Flexible production of benzene and its derivatives via oligomerization of ethylene

Abstract

The oligomerization of ethylene forming 1-hexene and the aromatization of the 1-hexene formed by the oligomerization of benzene are disclosed.

Description

Technical Field

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

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

[0003] A method is disclosed comprising: contacting ethylene and an oligomerization catalyst in an oligomerization reactor to produce an oligomerization reactor effluent containing 1-hexene; recovering 1-hexene from the oligomerization reactor effluent; and contacting the 1-hexene recovered from the oligomerization reactor effluent with an aromatization catalyst in an aromatization reactor to produce an aromatization reactor effluent containing benzene.

[0004] A system comprising: an oligomerization reactor configured to contact ethylene with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; and an aromatization reactor configured to contact 1-hexene recovered from the oligomerization reactor effluent with an aromatization catalyst to produce an aromatization reactor effluent containing benzene. Attached Figure Description

[0005] Figure 1 A schematic diagram of the integrated conversion system is provided.

[0006] Figure 2 A schematic diagram illustrating the pyrolysis process is provided.

[0007] Figure 3 A schematic diagram illustrating the oligomerization process is provided.

[0008] Figure 4 A schematic diagram illustrating the aromatization process is provided.

[0009] Figure 5 A schematic diagram illustrating the derivatization process is provided.

[0010] Figure 6 A schematic diagram of another integrated conversion system is shown.

[0011] Figure 7 A schematic diagram of another integrated conversion system is shown.

[0012] Figure 8 A schematic diagram of another integrated conversion system is shown.

[0013] Figure 9 A schematic diagram of another integrated conversion system is shown.

[0014] Figure 10 A schematic diagram of another integrated conversion system is shown.

[0015] Figure 11 A schematic diagram of another integrated conversion system is shown.

[0016] Figure 12 This illustrates a comparison between the prices of ethylene and benzene.

[0017] Figure 13 The conversion rate of 1-hexene to benzene is shown.

[0018] Figure 14 The selectivity for the conversion of 1-hexene to benzene was demonstrated. Detailed Implementation

[0019] First, it should be understood that although illustrative embodiments of one or more aspects are provided below, the disclosed systems, processes, and / or methods can be implemented using any number of techniques, whether currently known or existing. This disclosure should not be limited to the illustrative embodiments, drawings, and techniques shown below, including the exemplary designs and embodiments described herein, but modifications can be made within the scope of the appended claims and their equivalents.

[0020] This document discloses systems, processes, apparatus, and methods for multi-step chemical conversions, in which several chemical conversions are integrated into a single continuous flow system. Integrated conversion systems, along with associated processes, apparatus, and methods, typically involve continuous flow systems that convert C4 hydrocarbons (such as hydrocarbons derived from natural gas (e.g., ethane)) into oligomeric intermediates (e.g., 1-hexene), which are then further converted into aromatics (e.g., benzene).

[0021] As disclosed herein, methods utilizing integrated conversion systems typically include the following steps: (a) cracking a hydrocarbon feedstock (e.g., natural gas) in a cracking process (e.g., a steam cracker) to produce a cracker effluent containing monomers (e.g., ethylene); (b) allowing monomers recovered from the cracker effluent to flow into an oligomerization process; (c) contacting the monomers with an oligomerization catalyst in the oligomerization process to produce an oligomerization reactor effluent containing oligomers (e.g., 1-hexene); (d) allowing oligomers recovered from the oligomerization reactor effluent to flow into an aromatization process; and (e) contacting the oligomers with an aromatization catalyst in the aromatization process to produce an aromatization effluent containing aromatics (e.g., benzene). In one aspect, the integrated conversion system of this disclosure is a continuous tandem flow system in which the cracking process is connected to the oligomerization process, which in turn is connected to the aromatization process, wherein the cracker effluent or a stream from which it originates flows into the oligomerization process, and wherein the resulting oligomerization reactor effluent or a stream from which it originates flows into the aromatization process. In some respects, as described in more detail herein, the integrated conversion system may include a hydrogenation process connecting the oligomerization process and the aromatization process.

[0022] In the systems, processes, and methods disclosed herein, multiple streams and products (e.g., ethylene, 1-hexene, benzene, ethylbenzene, styrene) are recovered from reactors and / or process streams. Those skilled in the art will recognize that streams or products can be recovered directly from the reactor or process that forms the stream or product; alternatively, streams or products can be recovered from another process and / or stream located downstream of the stream or product formation.

[0023] The following definitions are provided to assist those skilled in the art in understanding the detailed description of this disclosure. Unless otherwise defined herein, scientific and technical terms used in conjunction with this disclosure should have the meanings commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, unless the context otherwise requires, singular terms should include plural terms and plural terms should include singular terms.

[0024] Furthermore, for clarity, certain features of this disclosure described herein in the context of a single aspect may also be provided in combination within that single aspect. Conversely, for the sake of brevity, the various features of this disclosure described herein in the context of a single aspect may also be provided separately or in any sub-combination.

[0025] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise specified, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0026] use Chemical and Engineering News The numbering scheme indicated in the version of the periodic table published in 63(5), 27, 1985 is used to indicate the groups of elements in the periodic table. In some cases, the groups of elements may be indicated by the common names assigned to the groups; for example, alkaline earth metals (or alkali metals) of Group 1 elements, alkaline earth metals (or alkaline metals) of Group 2 elements, transition metals of Groups 3-12 elements, and halogens of Group 17 elements.

[0027] General formula C A+ and C A- This represents the number of carbon atoms in the molecular formula of an organic molecule (e.g., a hydrocarbon), where A is the whole number. For example, C 3+ This indicates a compound in which each molecule contains three or more carbon atoms, and C 5- This indicates a compound in which each molecule contains five or fewer carbon atoms.

[0028] Unless otherwise expressly stated in the prescribed circumstances, all percentages, parts, ratios and similar quantities used herein are defined by weight.

[0029] Whenever used in this specification and claims, the term "olefin" refers to a compound having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Unless explicitly stated otherwise, the term "olefin" includes aliphatic and aromatic, acyclic and cyclic, and / or straight-chain and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Unless explicitly indicated, the term "olefin" itself does not indicate the presence of heteroatoms and / or the presence of other carbon-carbon double bonds. Olefins having only one, only two, only three, etc., carbon-carbon double bonds can be identified by using the terms "mono," "di," "tri," etc., in the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bonds.

[0030] The term "reactor effluent" and its derivatives (e.g., oligomer reactor effluent) generally refer to all substances leaving the reactor. The term "reactor effluent" and its derivatives may also begin with other descriptors that limit the portion of the reactor effluent referred to. For example, while the term "reactor effluent" refers to all substances leaving the reactor (e.g., products and solvents or diluents), the term "olefin reactor effluent" refers to reactor effluent containing olefin (i.e., carbon-carbon) double bonds.

[0031] The term "oligomer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product comprising 2 to 30 monomer units. Similarly, "oligomer" is a product containing 2 to 30 monomer units, while "oligomeric product" includes all products produced by an "oligomer" process, including both "oligomers" and products that are not "oligomers" (e.g., products containing more than 30 monomer units). It should be noted that the monomer units in an "oligomer" or "oligomeric product" need not be identical. For example, an "oligomer" or "oligomeric product" produced by an "oligomer" process using ethylene and propylene as monomers may contain both ethylene and / or propylene units.

[0032] The term "trimer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing three and only three monomer units. A "trimer" is a product containing three and only three monomer units, while a "trimer product" includes all products produced by a trimer process, including trimers and non-trimer products (e.g., dimers or tetramers). Generally, when considering the number of olefin bonds (i.e., carbon-carbon double bonds) in a monomer unit and the number of olefin bonds in a trimer, olefin trimer reduces the number of olefin bonds by two. It should be noted that the monomer units in a "trimer" or "trimer product" need not be identical. For example, a "trimer" produced by a trimer process using ethylene and butene as monomers may contain ethylene and / or butene monomer units. That is, the "trimer" will include C6, C8, C96 ... 10and C 12 Products. In another example, the "trimer" produced by a "trimerization" process using ethylene as a monomer may contain ethylene monomer units. It should also be noted that a single molecule may contain two monomer units. For example, dienes such as 1,3-butadiene and 1,4-pentadiene have two monomer units within a single molecule.

[0033] The term "monomer" refers to a C4 hydrocarbon whose molecular structure contains a single carbon-carbon double bond. For example, a monomer can be a C2 monoalkene.

[0034] The term "oligomer" refers to a C0 group of molecules containing at least one carbon-carbon double bond. 6+ Hydrocarbons. For example, oligomers can be C6 monoolefins.

[0035] The term aromatic hydrocarbons refer to monocyclic hydrocarbons with C6 to C4 rings. 14 Aromatic compounds.

[0036] Cetane number is a measure of diesel fuel's performance relative to cetane (C60). 16 H 34 The standard for the ignition properties of ).

[0037] The smoke point of an oil or fat is the temperature at which, under specific and defined conditions, it begins to produce a clearly visible, continuous blue smoke.

[0038] Aspects of this disclosure can be further understood by referring to the accompanying flow diagrams in conjunction with the following description. Those skilled in the art will recognize the various additional pumps, valves, heaters, coolers, and other conventional devices necessary for implementing this disclosure. In some cases, these additional devices have been omitted from the figures for clarity. The description of the figures provides a method for operating the process. However, it should be understood that while these figures are general representations of the process, minor modifications may be made to adapt the figures to various conditions within the scope of this disclosure. It should also be understood that numerical references in the figures are consistent throughout all figures. For example, inlet flow 10 containing hydrocarbon feedstock is the hydrocarbon feedstock inlet flow in all figures. Unless otherwise explicitly disclosed, the function and components (e.g., process components or units) of a process in one integrated conversion system are substantially the same as those of another integrated conversion system including the process (e.g., the same process components or units). In other words, unless otherwise explicitly disclosed, the function and components of cracking process 200 in integrated conversion system 1000 are substantially the same as those of cracking process 200 in integrated conversion system 1100, or cracking process 200 in integrated conversion system 1200, etc.

[0039] refer to Figure 1The integrated conversion system 1000 is described. The integrated conversion system 1000 typically includes a cracking process 200, an oligomerization process 300, an aromatization process 400, and a derivatization process 500.

[0040] In an integrated conversion system, various system components can be fluidly connected via one or more conduits (e.g., pipes, tubes, streamlines, etc.) suitable for conveying specific flows, for example, Figure 1 The numbering stream is displayed in detail.

[0041] Hydrocarbon feedstock 10 flows into cracking process 200, where the hydrocarbons are converted (i.e., cracked) into monomers. In one aspect, the monomers include ethylene. Cracking process 200 may include any cracking process suitable for producing ethylene as disclosed herein. Cracking process 200 may be a steam cracker for converting one or more hydrocarbons into ethylene. U.S. Patent No. 6,790,342 discloses a method for converting hydrocarbons into ethylene, which is incorporated herein by reference in its entirety. Any method for producing ethylene disclosed in U.S. Patent No. 6,790,342 may be utilized herein. Hydrocarbon feedstock 10 contains any one or more hydrocarbons suitable for the uses disclosed herein. For example, the hydrocarbons may include non-aromatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. The hydrocarbons may be derived from natural gas, gas condensates, oil gas, or combinations thereof. In one aspect, the hydrocarbons include ethane, propane, butane, pentane, naphtha, or combinations thereof. In a further aspect, hydrocarbon feedstock 10 contains ethane, wherein the ethane may be derived from a natural gas source.

[0042] In one specific aspect, based on the total weight of the hydrocarbon feedstock 10, the amount of ethane in the hydrocarbon feedstock 10 is in the range of about 10% by weight to about 95% by weight; alternatively, about 20% by weight to about 80% by weight, or alternatively, about 40% by weight to about 60% by weight.

[0043] refer to Figure 2 This describes aspects of the cracking process 200. The hydrocarbon feedstock 10 is optionally combined with the hydrocarbon recycle stream 201. The hydrocarbon recycle stream 201 may include other streams from the integrated reforming system disclosed herein. For example, the hydrocarbon recycle stream 201 may include one or more streams selected from the group consisting of: C0 of the cracking process 200... 3+ Flow 262 and / or alternative C 3+ Stream 282; Figure 3 Heavy effluent 336 and / or byproduct effluent 352; Figure 4 C2 effluent 488; Figure 5 The polyalkylation stream 527 and / or aromatic stream 545 are present in the middle. Figure 9Ethane separation stream 162 in the process; and combinations thereof, all of which will be further described herein. Some aspects of the cracking process 200 are considered for operation in the absence of hydrocarbon recycle stream 201.

[0044] refer to Figure 2 Hydrocarbon feedstock 10 is diluted with a stream and fed into a cracking zone 205, which includes a steam cracker, where it is heated to a high temperature in the absence of oxygen to produce cracker effluent 210. The cracking zone 205 includes one or more radiant furnace reactors capable of producing cracker effluent 210. The products present in the cracker effluent 210 can vary depending on the feed composition, the hydrocarbon-to-steam ratio, the cracking temperature, and the residence time in the furnace. In one aspect, the cracking zone 205 may have a temperature in the range of about 600°C to about 1500°C; alternatively, about 750°C to about 900°C. In a further aspect, the pyrolysis zone 205 may have an inlet pressure in the range of about 5 psig to about 400 psig (about 0.03 MPag to about 2.76 MPag); or alternatively, an inlet pressure in the range of 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, an outlet pressure in the range of about 3.5 psig to about 11 psig (about 0.024 MPag to about 0.076 MPag). Radiation furnace reactors are disclosed in U.S. Patents 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 pyrolyzer effluent 210 contains one or more monomers, hydrogen, methane, acetylene, ethane, and C. 3+ Saturated hydrocarbons, streams, and combinations thereof. In a further aspect, monomers include ethylene, propylene, butene, or combinations thereof; or alternatively, ethylene.

[0045] Based on the total weight of the pyrolysis effluent 210, the amount of ethylene in the pyrolysis effluent 210 may range from about 10% by weight to about 95% by weight; alternatively, from about 20% by weight to about 80% by weight; or alternatively, from about 40% by weight to about 70% by weight. In a further aspect, the pyrolysis effluent 210 may contain about 1% by weight to about 20% by weight hydrogen, about 1% by weight to about 30% by weight methane, about 1% by weight to about 30% by weight acetylene, about 3% by weight to about 45% by weight ethane, and about 0% by weight to about 25% by weight C. 3+ hydrocarbon.

[0046] The pyrolysis effluent 210 flows into a quenching zone 215 to generate a quenched gas stream 220. In one aspect, the operating temperature of the quenching zone 215 may be lower than the temperature required to sustain the pyrolysis reaction occurring within the pyrolysis effluent 210. In another aspect, the pyrolysis effluent 210 is cooled to a temperature below about 595°C; alternatively, it is cooled to a temperature in the range of about 30°C to about 110°C to form the quenched gas stream 220. Quenching can be performed by any means suitable to those skilled in the art. For example, the pyrolysis effluent 210 may be fed to a quenching boiler and a quenching tower, where the dilution stream can be removed and recycled back to the pyrolysis furnace. Methods for cooling the pyrolysis effluent 210 are disclosed in U.S. Patents 3,407,798; 5,427,655; 3,392,211; 4,351,275; and 3,403,722, each of which is incorporated herein by reference in its entirety. A quenched gas flow 220 flows into a first compression zone 225 to generate a pressurized gas flow 230. In one aspect, the pressurized gas flow 230 may include pressures ranging from about 150 psig to about 650 psig (about 1.034 MPag to about 4.48 MPag). The first compression zone 225 includes one or more gas compressors, wherein the gas compressors may be any gas compressor suitable for the purposes disclosed herein.

[0047] A pressurized gas stream 230 flows into a 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 from 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, it may be in the range of about 25 ppb to about 100 ppb by weight. In yet another aspect, the CO2 concentration of the wet gas stream 240 may be less than about 5 ppm by weight. The removal of H2S and CO2 can be achieved by any suitable means as determined by those skilled in the art and by means of this disclosure. In yet another aspect, diethanolamine or a caustic contactor may be used to remove at least a portion of the H2S and CO2 contained in the pressurized gas stream 230. The wet gas stream 240 flows into a drying zone 245, producing a cracked gas stream 250. In one aspect, the water content of the pyrolysis gas stream 250 is below the amount required to cause downstream operational problems. In a further aspect, the water content of the pyrolysis gas stream 250 is less than about 10 ppm by weight. Drying in the drying zone 245 can be achieved by any suitable means as determined by those skilled in the art and by means of this disclosure. In one aspect, water can be removed from the wet gas stream 240 using a molecular sieve bed.

[0048] The cracked gas stream 250 flows into the deethanizer section 255 to produce C. 2- Stream 260 and C 3+ Stream 262. Deethaner section 255 includes sections capable of producing C 2- Stream 260 and C 3+ Fractionator of flow 262. C 2- Stream 260 may contain hydrogen, methane, ethane, acetylene, ethylene, or combinations thereof. 3+ Stream 262 contains C3 hydrocarbons and heavier components, and in one respect, can be merged with hydrocarbon recycling stream 201. 2- Flow 260 flows into hydrogenation zone 265, where C can be removed. 2- A portion of the acetylene in stream 260. Ethylene stream 270 is recovered from hydrogenation zone 265. This can be done by any suitable means as determined by a person skilled in the art and by means of this disclosure. 2- Hydrogenation at 260°C. For example, an acetylene reactor containing a selective hydrogenation catalyst can be used for C. 2- A portion of the acetylene in stream 260 is hydrogenated to ethylene (preferably to ethane). Group VIII metal hydrogenation catalysts are typically used. Selective hydrogenation catalysts are disclosed in U.S. Patents 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 the hydrogenation zone 265 can be any combination of suitable conditions as determined by a person skilled in the art with the aid of this disclosure. In one aspect, the temperature and pressure in the hydrogenation zone 265 can be at a level capable of supporting C 2- A portion of the acetylene in stream 260 is hydrogenated to ethylene. In a further aspect, hydrogenation zone 265 may have a temperature in the range of about 10°C to about 205°C. In yet another aspect, hydrogenation zone 265 may have a pressure in the range of about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag). In some aspects, the amount of residual acetylene in ethylene stream 270 may be less than about 5 ppm by weight; alternatively, it may be in the range of about 0.5 ppm to about 3 ppm by weight.

[0049] Alternatively, C 2- All or part of flow 260 is fed through pipeline 266 (with valves in flow 260 and flow 268) and flows into the second compression zone 267 to generate pressurization C.2- Flow 268. Pressurized C 2- Flow 268 may have a pressure ranging from about 100 psig to about 750 psig (about 0.68 MPag to about 5.17 MPag); alternatively, from about 200 psig to about 650 psig (about 1.37 MPag to about 4.48 MPag). The second compression zone 267 includes one or more gas compressors, wherein the gas compressors may be any gas compressor suitable for the purposes disclosed herein. Pressurization C 2- Flow 268 flows into hydrogenation zone 265, where pressurized C is removed. 2- A portion of the acetylene contained in stream 268 is converted to ethylene, for example, via selective hydrogenation. Ethylene stream 270 is recovered from hydrogenation zone 265 as disclosed herein.

[0050] In another alternative, all or part of the effluent from drying zone 245 is a substitute gas stream 272. Substitute gas stream 272 flows into substitute hydrogenation zone 275, where a portion of the acetylene contained in substitute gas stream 272 is removed to produce reducing gas stream 276. In one aspect, substitute hydrogenation zone 275 operates similarly to hydrogenation zone 265. Reducing gas stream 276 flows into substitute deethaner zone 277, where it recovers substitute ethylene stream 280 and produces substitute C. 3+ Stream 282. In one aspect, the alternative deethaner section 277 operates similarly to the deethaner section 255. In a further aspect, the alternative ethylene stream 280 and the alternative C... 3+ The composition of stream 282 is similar to that of ethylene stream 270 and C. 3+ The composition of Stream 262 is quite similar. In one respect, it replaces C. 3+ Stream 282 may be combined with hydrocarbon recycling stream 201. Ethylene stream 270 and / or alternative to ethylene stream 280 flow into cracking process effluent 25.

[0051] In one aspect, the cracking process effluent 25 contains ethylene. Based on the total weight of the cracking process effluent 25, the amount of ethylene in the cracking process effluent 25 may range from about 30% by weight to about 95% by weight; alternatively, from about 30% by weight to about 70% by weight; or alternatively, from about 40% by weight to about 60% by weight.

[0052] Return to Figure 1The pyrolysis process effluent 25 flows into the oligomerization process 300, where a monomer (e.g., ethylene) is converted into an oligomer (e.g., 1-hexene). In one aspect, the pyrolysis process effluent 25 flows continuously from the pyrolysis process 200 and into the oligomerization process 300. Those skilled in the art will understand that, as described herein with respect to the pyrolysis process effluent 25, each stream described throughout this disclosure flows continuously from one process to the next. For simplicity, the continuous flow of each stream is not explicitly stated, but it is characteristic of each stream. The oligomerization process 300 may include a trimerization process in which ethylene monomer is contacted with an oligomerization catalyst in an oligomerization reactor to produce a 1-hexene oligomer. In one aspect, the trimerization process includes a trimerization reaction. For the purposes of this disclosure, the terms oligomerization and trimerization are used interchangeably. The oligomerization process 300 may include any trimerization process and / or trimerization reaction suitable for producing 1-hexene as disclosed herein. U.S. Patent No. 7,157,612 discloses a method for converting ethylene to 1-hexene using an oligomerization catalyst system, which is incorporated herein by reference in its entirety.

[0053] Optionally, the cracking process effluent 25 can be further divided into ethylene feed 27 and / or utilities stream 29. The ethylene feed 27, containing ethylene, flows into the derivatization process 500. The utilities stream 29, containing ethylene, can be sent for storage or sale.

[0054] refer to Figure 3 This describes aspects of the oligomerization process 300. The cracking process effluent 25 may optionally be combined with the ethylene recirculation stream 306 to form the oligomer feed stream 301. In one aspect, the ethylene recirculation stream 306 may be combined with one or more streams selected from the group consisting of: ethylene effluent 340; Figure 4 C2 effluent 488; Figure 9 Ethylene separation stream 165; and combinations thereof, as further described herein. In a further aspect, ethylene recirculation stream 306 comprises a light effluent from the polyethylene polymerization process. Some aspects of the oligomerization process 300 are considered for operation without ethylene recirculation stream 306. Oligomer feed stream 301 flows into oligomerization reactor 305. In one aspect, oligomer feed stream 301 comprises ethane, ethylene, or a combination thereof. First hydrogen feed stream 302 flows into oligomerization reactor 305. Hydrogen feed stream 302 may be fed into oligomerization reactor 305 as a separate feed stream, or may be combined with oligomer feed stream 301 and fed into oligomerization reactor as a combined feed stream. In one aspect, first hydrogen feed stream 302 may be combined with a stream from another part of the integrated reforming system of this disclosure. For example, first hydrogen feed stream 302 may be combined with one or more streams selected from the group consisting of: Figure 4 Hydrogen effluent 41; Figure 5The outflowing hydrogen stream 537; and combinations thereof, as further described herein. It is not desired to be theoretically limited to the fact that oligomerization in the presence of hydrogen can enhance product selectivity, reduce polymer product formation, or both. Some aspects of the oligomerization process 300 have been considered for operation in the absence of the first hydrogen feed stream 302.

[0055] In one aspect of the oligomerization process 300, ethylene is contacted with an oligomerization catalyst in an oligomerization reactor 305 in the presence of a solvent. In this aspect, 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 disclosed herein. In one aspect, the solvent is not necessarily an inert substance, and the solvent can participate in the oligomerization. In a further aspect, the solvent can be a n-alkanes, branched alkanes, isoalkanes, alkanes, cycloalkanes, aromatic hydrocarbons, or combinations thereof. In a further aspect, the solvent can be isobutane, cyclohexane, methylcyclohexane, 2,2,4-trimethylpentane, or combinations thereof. In one aspect where 1-hexene is the product of the oligomerization reaction, the 1-hexene formed (i.e., the reaction product) can also be used as a solvent, and in this case, the oligomerization reaction can be referred to as a "solvent-free" oligomerization reaction. Alternatively, in one aspect where 1-hexene is the product of the oligomerization reaction, the solvent is cyclohexane. In one aspect, solvent feed 308 may be combined with one or more streams selected from the group consisting of solvent effluent 354; Figure 7 Cyclohexane recycle stream 123; Figure 10 The raffinate stream 419 in the process; and combinations thereof, as further disclosed herein. Some aspects of the oligomerization process 300 are considered for operation in the absence of solvent feed 308.

[0056] Oligopolymer catalyst stream 304 flows into oligopolymer reactor 305. As disclosed herein, U.S. Patent No. 7,157,612 describes an oligopolymer catalyst system suitable for trimerizing ethylene to 1-hexene. In one aspect, the oligopolymer catalyst system of this disclosure includes a chromium source, a pyrrole-containing compound, and a metallic alkyl group, all of which are contacted and / or reacted in the presence of an unsaturated hydrocarbon. Optionally, the oligopolymer catalyst system may be supported on an inorganic oxide support.

[0057] The chromium source can be one or more organic or inorganic compounds, wherein the chromium oxidation state is 0 to 6. Typically, the chromium source will have the general formula CrX. nWhere X can be the same or different and can be any organic or inorganic group, and n is an integer from 1 to 6. In one aspect, the organic group can have about 1 to about 20 carbon atoms per group and is selected from the group consisting of alkyl, alkoxy, ester, ketone, and / or amide groups. The organic group can be straight-chain or branched, cyclic or acyclic, aromatic or aliphatic, and can be made from a mixture of aliphatic, aromatic, and / or alicyclic groups. In a further aspect, the inorganic group includes, but is not limited to, halides, sulfates, and / or oxides.

[0058] In one aspect, the chromium source is a chromium (II) and / or chromium (III) compound that can produce a catalyst system with trimerizing activity suitable for use herein. In a further aspect, the chromium source is a chromium (III) compound due to its ease of use, availability, and ability to enhance the activity of the catalyst system. Non-limiting examples of chromium (III) compounds suitable for use in this disclosure include chromium carboxylate, chromium naphthenate, chromium halide, chromium pyrroleate, and / or chromium dionate. In one aspect, the chromium(III) compound may be chromium(III) 2,2,6,6-tetramethylheptanedione [Cr(TMHD)3], chromium(III) 2-ethylhexanoate [Cr(EH)3, also known as tri(2-ethylhexanoate)chromium(III)], chromium(III) naphthenate [Cr(NP)3], chromium(III) chloride, chromium bromide, chromium fluoride, chromium(III) acetylacetonate, chromium(III) acetate, chromium(III) butyrate, chromium(III) neopentanoate, chromium(III) laurate, chromium(III) stearate, chromium(III) oxalate, or combinations thereof. In a further aspect, the chromium(III) compound may be chromium(III) pyrroleate.

[0059] Non-limiting examples of chromium(II) compounds suitable for use in this disclosure include chromium(II) bromide, chromium(II) fluoride, chromium(II) chloride, chromium(II) di(2-ethylhexanoate), chromium(II) acetate, chromium(II) butyrate, chromium(II) neopentanoate, chromium(II) laurate, chromium(II) stearate, chromium(II) oxalate, or combinations thereof. In a further aspect, the chromium(II) compound may be chromium(II) pyrroleate.

[0060] The pyrrole-containing compound can be any pyrrole-containing compound or pyrrolidinide that reacts with a chromium source to form a chromium pyrrolidinide complex. As used in this disclosure, the term "pyrrole-containing compound" can refer to hydrogen pyrrolidinide (i.e., pyrrole (C4H5N)), a derivative of hydrogen pyrrolidinide, a substituted pyrrolidinide, or a metal pyrrolidinide complex. As used in this disclosure, the term "pyrrolidinide" refers to a 5-membered nitrogen-containing heterocycle, such as pyrrole, pyrrole derivatives, and mixtures thereof. Broadly, the pyrrole-containing compound can be any heterocoordinate or isocoordinate metal complex or salt containing pyrrole and / or a pyrrole group or ligand. The pyrrole-containing compound can be added definitively to a reactor or generated in situ.

[0061] Generally, pyrrole-containing compounds will have about 4 to about 20 carbon atoms per molecule. In one aspect, the pyrroles suitable for use in this disclosure may be selected from the group consisting of: hydrogen pyrrole (pyrrole), lithium pyrrole, sodium pyrrole, potassium pyrrole, cesium pyrrole, and / or salts of substituted pyrroles, because they are highly reactive with other reactants. Examples of substituted pyrroles suitable for use include, but are not limited to, pyrrole-2-carboxylic acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydroindole, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyrrole, ethyl 2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrolepropionate, ethyl 3,5-dimethyl-2-pyrrolecarboxylate, or combinations thereof. When the pyrrole-containing compound contains chromium, the resulting chromium compound may be called chromium pyrrole.

[0062] In one aspect, the pyrrole-containing compound used in the catalyst system is selected from the group consisting of: hydrogen pyrrole (i.e., pyrrole (C4H5N)), 2,5-dimethylpyrrole, and / or chromium pyrrole, all of which can provide enhanced trimerization activity. Optionally, for ease of use, chromium pyrrole can provide both a chromium source and a pyrrole-containing compound. As used in this disclosure, when chromium pyrrole is used to form a catalyst system, it is considered to provide both a chromium source and a pyrrole-containing compound. While all pyrrole-containing compounds can produce catalyst systems with high activity and high productivity, the use of pyrrole and / or 2,5-dimethylpyrrole can produce catalyst systems with desired levels of activity and selectivity for one or more desired products.

[0063] In one aspect, the metal alkyl group includes heteroaqueous or homoaqueous metal alkyl compounds. In a further aspect, any heteroaqueous or homoaqueous metal alkyl group suitable for use as described herein may be utilized. In a further aspect, one or more metal alkyl groups may be used. The alkyl ligand on the metal may be aliphatic and / or aromatic. In a further aspect, the alkyl ligand may be any saturated or unsaturated aliphatic group. The metal alkyl group may have any number of carbon atoms. However, for commercial availability and ease of use, metal alkyl groups typically contain fewer than about 70 carbon atoms per molecule; alternatively, fewer than 20 carbon atoms. Non-limiting examples of metal alkyl groups suitable for use herein include alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds, alkylzinc compounds, and / or alkyllithium compounds. In a further aspect, the metal alkyl group includes n-butyllithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, triisobutylaluminum, or combinations thereof.

[0064] In a further aspect, the metal alkyl group can be an unhydrolyzed metal alkyl group, i.e., one that has not been pre-contaminated with water. In some aspects, the metal alkyl group can be selected from the group consisting of: unhydrolyzed alkylaluminum compounds, unhydrolyzed derivatives of alkylaluminum compounds, unhydrolyzed haloalkylaluminum compounds, or mixtures thereof. In a further aspect, the use of unhydrolyzed metal alkyl groups can improve product selectivity and / or the reactivity, activity, and / or productivity of the catalyst system. While not wishing to be limited by theory, the use of hydrolyzed metal alkyl groups can lead to a decrease in olefin (i.e., liquid) yield and an increase in polymer (i.e., solid) yield.

[0065] In one aspect, the metallic alkyl group includes unhydrolyzed alkylaluminum compounds represented by the general formulas AlR3, AlR2X, AlRX2, AlR2OR, AlRXOR, and / or Al2R3X3, wherein R is an alkyl group and X is a halogen atom. Non-limiting examples of metallic alkyl groups suitable for use herein include triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylethoxyaluminum, diethylphenylaluminum oxide, dichloroethylaluminum, sesquiethylaluminum chloride, or combinations thereof. In a specific aspect, the alkylaluminum compound may be triethylaluminum.

[0066] In a further aspect, unsaturated hydrocarbons are present during the contact and / or reaction of the chromium source, the pyrrole-containing compound, and the metallic alkyl group, wherein the contact and / or reaction can be carried out in any manner suitable for the purposes of this disclosure. For example, the pyrrole-containing compound may be contacted with the chromium source and then with the metallic alkyl group. Optionally, the pyrrole-containing compound may be contacted with the metallic alkyl group and then with the chromium source. Many other contacting procedures may also be used, such as contacting all components of the oligomerization catalyst system in oligomerization reactor 305.

[0067] Unsaturated hydrocarbons can be any aromatic or aliphatic hydrocarbon in a gaseous, liquid, or solid state. In one aspect, liquid unsaturated hydrocarbons allow for adequate contact between the chromium source, the pyrrole-containing compound, and the metallic alkyl group. Unsaturated hydrocarbons can have any number of carbon atoms per molecule. Due to commercial availability and ease of use, unsaturated hydrocarbons may contain fewer than about 70 carbon atoms per metallic alkyl molecule; alternatively, fewer than 20 carbon atoms. Non-limiting examples of unsaturated aliphatic hydrocarbons suitable for use herein include ethylene, 1-hexene, 1,3-butadiene, or combinations thereof. In one aspect, the unsaturated aliphatic hydrocarbon may be 1-hexene, which can be produced in an oligomerization reactor. While not wishing to be theoretically limited, aromatic hydrocarbons can improve the stability, activity, and / or selectivity of a catalyst system. Non-limiting examples of aromatic hydrocarbons suitable for use herein include toluene, benzene, xylene, ethylbenzene, mesitylene, hexamethylbenzene, or combinations thereof. In one aspect, the aromatic hydrocarbon may be toluene or ethylbenzene; alternatively, toluene; alternatively, ethylbenzene.

[0068] In one specific aspect, the oligomerizing catalyst system may optionally include a halide source. While not wishing to be theoretically limited, the presence of a halide source can improve the stability, activity, and / or selectivity of the oligomerizing catalyst system. The halide source can be any compound containing a halogen. For example, the halide source may include fluorides, chlorides, bromides, iodides, or combinations thereof. In a further aspect, the halide source may be a chloride or a bromide; alternatively, a chloride; alternatively, a bromide.

[0069] Non-limiting examples of halide sources applicable to the use of this document include those having the general formula R m X n The compound, wherein R can be any organic and / or inorganic group, X can be a halide selected from the group consisting of fluorides, chlorides, bromides and / or iodides, and m+n can be any number greater than 0. When R is an organic group, R has about 1 to about 70 carbon atoms per group; alternatively, each group has 1 to 20 carbon atoms. When R is an inorganic group, R can be selected from the group consisting of aluminum, silicon, germanium, hydrogen, boron, lithium, tin, gallium, indium, lead or combinations thereof. In one aspect, the halide source can be dichloromethane, chloroform, benzyl chloride, silicon tetrachloride, tin(II), tin(IV), germanium tetrachloride, boron trichloride, aluminum tribromide, aluminum trichloride, 1,4-dibromobutane, 1-bromobutane or combinations thereof. In a further aspect, the halide source can be tin(IV), germanium halide or combinations thereof.

[0070] In a further aspect, the halide source can be provided by a chromium source, a metallic alkyl group, an unsaturated hydrocarbon, or a combination thereof. In one aspect, the halide source can be an alkyl aluminum halide used in combination with an alkyl aluminum compound. Non-limiting examples of alkyl aluminum halides suitable for use as halide sources include, but are not limited to, diisobutylaluminum chloride, diethylaluminum chloride, sesquiethylaluminum chloride, dichloroethylaluminum, diethylaluminum bromide, diethylaluminum iodide, or combinations thereof.

[0071] Those skilled in the art will understand that reaction mixtures containing chromium sources, pyrrole compounds, metallic alkyl groups, unsaturated hydrocarbons, and optionally halide sources may further contain additional components that will not adversely affect the oligomeric catalyst system disclosed herein and may enhance the system.

[0072] In one aspect, the oligomeric catalyst system comprises a pyrrole-containing compound and chromium in a chromium source in a molar ratio ranging from about 1:1 to about 80:1; alternatively, about 3:1 to about 50:1; alternatively, about 10:1 to about 20:1. In a further aspect, the molar ratio of the pyrrole-containing compound to chromium in the chromium source may be about 16:1; or alternatively, about 3:1. In yet another aspect, the oligomeric catalyst system comprises a metal alkyl group and chromium in a chromium source in a molar ratio ranging from about 5:1 to about 200:1; alternatively, about 10:1 to about 100:1; or alternatively, about 40:1 to about 60:1. In one aspect, the molar ratio of the metal alkyl group to chromium in the chromium source may be about 50:1; or alternatively, about 11:1. In a further aspect, the oligomerization catalyst system comprises chromium in a halide source to a chromium source in a molar ratio ranging from about 2:1 to about 300:1; alternatively, about 5:1 to about 200:1; or alternatively, about 50:1 to about 80:1. In one aspect, the molar ratio of the halide source to the chromium source may be about 63:1; alternatively, about 8:1.

[0073] Contact between ethylene and the oligomerization catalyst system within the oligomerization reactor 305 can occur in any suitable manner and by means of this disclosure. In one aspect, contact between ethylene and the oligomerization catalyst system can occur through solution reaction, slurry reaction, gas-phase reaction, or a combination thereof. In a specific aspect, the suspension formed between the oligomerization catalyst system and the solvent can be stirred to maintain a uniform concentration of the oligomerization catalyst system throughout the suspension; or alternatively, the solution formed between the oligomerization catalyst system and the solvent can be stirred to maintain the oligomerization catalyst system in solution throughout the oligomerization process. The temperature within the oligomerization reactor 305 can be any temperature suitable for the ethylene trimerization reaction. In one aspect, the temperature is within a range that is low enough to avoid a decrease in the activity of the oligomerization catalyst system and high enough to avoid the formation and / or precipitation of polymer products. In a further aspect, the temperature within the oligomerization reactor 305 can be in the range of about 0°C to about 300°C; alternatively, about 60°C to about 275°C; or alternatively, about 110°C to about 125°C. The pressure within the oligomerization reactor 305 can be any pressure suitable for the ethylene trimerization reaction. In one respect, the pressure range is high enough to avoid a decrease in the activity of the oligomerization catalyst system. In a further respect, the pressure within the oligomerization reactor 305 can range from about atmospheric pressure to about 2500 psig (about 0.101 MPag to about 17.24 MPag). When 1-hexene is used as a diluent, the pressure can range from about atmospheric pressure to about 2000 psig (about 0.101 MPag to about 13.79 MPag); alternatively, from about 1100 psig to about 1600 psig (about 7.58 MPag to about 11.03 MPag). When a diluent other than 1-hexene is used, the pressure can range from about atmospheric pressure to about 1500 psig (about 0.101 MPag to about 10.34 MPag); alternatively, from about 600 psig to about 1000 psig (about 4.13 MPag to about 6.9 MPag).

[0074] Return to Figure 3The oligomer reactor effluent 310 flowing from oligomer reactor 305 contains all components that may be present in and can be removed from the oligomer reactor. Oligomer reactor effluent 310 may contain oligomer products, by-products, co-products, side-products, light hydrocarbons, heavy hydrocarbons, unreacted monomers, catalyst system, solvents, and other reactor components. In one aspect, oligomer reactor effluent 310 contains 1-hexene, cyclohexane, and unreacted ethylene; or alternatively, 1-hexene and unreacted ethylene. Those skilled in the art will understand that streams 301, 302, 304, and 310 may be located on oligomer reactor 305 at any location suitable for allowing sufficient contact between ethylene and the oligomer catalyst system within oligomer reactor 305. A catalyst kill stream 312 is merged with oligomer reactor effluent 310. Catalyst kill stream 312 contains a catalyst deactivation composition that can partially or completely deactivate the oligomer catalyst system as disclosed herein. Some aspects of the oligomerization process 300 may eliminate the need for catalyst suppression stream 312. Filter 315 removes particulates (e.g., catalyst fines and undesirable polymer products) from the oligomerization reactor effluent stream 310. While not wishing to be bound by theory, it is believed that higher reactor and flow temperatures can suppress the solidification of undesirable polymer particles. When the oligomerization reactor effluent stream 310 is maintained at a high temperature, fewer particulates can form, and filter 315 may not be necessary. Filter 315 may be used where process conditions favor particulate formation (e.g., cooling of the oligomerization reactor effluent stream 310). Some aspects of the oligomerization process 300 may eliminate the need for filter 315. Process stream 320 contains either the effluent from filter 315 or a continuation of the oligomerization reactor effluent stream 310, wherein process stream 320 contains little or no particulates.

[0075] Process stream 320 flows into first separator 325 to produce light effluent 330 and heavy effluent 336. Heavy effluent 336 contains heavy hydrocarbons and an oligomerization catalyst system. Light effluent 330 may contain 1-hexene, unreacted ethylene, unwanted oligomers, solvents, and combinations thereof. In one aspect, light effluent 330 contains methane, ethane, ethylene, propane, propylene, butane, or combinations thereof. In a further aspect, first separator 325 includes a washing process that facilitates the removal of the oligomerization catalyst system from light effluent 330 (e.g., 1-hexene). For the purposes of this disclosure, the heavy hydrocarbons present in heavy effluent 336 may include C 8+ Hydrocarbons, C formed through oligomerization 8+ Oligomers, polymer products, or combinations thereof. In one aspect, C formed through oligomerization... 8+Oligopolymers include octene, decene, dodecene, and tetradecene. Throughout this disclosure, the terms heavy effluent and heavy hydrocarbon are used interchangeably. In one aspect, heavy effluent 336 may be used with as disclosed herein. Figure 2 The hydrocarbon recycle stream 201 is combined. In one aspect, heavy feed 322 optionally enters the first separator 325. Heavy feed 322 may contain the desired 1-hexene product and / or heavy components as described herein. In one aspect, heavy feed 322 may be an effluent from a polyethylene production facility.

[0076] The light effluent 330 flows into the second separator 335, producing ethylene effluent 340 and hexene effluent 342. Ethylene effluent 340 can be combined with the ethylene recycle stream 306. In a further aspect, ethylene effluent 340 can be sent for storage or sale, for example, separately or with... Figure 2 The practical ethylene stream 29 is fed into the system. Hexene effluent 342 flows into a third separator 345, which recovers 1-hexene effluent 35. The third separator 345 produces a byproduct effluent 352 containing undesirable oligomerization products. In one aspect, byproduct effluent 352 may be combined with... Figure 2 The hydrocarbon recycle stream 201 is combined. In one aspect, solvent effluent 354 is recovered from the third separator 345, wherein the solvent may include cyclohexane. In another aspect, the third separator 345 facilitates the removal of solvent from the 1-hexene effluent 35. Solvent effluent 354 may be combined with solvent feed 308 as disclosed herein. The first separator 325, the second separator 335, and the third separator 345 may be adapted to operate in any manner that produces their effluents. In a further aspect, the first separator 325, the second separator 335, and the third separator 345 each include at least one fractionator or distillation column.

[0077] Alternatively, some aspects of the oligomerization process 300 can be operated in the absence of one or more of the filters 315, the first separator 325, the second separator 335, and the third separator 345, wherein the 1-hexene effluent 35 can be directly recovered from the oligomerization reactor effluent 310. In such respects, the 1-hexene effluent 35 further comprises any components that may be present in the oligomerization reactor effluent 310 as disclosed herein.

[0078] The following oligomerization processes were considered: 1) using monomers other than ethylene; 2) producing oligomers other than 1-hexene; and / or 3) carrying out oligomerization reactions other than trimerization.

[0079] In one aspect, the 1-hexene effluent 35 may comprise a C6 olefin, wherein, based on the total weight of the 1-hexene effluent 35, the amount of the C6 olefin may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the amount of the C6 olefin in the 1-hexene effluent 35 may range from 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 99.6 wt%. In a further aspect, the 1-hexene effluent 35 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 1-hexene effluent 35 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0080] Return to Figure 1 1-Hexene effluent 35 flows into aromatization process 400. In one aspect, aromatization process 400 includes an aromatization reactor system in which acyclic oligomers are contacted with an aromatization catalyst and undergo an aromatization reaction to produce aromatics. In a further aspect, the aromatization reaction converts 1-hexene to benzene. U.S. Patent No. 7,932,425 discloses a method for converting 1-hexene to benzene, which is incorporated herein by reference in its entirety. Any suitable method for producing benzene disclosed in U.S. Patent No. 7,932,425 may be utilized herein. It is contemplated that aromatization process 400 may be used in conjunction with acyclic hydrocarbons other than 1-hexene to produce aromatics other than benzene.

[0081] In one aspect, auxiliary aromatization feed 37 flows into aromatization process 400. Auxiliary aromatization feed 37 may contain non-aromatic hydrocarbons containing at least six carbon atoms. In a further aspect, auxiliary aromatization feed 37 may contain a hydrocarbon mixture comprising C6 to C8 hydrocarbons, said hydrocarbon mixture containing up to about 15% by weight of C6 hydrocarbons. 5- Hydrocarbons and up to about 10% by weight of C 9+Hydrocarbons, wherein the weight percentage is based on the total weight of the auxiliary aromatization feed 37. In one specific aspect, the auxiliary aromatization feed 37 may include a naphtha feed. In one aspect, the naphtha feed may be light naphtha with a boiling range of about 70℉ to about 450℉ (e.g., about 21.1℃ to about 232.2℃), wherein the naphtha feed may contain aliphatic, naphthenic acids and / or alkanes. Some aspects of the aromatization process 400 are considered for operation without the auxiliary aromatization feed 37.

[0082] refer to Figure 4 This describes an aspect of the aromatization process 400. In the illustrated aspect, the aromatization reactor system includes a catalytic reactor system in which four aromatization reactors are connected in series (i.e., reactors 410, 420, 430, and 440). However, the catalytic reactor system may include any suitable number and configuration of aromatization reactors, such as one, two, three, five, six, or more reactors connected in series or in parallel. Because the aromatization reaction is highly endothermic, a significant temperature drop occurs in reactors 410, 420, 430, and 440. Therefore, each reactor 410, 420, 430, and 440 connected in series may include corresponding furnaces 411, 421, 431, and 441, respectively, for heating the reactor feed components to a desired temperature (e.g., a temperature associated with the desired reaction rate within a given reactor). Alternatively, where feasible, one or more reactors 410, 420, 430, and 440 may share a common furnace. Reactors 410, 420, 430 and 440, furnaces 411, 421, 431 and 441, and related pipelines are all referred to as aromatization zones in this document.

[0083] 1-Hexene effluent 35, auxiliary aromatization feed 37 (if present), and optional raffinate stream 419 are combined to form a mixed feed stream 402 flowing into purification process 480. Purification process 480 employs known processes (including fractionation or other separation techniques) to purify mixed feed stream 402 to remove impurities such as oxygen-containing compounds, sulfur, and / or metals. In one aspect, purification process 480 includes a sulfur removal system. In a further aspect, the sulfur removal system includes a sulfur guard bed. Purification feed stream 403 originates from purification process 480. Purification feed stream 403 may optionally be combined with a dry hydrogen recirculation stream 465 to produce a hydrogen-rich purification feed stream 404. Oxygen-containing and / or nitrogen-containing compound stream 405 (i.e., O / N stream) may optionally be combined with hydrogen-rich purification feed stream 404 to produce an aromatization reactor feed stream 406. In addition to, or as an alternative to, the O / N stream 405, oxygen-containing and / or nitrogen-containing compounds may be fed to one or more locations in the catalytic reactor system, as described in more detail herein. Some aspects of the aromatization process 400 are considered for operation without the purification process 480, wherein the mixed feed stream 402 continues directly into stream 403.

[0084] The aromatization reactor feed stream 406 is preheated in a first furnace 411, which heats the contents of the feed stream 406 to a desired temperature, thereby producing a first aromatization reactor feed stream 412. The first aromatization reactor feed stream 412 flows into a first aromatization reactor 410, where the first aromatization reactor feed is contacted with an aromatization catalyst under suitable reaction conditions (e.g., temperature and pressure) to aromatize one or more components in the feed (e.g., 1-hexene), thereby increasing its aromatic content. A first aromatization reactor effluent stream 415, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the first aromatization reactor 410.

[0085] The first aromatization reactor effluent 415 is then preheated in a second furnace 421, which heats the contents of effluent 415 to a desired temperature, thereby generating a second aromatization reactor feed stream 422. The second aromatization reactor feed stream 422 flows into a second aromatization reactor 420, where the second aromatization reactor feed is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed (e.g., 1-hexene) to increase its aromatic content. The second aromatization reactor effluent 425, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the second aromatization reactor 420.

[0086] The second aromatization reactor effluent 425 is then preheated in a third furnace 431, which heats the contents of effluent 425 to the desired temperature, thereby producing a third aromatization reactor feed stream 432. The third aromatization reactor feed stream 432 flows into a third aromatization reactor 430, where the feed is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed (e.g., 1-hexene) to increase its aromatic content. The third aromatization reactor effluent 435, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the third aromatization reactor 430.

[0087] The third aromatization reactor effluent 435 is then preheated in a fourth furnace 441, which heats the contents of effluent 435 to the desired temperature, thereby producing a fourth aromatization reactor feed stream 442. The fourth aromatization reactor feed stream 442 is then fed into a fourth aromatization reactor 440, where the fourth aromatization reactor feed is contacted with an aromatization catalyst under suitable reaction conditions for aromatizing one or more components in the feed (e.g., 1-hexene) to increase its aromatic content. The fourth aromatization reactor effluent 445, containing aromatics (e.g., benzene), unreacted feed, and optionally other hydrocarbon compounds or byproducts, is recovered from the fourth aromatization reactor 440.

[0088] The effluent 445 from the fourth aromatization reactor flows into a hydrogen separation process 450, where the recovered hydrogen stream 455 is separated from the first reformate stream 417. The first reformate stream 417 comprises aromatization reaction products from reactors 410, 420, 430, and 440, as well as optional aromatization reaction byproducts and / or byproducts, unreacted feed, other hydrocarbons, or combinations thereof. In one aspect, the aromatization reaction byproducts include toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, hexamethylbenzene, or combinations thereof. The first reformate stream 417 flows into a reformate purification process 470, where the second reformate 477 is separated from the light reformate effluent 472. In one aspect, the light reformate effluent 472 comprises C 5- Hydrocarbons. The second reformate 477 flows into a purification extraction process 490, which recovers benzene effluent 45. The purification extraction process 490 produces a raffinate stream 419 and optionally a stream containing aromatization reaction byproducts and / or byproducts. In one aspect, the raffinate stream 419 may contain benzene, toluene, xylene, branched alkanes, or combinations thereof. In one aspect, the raffinate stream 419 is recycled and combined with a mixed feed stream 402 as disclosed herein. The recovered hydrogen stream 455 may be divided into a hydrogen recycle stream 457 and a hydrogen effluent 41 at a ratio of 0% to 100%. In one aspect, the hydrogen effluent 41 may be combined with a mixed feed stream 402 as disclosed herein. Figure 3The first hydrogen feed stream 302 is combined. In a further aspect, the hydrogen effluent 41 may be sent for storage or sale. A first portion of the hydrogen recirculation stream 457 is fed into the second hydrogen feed 459. A second portion of the hydrogen recirculation stream 457 is dried in a dryer 460 to form a dried hydrogen recirculation stream 465, which can then be recycled back to the purified feed stream 403 as disclosed herein.

[0089] Second hydrogen feed 459 and containing C 5- The light reformate effluent 472 of the hydrocarbon enters the C2 recovery zone 485. In one aspect, the C2 recovery zone 485 includes a demethanizer; alternatively, a depropanizer; alternatively, a demethanizer located upstream of the depropanizer, or alternatively, a demethanizer located downstream of the depropanizer. C2 effluent 488 flows out of the C2 recovery zone 485. In one aspect, C2 effluent 488 contains ethane, ethylene, or a combination thereof, and may be combined with… Figure 2 Hydrocarbon recirculation stream 201 Figure 3 The ethylene recirculation stream 306 or both are combined.

[0090] Hydrogen separation process 450 and purification extraction process 490 can be employed, as described, for example, in U.S. Patent Nos. 5,401,386, 5,877,367, and 6,004,452, each of which is incorporated herein by reference in its entirety. For simplicity, Figure 4 Byproduct streams removed from the catalytic reactor system at various points throughout the system are not shown. However, those skilled in the art are aware of the composition and location of such byproduct streams. Furthermore, although... Figure 4 The diagram shows the addition of O / N stream 405 to hydrogen-rich purification feed stream 404, but those skilled in the art will understand that oxygen-containing and / or nitrogen-containing compounds can be added to any of streams 402, 403, 404, 406, 412, 415, 417, 419, 422, 425, 432, 435, 442, 445, 455, 465, 457, or combinations thereof.

[0091] In various aspects, the catalytic reactor systems described herein may include fixed catalyst bed systems, moving catalyst bed systems, fluidized catalyst bed systems, or combinations thereof. In one aspect, the catalytic reactor system is a fixed-bed system comprising one or more fixed-bed reactors. In a fixed-bed system, the aromatization reactor feed may be preheated in a furnace tube and enter at least one reactor containing a fixed bed of catalyst. The aromatization reactor feed flow may pass upward, downward, or radially through the reactor. In various aspects, the catalytic reactor systems described herein may operate as adiabatic catalytic reactor systems or isothermal catalytic reactor systems. As used herein, the terms “catalytic reactor” and “reactor” are used interchangeably to refer to reactor vessels, reactor interiors, and associated process units, including but not limited to catalysts, inert packing, pits, flow distributors, central tubes, reactor ports, catalyst transfer and distribution systems, furnaces and other heating instruments, heat transfer devices, and piping.

[0092] In one aspect, a catalytic reactor system is an aromatization reactor system comprising at least one aromatization reactor and its corresponding process unit. As used herein, the terms "aromatization" and "reforming" refer to the treatment of a feed to provide an aromatic-rich product, wherein the aromatic content of the product is higher than that of the feed. Typically, one or more components of the feed undergo one or more reforming reactions to produce aromatics. Some reforming reactions occurring within an aromatization reactor system include dehydrogenation cyclization reactions of acyclic hydrocarbons to aromatics (e.g., 1-hexene to benzene), dehydrogenation reactions of cyclohexane to aromatics, dehydrogenation isomerization reactions of alkylcyclopentanes to aromatics, or combinations thereof. Depending on the composition of the feed, many other reactions may also occur, including dealkylation reactions of alkylbenzenes, isomerization reactions of alkanes, hydrocracking reactions to produce light gaseous hydrocarbons (e.g., methane, ethane, ethylene, propane, propylene, and butane), or combinations thereof. A specific aspect of the integrated reforming system described herein utilizes the dehydrogenation cyclization reaction of 1-hexene, n-hexane, or combinations thereof to produce benzene. In a further aspect, the integrated reforming system utilizes the dehydrogenation reaction of cyclohexane to produce benzene.

[0093] In one respect, the aromatization reaction occurs thermodynamically under process conditions that favor dehydrogenation cyclization and limit undesirable hydrocracking reactions. The reactor pressure can range from about 0 psig to about 500 psig (about 0 MPag to about 3.45 MPag), alternatively from about 25 psig to about 300 psig (about 0.17 MPag to about 2.07 MPag). Operating temperatures include reactor inlet temperatures ranging from about 370°C to about 565°C, alternatively from about 480°C to about 540°C. The molar ratio of hydrogen to hydrocarbons (e.g., 1-hexene) in the aromatization reactor feed can range from about 0.1:1 to about 20:1, alternatively from about 1:1 to about 6:1.

[0094] The aromatization reaction disclosed herein is characterized by the conversion of 1-hexene to benzene based on the total weight of 1-hexene fed into the aromatization reactor. In one aspect, the conversion of 1-hexene to benzene is greater than about 40% by weight; alternatively, greater than about 50% by weight; alternatively, greater than about 60% by weight; or alternatively, greater than about 70% by weight.

[0095] The aromatization reaction of this disclosure is characterized by a selectivity for the conversion of 1-hexene to benzene based on the total amount of 1-hexene converted in the aromatization reactor by weight. In one aspect, the selectivity for the conversion of 1-hexene to benzene is greater than about 50% by weight; alternatively, greater than about 60% by weight; alternatively, greater than about 70% by weight; or alternatively, greater than about 75% by weight.

[0096] 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, and platinum. An example of a catalyst suitable for the catalytic reactor systems described herein is AROMAX. ® Branded catalysts (purchased from Chevron Phillips Chemical Company of The Woodlands, Tex.), including those discussed in U.S. Patent Nos. 7,932,425, 6,812,180, and 7,153,801, each of which is incorporated herein by reference in its entirety.

[0097] The inorganic support used in the aromatization catalysts of this disclosure can generally comprise any inorganic oxide. These inorganic oxides include bonded macroporous aluminosilicates (zeolite supports), amorphous inorganic oxides, and mixtures thereof. Macroporous aluminosilicates include, but are not limited to, L-type zeolites, Y-type zeolites, mordenite, ω-type zeolites, β-type zeolites, etc. Amorphous inorganic oxides include, but are not limited to, alumina, silica, and titanium dioxide. Suitable binders for the inorganic oxides include, but are not limited to, silica, alumina, clay, titanium dioxide, and magnesium oxide.

[0098] In one aspect, the support is a bonded potassium L-type zeolite or KL zeolite. As used herein, the term "KL zeolite" refers to an L-type zeolite in which the dominant cation M incorporated into the zeolite is potassium. KL-type zeolites can be cation exchanged or impregnated with another metal and one or more halides to produce, for example, platinum-impregnated halide-containing zeolites or KL-supported Pt halide zeolite catalysts.

[0099] In one aspect, Group VIII metals may be platinum. Platinum and optionally one or more halides may be added to the zeolite support by any suitable method, for example, by impregnation with a solution of a platinum-containing compound and one or more halide-containing compounds. For example, the platinum-containing compound may be any decomposable platinum-containing compound. Examples of such compounds include, but are not limited to, ammonium tetrachloroplatinate, chloroplatinic acid, dinitrosodiamineplatinum, bis(ethylenediamine)platinum chloride (II), platinum acetylacetonate (II), dichlorodiamineplatinum, platinum chloride (II), tetraammineplatinum hydroxide (II), tetraammineplatinum chloride, and tetraammineplatinum nitrate (II).

[0100] In a further aspect, the catalyst may be a macroporous zeolite support having a platinum-containing compound and at least one organoammonium halide compound. The organoammonium halide compound may include one or more compounds represented by the formula N(R)4X, where X is a halide and R represents hydrogen or a substituted or unsubstituted carbon chain molecule having 1-20 carbons, wherein each R may be the same or different. In one aspect, R is selected from the group consisting of methyl, ethyl, propyl, butyl, and combinations thereof, more specifically methyl. Examples of suitable organoammonium compounds represented by the formula N(R)4X include ammonium chloride, ammonium fluoride, and tetraalkylammonium halides, such as tetramethylammonium chloride, tetramethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium fluoride, tetrapropylammonium chloride, tetrapropylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium fluoride, methyltriethylammonium chloride, methyltriethylammonium fluoride, and combinations thereof.

[0101] III.C.4. Oxygen-containing compounds / Nitrogen-containing compounds In one specific aspect of this disclosure, oxygen-containing compounds, nitrogen-containing compounds, or both, may be added to one or more process streams and / or components of a catalytic reactor system. While not intended to be theoretically limited, oxygen-containing compounds and / or nitrogen-containing compounds (e.g., water) may be beneficial for activating, preserving, and / or increasing the productivity of certain types of aromatization catalysts (as described in U.S. Patent No. 7,932,425). In one aspect, the 1-hexene effluent 35, the auxiliary aromatization feed 37, and the optional raffinate recycle 419 are substantially free of sulfur, metals, and other known aromatization catalyst poisons, and are initially substantially free of oxygen-containing and nitrogen-containing compounds. If present, such poisons can be removed using methods known to those skilled in the art. In some aspects, the 1-hexene effluent 35, the auxiliary aromatization feed 37, and the optional raffinate recycle 419 can be purified by first using conventional hydrorefining techniques followed by the removal of remaining poisons using an adsorbent. Such hydrorefining techniques and adsorbents are included in the purification processes related to oxygen-containing and / or nitrogen-containing compounds described below.

[0102] As used herein, the term "oxygen-containing compound" refers to water or any chemical compound that forms water under catalytic aromatization conditions, such as oxygen, oxygen-containing compounds, hydrogen peroxide, alcohols, ketones, esters, ethers, carbon dioxide, aldehydes, carboxylic acids, lactones, ozone, carbon monoxide, or combinations thereof. In one aspect, water and / or steam are used as the oxygen-containing compound. In another aspect, oxygen can be used as the oxygen-containing compound, wherein such oxygen is converted in situ to water under typical aromatization conditions in one or more aromatization reactors, or under normal hydrorefining conditions in one or more hydrorefining catalyst or adsorbent beds. Furthermore, the oxygen-containing compound can be any alcohol-containing compound. Specific examples of suitable alcohol-containing compounds are methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, amyl alcohol, hexanol, cyclohexanol, phenol, or combinations thereof.

[0103] 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, nitrogen-containing compounds, alkylamines, aromatic amines, pyridines, pyridazines, pyrimidines, pyrazines, triazines, heterocyclic N-oxides, pyrroles, pyrazoles, imidazoles, triazoles, nitriles, amides, ureas, imides, nitro compounds, nitroso compounds, or combinations thereof. While not wishing to be theoretically limited, ammonia is believed to enhance catalyst activity in the same manner as water. Furthermore, all methods for adding and controlling oxygen-containing compounds described herein can also be applied, additionally or alternatively, entirely to methods for adding and controlling nitrogen-containing compounds.

[0104] Those skilled in the art will understand that any oxygen-containing compound, nitrogen-containing compound, or mixture thereof described herein can be used alone, in combination, or further combined to produce other suitable oxygen-containing or nitrogen-containing compounds. In some aspects, the oxygen-containing and nitrogen-containing compounds may be contained in a single bifunctional compound. The oxygen-containing and / or nitrogen-containing compounds may be added to any suitable physical phase, such as a gas, liquid, or combination thereof. The oxygen-containing and / or nitrogen-containing compounds may be added to one or more process streams and / or components via any suitable means of addition, such as pumps, syringes, distributors, bubblers, etc. The oxygen-containing and / or nitrogen-containing compounds may be introduced as a blend with a carrier. In some aspects, the carrier is hydrogen, hydrocarbons, nitrogen, rare gases, or mixtures thereof. In one aspect, the carrier is hydrogen. In a further aspect, the oxygen-containing and / or nitrogen-containing compounds may be added at various locations within the aromatization process, at any time during the lifetime of the aromatization catalyst, and in any suitable manner. In a further aspect, oxygen-containing and / or nitrogen-containing compounds are added to activate the aromatization catalyst, increase the lifetime of the aromatization catalyst, increase the selectivity and / or productivity of the aromatization catalyst, and combinations thereof.

[0105] In one aspect, prior to the addition of oxygenated and / or nitrogenous compounds, the existing oxygenated and / or nitrogenous compound content of the stream to be added is measured and / or adjusted. For example, refer to Figure 4 Before adding oxygen- and / or nitrogen-containing compounds, the oxygen- and / or nitrogen-containing compound content of one or more feed streams (such as 1-hexene effluent 35, auxiliary aromatization feed 37, raffinate stream 419, mixed feed stream 402, or dry hydrogen recirculation stream 465) can be measured and adjusted. Similarly, before adding nitrogen-containing compounds, the nitrogen-containing compound content of the same stream can be measured and / or adjusted. Generally, raw or untreated feed streams (such as 1-hexene effluent 35) may contain a certain amount of oxygen- or nitrogen-containing compounds when flowing into the catalytic reaction system described herein. Furthermore, depending on the facility configuration, the duration of feed storage, and / or weather conditions, the feed may absorb oxygen- or nitrogen-containing compounds from the air. To precisely control the amount of oxygen- or nitrogen-containing compounds flowing into one or more aromatization reactors (e.g., reactor 410, reactor 420, reactor 430, reactor 440), the amount of oxygen- and / or nitrogen-containing compounds in one or more feed streams entering the reactor can be measured, adjusted, or both.

[0106] In one aspect, the oxygen and / or nitrogen content of a given stream (such as a feed stream) can be measured, for example, using a real-time online analyzer (not shown). In response to such measurement, the oxygen and / or nitrogen content of the stream can be adjusted by processing and / or adding oxygen and / or nitrogen compounds to the stream to obtain a desired amount of oxygen and / or nitrogen compounds therein. In one aspect, a control loop connects the analyzer to a processor and an oxygen and / or nitrogen injector, such that the amount of oxygen and / or nitrogen compounds in one or more streams is controlled in response to a setpoint for the oxygen and / or nitrogen compounds in such streams. In one aspect, measuring and / or adjusting the oxygen and / or nitrogen content, along with associated equipment (such as a processor and / or chemical injector), is included as part of a purification process 480. The oxygen and / or nitrogen processor varies depending on the type and amount of oxygen and / or nitrogen compounds. In cases where the oxygen compounds contain water, adsorbent material beds can be used. These adsorbent beds are commonly referred to as dryers. In cases involving oxygen-containing compounds, such as oxygen, a processor that converts oxygen into water can be used in conjunction with a dryer. In a further case involving nitrogen-containing compounds, such as alkaline chemicals, an adsorbent material bed can be used.

[0107] In one aspect, one or more streams (such as 1-hexene effluent 35, auxiliary aromatization feed 37, raffinate stream 419, mixed feed stream 402, or dry hydrogen recirculation stream 465) are treated before the addition of oxygen-containing and / or nitrogen-containing compounds. In this aspect, the oxygen-containing and / or nitrogen-containing compound content of the stream is measured before such treatment can optionally be omitted. If equipment for easily measuring the oxygen-containing and / or nitrogen-containing compound content in the feed is not available, it is difficult to reliably maintain the desired levels in the aromatization reactor.

[0108] Pretreatment of one or more streams prior to the addition of oxygenated and / or nitrogenous compounds can help to comprehensively control the amount of water and / or ammonia flowing into one or more streams in the aromatization reactor by removing variations in the levels of oxygenated and / or nitrogenous compounds in such streams. Pretreatment of such streams can provide a consistent, baseline amount of oxygenated and / or nitrogenous compounds in these streams to add oxygenated and / or nitrogenous compounds to form oxygenated streams, such as aromatization reactor feed stream 406. When the reactor feed is sufficiently free of oxygenated and / or nitrogenous compounds, precise amounts of oxygenated and / or nitrogenous compounds can be added to the reactor feed to reliably maintain the levels of oxygenated and / or nitrogenous compounds in the reactor. In one aspect, purification process 480 may include a hydrocarbon dryer that dries the feed stream (e.g., 1-hexene effluent 35) to a suitable moisture content. In other aspects, purification process 480 may include a reducing copper bed or a triethylaluminum bed over silica for the removal of oxygenated compounds. In a further aspect, a triethylaluminum bed over a reduced copper bed or silica bed is used in combination with a hydrocarbon dryer. Similarly, dryer 460 can be used to dry hydrogen recirculation stream 457 and / or other process streams (e.g., 1-hexene effluent 35) to a suitable moisture content. In one aspect, suitable oxygen-containing compound levels in one or more streams (such as 1-hexene effluent 35, auxiliary aromatization feed 37, raffinate stream 419, mixed feed stream 402, or dried hydrogen recirculation stream 465) result in a water concentration of less than about 1 ppmv, alternatively less than about 0.5 ppmv, or alternatively less than about 0.1 ppmv in the untreated recovered hydrogen stream 455. In one aspect, one or more streams fed to the aromatization reactor (such as 1-hexene effluent 35, auxiliary aromatization feed 37, raffinate stream 419, mixed feed stream 402, or dried hydrogen recirculation stream 465) are substantially free of water after their drying. In one respect, precise amounts of oxygen- and / or nitrogen-containing compounds can be added by partially or completely bypassing such processing techniques. Alternatively, precise amounts of oxygen- and / or nitrogen-containing compounds can be added by partially or completely running the hydrogen recirculation stream 457 through a wet (e.g., waste) molecular sieve bed.

[0109] Benzene effluent 45 may contain C6 aromatic hydrocarbons. In one aspect, based on the total weight of benzene effluent 45, the amount of C6 aromatic hydrocarbons in benzene effluent 45 may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the amount of C6 aromatic hydrocarbons in benzene effluent 45 may range from 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 99.6 wt%. In a further aspect, the amount of benzene in benzene effluent 45 may be at least 85% by weight; alternatively, at least 87.5% by weight; alternatively, at least 90% by weight; alternatively, at least 92.5% by weight; alternatively, at least 95% by weight; alternatively, at least 97% by weight; or alternatively, at least 98% by weight. In one aspect, the amount of benzene in benzene effluent 45 may be in the range of about 85% by weight to about 99.9% by weight; alternatively, about 87.5% by weight to about 99.9% by weight; alternatively, about 90% by weight to about 99.9% by weight; alternatively, about 92.5% by weight to about 99.9% by weight; alternatively, about 95% by weight to about 99.9% by weight; alternatively, about 97% by weight to about 99.9% by weight; or alternatively, about 98% by weight to about 99.9% by weight.

[0110] Return to Figure 1 Benzene effluent 45 may be sent for storage or sale. In a further aspect, a portion of benzene effluent 45 is fed through a benzene feed 47 containing benzene, which flows into derivatization process 500. In a further aspect, derivatization process 500 includes an ethylbenzene-styrene production process. U.S. Patent Nos. 5,602,290, 5,880,320, 5,856,607, 6,252,126, and 6,790,342 disclose processes for producing ethylbenzene and styrene from benzene; all of these patents are each incorporated herein by reference. It is contemplated that derivatization process 500 may include processes other than the ethylbenzene-styrene production process.

[0111] refer to Figure 5The description covers aspects of a derivatization process 500. Benzene feed 47 and ethylene feed 27 flow into an alkylation zone 510. In one aspect, the alkylation zone 510 includes at least one alkylation reactor. Benzene and ethylene are contacted with an alkylation catalyst within the alkylation zone 510 to produce an alkylation reactor effluent 515. Benzene, ethylene, and the alkylation catalyst can be contacted in any manner suitable for forming ethylbenzene. In one aspect, the alkylation catalyst comprises a zeolite catalyst, non-limiting examples of which include ZSM-based zeolites. ZSM-based zeolites are those having the chemical formula Na... n Al n Si 96-n O 192 Aluminosilicate zeolite of 16H2O, where n is an integer between 0 and 27. Further, when using ZSM-based zeolite to form ethylbenzene from ethylene and benzene, it can impart a selectivity greater than 99%.

[0112] In one aspect, the alkylation reactor effluent 515 comprises benzene and ethylbenzene. The alkylation reactor effluent 515 flows into a first separation zone 520, which recovers an ethylbenzene stream 525 containing ethylbenzene. The first separation zone 520 further produces a polyalkylation stream 527 and a benzene recycle stream 529. The first separation zone 520 can be operated in any manner known to those skilled in the art and with the aid of this disclosure. In a further aspect, the first separation zone 520 includes at least one fractionator. The polyalkylation stream 527 contains C 10+ Aromatic hydrocarbons, including but not limited to diethylbenzene and triethylbenzene. In one aspect, polyalkylate stream 527 can be used with as disclosed herein. Figure 2 The hydrocarbon recycle stream 201 is combined. The benzene recycle stream 529 is combined with the benzene feed 47.

[0113] Ethylbenzene stream 525 flows into dehydrogenation zone 530. In one aspect, dehydrogenation zone 530 includes at least one dehydrogenation reactor. Within dehydrogenation zone 530, ethylbenzene is contacted with a dehydrogenation catalyst to produce dehydrogenation reactor effluent 535 and an effluent hydrogen stream 537. In one aspect, dehydrogenation reactor effluent 535 contains styrene. Ethylbenzene and the dehydrogenation catalyst can be contacted in any manner suitable for forming styrene. Dehydrogenation reactor effluent 535 flows into a second separation zone 540, forming styrene effluent 51 and aromatics stream 545. Second separation zone 540 can be operated in any manner known to those skilled in the art and by means of this disclosure. In a further aspect, second separation zone 540 includes at least one fractionator. Styrene effluent 51 can be sent for storage or sale. Aromatics stream 545 may contain C 6+ Aromatic hydrocarbons, including but not limited to unreacted ethylbenzene and / or undesirable products from processes occurring in zones 510, 520, and / or 530. In one aspect, aromatic hydrocarbon stream 545 may be combined with polyalkylation stream 527 (not shown). In a further aspect, aromatic hydrocarbon stream 545 may be combined with as disclosed herein. Figure 2 The hydrocarbon recycle stream 201 is combined (not shown). In one aspect, the effluent hydrogen stream 537 may be combined with the hydrocarbon recycle stream 201 as disclosed herein. Figure 3 The first hydrogen feed stream 302 or Figure 1 The hydrogen flow out of the stream 41 is combined.

[0114] In one aspect, styrene effluent 51 may contain C8 aromatics, wherein, based on the total weight of styrene effluent 51, the amount of C8 aromatics may be at least 60 wt%; alternatively, at least 70 wt%; alternatively, at least 75 wt%; alternatively, at least 80 wt%; alternatively, at least 85 wt%; or alternatively, at least 90 wt%. In a further aspect, the amount of C8 aromatics in styrene effluent 51 may range from 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 99.6 wt%. In a further aspect, the amount of styrene in styrene effluent 51 may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In a further aspect, the amount of styrene in styrene effluent 51 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0115] refer to Figure 6 It describes an integrated conversion system 1100, where similar numbers represent combinations. Figure 1 Similar components as described. (And) Figure 1Unlike other processes, the integrated conversion system 1100 includes a hydrotreating process 110 connected between the oligomerization process 300 and the aromatization process 400. In one aspect, the hydrotreating process 110 includes at least one hydrotreating reactor. At least a portion of a 1-hexene effluent 35 containing 1-hexene flows into the hydrotreating reactor of the hydrotreating process 110 and contacts a hydrotreating catalyst to produce a hydrotreating reactor effluent. In the hydrotreating process 110, the hydrotreating reactor effluent undergoes a purification stage (not shown) to recover a hexane effluent 115 containing hexane (e.g., n-hexane). The hydrotreating catalyst can be suitable for contacting 1-hexene in any manner that forms hexane. Further processes in the hydrotreating process 110 (e.g., fractionation) can affect the amount of sulfur, nitrogen, and / or aromatic compounds entering the hydrotreating process 110, thereby reducing the amount of sulfur, nitrogen, and / or aromatic compounds in the hexane effluent 115. In one aspect, the hydrotreating process 110 includes a sulfur removal system. In one aspect, lower levels of sulfur, nitrogen, and / or aromatic compounds in the feedstock (e.g., hexane effluent 115) of aromatization process 400 can lead to slower degradation and deactivation of the aromatization catalyst, resulting in less facility turnaround and higher aromatic compound selectivity. In a further aspect, the process in hydrotreating process 110 can enhance the cetane number, density, and / or smoke point of the components of hexane effluent 115. In a further aspect, aromatization auxiliary feedstock 37 flows into hydrotreating process 110.

[0116] In one aspect, the hexane effluent 115 comprises n-hexene. In a further aspect, based on the total weight of the hexane effluent 115, the amount of n-hexane in the hexane effluent 115 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 yet another further aspect, the amount of n-hexane in the hexane effluent 115 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%. In one aspect, the amount of sulfur in hexane effluent 115 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 hexane effluent 115 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 hexane effluent 115 may be in the range of about 0.01 ppm to about 1 ppm; or alternatively, in the range of about 0.02 ppm to about 0.2 ppm. The ppm values ​​are weight-to-weight values ​​based on the total weight of hexane effluent 115.

[0117] refer to Figure 6 Hexane effluent 115 flows into aromatization process 400, replacing 1-hexene effluent 35. In one aspect, aromatization process 400 of integrated conversion system 1100 includes an aromatization reactor system in which hexane (e.g., n-hexane) is contacted with an aromatization catalyst to produce benzene. All other functions and components of aromatization process 400 of integrated conversion system 1100 (e.g., benzene effluent 45) operate in a similar manner to aromatization process 400 of integrated conversion system 1000 as disclosed herein.

[0118] refer to Figure 7 It describes an integrated conversion system 1200, where similar numbers represent combinations. Figure 6 Similar components as described. (And) Figure 6 Unlike other systems, the integrated conversion system 1200 lacks the derivatization process 500 (also known as the ethylbenzene-styrene production process) and the associated ethylene feed 27 and styrene effluent 51. Within the integrated conversion system 1200, a cyclohexane recycling stream 123 flows into the oligomerization process 300, where cyclohexane is used as a solvent (i.e., a diluent). In one aspect, the cyclohexane recycling stream 123 differs from that disclosed herein. Figure 3 Solvent feed 308 is combined. Cyclohexane recycle stream 123 includes a portion of cyclohexane effluent 125 from benzene hydrogenation process 120, as further described herein. Mixed C6 effluent 31 flows from oligomerization process 300 of integrated conversion system 1200. In one aspect, mixed C6 effluent 31 comprises 1-hexene and cyclohexane. Mixed C6 effluent 31 flows into hydrotreating process 110 to produce mixed hexane effluent 117. In one aspect, mixed hexane effluent 117 comprises hexane (e.g., n-hexane) and cyclohexane. Hexane effluent 117 flows into aromatization process 400, where hexane (e.g., n-hexane) and cyclohexane are converted to benzene. A portion of benzene effluent 45 is fed through benzene feed 47, and a portion of hydrogen effluent 41 is fed through reduction feed 43. Benzene feed 47 and reduction feed 43 flow into benzene hydrogenation process 120, whereby benzene hydrogenation produces cyclohexane effluent 125. In one aspect, at least a portion of cyclohexane effluent 125 contains cyclohexane and may be sent for storage or sale. Benzene hydrogenation can be carried out by any suitable means determined by those skilled in the art and by means of this disclosure. For example, a hydrogenation catalyst may be used. The operating conditions in hydrogenation process 120 may be a combination of any suitable conditions determined by those skilled in the art by means of this disclosure. In one aspect, the temperature and pressure in hydrogenation process 120 may be at levels capable of hydrogenating benzene. In a further aspect, hydrogenation process 120 may have a temperature in the range of about 10°C to about 205°C. In yet another further aspect, hydrogenation process 120 may have a pressure in the range of about 360 psig to about 615 psig (about 2.48 MPag to about 4.24 MPag).

[0119] In one aspect, based on the total weight of the cyclohexane effluent 125, the amount of cyclohexane in the cyclohexane effluent 125 may be at least 85 wt%; alternatively, at least 87.5 wt%; alternatively, at least 90 wt%; alternatively, at least 92.5 wt%; alternatively, at least 95 wt%; alternatively, at least 97 wt%; or alternatively, at least 98 wt%. In a further aspect, the amount of cyclohexane in the cyclohexane effluent 125 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0120] refer to Figure 8 It describes an integrated conversion system 1300, where similar numbers represent combinations. Figure 7Similar components are described. A low-purity 1-hexene (LPH) stream 33 flows out from the oligomerization process 300 of the integrated conversion system 1300. In one aspect, the LPH stream 33 comprises 1-hexene and cyclohexane. A first portion of the LPH stream 33 flows into a hydrotreating process 110 to produce a mixed hexane effluent 117, which flows into an aromatization process 400. A second portion of the LPH stream 33 is fed through a mixed C6 feed 32, which flows into a C6 separator 130. Within the C6 separator 130, the mixed C6 feed 32 is separated into a higher-purity 1-hexene (HPH) stream 135 and a solvent recycling stream 132. The HPH stream 135 may be sent for storage or sale. In one aspect, the HPH stream 135 may be used in polymerization or oligomerization processes independent of the integrated conversion system of this disclosure. In one aspect, the solvent recycling stream 132 may be combined with the cyclohexane recycling stream 123; or alternatively, with as described herein. Figure 3 The solvent feed 308 is combined. The C6 separator 130 can be adapted to operate in any manner that produces the HPH stream 135 and the solvent recirculation stream 132. In one aspect, the C6 separator 130 includes at least one fractionator.

[0121] In one aspect, HPH stream 135 comprises 1-hexene. In another aspect, based on the total weight of the C6 hydrocarbons in HPH stream 135, the amount of 1-hexene in HPH stream 135 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%; alternatively, at least 98 wt%; or alternatively, at least 99 wt%. In a further aspect, the amount of 1-hexene in HPH stream 135 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0122] refer to Figure 9 It describes an integrated conversion system 1400, where similar numbers represent combinations. Figure 8 Similar components are described. Before flowing into the cracking process 200, the hydrocarbon feedstock 10 is combined with the ethane separation stream 162, as further disclosed herein. A portion of the cracking process effluent 25 is fed through a practical ethylene stream 29, which flows into a C2 separator 160. Within the C2 separator 160, the practical ethylene stream 29 is separated into an ethylene separation stream 165 and an ethane separation stream 162. In one aspect, the ethylene separation stream 165 may be combined with the components disclosed herein. Figure 3The ethylene recycle stream 306 is combined. In a further aspect, the ethylene separation stream 165 can be used for polymerization or oligomerization processes independent of the integrated conversion system of this disclosure. In yet another aspect, the ethylene separation stream 165 can be sent for storage or sale. The C2 separator 160 can be adapted to operate in any manner that produces the ethylene separation stream 165 and the ethane separation stream 162. In one aspect, the C2 separator 160 includes at least one fractionator.

[0123] In one aspect, the ethylene separation stream 165 contains ethylene. In a further aspect, based on the total weight of the ethylene separation stream 165, the amount of ethylene in the ethylene separation stream 165 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 yet another further aspect, the amount of ethylene in the ethylene separation stream 165 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0124] In one aspect, the ethane separation stream 162 contains ethane. In a further aspect, based on the total weight of the ethane separation stream 162, the amount of ethane in the ethane separation stream 162 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 yet another further aspect, the amount of ethane in the ethane separation stream 162 may be in the range of about 85 wt% to about 99.9 wt%; alternatively, about 87.5 wt% to about 99.9 wt%; alternatively, about 90 wt% to about 99.9 wt%; alternatively, about 92.5 wt% to about 99.9 wt%; alternatively, about 95 wt% to about 99.9 wt%; alternatively, about 97 wt% to about 99.9 wt%; or alternatively, about 98 wt% to about 99.9 wt%.

[0125] refer to Figure 10 It describes an integrated conversion system 1500, where similar numbers represent combinations. Figure 8 Similar components as described. (And) Figure 8 Unlike other systems, the integrated conversion system 1500 lacks the benzene hydrogenation process 120 and its associated reduction feed 43, benzene feed 47, cyclohexane recycle stream 123, and cyclohexane effluent 125. From what is disclosed herein... Figure 4 The raffinate stream 419 recovered from the purification and extraction process 490 flows into the oligomerization process 300 of the integrated conversion system 1500. The raffinate stream 419 is then mixed with... Figure 3 Solvent feed 308 is combined, wherein one or more components of raffinate stream 419 can be used as a solvent (i.e., diluent) within oligomerization process 300. In one aspect, benzene, toluene, xylene, branched alkanes, or combinations thereof can be used as a solvent (i.e., diluent) within oligomerization process 300. Lower purity 1-hexene stream 33 flows out of oligomerization process 300, and integrated conversion system 1500 continues as combined Figure 8 Continue publicly.

[0126] refer to Figure 11 It describes the integrated conversion system 1600, where similar numbers represent combinations. Figure 1 Similar components as described. (And) Figure 1 Conversely, the integrated conversion system 1600 lacks the derivatization process 500 (i.e., the ethylbenzene-styrene production process), and the associated ethylene feed 27, benzene feed 47, and styrene effluent 51. Within the integrated conversion system 1600, hydrocarbon feedstock 10 flows into cracking process 290, which, unless explicitly disclosed otherwise, operates in a manner similar to... Figure 2 The cracking process 200 is operated in the manner described in the cracking process 290. Cracking feed 141 flows into cracking process 290. In one aspect, cracking feed 141 and... Figure 2 The hydrocarbon recycle stream 201 in the middle is combined.

[0127] Cracking process effluent 25, light hydrocarbon stream 146, crude pyrolysis gasoline (CPG) stream 142, fuel gas stream 144, and steam effluent 148 exit from cracking process 290. Light hydrocarbon stream 146 can be obtained from... Figure 2 210, C from the pyrolysis effluent 3+ Flow 262 and / or substitute C 3+ Stream 282 is recovered. In one aspect, light hydrocarbon stream 146 comprises light hydrocarbons produced by cracking process 290, wherein said light hydrocarbons comprise methane, ethane, ethylene, propane, propylene, butane, or combinations thereof. A first portion 146a of light hydrocarbon stream 146 is fed into oligomerization process 300 and used therein for cooling and / or refrigeration. A second portion 146b of light hydrocarbon stream 146 enters aromatization process 400 and is used therein for cooling and / or refrigeration. Vapor effluent 148 comprises from... Figure 2 Steam recovered from the cracking process 290 (e.g., cracking zone 205) is used as a heat source. Steam effluent 148 flows into the oligomerization process 300 and is used therein as a heat source. CPG stream 142 flows into the aromatization process 400 and may be sent to… Figure 4 The first reforming stream 417. Fuel gas stream 144 enters the aromatization process 400. It exits from the oligomerization process 300. Figure 3 In one aspect, the heavy effluent 336 may be combined with the pyrolysis feed 141. The pyrolysis feed 141 effluent from the aromatization process 400 may, in one aspect, be combined with... Figure 4 The raffinate stream 419 was combined.

[0128] This document discloses a method for enriching an electric motor fuel stream (i.e., automotive gasoline (mogas)). In one aspect, the automotive gasoline comprises a fuel gas stream 144 of an integrated conversion system 1600. In a further aspect, the automotive gasoline is an enriched electric motor fuel. In a specific aspect, the automotive gasoline is enriched by blending one or more effluent streams generated by the integrated conversion system of this disclosure. For example, heavy effluent 336, raffinate stream 419, or combinations thereof can be blended into the automotive gasoline.

[0129] This document describes a set of restricted operating conditions (e.g., temperature, pressure) for the processes and systems disclosed herein. Those skilled in the art will understand that currently undisclosed operating conditions may have any values ​​suitable for operating processes and systems as disclosed herein, or alternatively, ranges of values. In a further aspect, those skilled in the art can utilize this disclosure to modify the operating conditions within any of the processes and systems disclosed herein to maintain the operation of the disclosed processes and systems.

[0130] In one respect, the integrated conversion system of this disclosure offers advantages in one or more areas compared to conventional benzene production methods that utilize non-integrated (i.e., stand-alone) conversion processes. Conventional benzene production methods utilize substances contained in crude oil (e.g., naphtha cracking), making benzene production costs linked to crude oil. This disclosure utilizes ethane contained in natural gas as a starting material (e.g., ethane steam cracking), advantageously decoupling benzene production costs from crude oil. With increasing natural gas supply and declining natural gas prices, other factors are increasing demand for benzene. For example, in North America, ample ethane reserves for steam cracking make naphtha cracking uneconomical. Future ethylene supply may also be significantly excessive. A further advantage is the ability to convert ethylene to benzene using the integrated conversion system of this disclosure according to market demand. Furthermore, a further advantage is the ability to increase or decrease the production of ethylbenzene or styrene according to market needs.

[0131] Figure 12 This illustrates a comparison of ethylene and benzene prices based on carbon. (Used to create...) Figure 12 The data in the charts was obtained from IHS Chemical Market Advisory Service. Figure 12This explains how the price of benzene relative to ethylene has risen over the past 20 years, and is expected to continue to rise in the future. A further advantage of using the integrated conversion system of this disclosure to convert ethylene to benzene is the ability to take advantage of the price difference between ethylene and benzene.

[0132] A further advantage of the integrated conversion system disclosed herein is the ability to produce large quantities of ethylene, 1-hexene, benzene, and styrene, and to sell portions of each compound according to global demand. The integrated conversion system of this disclosure is characterized by the flexibility to modify the production rates of the product streams to accommodate changes in demand and / or prices for 1-hexene, benzene, and / or styrene. In one aspect, up to 1.5 million tons of ethylene can be produced annually. Other products that can be generated for sale using the integrated conversion system of this disclosure include hydrogen (i.e., hydrogen effluent 41), styrene (i.e., styrene effluent 51), and cyclohexane (i.e., cyclohexane effluent 125).

[0133] A further advantage of the integrated conversion system disclosed herein is that 1-hexene can be used as feedstock for the aromatization process. Hydrogenating 1-hexene to n-hexane, as disclosed herein, offers further advantages, including slower catalyst deactivation, less facility turnaround, and higher aromatics selectivity. Because the cracking feedstock is derived from natural gas rather than crude oil, the 1-hexene / n-hexane fed to the aromatization process has a lower sulfur content, potentially allowing for removal by conventional staged combustion air pre-processors and subsequent reductions in capital costs.

[0134] A further advantage of the integrated conversion system disclosed herein is the use of light hydrocarbons produced by the cracking process 200 in the refrigeration of the oligomerization process 300. This method allows for the removal of a dedicated refrigeration unit in the oligomerization reaction process 300 and provides subsequent reductions in capital costs. A further advantage is that the cracking process 200 can produce hydrogen and methane (not shown), which can be used as fuel for heating and / or operating other processes within the integrated conversion system. This allows for design improvements to the facility or system, such as reducing the size of heat exchangers.

[0135] Example The subject matter has been generally described, and the following embodiments are given as specific aspects of this disclosure and demonstrate their practice and advantages. It should be understood that the embodiments are given by way of illustration and are not intended to limit the specification of the appended claims in any way. It should be clearly understood that various other aspects, modifications, and equivalents will conceive of by those skilled in the art upon reading this description without departing from the spirit of this disclosure or the scope of the appended claims.

[0136] Figure 13 and Figure 14 Demonstrating the use of AROMAX ®The catalyst was used to produce benzene from 1-hexene. Operating conditions were a constant temperature of 950℉ (510℃) and a liquid hourly space velocity of 12 h⁻¹. -1 The pressure is 100 psig (0.68 MPag), and the molar ratio of hydrogen to hydrocarbon is 1.2:1. Figure 13 It is shown that, under specified conditions, the conversion rate of 1-hexene to benzene approaches 100% after about 5 hours. Figure 14 It is shown that, under specified conditions, the selectivity for the conversion of 1-hexene to benzene remains at approximately 85% after about 5 hours. After about 1 hour, the selectivity for benzene under the above conditions is approximately 80%.

[0137] Other publicly available information Therefore, the scope of protection is not limited to the description set forth above, but only to the following claims, the scope of which includes all equivalents of the subject matter of the claims. Each claim is incorporated herein as an embodiment of this disclosure. Thus, the claims are a further description and an addition to the specific embodiments of this disclosure. All disclosures of patents, patent applications, and publications cited herein are hereby incorporated by reference.

[0138] The methods and systems have been described. The following are aspects of specific, non-limiting embodiments according to this disclosure: In a first aspect, the technology described herein relates to a method comprising: contacting ethylene and an oligomerization catalyst in an oligomerization reactor to produce an oligomerization reactor effluent containing 1-hexene; recovering 1-hexene from the oligomerization reactor effluent; and contacting the 1-hexene recovered from the oligomerization reactor effluent with an aromatization catalyst in an aromatization reactor to produce an aromatization reactor effluent containing benzene.

[0139] In a second aspect, the technology described herein relates to the method as described in the first aspect, which further includes: cracking ethane, propane, butane, pentane, naphtha, or mixtures thereof in a steam cracker to produce a cracker effluent containing ethylene; and causing ethylene recovered from the cracker effluent to flow into the oligomerization process.

[0140] In a third aspect, the technology described herein relates to the method as described in the second aspect, which further includes: recovering light hydrocarbons from pyrolysis effluent; and using the light hydrocarbons recovered from pyrolysis effluent to cool an oligomerization process containing an oligomerization reactor or an aromatization process containing an aromatization reactor.

[0141] In a fourth aspect, the technology described herein relates to the method as described in the second or third aspect, further comprising: recovering steam from a steam pyrolyzer; and using the steam recovered from the steam pyrolyzer in an oligomerization process containing an oligomerization reactor.

[0142] In a fifth aspect, the technology described herein relates to a method as described in any one of aspects 2 through 4, further comprising: feeding ethylene recovered from the pyrolysis effluent into an alkylation reactor; feeding benzene recovered from the aromatization reactor effluent into the alkylation reactor; and in the alkylation reactor, contacting the ethylene recovered from the pyrolysis effluent and the benzene recovered from the aromatization reactor effluent with an alkylation catalyst to produce an alkylation reactor effluent containing ethylbenzene.

[0143] In a sixth aspect, the technology described herein relates to the method as described in the fifth aspect, which further comprises: flowing ethylbenzene recovered from the alkylation reactor effluent into a dehydrogenation reactor; and in the dehydrogenation reactor, contacting the ethylbenzene with a dehydrogenation catalyst to produce a dehydrogenation reactor effluent containing styrene.

[0144] In a seventh aspect, the technology described herein relates to a method as described in any one of aspects 1 to 6, further comprising: feeding at least a portion of 1-hexene recovered from an oligomerization reactor effluent into a hydrogenation reactor; in the hydrogenation reactor, contacting at least a portion of the 1-hexene with a hydrogenation catalyst to produce a hydrogenation reactor effluent containing hexane; recovering hexane from the hydrogenation reactor effluent; and in an aromatization reactor, contacting the hexane recovered from the hydrogenation reactor effluent with the aromatization catalyst to produce an aromatization reactor effluent containing benzene.

[0145] In the eighth aspect, the technology described herein relates to a method as described in any one of aspects 1 to 7, wherein the step of contacting ethylene with the oligomeric catalyst is carried out in the presence of a diluent selected from the group consisting of isobutane, cyclohexane, methylcyclohexane, n-alkanes, branched alkanes, isoalkanes, 2,2,4-trimethylpentane, and combinations thereof.

[0146] In a ninth aspect, the technology described herein relates to a method as described in any one of aspects 1 to 8, wherein the 1-hexene is recovered from the effluent of the oligomerizing reactor by washing to remove the catalyst and fractionating to remove the diluent.

[0147] In a 10th aspect, the technology described herein relates to a method as described in any one of aspects 1 to 9, wherein the oligomerization catalyst comprises a chromium source, a pyrrole-containing compound, and a metal alkyl group, optionally supported on an inorganic oxide support; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal, and one or more halides.

[0148] In aspect 11, the technology described herein relates to a method as described in any one of aspects 1 to 10, wherein the conversion of 1-hexene to benzene is greater than about 70% by weight, based on the total amount of 1-hexene fed to the aromatization reactor.

[0149] In aspect 12, the technology described herein relates to a method as described in any one of aspects 1 to 11, wherein the selectivity for converting 1-hexene to benzene is greater than about 75% by weight based on the total weight of 1-hexene converted in the aromatization reactor.

[0150] In aspect 13, the technology described herein relates to a method as described in any one of aspects 1 to 12, further comprising: in a hydrogenation reactor, contacting benzene recovered from an aromatization reactor effluent with a hydrogenation catalyst to produce a hydrogenation reactor effluent containing cyclohexane; recovering cyclohexane from the hydrogenation reactor effluent; and recycling the cyclohexane recovered from the hydrogenation reactor effluent to an oligomerization reactor.

[0151] In aspect 14, the technology described herein relates to a method as described in any one of aspects 1 to 13, further comprising: recovering a lower purity 1-hexene stream from the effluent of the oligomerization reactor; recovering a higher purity 1-hexene stream from the lower purity 1-hexene stream; and causing a portion of the lower purity 1-hexene stream to flow into a hydrogenation reactor.

[0152] In aspect 15, the technology described herein relates to a method as described in any one of aspects 1 to 14, wherein a sulfur removal system is not used in the step of allowing 1-hexene recovered from the effluent of the oligomerization reactor to flow into the aromatization reactor.

[0153] In aspect 16, the technology described herein relates to a method as described in any one of aspects 1 to 15, wherein the step of contacting ethylene with the oligomerization catalyst is carried out in the presence of a diluent recovered from the effluent of the aromatization reactor, wherein the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof.

[0154] In aspect 17, the technology described herein relates to a method as described in any one of aspects 1 to 16, wherein the oligomerization reactor effluent further comprises heavy hydrocarbons having more than 8 carbon atoms, the method further comprising: flowing the heavy hydrocarbons recovered from the oligomerization reactor effluent into a steam cracker; and cracking the heavy hydrocarbons in the steam cracker.

[0155] In aspect 18, the technology described herein relates to a method as described in any one of aspects 1 to 17, further comprising: flowing raffinate recovered from the effluent of the aromatization reactor into a steam pyrolyzer; and pyrolyzing the raffinate in the steam pyrolyzer.

[0156] In aspect 19, the technology described herein relates to a method as described in any one of aspects 1 to 18, wherein the oligomerization reactor effluent further comprises a heavy hydrocarbon having more than 8 carbon atoms, the method further comprising: blending the heavy hydrocarbon, raffinate obtained from the aromatization reactor effluent, or both the heavy hydrocarbon and the raffinate into an electric motor fuel stream.

[0157] In aspect 20, the technology described herein relates to a method as described in any one of aspects 1 to 19, further comprising: causing hydrogen recovered from the effluent of the aromatization reactor and light hydrocarbons having fewer than 6 carbon atoms to flow into a demethanizer, a depropanizer, or both a demethanizer and a depropanizer.

[0158] In aspect 21, the technology described herein relates to a method as described in any one of aspects 1 to 20, wherein the ethylene is fed into the oligomerizing reactor in the form of a stream comprising ethylene and ethane.

[0159] In aspect 22, the technology described herein relates to a system comprising: an oligomerization reactor configured to contact ethylene with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; and an aromatization reactor configured to contact 1-hexene recovered from the oligomerization reactor effluent with an aromatization catalyst to produce an aromatization reactor effluent containing benzene.

[0160] In aspect 23, the technology described herein relates to a system as described in aspect 22, wherein, based on the total weight of 1-hexene fed to the aromatization reactor, the conversion of 1-hexene to benzene in the aromatization reactor is greater than about 70% by weight.

[0161] In aspect 24, the technology described herein relates to a system as described in aspect 22 or 23, wherein, based on the total weight of 1-hexene converted in the aromatization reactor, the selectivity for the conversion of 1-hexene to benzene in the aromatization reactor is greater than about 75% by weight.

[0162] In aspect 25, the technology described herein relates to a system as described in any one of aspects 22 to 24, further comprising: a steam pyrolyzer that produces a pyrolyzer effluent containing ethylene, wherein the oligomerization reactor is configured to receive ethylene recovered from the pyrolyzer effluent for oligomerization in the oligomerization reactor.

[0163] In aspect 26, the technology described herein relates to a system as described in aspect 25, which further comprises: an alkylation reactor configured to contact benzene recovered from the effluent of the aromatization reactor and ethylene recovered from the steam cracker with an alkylation catalyst to produce an alkylation reactor effluent containing ethylbenzene.

[0164] In aspect 27, the technology described herein relates to a system as described in aspect 26, which further includes: a dehydrogenation reactor configured to contact ethylbenzene recovered from the alkylation reactor effluent with a dehydrogenation catalyst to produce a dehydrogenation reactor effluent containing styrene.

[0165] In aspect 28, the technology described herein relates to a system as described in any one of aspects 25 to 27, wherein the pyrolysis effluent further comprises light hydrocarbons, wherein an oligomerization process containing the oligomerization reactor, an aromatization process containing the aromatization reactor, or both the oligomerization process and the aromatization process are configured to receive at least a portion of the light hydrocarbons.

[0166] In aspect 29, the technology described herein relates to a system as described in any one of aspects 25 to 28, wherein the steam pyrolyzer is configured to generate steam, and wherein an oligomerization process containing the oligomerization reactor is configured to receive steam recovered from the steam pyrolyzer.

[0167] In aspect 30, the technology described herein relates to a system as described in any one of aspects 22 to 29, wherein the oligomerization catalyst comprises a chromium source, a pyrrole-containing compound and a metal alkyl group, optionally supported on an inorganic oxide support; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides.

[0168] In aspect 31, the technology described herein relates to a system comprising: an oligomerization reactor configured to contact ethylene with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; a hydrogenation reactor configured to contact 1-hexene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to produce an aromatization feed containing hexane; and an aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce an aromatization reactor effluent containing benzene.

[0169] In aspect 32, the technology described herein relates to a system as described in aspect 31, which further comprises: a steam pyrolyzer that produces a pyrolyzer effluent containing ethylene, wherein the oligomerization reactor is configured to receive ethylene recovered from the pyrolyzer effluent for oligomerization in the oligomerization reactor.

[0170] In aspect 33, the technology described herein relates to a system as described in aspect 32, which further comprises: an alkylation reactor configured to contact benzene recovered from the effluent of the aromatization reactor and ethylene recovered from the steam cracker with an alkylation catalyst to produce an alkylation reactor effluent containing ethylbenzene.

[0171] In aspect 34, the technology described herein relates to a system as described in aspect 35, which further includes: a dehydrogenation reactor configured to contact ethylbenzene recovered from the alkylation reactor effluent with a dehydrogenation catalyst to produce a dehydrogenation reactor effluent containing styrene.

[0172] In aspect 35, the technology described herein relates to a system as described in any one of aspects 31 to 34, wherein the aromatization reactor is further configured to produce a hydrogen effluent, the system further comprising: a second hydrogenation reactor configured to contact benzene recovered from the aromatization reactor effluent and hydrogen recovered from the hydrogen effluent with a second hydrogenation catalyst to produce a second hydrogenation reactor effluent containing cyclohexane, wherein the oligomerization reactor is configured to receive at least a portion of the cyclohexane from the second hydrogenation reactor effluent.

[0173] In aspect 36, the technology described herein relates to a system as described in any one of aspects 31 to 35, wherein the oligomerization reactor effluent comprises a lower purity 1-hexene stream, the system further comprising: a C6 separator configured to recover a higher purity 1-hexene stream from a first portion of the lower purity 1-hexene stream, wherein the hydrogenation reactor is configured to receive a second portion of the lower purity 1-hexene stream.

[0174] In aspect 37, the technology described herein relates to a system as described in any one of aspects 31 to 36, further comprising: a steam cracker that produces a cracker effluent containing ethylene, wherein the oligomerization reactor is configured to receive ethylene recovered from the cracker effluent for oligomerization in the oligomerization reactor; and a C2 separator configured to separate a portion of the cracker effluent into ethylene and ethane, wherein the steam cracker is configured to receive ethane recovered from the C2 separator.

[0175] In aspect 38, the technology described herein relates to a system as described in any one of aspects 31 to 37, wherein the oligomerization reactor is configured to receive raffinate from the aromatization reactor, wherein the raffinate comprises benzene, toluene, xylene, branched alkanes, or combinations thereof, wherein the effluent from the oligomerization reactor comprises a low-purity 1-hexene stream, and the system further comprises: a C6 separator configured to recover a higher-purity 1-hexene stream from a first portion of the lower-purity 1-hexene stream, wherein the hydrogenation reactor is configured to receive a second portion of the lower-purity 1-hexene stream.

[0176] In aspect 39, the technology described herein relates to a system as described in any one of aspects 31 to 38, wherein the oligomerization catalyst comprises a chromium source, a pyrrole-containing compound and a metal alkyl group, optionally supported on an inorganic oxide support; and wherein the aromatization catalyst comprises a zeolite support, a Group VIII metal and one or more halides.

[0177] Although several aspects and embodiments of this disclosure have been shown and described, modifications can be made thereto by those skilled in the art without departing from the spirit and teachings of this disclosure. The aspects, embodiments, and examples described herein are exemplary only and are not intended to be limiting. Many variations and modifications of this disclosure are possible and within the scope of the subject matter.

[0178] Regarding transitional terms or phrases in claims, the transitional term "comprising," synonymous with "including," "containing," "having," or "characterized by," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting substantially of" limits the scope of the claim to the specified materials or steps, as well as those that do not substantially affect the essential and novel features of the claim. Claims "consisting substantially of" occupy an intermediate zone between closed claims drafted in the "consisting of" format and fully open claims drafted in the "comprising" format. Unless otherwise indicated, describing a compound or composition as "consisting substantially of" should not be interpreted as "comprising," but rather is intended to describe the listed components that include materials that do not significantly alter the composition or method to which the term is applied. For example, a raw material substantially composed of material A may include impurities typically present in commercially produced or commercially available samples of the listed compounds or compositions. When a claim includes different features and / or feature categories (e.g., method steps, raw material features, and / or product features, and other possibilities), transitional terms such as "consistent with," "substantially composed of," and "composed of" apply only to the feature category utilized, and different transitional terms or phrases may be used for different features in the claim. For example, a method may include several listed steps (and other unlisted steps), but utilizes a catalyst system composed of specific components; alternatively, substantially composed of specific components; or alternatively, includes specific components and other unlisted components.

[0179] In this disclosure, while systems, processes, and methods are generally described as “comprising” various components, instruments, or steps, unless otherwise stated, systems, processes, and methods may also “consist substantially of” or “comprise” various components, instruments, or steps.

[0180] As used herein, the term "about" means that a quantity, size, formulation, parameter, or other quantity and characteristic is not and does not need to be precise, but may be an approximation and / or larger or smaller as required, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, whether explicitly stated or not, a quantity, size, formulation, parameter, or other quantity or characteristic is "about" or "approximately". The term "about" also covers amounts that vary due to different equilibrium conditions of the composition resulting from a particular initial mixture. The claims include equivalents of the stated quantities, whether or not modified by the term "about". The term "about" may mean within 10% of the reported value, preferably within 5% of the reported value.

[0181] Unless otherwise stated, when disclosing or requesting any type of range (e.g., ranges of carbon atom number, molar ratio, temperature, etc.), it is intended to individually disclose or request every possible number that the range could reasonably cover, including any subranges covered therein. For example, when describing a range of carbon atom number, every possible single integer included in the range, as well as the range between atomic integers, is included. Thus, by disclosing C1 to C 10 The alkyl group, or an alkyl group having 1 to 10 carbon atoms or "at most" 10 carbon atoms, is described by the applicant. The applicant intends to show that the alkyl group can have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and that these methods of describing such groups are interchangeable. When describing a range of measurements (such as a molar ratio), each possible number that the range can reasonably cover can, for example, refer to a value within the range, but with one more significant figure than the endpoints of the range. In this example, molar ratios between 1.03:1 and 1.12:1 include molar ratios of 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, 1.10:1, 1.11:1, and 1.12:1, respectively. The applicant intends that these two methods of describing ranges are interchangeable. Furthermore, when disclosing or claiming protection for a range of values, the applicant aims to reflect each possible number that such a range can reasonably cover, and the applicant also aims to disclose a range that reflects any and all subranges and combinations of subranges covered therein, and is interchangeable with disclosing that range. In this respect, the applicant discloses C1 to C... 10 Alkyl is intended to literally encompass C1 to C6 alkyl, C4 to C8 alkyl, C2 to C7 alkyl, combinations of C1 to C3 and C5 to C7 alkyl, and so on. When the endpoints of a range describe ranges with different numbers of significant figures (such as molar ratios of 1:1 to 1.2:1), each possible number that such a range can reasonably cover can, for example, refer to a value within the range that has one more significant figure than the endpoint of the range with the most significant figures, in this case 1.2:1. In this example, molar ratios from 1:1 to 1.2:1 include individual molar ratios of 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.19, and 1.20 (all molar ratios relative to 1) and any and all subranges and combinations thereof covered therein. Therefore, if the applicant chooses to claim protection for any measure smaller than the full scope of this disclosure for any reason (e.g., considering references unknown to the applicant at the time of filing), the applicant reserves the right to exclude or exclude any individual member of any such group (including any subranges or combinations of subranges within said group).

[0182] For the purposes of any U.S. national phase filing of this application, all publications and patents mentioned in this disclosure are incorporated herein by reference in their entirety for the purpose of describing and disclosing the constructions and methods described in those publications, which may be used in conjunction with the methods of this disclosure. Any publications and patents discussed herein are provided only for the purposes of their prior disclosure prior to the filing date of this application. Nothing herein shall be construed as an admission that the inventor has no prior rights to such disclosures due to previous disclosures.

[0183] In any application filed with the United States Patent and Trademark Office, an abstract of this application is provided to satisfy the requirements of 37 CFR § 1.72 and the purpose set forth in 37 CFR § 1.72(b), namely, “to enable the United States Patent and Trademark Office and the public to quickly determine the nature and essence of the technical disclosure by means of a cursory examination.” Therefore, the abstract of this application is not intended to construe the scope of the claims or to limit the scope of the subject matter disclosed herein. Furthermore, any headings that may be used herein are not intended to construe the scope of the claims or to limit the scope of the subject matter disclosed herein. Any use of past tenses to describe instances otherwise indicated as constructive or prophetic is not intended to reflect instances that have actually been implemented.

[0184] At least one embodiment is disclosed, and variations, combinations, and / or modifications made by those skilled in the art to the embodiment and / or its features are within the scope of this disclosure. Alternative embodiments resulting from combining, integrating, and / or omitting features of the embodiment are also within the scope of this disclosure. When numerical ranges or limitations are explicitly stated, it should be understood that such explicit ranges or limitations include iterative ranges or limitations of similar values ​​falling within the explicitly stated ranges or limitations (e.g., "about 1 to about 10" includes 2, 3, 4, etc.; "greater than 0.10" includes 0.11, 0.12, 0.13, etc.). For example, whenever a lower limit R is disclosed... l and upper limit R u When specifying the numerical range, any number falling within that range will be explicitly disclosed. Specifically, the following numbers within the range are explicitly disclosed: R = R l + k • (R u – R l), where k is a variable ranging from 1% to 100% in increments of 1%, i.e., k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99%, or 100%. Furthermore, any numerical range defined by the two R numbers as defined above is explicitly disclosed. The use of the term "optional" with respect to any element of the claim means that the element is required, or alternatively, the element is not required, both of which are within the scope of the claim.

Claims

1. A method comprising: In an oligomerization reactor, ethylene is contacted with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; 1-Hexene was recovered from the effluent of the oligomerizing reactor. as well as In an aromatization reactor, the 1-hexene recovered from the oligomerization reactor effluent is contacted with an aromatization catalyst to produce an aromatization reactor effluent containing benzene.

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

3. The method of claim 2, further comprising: Light hydrocarbons are recovered from the pyrolysis effluent; as well as The light hydrocarbons recovered from the pyrolysis effluent are used to cool the oligomerization process containing the oligomerization reactor or the aromatization process containing the aromatization reactor.

4. The method of claim 2, further comprising: Steam is recovered from the steam pyrolysis unit; as well as The steam recovered from the steam pyrolyzer is used in the oligomerization process containing the oligomerization reactor.

5. The method of claim 2, further comprising: Ethylene recovered from the pyrolysis effluent is fed into the alkylation reactor; Benzene recovered from the effluent of the aromatization reactor is then fed into the alkylation reactor; as well as In the alkylation reactor, the ethylene recovered from the pyrolysis effluent and the benzene recovered from the aromatization reactor effluent are contacted with an alkylation catalyst to produce an alkylation reactor effluent containing ethylbenzene.

6. The method of claim 5, further comprising: The ethylbenzene recovered from the effluent of the alkylation reactor is then fed into the dehydrogenation reactor; as well as In the dehydrogenation reactor, ethylbenzene is contacted with a dehydrogenation catalyst to produce a dehydrogenation reactor effluent containing styrene.

7. The method of claim 1, further comprising: At least a portion of the 1-hexene recovered from the effluent of the oligomerizing reactor is fed into the hydrogenation reactor; In the hydrogenation reactor, at least a portion of the 1-hexene is contacted with a hydrogenation catalyst to produce a hydrogenation reactor effluent containing hexane; Hexane is recovered from the effluent of the hydrogenation reactor; as well as In the aromatization reactor, hexane recovered from the effluent of the hydrogenation reactor is contacted with the aromatization catalyst to produce the aromatization reactor effluent containing benzene.

8. The method of claim 1, wherein the contacting of ethylene with the oligomerizing catalyst is carried out in the presence of a diluent selected from the group consisting of isobutane, cyclohexane, methylcyclohexane, n-alkanes, branched alkanes, isoalkanes, 2,2,4-trimethylpentane, and combinations thereof.

9. The method of claim 1, wherein the 1-hexene is recovered from the effluent of the oligomerizing reactor by washing to remove the catalyst and fractionation to remove the diluent.

10. The method of claim 1, wherein the conversion of 1-hexene to benzene is greater than about 70% by weight based on the total amount of 1-hexene fed to the aromatization reactor, and the selectivity of 1-hexene to benzene is greater than about 75% by weight based on the total weight of 1-hexene converted in the aromatization reactor.

11. The method of claim 1, further comprising: In a hydrogenation reactor, benzene recovered from the effluent of the aromatization reactor is contacted with a hydrogenation catalyst to produce a hydrogenation reactor effluent containing cyclohexane. Cyclohexane is recovered from the effluent of the hydrogenation reactor; as well as The cyclohexane recovered from the effluent of the hydrogenation reactor is recycled back to the oligomerization reactor.

12. The method of claim 1, further comprising: A lower purity 1-hexene stream is recovered from the effluent of the oligomerizing reactor; Recover higher purity 1-hexene stream from the lower purity 1-hexene stream; as well as A portion of the lower purity 1-hexene stream is then fed into the hydrogenation reactor.

13. The method of claim 1, wherein no sulfur removal system is used in causing the 1-hexene recovered from the effluent of the oligomerization reactor to flow into the aromatization reactor.

14. The method of claim 1, wherein the contacting of ethylene with the oligomerization catalyst is carried out in the presence of a diluent recovered from the effluent of the aromatization reactor, wherein the diluent is selected from raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof.

15. The method of claim 1, wherein the oligomerization reactor effluent further comprises heavy hydrocarbons having more than 8 carbon atoms, the method further comprising: The heavy hydrocarbons recovered from the effluent of the oligomerizing reactor are then fed into the steam cracker; as well as The heavy hydrocarbons are cracked in the steam cracker.

16. The method of claim 1, further comprising: The raffinate recovered from the effluent of the aromatization reactor is fed into the steam cracker; and The raffinate is pyrolyzed in the steam pyrolyzer.

17. The method of claim 1, wherein the oligomerization reactor effluent further comprises heavy hydrocarbons having more than 8 carbon atoms, the method further comprising: The heavy hydrocarbons, the raffinate obtained from the effluent of the aromatization reactor, or both the heavy hydrocarbons and the raffinate are mixed into the motor fuel stream.

18. The method of claim 1, further comprising: Hydrogen recovered from the effluent of the aromatization reactor and light hydrocarbons having fewer than 6 carbon atoms are fed into a demethanizer, a depropanizer, or both a demethanizer and a depropanizer.

19. A system comprising: An oligomerization reactor configured to contact ethylene with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; as well as An aromatization reactor configured to contact 1-hexene recovered from the oligomerization reactor effluent with an aromatization catalyst to produce an aromatization reactor effluent containing benzene.

20. A system comprising: An oligomerization reactor configured to contact ethylene with an oligomerization catalyst to produce an oligomerization reactor effluent containing 1-hexene; A hydrogenation reactor configured to contact 1-hexene recovered from the effluent of the oligomerization reactor with a hydrogenation catalyst to produce an aromatized feed comprising hexane. as well as An aromatization reactor configured to contact the aromatization feed with an aromatization catalyst to produce an aromatization reactor effluent containing benzene.

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