dryer. Similarly, dryer 460 may be used to dry recovered hydrogen stream 455 and / or other process streams (e.g., aromatization feed 75) to a suitable moisture content. In one aspect, suitable oxygenates in one or more streams (such as aromatization feed 75, raffinate recycle 90, mixed feed 402, or dry hydrogen recycle stream 465) are such that their combination produces a water concentration of less than about 1 volume parts per million (ppmv) in untreated recovered hydrogen stream 455, or alternatively less than about 0.5ppmv, or alternatively less than about 0.1ppmv. In one aspect, one or more of the streams fed to the aromatization reactor, aromatization feed 75, raffinate recycle 90, mixed feed 402, or dried hydrogen recycle stream 465, are substantially free of water after drying thereof. In one aspect, precise amounts of oxygenates and / or nitrogenates can be added by partially or completely bypassing such treatment processes. Alternatively, precise amounts of oxygenates and / or nitrogenates can be added by passing the recovered hydrogen stream 455 partially or completely through a wet (e.g., spent) molecular sieve bed.

[0110] The reformate effluent 45 may include C6 aromatics. In one aspect, the C6 aromatics concentration in the reformate effluent 45 may be at least 60 wt % based on the total weight of the reformate effluent 45; alternatively, at least 70 wt %; alternatively, at least 75 wt %; alternatively, at least 80 wt %; alternatively, at least 85 wt %; or alternatively, at least 90 wt %. In a further aspect, the C6 aromatics concentration in the reformate effluent 45 may be in the range of about 60 wt % to about 99.9 wt %; alternatively, about 70 wt % to about 99.8 wt %; alternatively, about 75 wt % to about 99.7 wt %; or alternatively, about 80 wt % to about 99.6 wt %; or alternatively, about 85 wt % to about 99.5 wt %. In further aspects, the benzene concentration 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 one aspect, the benzene concentration in the reformate effluent 45 can be in the range of about 85 wt % to about 99.9 wt %; alternatively, about 87.5 wt % to about 99.9 wt %; alternatively, about 90 wt % to about 99.9 wt %; alternatively, about 92.5 wt % to about 99.9 wt %; alternatively, about 95 wt % to about 99.9 wt %; alternatively, about 97 wt % to about 99.9 wt %; or alternatively, about 98 wt % to about 99.9 wt %.

[0111] Back to Figure 1 , the reforming effluent 45 flows into a second fractionation process 80, wherein 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 can be sent to storage and / or for sale. In one aspect, the xylene stream 86 comprises xylene(s). In a further aspect, the xylene stream 86 further comprises ethylbenzene, for example, for embodiments where 1-octene is recovered from the oligomerization reactor effluent 36 and / or a naphtha feed 60 is received in the hydroprocessing process 70. In one aspect, the raffinate stream 88 comprises C 9+ Aromatics, non-aromatic C 9+hydrocarbons or combinations thereof. In a further aspect, stream 88 comprises benzene, toluene, xylenes or combinations thereof. In a further aspect, raffinate stream 88 comprises ethylbenzene, for example, for embodiments where 1-octene is recovered from oligomerization reactor effluent 36 and / or naphtha feed 60 is received in hydroprocessing process 70. As disclosed herein, raffinate stream 88 may be sent to hydrocarbon recycle 201 of cracking process 200, or alternatively, may be sent to storage and / or for sale. In one aspect, as disclosed herein, a portion of raffinate stream 88 is optionally sent to raffinate recycle 90. In some aspects, as disclosed herein, raffinate recycle 90 flows into aromatization process 400.

[0112] Those skilled in the art will appreciate that the second fractionation process 80 can be operated in any manner suitable for producing its effluent. For example, the second fractionation process 80 can include a series of separation units, such as a flash column, a fractionation distillation column, a liquid-liquid extraction unit, etc. Some aspects of the second fractionation process 80 can include Figure 4 In such aspects, a hydrogen effluent 81 is recovered from the second fractionation process 80. As disclosed herein, the hydrogen effluent 81 may be separated from the hydrogen effluent 81 by a hydrogen separation process 450 substantially similar to the hydrogen separation process 450 of FIG. Figure 3 The hydrogen feed 302 is combined. In a further aspect, the hydrogen effluent 81 can be sent to storage and / or for sale.

[0113] refer to Figure 5 , describes an integrated conversion system 1100, wherein like reference numerals represent the same Figure 1 The same components as described above. Figure 1 In contrast, the first portion of octene effluent 54 is used as octene feed 55. The octene effluent 54 and hexene effluent 52 of the remainder can be sent to storage and / or for sale. In one aspect, octene feed 55 is optionally merged with naphtha feed 60 to form processor feed 65, which is sent to aromatization process 400. In the aspect that the oligomer product in the processor feed 65 comprises octene, the hydrogenated effluent (not shown) produced in the hydroprocessing process 70 comprises octane. In such aspect, the oligomer product can contact with a hydrogenation catalyst in any manner suitable for forming octane. In the hydroprocessing process 70, the hydrogenated effluent passes through a purification stage, thereby reclaiming an aromatization feed 75 comprising octane (e.g., n-octane).

[0114] refer to Figure 6 , describes an integrated conversion system 1200, wherein like reference numerals represent the same as those in Figure 1The same components are described. The first portion of the hexene effluent 52 is used as the hexene feed 53, and the first portion of the octene effluent 54 is used as the octene feed 55. The remainder of the hexene effluent 52 and the octene effluent 54 can be sent to storage and / or sold. 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 the hydroprocessing process 70. In the hydroprocessing process 70, the hydrogenated effluent passes through a purification stage, thereby recovering an aromatization feed 75 comprising hexane (e.g., normal hexane), octane (e.g., normal octane) or a combination thereof.

[0115] refer to Figure 7 , describes an integrated conversion system 1300, wherein like reference numerals represent the same as those in Figure 1 The same components. The middle distillate (mid-cut) feed 57 flows out of the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form a processor feed 65 that is sent to the hydrotreating process 70. In one aspect, the middle distillate feed 57 comprises C6 to C8 hydrocarbons. In a further aspect, the middle distillate feed 57 comprises C6 and C8 olefins, wherein the C6 and C8 olefins include hexene, octene or a combination thereof. In a specific aspect, the middle distillate feed 57 comprises 1-hexene and 1-octene.

[0116] refer to Figure 8 , describes an integrated conversion system 1400, wherein like reference numerals represent the same as those in Figure 7 The same components are described. A heavy-cut feed 59 flows from the first fractionation process 50 and is optionally combined with a naphtha feed 60 to form a treater feed 65 that is sent to a hydrotreating process 70. In one aspect, the heavy-cut feed 59 comprises C6 to C 12 In a further aspect, the heavy fraction feed 59 comprises C6 and C 12 Olefins, including C6 and C 12 The olefins include hexene, octene, decene, dodecene, or combinations thereof. In a specific aspect, the heavy ends feed 59 comprises 1-hexene and 1-octene.

[0117] The integrated conversion systems 1300 and 1400 do not have the hexene effluent 52 and the octene effluent 54. The integrated conversion systems 1300 and 1400 integrate all the hexene and octene produced in the oligomerization process 300 into the hydroprocessing process 70.

[0118] refer to Fig. 9 , describes an integrated conversion system 1500, wherein like reference numerals represent the same as those in Figure 1The cyclohexane recycle 62 flows into the oligomerization process 300, where the cyclohexane is used as a solvent (i.e., a diluent). In one aspect, the cyclohexane recycle 62 is mixed with Figure 3 The solvent feed 308 is combined. The C6 cut feed 58 flows out of the first fractionation process 50 and flows into the C6 separator 151. In one aspect, the C6 cut feed 58 comprises C6 hydrocarbons. In the C6 separator 151, a hexene effluent 52 and a depleted C6 cut 61 are recovered from the C6 cut feed 58. In one aspect, the composition and disposal of the hexene effluent 52 are the same as those described herein. Figure 1 The same as disclosed. The depleted C6 fraction 61 flows out of the C6 splitter 151 and flows into the cyclohexane recovery (CHR) tower 153, wherein the residual C6 feed 63 and the cyclohexane recycle 62 are recovered from the depleted C6 fraction 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 one aspect, the residual C6 feed 63 comprises C6 hydrocarbons (e.g., hexane). The C6 splitter 151 and the CHR tower 153 can be operated in any manner suitable for producing their effluents. In one aspect, the C6 splitter 151 and the CHR tower 153 each comprise at least one fractionator.

[0119] As disclosed herein, all of the C6 fraction feed 58 enters the C6 splitter 151. This configuration of the integrated conversion system 1500 advantageously produces a hexene effluent 52 at full capacity. Some aspects of the integrated conversion system 1500 are configured to operate in the absence of the C6 splitter 151, wherein no hexene effluent 52 is produced. In such aspects, the optional bypass line 51 sends all of the C6 fraction feed 58 to the CHR column 153, wherein the C6 fraction feed 58 enters the CHR column 153 via line 61. This configuration of the integrated conversion system 1500 can be utilized when, for example, the demand for C6 olefins (e.g., 1-hexene) is low, and / or when the supply of a source of naphtha feed 60 is low, or alternatively to avoid costs associated with a source of naphtha feed 60. In a further aspect, the flow of C6 fraction feed 58 is divided between C6 splitter 151 and CHR column 153 by metering the flow of optional bypass line 51.

[0120] In one aspect, the flexible configuration of the integrated conversion system 1500 beneficially allows an operator to quickly respond to, for example, business (market), weather, and / or production factors.

[0121] refer to Fig.10 , describes an integrated conversion system 1500, wherein like reference numerals represent the same as those in Fig. 9The cyclohexane feed 64 flows into the oligomerization process 300, where the cyclohexane is used as a solvent (i.e., a diluent). In one aspect, as disclosed herein, the cyclohexane feed 64 is Figure 3 The solvent feed 308 of the first fractionation process 50 is combined. The C6 fraction feed 58 flows out of the first fractionation process 50 and is optionally combined with the naphtha feed 60 to form a processor feed 65 that is sent to the hydrotreating process 70. Regarding the second fractionation process 80, a portion of the benzene stream 82 is transported through the benzene feed 83, and a portion of the hydrogen effluent 81 is transported through the reducing feed 85. The benzene feed 83 and the reducing feed 85 flow into the benzene hydrogenation process 160, wherein the hydrogenation of benzene produces a cyclohexane effluent 67. In one aspect, the cyclohexane effluent 67 contains cyclohexane and can be sent to storage or sale. As disclosed herein, a portion of the cyclohexane effluent 67 can be sent to the cyclohexane feed 64. The hydrogenation of benzene can be carried out by any means suitable for those of ordinary skill in the art and with the aid of the present disclosure. For example, in non-limiting aspects, a hydrogenation catalyst can be utilized. The operating conditions in the hydrogenation process 160 can be any suitable combination of conditions as determined by those of ordinary skill in the art with the aid of the present disclosure. In one aspect, the temperature and pressure in the hydrogenation process 160 can be at a level capable of hydrogenating benzene. The temperature in the hydrogenation process 160 can be in the range of about 10° C. to about 205° C. The pressure in the hydrogenation process 160 can be in the range of about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag).

[0122] In one aspect, the cyclohexane concentration 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 cyclohexane concentration in the cyclohexane effluent 67 can be in the range of about 85 wt % to about 99.9 wt %; alternatively, about 87.5 wt % to about 99.9 wt %; alternatively, about 90 wt % to about 99.9 wt %; alternatively, about 92.5 wt % to about 99.9 wt %; alternatively, about 95 wt % to about 99.9 wt %; alternatively, about 97 wt % to about 99.9 wt %; or alternatively, about 98 wt % to about 99.9 wt %.

[0123] refer to Fig.11 , describes an integrated conversion system 1700, wherein like reference numerals represent the same as those in Fig. 9 and Fig.10The second solvent recycle 68 flows into the oligomerization process 300, where cyclohexane is used as a solvent (i.e., a diluent). In one aspect, as disclosed herein, the second solvent recycle 68 is Figure 3 The second solvent recycle 68 may be formed from a combination of the cyclohexane recycle 62 and the cyclohexane feed 64 as described herein.

[0124] refer to Fig.12 , describes an integrated conversion system 1800, wherein like reference numerals represent the same as those in Figure 1 The same components as described above. Figure 1 In contrast, hydrocarbon feedstock 10 flows into cracking process 290, which operates in the same manner as Figure 2 The pyrolysis process 200 of FIG. 2 is similar to that of FIG. 200 , unless otherwise expressly disclosed. As previously described, the raffinate recycle 90 flows out of the second fractionation process 80, and the heavy recycle 180 flows into the pyrolysis process 290. In one aspect, the raffinate recycle 90 and the heavy recycle 180 are similar to those of FIG. Figure 2 The heavy recycle 180 may be obtained from the first fractionation process 50. The heavy recycle 180 may contain heavy hydrocarbons, including C 9+ Hydrocarbons, C formed by oligomerization 9+ oligomers, polymer products formed by oligomerization, or combinations thereof. 9+ The oligomers include decene, dodecene, tetradecene, and combinations thereof.

[0125] From the cracking process 290 flow cracking process effluent 25 as previously described, refrigerant stream 146, crude pyrolysis gasoline (CPG) stream 142, fuel gas stream 144, and steam effluent 148. Refrigerant stream 146 may be obtained from Figure 2 The cracker effluent 210, C 3+ STREAM 262 and / or alternative C 3+ The refrigerant stream 146 is recycled to stream 282. In one aspect, the refrigerant stream 146 comprises light hydrocarbons produced by the cracking process 290, wherein the light hydrocarbons comprise methane, ethane, ethylene, propane, propylene, butane, and combinations thereof. The three portions 146a, 146b, and 146c of the 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 therein (e.g., in an overhead condenser of a fractionation column of the first fractionation process 50). The vapor effluent 148 constitutes the vapor effluent from the first fractionation process 50. Figure 2The three portions 148a, 148b, and 148c of the steam 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 used as a heat source therein, for example, 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 a hydrogen efflux 87. A first portion 87a of the hydrogen effluent 87 flows into the oligomerization process 300, where it is mixed with Figure 3 The second portion 87b of the hydrogen outflow 87 flows into the hydroprocessing process 70.

[0126] In one aspect, utilization of the refrigerant stream 146 and / or the vapor effluent 148 provides a portion of the utility requirements (eg, heating and cooling) of the integrated conversion system 1800 and advantageously reduces associated operating costs.

[0127] refer to Fig.13 , describes an integrated conversion system 1900, wherein like reference numerals represent the same as those in Fig.11 and 12 The system 1900 is characterized by having a flexible configuration of the integrated conversion system 1500 and an integrated utility of a portion of the integrated conversion system 1800.

[0128] Disclosed herein is a method of enriching a motor fuel stream (i.e., mogas). In one aspect, the mogas comprises 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 motor fuel. In a specific aspect, the mogas is enriched by blending one or more effluent streams produced by the integrated conversion system of the present disclosure. For example, the heavy effluent 56, the raffinate stream 88, or a combination thereof can be blended into the mogas.

[0129] A limited set of operating conditions (e.g., temperature, pressure) for the processes and systems disclosed herein are described herein. It will be understood by one of ordinary skill in the art that any operating condition not currently disclosed may have any value suitable for the operation of the processes and systems disclosed herein, or alternatively, a range of values. In a further aspect, one of ordinary skill in the art may implement changes to the operating conditions within any process and system disclosed herein with the aid of the present disclosure to maintain the operation of the disclosed processes and systems.

[0130] In one aspect, when compared to conventional benzene production methods utilizing non-integrated (i.e., stand-alone) conversion processes, the production of benzene using the integrated conversion system of the present disclosure may have advantages in one or more areas. Conventional benzene production methods utilize substances contained in crude oil (e.g., materials obtained via naphtha cracking) so that the production cost of benzene is linked to crude oil. The present disclosure utilizes ethane contained in natural gas as a starting material (e.g., ethane produced via steam cracking of ethane), so that the production cost of benzene is advantageously decoupled from crude oil. With the increasing amount of natural gas, the price of natural gas is falling, and other factors are the increasing demand for benzene. For example, in North America, the sufficient reserves of ethane for steam cracking make naphtha cracking uneconomical. Visually, there is a possibility that ethylene may be significantly oversupplied in the future. A further advantage is that the integrated conversion system of the present disclosure can be used to convert ethylene to benzene to best comply with relevant financial and / or market conditions, particularly in light of the significant global price increases associated with benzene (see, e.g., https: / / www.statista.com / statistics / 1171072 / price-benzene-forecast-global ly / ).

[0131] The further advantage of the integrated conversion system of the present disclosure is that a large amount of ethylene, 1-hexene, 1-octene and benzene can be produced, and the part of each compound is sold according to relevant global demand subsequently. According to the integrated conversion system of the present disclosure, there is the following characteristics: the production rate of the product stream can be modified flexibly to adapt to the demand and / or price change of 1-hexene, 1-octene and / or benzene. In some aspects, up to 1.5 million tons of ethylene can be produced every year. Other products that can be generated for sale by utilizing the integrated conversion system of the present disclosure include hydrogen (that is, hydrogen effluent 81), cyclohexane (that is, cyclohexane effluent 67) and toluene (that is, toluene stream 84).

[0132] A further advantage of the integrated conversion system of the present disclosure is that 1-hexene can potentially be used as a feedstock for an aromatization process. Hydrogenation of 1-hexene to normal hexane as disclosed herein can provide further production advantages, including slower catalyst deactivation, less facility turnover, and higher aromatics selectivity. Since the cracking feedstock is derived from natural gas, plastic or polymer waste, biomass, other natural sources, etc. instead of crude oil, the sulfur content of the 1-hexene / normal hexane fed to the aromatization process is low, potentially allowing removal, recycling, conversion, etc. of a conventional staged combustion air preprocessor and subsequent reduction in capital costs.

[0133] A further advantage of the integrated conversion system of the present disclosure is that by using the light hydrocarbons produced by the cracking process 200 as a cooling source and / or refrigeration source in the oligomerization process 300. This approach allows for the removal of a dedicated refrigeration unit in the oligomerization process 300 and provides a subsequent reduction in capital costs. A further advantage is that the cracking process 200 can produce hydrogen and methane (not shown), which can be used as fuel for heating and / or operating other processes in the integrated conversion system. This can allow for beneficial design improvements to the facility or system, such as reducing the size of the heat exchanger.

[0134] Example

[0135] Having generally described the subject matter, the following examples are given as specific aspects of the present disclosure and demonstrate its practice and advantages. It should be understood that the embodiments are given by way of example and are not intended to limit the limitations of the appended claims in any way. It should be clearly understood that various other aspects, modifications and their equivalents may be adopted, which are conceivable by those of ordinary skill in the art after reading the description herein, without departing from the spirit of the present disclosure or the scope of the appended claims.

[0136] Fig.14 and 15 Demonstrated the use of The catalyst produces benzene from 1-hexene. The operating conditions are a constant temperature of 950°F (510°C) and a liquid hourly space velocity of 12h -1 , the pressure was 100 psig (0.68 MPag), and the molar ratio of hydrogen to hydrocarbon was 1.2:1. Fig.14 It is shown that, under the specified conditions, the conversion rate of 1-hexene to benzene is close to 100% in about 5 hours. Fig.15 It is shown that under the specified conditions, the selectivity of 1-hexene to benzene is maintained at about 85% at about 5 hours. After about 1 hour, the benzene selectivity under the above conditions is about 80%.

[0137] The scope of protection of the present disclosure is not limited by the above description, but only by the attached claims, which include all equivalent forms of the subject matter of the claims. Each claim is incorporated into the specification as an embodiment of the present disclosure. Therefore, the claims are further descriptions and are supplementary to the specific description of the present disclosure. The disclosures of all patents, patent applications and publications cited herein are hereby incorporated by reference.

[0138] Aspects of the processor regeneration method have been described. The following is a first set of non-limiting specific embodiments according to the present disclosure:

[0139] Although several aspects and embodiments of the present disclosure have been shown and described, those skilled in the art may modify them without departing from the spirit and teachings of the present disclosure. The aspects, embodiments and examples described herein are merely exemplary and are not intended to be limiting. Many variations and modifications of the present disclosure are possible and within the scope of the subject matter.

[0140] With respect to claim transition terms or phrases, the transition 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 transition phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transition phrase "consisting essentially of" limits the scope of the claim to the specified materials or steps and those that do not materially affect the basic and novel characteristics of the claim. "Consisting essentially of" claims are in a middle ground between closed claims written in the "consisting of" format and fully open claims written in the "comprising" format. In the absence of contrary indications, describing a compound or composition as "consisting essentially of" should not be interpreted as "comprising," but is intended to describe that the recited components include materials that do not significantly change the composition or method to which the term is applied. For example, a feedstock consisting essentially of a certain material may include impurities that are typically present in commercially produced or commercially available samples of the recited compound or composition. When a claim includes different features and / or categories of features (e.g., process steps, feedstock features, and / or product features, among other possibilities), the transition terms comprising, consisting essentially of, and consisting of apply only to the categories of features to which they are applied, and different transition terms or phrases may be used for different features in the claim. For example, a process may include several recited steps (and other unrecited steps) but utilizes a catalyst system that consists of specified components; alternatively, consists essentially of specified components; or alternatively, includes specified components and other unrecited components.

[0141] In the present disclosure, although systems, processes and methods are generally described as “comprising” various components, instruments or steps, unless otherwise stated, the systems, processes and methods may also “consist essentially of” or “consist of” the various components, instruments or steps.

[0142] As used herein, the term "about" means that the amount, size, formula, parameter and other quantities and features are not and need not be exact, but may be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, etc. and other factors known to those skilled in the art. In general, whether or not explicitly stated, the amount, size, formula, parameter or other quantity or feature is "approximately" or "approximately". The term "about" also encompasses amounts that differ due to differences in equilibrium conditions of the composition produced by a specific initial mixture. Whether or not modified by the term "about", the claims include equivalent forms of the quantities. The term "about" may mean within 10% of the reported value, alternatively within 5% of the reported value.

[0143] Unless otherwise indicated, when any type of range is disclosed or claimed (e.g., a range of carbon number, molar ratio, temperature, etc.), it is intended to disclose or claim each possible value that the range may reasonably encompass, including any sub-ranges encompassed therein. For example, when describing a range of carbon number, each possible individual integer included in the range and the atoms in the range between the integers are encompassed. Thus, by disclosing C1 to C2 10 Alkyl or alkyl with 1 to 10 carbon atoms or "up to" 10 carbon atoms, the applicant intends to state that the alkyl can have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, and these methods of describing such groups are interchangeable. When describing the scope of a measurement result (such as a molar ratio), each possible numerical value that such a range can reasonably cover can, for example, refer to a value with one more significant figure than the range endpoints in the described range. In the present example, the molar ratio between 1.03:1 and 1.12:1 includes individual molar ratios 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, 1.10:1, 1.11:1 and 1.12:1. The applicant's intention is that these two methods of describing the range are interchangeable. In addition, when disclosing or claiming a numerical range, applicants intend to reflect each possible individual value that such a range could reasonably encompass, and applicants also intend to disclose a range to reflect disclosure of any and all subranges and combinations of subranges encompassed therein and interchangeable therewith. In this regard, applicants disclose C1 to C 10Alkyl is intended to literally encompass C1 to C6 alkyl, C4 to C8 alkyl, C2 to C7 alkyl, combinations of C1 to C3 and C5 to C7 alkyl, etc. When a range is described with different numbers of significant digits at the range endpoints (e.g., a molar ratio of 1:1 to 1.2:1), each possible value that such a range could reasonably encompass may, for example, refer to the value within the range with one more significant digit than is present in the endpoint of the range (in this example, 1.2:1) having the greatest number of significant digits. In this example, a molar ratio of 1:1 to 1.2:1 includes individual molar ratios of 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, and 1.20 - all relative to 1, and any and all subranges and subrange combinations encompassed therein. Accordingly, applicants reserve the right to exclude or exclude any individual member of any such group (including any subranges or subrange combinations within the group) if applicants, for any reason, choose to claim less than the full measure of the present disclosure (e.g., to take into account references not known to applicants at the time of filing the application).

[0144] Unless otherwise specified, the terms "contacting," "combining," and "in the presence of" refer to any order of addition, sequence, or concentrations that contact or combine two or more components of any process disclosed herein. The combining or contacting of components according to the various methods described herein can be carried out in one or more contact zones under appropriate contact conditions (such as temperature, pressure, contact time, etc.). The contact zone can be disposed in a vessel (e.g., a storage tank, a suitcase, a container, a mixing vessel, a reactor, etc.), a section of pipe (e.g., a tee, an inlet, an injection port, or a head - used to combine and merge component feed lines into a common line), or any other suitable equipment for contacting the components.

[0145] For the purpose of submitting any U.S. national phase application of the present application, all publications and patents mentioned in the present disclosure are incorporated herein by reference in their entirety, with the purpose of describing and disclosing the structures and methods described in those publications that can be used in conjunction with the method of the present disclosure. Any publications and patents discussed herein are provided only because of their disclosures prior to the filing date of the present application. Any content of this article is not to be construed as admitting that the inventor has no right to precede these disclosures due to the previous disclosure.

[0146] In any application filed with the United States Patent and Trademark Office, the Abstract of this application is provided to satisfy the requirements of 37 C.FR § 1.72 and the purpose stated in 37 C.FR § 1.72(b), namely, "to enable the United States Patent and Trademark Office and the public generally to quickly ascertain the nature and gist of the technical disclosure by a cursory inspection." Therefore, the Abstract of this application is not intended to be used to interpret the scope of the claims or to limit the scope of the subject matter disclosed herein. In addition, any headings that may be adopted herein are not intended to be used to interpret the scope of the claims or to limit the scope of the subject matter disclosed herein. Any use of the past tense to describe an example (otherwise indicated as constructive or prophetic) is not intended to reflect that the constructive or prophetic example has actually been implemented.

[0147] At least one embodiment is disclosed, and variations, combinations and / or modifications made to the embodiments and / or features of the embodiments by those of ordinary skill in the art are within the scope of the present disclosure. Alternative embodiments produced by combining, integrating and / or omitting features of the embodiments are also within the scope of the present disclosure. When a numerical range or limitation is explicitly stated, it should be understood that such explicit ranges or limitations include iterative ranges or limitations of similar magnitude that fall within the explicitly stated range or limitation (e.g., "about 1 to about 10" includes 2, 3, 4, etc.; "greater than 0.10" includes 0.11, 0.12, 0.13, etc.). For example, whenever a lower limit R is disclosed, l and upper limit R u When a numerical range is given, any value falling within the range is explicitly disclosed. Specifically, the following values ​​are explicitly disclosed: R = R l +k·(R u -R l ), wherein k is a variable in increments of 1% within a range of 1% to 100%, i.e., k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52% ..., 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range defined by two R values ​​as defined above is also explicitly disclosed. The use of the term "optionally" with respect to any element of a claim means that the element is required, or alternatively, the element is not required, both of which alternatives are within the scope of the claim.

[0148] Additional public content

[0149] The following enumerated embodiments of the present disclosure are provided as non-limiting examples.

[0150] Embodiment 1 is a method comprising: in an oligomerization process, contacting ethylene with a selective higher olefin catalyst to produce an oligomerization reactor effluent, the oligomerization reactor effluent comprising C6 hydrocarbons including 1-hexene and C8 hydrocarbons including 1-octene; 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 hydrogenation catalyst to produce an aromatization feed comprising hexane, octane, or both; and in an aromatization process, contacting the aromatization feed with an aromatization catalyst to produce a reforming effluent comprising benzene.

[0151] Embodiment 2 is a method as described in Embodiment 1, 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.

[0152] Embodiment 3 is a method as described in embodiment 1 or 2, 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.

[0153] Embodiment 4 is a method as described in any one of embodiments 1 to 3, 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.

[0154] Embodiment 5 is a method as described in any one of embodiments 1 to 4, wherein the oligomerization reactor effluent further comprises C 10 Hydrocarbon, C 12 Hydrocarbon, C 14+ hydrocarbons or combinations thereof.

[0155] Embodiment 6 is a method as described in embodiment 5, wherein the C 10 The hydrocarbon is present in an amount of about 1 wt % to about 4 wt % based on the total weight of the oligomerization reactor effluent, 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+ The hydrocarbon is present in an amount from about 0 wt % to about 3.5 wt % based on the total weight of the oligomerization reactor effluent.

[0156] Embodiment 7 is a method as described in any one of embodiments 1 to 6, wherein the selective higher olefin catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PNGuan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh or a combination thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides.

[0157] Embodiment 8 is a method as described in any one of embodiments 1 to 7, wherein the step of contacting ethylene with a selective higher olefin catalyst is carried out in the presence of a diluent selected from isobutane, cyclohexane, methylcyclohexane, isobutylene, 1-hexene or a combination thereof.

[0158] Embodiment 9 is a method as described in any one of embodiments 1 to 8, wherein recovering 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, wherein among the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the hydrotreatment process.

[0159] Embodiment 10 is a method as described in any one of embodiments 1 to 8, wherein recovering 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, wherein among the first stream, the second stream, and the third stream, only a portion of the second stream and only a portion of the third stream are fed to the hydrotreatment process.

[0160] Embodiment 11 is a method as described in any one of embodiments 1 to 8, wherein recovering 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 and a second stream comprising hexene and octene, wherein of the first stream and the second stream, only a portion of the second stream is fed to the hydrotreating process.

[0161] Embodiment 12 is a method as described in any one of embodiments 1 to 8, wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises: fractionating the oligomerization reactor effluent into a first stream comprising spent catalyst and a second stream comprising hexene, octene, and heavy hydrocarbons, wherein of the first stream and the second stream, only a portion of the second stream is fed to the hydrotreatment process.

[0162] Embodiment 13 is a method as described in any one of embodiments 1 to 8, wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises: separating 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; fractionating the third stream to obtain a high-purity 1-hexene stream and a C6 feed stream; and passing the C6 feed stream into the hydrotreatment process.

[0163] Embodiment 14 is a method as described in any one of embodiments 1 to 13, further comprising: fractionating a refinery stream to recover a naphtha stream; feeding the naphtha stream to the hydrotreating process; and in the hydrotreating process, contacting the naphtha with the hydrogenation catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0164] Embodiment 15 is a method as described in any one of embodiments 1 to 14, wherein the reforming effluent further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene or a combination thereof, and the method further comprises: fractionating the reforming effluent into a benzene stream, a toluene stream, a xylene stream and a raffinate stream.

[0165] Embodiment 16 is a method as described in embodiment 15, wherein the 1-hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

[0166] Embodiment 17 is a method as described in Embodiment 15, wherein the 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

[0167] Embodiment 18 is a method as described in any one of Embodiments 1 to 17, wherein the aromatization process is further configured to produce a hydrogen effluent, and the method further comprises: passing a portion of the benzene stream and a portion of the hydrogen effluent into a hydrogenation process to produce cyclohexane; and recycling the cyclohexane to the oligomerization process.

[0168] Embodiment 19 is a method as described in any one of embodiments 1 to 18, wherein the oligomerization reactor effluent further contains cyclohexane and other hexanes, and the method further comprises: recovering cyclohexane and the other hexanes from the oligomerization reactor effluent; passing the other hexanes recovered from the oligomerization reactor effluent into the hydrotreatment process; and recycling the cyclohexane recovered from the oligomerization reactor effluent to the oligomerization process.

[0169] Embodiment 20 is a method as described in any one of Embodiments 1 to 19, further comprising: cracking ethane, propane, butane, pentane, naphtha or a mixture thereof in a steam cracker to produce a cracker effluent containing ethylene; and allowing ethylene recovered from the cracker effluent to flow into the oligomerization process.

[0170] Embodiment 21 is a method as described in Embodiment 20, 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 an 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.

[0171] Embodiment 22 is a method as described in any one of embodiments 1 to 21, further comprising: recovering steam from the steam cracker; and using the steam as a heating source for the oligomerization reaction process, for a first fractionation process located downstream of the oligomerization reaction process, for a second fractionation process located downstream of the aromatization process, or a combination thereof.

[0172] Embodiment 23 is a method as described in 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 reforming effluent, wherein the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes or combinations thereof.

[0173] Embodiment 24 is a method as described in any one of embodiments 1 to 23, further comprising: passing the raffinate recovered from the aromatization process into a steam cracker; and cracking the raffinate in the steam cracker.

[0174] Embodiment 25 is a method as described in any one of embodiments 1 to 24, wherein the oligomerization reactor effluent further comprises C 9+ hydrocarbons, the method further comprising: 9+ hydrocarbons, a raffinate stream obtained from the reforming effluent, or the C 9+ Both hydrocarbons and the raffinate stream are blended into the motor fuel stream.

[0175] Embodiment 26 is a method as described in any one of embodiments 1 to 25, further comprising: allowing hydrogen obtained from the reforming effluent to flow into the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process.

[0176] Embodiment 27 is a method as described in any one of embodiments 1 to 26, wherein the ethylene contacted in the oligomerization process is received in a stream comprising ethylene and ethane.

[0177] Embodiment 28 is the method of any one of embodiments 1 to 27, wherein no sulfur removal system is used between the oligomerization process and the aromatization process.

[0178] Embodiment 29 is a system comprising: an oligomerization reactor configured to contact ethylene with a selective higher olefin catalyst to produce an oligomerization reactor effluent, the 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 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, the aromatization feed comprising hexane, octane, or both; and an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce a reforming effluent comprising benzene, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

[0179] Embodiment 30 is a system as described in Embodiment 29, further comprising: a steam cracker configured to produce a cracker effluent comprising ethylene, wherein ethylene is recovered from the cracker effluent for oligomerization in the oligomerization reactor.

[0180] Embodiment 31 is a system as described in Embodiment 30, wherein the cracker effluent further comprises light hydrocarbons, wherein the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reforming effluent, or a combination thereof is configured to use the light hydrocarbons as a cooling source.

[0181] Embodiment 32 is a system as described in Embodiment 30, wherein the steam cracker is configured to produce a steam effluent, wherein the oligomerization reactor, the first separation unit, a second separation unit configured to receive and separate the reforming effluent, or a combination thereof is configured to use the steam effluent as a heat source.

[0182] Embodiment 33 is a system as described in any of Embodiments 29 to 32, further comprising: a fractionator configured to fractionate a refinery stream to recover a naphtha stream, wherein in the hydrogenation reactor, the naphtha contacts the hydrogenation catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

[0183] Embodiment 34 is a system as described in any one of embodiments 29 to 32, wherein the reforming effluent further comprises toluene, ethylbenzene, xylenes, 1-hexene, 1-octene or a combination thereof, and the system further comprises: a second separation unit configured to fractionate the reforming effluent into a benzene stream, a toluene stream, a xylene stream comprising ethylbenzene and xylenes, and a raffinate stream.

[0184] Embodiment 35 is a system as described in Embodiment 34, wherein 1-hexene is present in the benzene stream, the toluene stream, or both the benzene stream and the toluene stream.

[0185] Embodiment 36 is a system as described in Embodiment 34, wherein 1-octene is present in the xylene stream, the raffinate stream, or both the xylene stream and the raffinate stream.

[0186] Embodiment 37 is a system as described in Embodiment 34, wherein the aromatization reactor is further configured to produce a hydrogen effluent, wherein the hydrogenation reactor is configured to receive a portion of the benzene stream and a portion of the hydrogen effluent and produce cyclohexane therefrom, and wherein the oligomerization reactor is configured to receive the cyclohexane.

[0187] Embodiment 38 is a system as described in any one of embodiments 29 to 37, further comprising: a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the aromatization reactor.

[0188] Embodiment 39 is a system as described in any one of embodiments 29 to 38, further comprising: a second separation unit configured to fractionate the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the second stream is fed to the aromatization reactor.

[0189] Embodiment 40 is a system as described in any one of embodiments 29 to 38, further comprising: 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the second stream and at least a portion of the third stream are fed to the aromatization reactor.

[0190] Embodiment 41 is a system as described in any one of embodiments 29 to 38, further comprising: 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, wherein of the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

[0191] Embodiment 42 is a system as described in any one of embodiments 29 to 38, further comprising: 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, wherein of the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

[0192] Embodiment 43 is a system as described in any one of Embodiments 29 to 42, wherein the first separation unit is configured to recover a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octene, and a third stream comprising hexene and hexane, the system further comprising: a C6 separator configured to separate the third stream into a high purity 1-hexene stream and a hexane stream; and a cyclohexane recovery tower configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle, wherein the residual C6 feed is fed to the aromatization reactor, and wherein the cyclohexane recycle is fed to the oligomerization reactor.

[0193] Embodiment 44 is a system as described in any of Embodiments 29 to 43, wherein the selective higher olefin catalyst is selected from PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PNGuan-DIP, PN Mes-Ph-DIP, PN Xyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh or a combination thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides.

Claims

1. A method comprising: In an oligomerization process, ethylene is contacted with a selective higher olefin catalyst to produce an oligomerization reactor effluent comprising C6 hydrocarbons including 1-hexene and C8 hydrocarbons including 1-octene; recovering 1-hexene and 1-octene from the oligomerization reactor effluent; contacting 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst in a hydrotreating process to produce an aromatization feed comprising hexane, octane, or both; as well as In the aromatization process, the aromatization feed is contacted with an aromatization catalyst to produce a reformed effluent comprising benzene.

2. The process of claim 1, 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.

3. The process of claim 2, wherein the purity of 1-hexene is from about 60 wt% to about 99.9 wt% based on the total weight of the C6 hydrocarbons in the oligomerization reactor effluent.

4. The process of claim 2, wherein the purity of 1-octene is from about 95 wt% to about 99.3 wt% based on the total weight of the C8 hydrocarbons in the oligomerization reactor effluent.

5. The method of claim 1, wherein the oligomerization reactor effluent further comprises C 10 Hydrocarbon, C 12 Hydrocarbon, C 14+ hydrocarbons or combinations thereof.

6. The method of claim 5, wherein the C 10 The hydrocarbon is present in an amount of about 1 wt % to about 4 wt % based on the total weight of the oligomerization reactor effluent, 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+ The hydrocarbon is present in an amount from about 0 wt % to about 3.5 wt % based on the total weight of the oligomerization reactor effluent.

7. The process of claim 1, wherein the selective higher olefin catalyst is selected from the group consisting of PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PN Guan-DIP, PN Mes-Ph-DIP, PNXyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh or a combination thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides.

8. The process of claim 1, wherein the step of contacting ethylene with a selective higher olefin catalyst is carried out in the presence of a diluent selected from the group consisting of isobutane, cyclohexane, methylcyclohexane, isobutylene, 1-hexene, or a combination thereof.

9. The method of claim 1, wherein recovering 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream and the third stream, only a portion of the third stream is fed to the hydroprocessing process.

10. The method of claim 1, wherein recovering 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream and the third stream, only a portion of the second stream and only a portion of the third stream are fed to the hydroprocessing process.

11. The method of claim 1 , wherein recovering 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 and a second stream comprising hexene and octene, wherein of the first stream and the second stream, only a portion of the second stream is fed to the hydroprocessing process.

12. The method of claim 1, wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises: fractionating the oligomerization reactor effluent into a first stream comprising spent catalyst and a second stream comprising hexene, octene and heavy hydrocarbons, wherein of the first stream and the second stream, only a portion of the second stream is fed to the hydroprocessing process.

13. The method of claim 1, wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises: separating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes; fractionating the third stream to produce a high purity 1-hexene stream and a C6 feed stream; and The C6 feed stream is passed to the hydrotreating process.

14. The method of claim 1, further comprising: fractionating refinery streams to recover a naphtha stream; feeding the naphtha stream to the hydrotreating process; as well as In the hydrotreating process, naphtha is contacted with the hydrogenation catalyst to produce one or more of n-hexane and n-octane in the aromatization feed.

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

16. The process of 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 process of 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 method of claim 1, wherein the aromatization process is further configured to produce a hydrogen effluent, the method further comprising: passing a portion of the benzene stream and a portion of the hydrogen effluent into a hydrogenation process to produce cyclohexane; as well as The cyclohexane is recycled to the oligomerization process.

19. The method of claim 1, wherein the oligomerization reactor effluent further comprises cyclohexane and other hexanes, the method further comprising: recovering cyclohexane and the other hexanes from the oligomerization reactor effluent; passing said additional hexane recovered from said oligomerization reactor effluent to said hydrotreating process; as well as Cyclohexane recovered from the oligomerization reactor effluent is recycled to the oligomerization process.

20. The method of claim 1, further comprising: cracking ethane, propane, butane, pentane, naphtha, or a mixture thereof in a steam cracker to produce a cracker effluent comprising ethylene; as well as Ethylene recovered from the cracker effluent is passed to the oligomerization process.

21. The method of claim 20, wherein the cracker effluent further comprises light hydrocarbons, the method further comprising: The light hydrocarbons recovered from the cracker effluent are used as a cooling source for an oligomerization reactor in the oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or a combination thereof.

22. The method of claim 1, further comprising: recovering steam from the steam cracker; as well as Steam is used as a heating source for the oligomerization process, for a first fractionation process downstream of the oligomerization process, for a second fractionation process downstream of the aromatization process, or a combination thereof.

23. The process of claim 1, wherein the step of contacting ethylene with a selective higher olefin catalyst is carried out in the presence of a diluent recovered from the reforming effluent, wherein the diluent is selected from the group consisting of raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof.

24. The method of claim 1, further comprising: passing the raffinate recovered from the aromatization process into a steam cracker; as well as The raffinate is cracked in the steam cracker.

25. The method of claim 1, wherein the oligomerization reactor effluent further comprises C 9+ hydrocarbons, the method further comprising: The C 9+ hydrocarbons, a raffinate stream obtained from the reforming effluent, or the C 9+ Both hydrocarbons and the raffinate stream are blended into the motor fuel stream.

26. The method of claim 1, further comprising: Hydrogen obtained from the reformed effluent is flowed into the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process.

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

28. The process of claim 1, wherein no sulfur removal system is used between the oligomerization process and the aromatization process.

29. A system comprising: an oligomerization reactor configured to contact ethylene with a selective higher olefin catalyst to produce 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 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to produce an aromatization feed comprising hexane, octane, or both; and An aromatization reactor is configured to contact the aromatization feed with an aromatization catalyst to produce a reformed effluent comprising benzene, wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

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

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

33. The system of claim 29, further comprising: a fractionator configured to fractionate a refinery stream to recover a naphtha stream, 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 system of claim 29, wherein the reformate effluent further comprises toluene, ethylbenzene, xylenes, 1-hexene, 1-octene, or a combination thereof, the system further comprising: A second separation unit is configured to fractionate the reformate effluent into a benzene stream, a toluene stream, a xylene stream comprising ethylbenzene and xylenes, 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, wherein the hydrogenation reactor is configured to receive a portion of the benzene stream and a portion of the hydrogen effluent and produce cyclohexane therefrom, and wherein the oligomerization reactor is configured to receive the cyclohexane.

38. The system of claim 29, further comprising: 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the aromatization reactor.

39. The system of claim 29, further comprising: 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the second stream is fed to the aromatization reactor.

40. The system of claim 29, further comprising: 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 octenes, and a third stream comprising hexenes, wherein among the first stream, the second stream, and the third stream, only a portion of the second stream and at least a portion of the third stream are fed to the aromatization reactor.

41. The system of claim 29, further comprising: 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, wherein of the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

42. The system of claim 29, further comprising: 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, wherein of the first stream and the second stream, only a portion of the second stream is fed to the aromatization reactor.

43. The system of claim 29, wherein the first separation unit is configured to recover a first stream comprising heavy hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes and hexanes, the system further comprising: a C6 splitter configured to separate the third stream into a high purity 1-hexene stream and a hexane stream; as well as a cyclohexane recovery column configured to separate the hexane stream into a residual C6 feed and a cyclohexane recycle, wherein the residual C6 feed is fed to the aromatization reactor, and wherein the cyclohexane recycle is fed to the oligomerization reactor.

44. The system of claim 29, wherein the selective higher olefin catalyst is selected from the group consisting of PN Mes-tBuPh-DIP, PN Mes-MeOPh-DIP, PN Xyl-Bz-DnB, PN Xyl-Bz-DPh, PN Guan-DIP, PN Mes-Ph-DIP, PNXyl-Ph-DEt, PNP DPh-Hex-DPh, PNP DPh-Cy-DPh, PNP DPh-iPR-DPh2-OMe, PNP DPh-1MeiPR-DPh, or combinations thereof; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

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