Systems and methods for producing high purity aromatics from mixed aromatic feed streams

Abstract

The present disclosure provides systems and methods for producing aromatic compounds at high yields from mixed aromatic feed streams. Systems and methods for producing aromatic compounds at high yields from oxygenated hydrocarbons, such as carbohydrates, sugars, sugar alcohols, and sugar degradation products, are also disclosed.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 255,812, filed October 14, 2021, the contents of which are hereby incorporated by reference in their entirety. [Background technology]

[0002] Aromatic hydrocarbons, particularly benzene, toluene, and xylene, are important industrial products used to produce numerous chemicals, fibers, plastics, and polymers, including styrene, phenol, aniline, polyester, and nylon. Typically, such aromatic hydrocarbons are produced from petroleum feedstocks using well-established refining or chemical processes. More recently, there has been growing interest in obtaining aromatic hydrocarbons from alternative sources, such as biomass, synthetic gas, and natural gas. Summary of the Invention

[0003] In one aspect, the present disclosure provides a method for separating aromatic compounds from a mixed aromatic feed stream. The method includes: (i) a C 7~10 The method may include contacting the mixed aromatic feed stream containing aromatics with an aromatic processing catalyst to produce a product stream, the aromatic processing catalyst comprising a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feed may comprise greater than 1 wt.% non-aromatic components based on the total weight of the mixed aromatic feed stream. The mixed aromatic feed may comprise greater than 1 wt.% non-aromatic components based on the total weight of the mixed aromatic feed stream. 12+ It may be substantially free of aromatics. The method may further comprise the step of (ii) fractionating the product stream to separate aromatic compounds from the product stream.

[0004] In some embodiments, based on the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream may contain 0.1 wt% to 45 wt% olefins, 0.1 wt% to 25 wt% naphthenes, 0.1 wt% to 40 wt% naphtheno-olefins, phenols in an amount of 10 ppm to 10 wt%, and / or oxygenates in an amount of 10 ppm to 10 wt%, based on the total weight of the mixed aromatic feed stream. 2 / mixed aromatic feedstock g~100mg Br 2 In some embodiments, the mixed aromatic feed stream has a Bromine Number of less than C / g of the mixed aromatic feed stream. In some embodiments, the mixed aromatic feed stream is substantially free of azeotropic contaminants of benzene, toluene, and combinations thereof. In some embodiments, the mixed aromatic feed stream has a Bromine Number of less than C / g of the mixed aromatic feed stream. 9 ~ 10 Contains aromatics.

[0005] In some embodiments, step (ii) of the method comprises: 8 The aromatics-containing product stream is fractionated to produce C 7- Stream to C 8+ C. 7- Stream is C 7- Stream to C 6- Stream and C 7 In some embodiments, the C2O may be fed to a second distillation column which fractionates the C2O into a C2O stream. 7 At least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

[0006] In some embodiments, step (ii) comprises 8+ Stream, C 8+ Stream to C 8 Stream and C 9+ and feeding the mixture to a third distillation column for fractionation into a third stream. 8 Stream is C 8 May contain aromatics. 9+ Stream is C 9+ Stream to C 9~10Stream and C 11+ The resulting mixture may be fed to a fourth distillation column which fractionates the product into streams C. 9~10 The stream may be recycled and combined with the mixed aromatic feed stream.

[0007] In some embodiments, the method further comprises: (iii) C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 and (iv) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream. The isomerized product stream may include at least one xylene isomer. At least a portion of the isomerized product stream may be combined with the product stream produced from the aromatics processing catalyst in step (i).

[0008] In some embodiments, at least a portion of the isomerization product stream is a C 8 Combined with streams.

[0009] In some embodiments, C 8+ At least a portion of the stream is a C 8 Combined with streams.

[0010] In some embodiments, step (ii) of the process comprises fractionating the product stream to obtain a C 7 Stream, C 8 Stream, and C 9~10 A step of separating the streams, comprising: 8 The stream is fed to an isomer recovery process unit and 7 The stream is recycled and combined with the mixed aromatic feed stream and 9~10 The stream is recycled and combined with the mixed aromatic feed stream.

[0011] In some embodiments, step (ii) comprises fractionating the product stream to produce a C 7 Stream, C 8 Stream, and C 9+ A step of separating the streams, comprising: 8 The stream is fed to an isomer recovery process unit and 7 The stream is recycled and combined with the mixed aromatic feed stream and 9+ The stream is recovered as a product.

[0012] In some embodiments, the isomer recovery process unit comprises an adsorption unit or a crystallization unit.

[0013] The aromatic processing catalyst of the present method may include an acid catalyst. The acid catalyst may include aluminosilicate, tungstate aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconia, sulfated zirconia, tungstate zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstate alumina, phosphated silica, tungstate silica, tungstate titania, tungstate phosphate, niobia, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstate heteropolyacid, inorganic acid, or combination thereof. The acid catalyst may also include metals including Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, or combinations thereof.

[0014] In some embodiments, step (i) of the process is conducted at a temperature between 200° C. and 600° C. In some embodiments, step (i) of the process is conducted at a pressure between 100 psig and 1500 psig. In some embodiments, step (i) of the process is conducted at a weight hourly space velocity (WHSV) between 0.1 and 10 mass feedstock / mass catalyst / hour. In some embodiments, step (i) of the process comprises supplying hydrogen in an amount of at least 0.1 mole hydrogen per mole mixed aromatic feedstock, for example at least 1 mole hydrogen per mole mixed aromatic feedstock.

[0015] In another aspect, the disclosure provides a method for producing and separating aromatic compounds from a mixed aromatic feed stream. The method includes: (i) contacting an aqueous hydrocarbon feed comprising water and one or more oxygenates with a condensation catalyst to produce and separate aromatic compounds from a C 4+ producing a condensation product stream comprising the compound. 4+ The compound is, for example, C 4+ Alcohol, C. 4+ Ketone, C 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ The condensation product stream may comprise a cycloalkene, an aryl, or a fused aryl. The method may further comprise (ii) fractionating the condensation product stream to produce a light stream and a heavy stream. In some embodiments, the light stream comprises benzene or toluene azeotropic non-aromatic contaminants, and the heavy stream is substantially free of benzene or toluene azeotropic non-aromatic contaminants. The method may further comprise (iii) recycling the light stream to the condensation catalyst; and (iv) recycling the heavy stream to a C 7+ and fractionating the mixed aromatic feed stream into a mixed aromatic feed containing aromatics. The method may further include (v) contacting the mixed aromatic feed stream with an aromatic processing catalyst to produce a product stream. The aromatic processing catalyst may include a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof.

[0016] In some embodiments, step (iv) comprises 7+ Mixed aromatic feedstock containing aromatics is treated as C 7~10 Stream and C 11+ In some embodiments, step (iv) further comprises fractionating the C 7+ Mixed aromatic feedstock containing aromatics is treated as C 9~10 Stream and C 11+ C. The method further comprises the step of fractionating the mixture into streams. 7~10 Stream or C 9~10 The stream may be contacted with an aromatic processing catalyst.

[0017] In some embodiments, step (iv) is carried out at a temperature between 200° C. and 600° C. and a pressure between 100 psig and 1500 psig, and a weight hourly space velocity (WHSV) between 0.1 and 10 mass feed / mass catalyst / hour.

[0018] In another aspect, the present disclosure provides a method for producing and separating xylene isomers. The method includes: (i) a C 7+ A mixed aromatic feed stream containing aromatics is contacted with an aromatic processing catalyst to produce an increased concentration of C relative to the mixed aromatic feed stream. 8 The method may include (ii) producing a product stream comprising aromatics, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. 7- Stream and C 8+ (iii) fractionating the C stream using a distillation column. 8+ Stream to C 8 Stream and C 9+ and (iv) fractionating the C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer. 8+ At least a portion of the stream is bypassed in step (iii) and is separated into C 2 -C 1 -C ... 8 Combined with streams.

[0019] In yet another aspect, the present disclosure provides a method for producing and separating xylene isomers. The method includes: (i) a process for producing and separating xylene isomers comprising: 7+ A mixed aromatic feed stream containing aromatics is contacted with an aromatic processing catalyst to produce an increased concentration of C relative to the mixed aromatic feed stream. 8 The method may include (ii) using a distillation column to produce a product stream comprising aromatics, the catalyst comprising a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. 7- Stream and C 8+ (iii) fractionating the C stream using a distillation column. 8+ Stream to C 8 Stream and C 9+ and (iv) fractionating the C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, the isomerized product stream comprising at least one xylene isomer. In some embodiments, at least a portion of the isomerized product stream is treated with an isomerization catalyst to produce an isomerized product stream comprising at least one xylene isomer. In some embodiments, at least a portion of the isomerized product stream is treated with an isomerization catalyst to produce an isomerized product stream comprising at least one xylene isomer prior to entering the isomer recovery process unit. 8 Combined with streams.

[0020] The xylene isomer stream may include, for example, para-xylene, ortho-xylene, or meta-xylene.

[0021] In some embodiments, C 8+ At least a portion of the stream is bypassed in step (iii) and is separated into C 2 -C 1 -C ... 8 Combined with streams.

[0022] In some embodiments, prior to step (i), the method further comprises: Contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to form a C 4+ generating a condensation product stream comprising the compound C; 4+ The compound is C 4+ Alcohol, C. 4+ Ketone, C 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ comprising a cycloalkene, an aryl, or a fused aryl, The condensation product stream is fractionated to obtain C 6- Stream to C 7+ Separating from the stream; C 6- recycling the stream to the condensation catalyst; C 7+ Stream to C 7~10 Stream and C 11+ fractionating the mixture into a stream comprising: 7~10 the stream forming a mixed aromatic feed stream. Including, C 8+ At least a portion of the stream is bypassed in step (iii) and is separated into C 2 -C 1 -C ... 8 Combined with streams. [Brief description of the drawings]

[0023] [Figure 1]FIG. 1 is a schematic diagram of an aromatic refining system in accordance with some embodiments of the present disclosure. [Diagram 2] FIG. 1 is a schematic diagram of a process configured to convert oxygenated hydrocarbons to form a mixed aromatic feed stream in accordance with some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] In order that this disclosure may be more readily understood, certain terms are first defined below. Additional definitions for the following terms, as well as other terms, are set forth throughout the specification.

[0025] In this application, unless otherwise clear from the context, the term "a" may be understood to mean "at least one." As used in this application, the term "or" may be understood to mean "and / or." As used in this application, the terms "comprising" and "including" may be understood to include the listed components or steps, whether presented alone or together with one or more additional components or steps. Unless otherwise stated, the terms "about" and "approximately" may be understood to allow for standard deviations (e.g., ±10%) as understood by those of skill in the art. When ranges are provided herein, the endpoints are included. As used in this application, the term "comprise" and variations of terms such as "comprising" and "comprises" are not intended to exclude other additives, components, integers, or steps.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All definitions, as defined and used herein, should be understood to supersede dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0027] The present disclosure provides systems and methods for producing aromatic hydrocarbons in high yield and purity. Exemplary aromatic hydrocarbons include, but are not limited to, benzene, toluene, ethylbenzene, para-xylene, meta-xylene, ortho-xylene, dimethylbenzene, and naphthalene. The systems and methods provided can produce aromatics with high purity, for example, at least 98.5%, or at least 99%, or at least 99.5%, or at least 99.9%.

[0028] The provided systems and methods provide various advantages. For example, processing of mixed aromatic feed streams typically requires a separation step, such as extraction, to produce high purity aromatics. In some embodiments, the provided systems and methods obtain high purity aromatics without implementing extraction techniques to remove impurities from the feed stream. Removing extraction from the separation scheme reduces energy requirements and capital costs. Some aromatic products are more difficult to separate than others. For example, in some embodiments of the present disclosure, xylene isomers (e.g., para-xylene) can be purified using an isomerization stage and an isomer recovery process unit (e.g., adsorption or crystallization) coupled with distillation. The crystallization and adsorption processes require a significant amount of energy in the form of heat and electricity to separate the xylene isomers from the intermediate products. In one aspect of the present disclosure, systems and methods are provided to reduce the energy burden of the separation by having a portion of the intermediate stream enter an isomer recovery process unit directly without distillation or by bypassing a portion of the distillation unit, thereby reducing the energy associated with the bypassed distillation. This reduces the overall system energy load and, surprisingly, maintains acceptable product purity despite bypassing a purification step.

[0029] In another aspect of the disclosure, systems and methods are provided for producing a mixed aromatic feed stream free or substantially free of azeotropic non-aromatic contaminants of benzene, toluene, and combinations thereof. As used herein, the term "substantially free" refers to less than 1% (w / w) of a particular compound or mixture of compounds in a particular stream. In some embodiments, the mixed aromatic feed stream contains less than 1% (w / w), or less than 0.5% (w / w), or less than 0.1% (w / w) of azeotropic non-aromatic contaminants of benzene, toluene, and combinations thereof. By feeding a mixed aromatic feed stream free or substantially free of azeotropic non-aromatic contaminants over a transalkylation and / or dealkylation catalyst, aromatic products with higher purity and yield are obtained compared to mixed aromatic streams containing non-aromatic contaminants.

[0030] As used herein, the term "azeotropic nonaromatic contaminants" refers to nonaromatic species that cannot be separated, or can only be separated with great difficulty, from the desired product by distillation. Azeotropic nonaromatics vary with each desired product and can include hydrocarbons, oxygenates, sulfur-containing species, and nitrogen-containing species. The benzene azeotropic range is defined herein as all components (including benzene) having standard boiling points equal to or greater than that of methylcyclopentane (normal boiling point 71.8°C) and equal to or less than that of 1,3 dimethylcyclopentane, cis (normal boiling point 91°C). Exemplary azeotropic nonaromatic contaminants of benzene include, but are not limited to, methylcyclopentane, cyclohexane, methylcyclopentene, C 7 Paraffin, and C 7 Contains olefins.

[0031] The azeotropic range of toluene is defined herein as all components (including toluene) having retention times up to and including 1,3 dimethylcyclopentane, cis (boiling point 91° C.), and up to and including trans 1,2-dimethyl-cyclohexane (boiling point 123° C.).

[0032] Referring to FIG. 1, an aromatic refining system 10 is illustrated according to some embodiments of the present disclosure. For clarity and brevity, equipment for controlling temperature and flow within the aromatic refining system 10 has been omitted from the drawing. However, it should be understood that the aromatic refining system 10 may include various equipment for controlling temperature (e.g., heat exchangers for heating or cooling process streams, combustion heaters, coolers, electric heaters, or combinations thereof) even if omitted from the drawing. The aromatic refining system 10 may include equipment for controlling fluid flow rates, including, but not limited to, pumps, valves, compressors, blowers, or combinations thereof, for regulating fluid flow throughout the system 10, even if omitted from the drawing.

[0033] In some aspects, aromatic purification system 10 includes an aromatic processing reactor 12 having an inlet fluidly connecting aromatic processing reactor 12 with a mixed aromatic feed stream 14. A pump may be configured within mixed aromatic feed stream 14 to transport mixed aromatic feed stream 14 from a mixed aromatic feed source 16, such as a reservoir or an upstream process unit, to aromatic processing reactor 12. In some embodiments, mixed aromatic feed stream 14 is a C 2 feed stream, as further defined below. 7 Streams 36 and C 9~10 Optionally combined with stream 46 .

[0034] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises non-aromatic and aromatic compounds that may be derived from a variety of original sources, including, but not limited to, oxygenates and condensation products derived from biomass, petroleum refining, thermal or catalytic cracking of hydrocarbons, coal coking, petrochemical conversion, or combinations thereof.

[0035] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises 0.1 wt% to 45 wt% non-aromatic hydrocarbons, such as paraffins, olefins, naphthenes, naphtheno-olefins, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 0.1 wt% non-aromatic hydrocarbons, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt%, or less than 45 wt% ... 3~30 Paraffin, C 3~30 Olefin, C 5~30 naphthenes, or combinations thereof.

[0036] As used herein, the term "paraffin" or "alkane" refers to a C 3~30 Paraffins refer to saturated straight or branched chain hydrocarbons. In some embodiments, paraffins are n H 2n+2 where n can range from 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, or 3 to 6.

[0037] As used herein, the term "olefin" or "alkene" refers to a C olefin having at least one carbon-carbon double bond. 3~30 Olefins refer to unsaturated straight or branched chain hydrocarbons. In some embodiments, olefins are C n H 2n where n can range from 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, or 3 to 6.

[0038] Examples of various paraffins and olefins include, but are not limited to, propane, propene, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, Includes undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.

[0039] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 contains at least 0.1 wt% olefins, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt%, or less than 45 wt% olefins.

[0040] As used herein, the term "naphthene" or "cycloalkane" refers to a saturated cyclic, bicyclic, or bridged cyclic hydrocarbon group. The saturated cyclic, bicyclic, or bridged cyclic (e.g., adamantane) hydrocarbon group may be substituted with one or more straight-chain or branched-chain alkyl or alkylene groups, e.g., the substituted groups may be straight-chain or branched-chain C 1~12 Alkyl, linear or branched chain C 3~12 Alkylene, linear or branched C 1~4 Alkyl, linear or branched chain C 3~4The naphthene may be mono- or polysubstituted. In some embodiments, the naphthene may be C n H 2n where n can range from 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 5 to 6.

[0041] Examples of naphthenes include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, propyl-cyclohexane, butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane, pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, decalin, ethyl-decalin, pentyl-decalin, hexyl-decalin, and isomers thereof.

[0042] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 contains at least 0.1 wt% naphthenes, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 6 wt%, or at least 7 wt%, or at least 8 wt%, or at least 9 wt%, or at least 10 wt% to less than 11 wt%, or less than 12 wt%, or less than 13 wt%, or less than 14 wt%, or less than 15 wt%, or less than 16 wt%, or less than 17 wt%, or less than 18 wt%, or less than 19 wt%, or less than 20 wt%, or less than 21 wt%, or less than 22 wt%, or less than 23 wt%, or less than 24 wt%, or less than 25 wt% naphthenes.

[0043] As used herein, the term "naphtheno-olefin" refers to a saturated cyclic, bicyclic, or bridged cyclic hydrocarbon group having mono- or poly-substituted olefins in the hydrocarbon group. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises at least 0.1 wt% naphtheno-olefins, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt% naphtheno-olefins.

[0044] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises between 10 wt% and 80 wt% aromatic hydrocarbons, e.g., aryls, fused aryls, polycyclics, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 10 wt% aromatic hydrocarbons, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt% to less than 50 wt%, less than 55 wt%, or less than 60 wt%, or less than 65 wt%, or less than 75 wt%, or less than 80 wt% aromatics. In some embodiments, the hydrocarbon feed stream comprises a plurality of C 6~30 Aryl, C 12~30 Fused Aryl, C 12~30 polycyclic compounds, or combinations thereof.

[0045] As used herein, the terms "aryl" and "aromatic" refer to aromatic hydrocarbons in unsubstituted (phenyl), mono- or poly-substituted form. In the case of mono- and poly-substituted compounds, the substituted groups are branched C 3+ Alkyl, linear C 1+ Alkyl, branched chain C 3+Alkylene, linear C 2+ As an example, at least one of the substituted groups may include a branched C 3+ Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 As a further example, at least one of the substituted groups may be a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4 Alkylene, linear C 2~4 Examples of various aryls include, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, para-xylene, meta-xylene, ortho-xylene, C 9+ Aromatics include butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, and their isomers.

[0046] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises phenol in an amount of at least 10 ppm to less than 10 wt% based on the total weight of the feed stream. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises at least 10 ppm phenol, or at least 50 ppm, or at least 100 ppm, or at least 200 ppm, or at least 300 ppm, or at least 400 ppm, or at least 500 ppm, or at least 600 ppm, or at least 700 ppm, or at least 800 ppm, or at least 900 ppm, or at least 0.1 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt% to less than 5 wt%, or less than 6 wt%, or less than 7 wt%, or less than 8 wt%, or less than 9 wt%, or less than 10 wt% phenol based on the total weight of the feed stream.

[0047] As used herein, the term "fused aryl" or "polynuclear aromatic (PNA)" refers to bicyclic and polycyclic aromatic hydrocarbons in either unsubstituted, monosubstituted, or polysubstituted form. In the case of mono- and polysubstituted compounds, the substituted groups are branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 Alkylene, Branched Chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, linear C 2~4 Examples of various fused aryls include, but are not limited to, naphthalene, anthracene, and their isomers.

[0048] As used herein, the term "polycyclic compound" refers to bicyclic and polycyclic hydrocarbons, either unsubstituted, monosubstituted, or polysubstituted, having at least one saturated or partially saturated ring. In the case of monosubstituted and polysubstituted compounds, the substituted groups are branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 Alkylene, Branched Chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, linear C 2~4 alkylene, or combinations thereof. Examples of various polycyclic compounds include, but are not limited to, tetralin (i.e., tetrahydronaphthalene), ethyl-tetralin, pentyl-tetralin, hexyl-tetralin, and isomers thereof.

[0049] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 has at least 1 mg Br 2 / feedstock g~100Br 2In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 has a bromine number of less than 1 mg Br 2 / g or at least 5 mg Br 2 / g, or at least 10 mg Br 2 / g, or at least 15 mg Br 2 / g, or at least 20 mg Br 2 / g, or at least 25 mg Br 2 / g, or at least 30 mg Br 2 / g, or at least 40 mg Br 2 / g, or at least 50 mg Br 2 / g, or 60 mg Br 2 / g or less than 70mg Br 2 / g or less than 80mg Br 2 / g or less than 90mg Br 2 / g or less than 100mg Br 2 / g. Bromine number is a measure of aliphatic unsaturation in a feedstock. Bromine number can be determined using known methods such as ASTM D1159.

[0050] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 contains oxygenates in an amount between 10 ppm and less than 10 wt %, based on the total weight of the feed stream. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 contains at least 10 ppm oxygenates, or at least 50 ppm, or at least 100 ppm, or at least 200 ppm, or at least 300 ppm, or at least 400 ppm, or at least 500 ppm, or at least 600 ppm, or at least 700 ppm, or at least 800 ppm, or at least 900 ppm, or at least 0.1 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt% to less than 5 wt%, or less than 6 wt%, or less than 7 wt%, or less than 8 wt%, or less than 9 wt%, or less than 10 wt% oxygenates based on the total weight of the feed stream.

[0051] As used herein, the term "C n+ " refers to a hydrocarbon compound having n or more carbons in the compound (e.g., at least 7 carbons), n- " refers to a hydrocarbon compound having n or fewer carbons in the compound (e.g., less than 7 carbon atoms). In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is 7+ In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises C 7~10 aromatic, C 8~10 Aromatic, or C 9~10 In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises C 11+In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is free or substantially free of azeotropic contaminants of benzene, toluene, or combinations thereof.

[0052] As described in more detail with reference to Figure 2, the mixed aromatic feed stream 14 may be produced from water soluble sugars derived from biomass. Additionally or alternatively, the mixed aromatic feed stream 14 may be derived from a variety of original sources including, but not limited to, petroleum refining, thermal or catalytic cracking of hydrocarbons, coal coking, or petrochemical conversion.

[0053] 1 , aromatic processing reactor 12 may optionally include a hydrogen inlet that fluidly connects aromatic processing reactor 12 with a hydrogen stream 18. A gas delivery device may be configured within hydrogen stream 18 to transport hydrogen from a hydrogen source 20, such as a reservoir or an upstream process unit, to aromatic processing reactor 12.

[0054] The aromatic processing reactor 12 is configured to produce an aromatic feed stream having an increased concentration of C relative to the aromatic feed stream 14 or the combined aromatic feed stream 15. 8The aromatic processing catalyst 22 is configured to reform the mixed aromatic feedstock stream 14 to produce a product stream having aromatics. Suitable aromatic processing catalysts 22 include, but are not limited to, transalkylation catalysts, dealkylation catalysts, hydrocracking catalysts, or combinations thereof. In some embodiments, the aromatic processing catalyst 22 may comprise a bifunctional acidic metal-containing catalyst. The aromatic processing catalyst 22 may include, but is not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof.

[0055] In some embodiments, aromatic processing catalyst 22 may include the above alone or in combination with modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or combinations thereof. Aromatic processing catalyst 22 may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof to provide metal functionality.

[0056] In some embodiments, aromatic processing reactor 12 is operated as a gas phase reactor, where optional hydrogen and the aromatic feed stream 14 are taken into aromatic processing reactor 12 and flowed downwardly over a fixed bed of aromatic processing catalyst 22. Alternatively, aromatic processing reactor 12 is operated as a radial flow or upflow reactor. In other embodiments, reactor 12 is operated as a fixed trickle bed reactor, where optional hydrogen and the combined aromatic feed stream are taken into reactor 12 and flowed downwardly over a fixed bed of catalyst 22. Although hydrogen conduit 18 and combined aromatic stream 15 are shown in a co-current orientation in FIG. 1, it should be understood that a counter-current orientation may be implemented.

[0057] In some embodiments, aromatic processing reactor 12 operates at a temperature between 200° C. and 600° C., between 250° C. and 550° C., or between 300° C. and 500° C. In some embodiments, the pressure in aromatic processing reactor 12 ranges from atmospheric to 1500 psig. In some embodiments, reactor 12 operates at a weight hourly space velocity (WHSV) between 0.1 and 10 mass feedstock / mass catalyst / hour, or between 0.5 and 8 WHSV.

[0058] Product stream 24 exits aromatics processing reactor 12 through a reactor outlet where it is cooled to condense the aromatics and is transported to separator 25 where unreacted hydrogen and non-condensable compounds are removed from product stream 24. Cooling of reactor outlet stream 24 may be accomplished using one or more heat exchangers. A portion of the unreacted hydrogen may be optionally recycled and combined with hydrogen stream 18 via gas outlet 29. Recycling of unreacted hydrogen may be accomplished by use of a gas transport device such as a compressor or blower. Liquid product stream 27 from separator 25 is then subjected to distillation to recover various product fractions. The order in which the fractions are recovered may vary depending on the implementation details.

[0059] In one embodiment, the liquid product stream 27 from separator 25 is directed to a first distillation column 26. Pumps may be configured in the liquid product stream 27 to facilitate transport of the liquid product stream 27, and heat exchangers may be configured in the liquid product stream 27 to control the temperature of the liquid product stream entering the first distillation column 26. Valves may be positioned in the product stream 27 to regulate flow. The first distillation column 26 converts the liquid product stream 27 into a C 7- Streams 28 and C 8+ Although FIG. 1 shows first distillation column 26 as a single column, liquid product stream 27 is fractionated into C 7- Streams 28 and C 8+ It should be understood that fractionation into stream 30 may occur over multiple distillation columns.

[0060] In some embodiments, C 7- Stream 28 is C 7- Stream 28 C 6- Streams 34 and C 7 The C2O is fed to a second distillation column 32 where it is fractionated into stream 36. 6- Stream 34 is collected or discarded from the process. 6- Stream 34 is a C 6- For isolation from stream 34, it may be optionally further processed in an aromatics purification unit. For example, 6- Stream 34 is benzene to C 6- For isolation from stream 34, it may be subjected to further distillation, crystallization, or adsorption. 6- At least part of stream 34 contains more C 8 It is recycled to an upstream process unit, such as an acid condensation catalyst, to produce aromatics or other desired aromatics.

[0061] In some embodiments, C 7 Stream 36 may be further reacted over aromatics processing catalyst 22. 7At least a portion of stream 36 is recycled and combined with mixed aromatic feed stream 14 to form combined mixed aromatic feed stream 15. Additionally or alternatively, C 7 At least a portion of stream 36 may be collected or discarded from the process. 7 The collected or discarded portion of stream 36 is a product of 7 For isolation from stream 36, it may be optionally further processed in an aromatics purification unit. For example, C 7 Stream 36 is toluene to C 7 For isolation from stream 36, it may be subjected to further distillation, crystallization, or adsorption.

[0062] In some embodiments, the C exiting the first distillation column 26 8+ Stream 30 is fed to a third distillation column 38. The third distillation column 38 is 8+ Stream 30 to C 8 Stream 40 and C 9+ In some embodiments, the C 8+ A portion of stream 30 is separated from the third distillation column 38 as C 8 To be combined with Stream 40, C 8+ At least a portion of stream 30 optionally bypasses third distillation column 38. The bypass stream provides a variety of advantages. First, bypassing third distillation column 38 reduces the overall system energy load by reducing the flow rate of material through distillation column 38, thereby reducing operating costs. Additionally, applicants have surprisingly and unexpectedly discovered that incorporating a bypass stream reduces operating costs while still maintaining acceptable product purity despite bypassing distillation column 38.

[0063] In some embodiments, C 9+ Stream 42 is fed to a fourth distillation column 44. The fourth distillation column is 9+ Stream 42 to C 9~10 Stream 46 and C 11+In some embodiments, the C 9~10 Stream 46 may be further reacted over aromatics processing catalyst 22. 9~10 At least a portion of stream 46 is recycled and combined with mixed aromatic feed stream 14 to form combined mixed aromatic feed stream 15. Additionally or alternatively, C 9~10 At least a portion of stream 46 may be collected or discarded from the process. 9~10 The collected or discarded portion of stream 46 is a product of 9~10 For isolation from stream 46, it may be optionally further processed in an aromatics purification unit. For example, naphthalene may be separated into C 9~10 To be isolated from stream 46, 9~10 Stream 46 may be subjected to further distillation, crystallization, or adsorption. 11+ Stream 48 is either discarded from the system or further processed in a downstream process unit. 11+ The stream may be collected or further separated for diesel fuel use or as lubricating or fuel oil. 11+ The stream can be cracked, separated and recycled to either the mixed aromatic feed stream or the acid condensation catalyst for further processing.

[0064] In some embodiments, C 8 Stream 40 is fed to an isomer recovery process unit 50 which produces a xylene isomer stream 52 and unrecovered C 8 Exemplary isomer recovery process units 50 include, but are not limited to, isomer recovery process units configured to convert xylene isomers into C 8 The isomer recovery process unit 50 includes a crystallization unit, an adsorption unit, or a combination thereof, configured to selectively purify para-xylene, ortho-xylene, or meta-xylene from stream 40. 8It may be configured to purify from stream 40.

[0065] In some embodiments, the unrecovered C 8 The raffinate stream 54 containing the compounds is fed to an isomerization reactor 56. Pumps and valves may be configured within the raffinate stream 54 to regulate the flow of the raffinate to the isomerization reactor 56. The isomerization reactor 56 includes an isomerization catalyst 58 configured to produce an isomerized product stream containing an increased concentration of a desired xylene isomer (e.g., para-xylene, ortho-xylene, or meta-xylene) with minimal conversion to lighter and heavier products. The isomerization reactor 56 may optionally include a hydrogen inlet fluidly connecting the isomerization reactor 56 with a hydrogen stream 59. A gas delivery device may be configured within the hydrogen stream 59 to transport hydrogen from a hydrogen source 57, such as a reservoir or an upstream process unit, to the isomerization reactor 56. In some embodiments, the hydrogen sources 20, 57 originate from the same reservoir or upstream process unit.

[0066] In some embodiments, the isomerization catalyst 58 is comprised of alumina, silica, aluminosilicates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), and combinations thereof. In some embodiments, the isomerization catalyst 58 includes the above alone or in combination with modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The isomerization catalyst 58 may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof to provide metal functionality. The isomerization reactor 56 may be operated as a fixed trickle bed reactor or as a slurry reactor. In some embodiments, isomerization reactor 56 is operated at a temperature between 100° C. and 500° C., at a pressure between atmospheric and 1500 psig, and at a WHSV between 0.1 and 10 mass feed / mass catalyst / hour.

[0067] In some embodiments, at least a portion of the isomerization product stream 60 exits through the reactor outlet where it is cooled to condense the products and is transported to a separator 61 which removes unreacted hydrogen and non-condensable compounds from the isomerization product stream 60. Cooling of the isomerization product stream 60 may be accomplished using one or more heat exchangers. Some or all of the unreacted hydrogen may be optionally recycled and combined with the hydrogen stream 59 via a gas outlet 63. Recycling of the unreacted hydrogen may be accomplished through the use of a gas delivery device such as a compressor or blower. A liquid product stream 65 from the separator 61 is transported to the first distillation column 26 for fractionation. In some embodiments, the liquid product stream 65 from the separator 61 is optionally recycled and combined with the liquid product stream 27 from the separator 25 before being transported to the first distillation column 26.

[0068] In some embodiments, at least a portion of the isomerization product 60 is optionally recycled to the C distillation column 38. 8 For example, a portion of the liquid product stream 65 may be split off into stream 62, which is then transported to 8 Stream 40 is combined with bypass stream 62. Bypass stream 62 provides various advantages. As discussed above, bypassing distillation columns 26, 32, 38 reduces the overall system energy load by reducing the flow rate of material through the distillation columns, thereby reducing operating costs. Additionally, applicants have surprisingly and unexpectedly discovered that incorporating bypass stream 62 reduces operating costs while still maintaining acceptable product purity despite bypassing distillation columns 26, 32, and 38. For example, when operating with one or both of bypass streams 30 and 62, a product purity of at least 98.5%, or at least 99%, or at least 99.5% can be obtained in xylene stream 52.

[0069] In some embodiments, the mixed aromatic feed stream 14 may be produced from biomass-derived oxygenated hydrocarbons. An exemplary system 100 for producing the mixed aromatic feed stream 14 from biomass-derived oxygenated hydrocarbons is shown in Figure 2. In some embodiments, the system 100 includes a hydrodeoxygenation (HDO) reactor 102 in fluid communication with a feed solution source 104 and a hydrogen source 106.

[0070] In some embodiments, the feedstock solution source 104 includes a feedstock solution that includes water-soluble sugars derived from biomass. As used herein, the term "biomass" refers to, but is not limited to, organic matter produced by plants (e.g., leaves, roots, seeds, and stems), as well as microbial and animal metabolic waste. Common biomass sources include (1) agricultural wastes such as corn stalks, straw, seed husks, sugar cane meal, bagasse, nut shells, and manure from cattle, poultry, and hogs, (2) woody materials such as wood or bark, sawdust, timber chips, and mill scraps, (3) municipal wastes such as wastepaper and yard clippings, and (4) energy crops such as poplar, willow, switchgrass, alfalfa, prairie bluestem, corn, soybeans, and the like.

[0071] Various sugar processing methods are well known in the art and are commercially practiced on a large scale to produce sugar liquor from biomass. For example, in processes using sugar cane, the sugar cane is typically washed, crushed or spread, and clarified with lime to isolate and obtain an aqueous biomass-derived intermediate feed stream rich in sucrose, fructose, and glucose. In processes using sugar beet, the sugar beet is similarly washed, sliced, extracted, and clarified to isolate and obtain an aqueous biomass-derived intermediate feed stream rich in sucrose, fructose, and glucose. For processes involving grain, the grain is washed and then processed to obtain wet-milled starch (corn) or dry-milled / floured starch (corn, wheat, barley, sorghum grain). The isolated sugar liquor may be adjusted to obtain a desired sugar concentration, for example, concentrated or diluted with water to obtain a feed solution 104. Generally, suitable concentrations are in the range of about 5% to about 70%, with a range of about 40% to 70% being more common in industrial applications.

[0072] For raw feedstocks of lignocellulosic biomass, the biomass feedstock may be degraded from complex biopolymers to sugars and soluble oxygenates to form the feedstock solution 104. In one embodiment, raw lignocellulosic feedstock (e.g., corn stover) undergoes decomposition by dilute acid thermochemical pretreatment, pH adjustment with bases such as ammonium hydroxide, lime, sodium hydroxide or potassium hydroxide, and enzymatic hydrolysis to form soluble sugars. Optional pre-conversion methods include fractionation of the feedstock at harvest, fractionation by sieving, chemical pretreatment to leach out undesirable components, fermentative pretreatment such as treatment with white rot fungi, mechanical methods such as steam explosion, torrefaction, or pelleting. Alternative means of decomposition include autohydrolysis (hot water only), alkali (e.g., ammonia, sodium hydroxide, potassium hydroxide), oxidation (e.g., hydrogen peroxide, oxygen, air), organosolv (e.g., ethanol, acetic acid, catalyst derived solvents), and thermochemical pretreatment with ionic liquids. The processing step of lignocellulosic biomass may also include additional processing to obtain chopped, shredded, compressed, pulverized or otherwise processed biomass of a size suitable for conversion.

[0073] In some embodiments, feedstock solution 104 may be formed using one or more of the processes described above and may be derived from one or more of the biomass sources described above. The feedstock solution may be made from biomass by any means now known or developed in the future, or may simply be a by-product of other processes.

[0074] In some embodiments, the feedstock solution comprises one or more oxygenated hydrocarbons. The term "oxygenated hydrocarbons" refers to water-soluble hydrocarbons containing three or more carbon atoms and two or more oxygen atoms, such as carbohydrates (e.g., monosaccharides, disaccharides, oligosaccharides, polysaccharides, and starches), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols (e.g., diols, triols, and polyols), and sugar degradation products (e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, and furfural), each of which is referred to herein as C3+ O 2+ As used herein, the term "oxygenated compound" or "oxygenate" refers to a molecule having two or more carbon atoms and one or more oxygen atoms (i.e., C 2+ O 1+ ), and the term "monoxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and one oxygen atom (i.e., C 2+ O 1 ), and the term "dioxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and two oxygen atoms (i.e., C 2+ O 2 ), and the term "polyoxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and three or more oxygen atoms (i.e., C 2+ O 3+ )

[0075] In addition to oxygenated hydrocarbons, the feedstock may also include lignin, one or more extractives, one or more ash components, or one or more organic species (e.g., lignin derivatives). Extractives include terpenoids, stilbenes, flavonoids, phenols, aliphatics, lignans, alkanes, proteinaceous matter, amino acids, and other inorganic products. Ash components include Al, Ba, Ca, Fe, K, Mg, Mn, P, S, Si, Zn, and the like. Other organic species include 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, vanillin, 4-propylsyringol, vitamin E, steroids, long chain hydrocarbons, long chain fatty acids, stilbenoids, and the like.

[0076] In some embodiments, the feed solution 104 is optionally hydrogenated prior to conversion in the hydrodeoxygenation reactor 102. For example, the feed solution may be contacted with a hydrogenation catalyst in a reactor (not shown) at a hydrogenation temperature and pressure to produce a hydrogenation product stream. Various processes are known for hydrogenating carboxylic acids. Hydrogenation catalysts generally include Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, and alloys or combinations thereof, alone or with promoters such as Ag, Au, Cr, Zn, Mn, Mg, Ca, Cr, Sn, Bi, Mo, W, B, P, and alloys or combinations thereof. The hydrogenation catalyst may also include any one of several supports, depending on the desired functionality of the catalyst. Such supports may include carbon, silica, alumina, zirconia, titania, vanadia, ceria, silica-aluminate, zeolites, diatomaceous earth, hydroxyapatite, zinc oxide, magnesium oxide, chromia, and mixtures thereof.

[0077] Generally, the hydrogenation reaction is carried out at a hydrogenation temperature between about 80° C. and 350° C. and at a hydrogenation pressure in the range of about 50 psig to 5000 psig. The hydrogen used in the reaction can be in situ hydrogen produced from other reactions occurring sequentially or in parallel within the reactor, external H 2 , recycled H 2 , or a combination thereof.

[0078] In some embodiments, the feed solution 104 contains a carboxylic acid that can be hydrogenated. The extent to which the carboxylic acid feed stream is hydrogenated can be measured by the amount of molecular hydrogen consumed during hydrogenation, which can range from 0.05 to 2.0 moles of molecular hydrogen consumed by one mole of carboxylic acid groups in the feedstock. Generally, the reaction should be carried out under conditions where the residence time of the carboxylic acid feed over the catalyst is appropriate to produce the desired oxygenates. For example, the residence time can be established at a weight hourly space velocity (WHSV) of between 0.01 and 30, or between 0.05 and 10, or between 0.1 and 5.

[0079] 2, the feed solution 104 is contacted with a deoxygenation catalyst 108 in the presence of hydrogen to produce a deoxygenation product stream 110 comprising a mixture of one or more oxygenates. The deoxygenation product stream 110 has an H:C ratio of 0.5 to less than 2, or between 0.8 and 1.8, or between 1 and 1.6, or between 1.2 and 1.6. eff In some embodiments, the ratio of H:C eff The ratio is at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1, or at least 1.1, or at least 1.2 but less than 1.3, or less than 1.4, or less than 1.5, or less than 1.6, or less than 1.8, or less than 1.9, or less than 2.0.

[0080] As used herein, the term "H:C eff The "carbon to hydrogen ratio" is based on the amounts of carbon, oxygen and hydrogen in the feedstock and is calculated as follows:

[0081]

number

[0082] In some embodiments, the deoxygenated product stream 110 is a C 2 O 3 , which is a compound having one or more carbon atoms and between one and three oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxycarboxylic acids, carboxylic acids, diols, and triols. 1+ O 1~3 In some embodiments, C 1+ O 1~3 The hydrocarbons have 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms. 1+ O 1~3 In addition to hydrocarbons, the deoxygenated product stream 110 may include hydrocarbons that do not have oxygen elements.

[0083] Exemplary alcohols in the deoxygenated product stream 110 include primary, secondary, linear, branched, or cyclic C alcohols, such as, but not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof. 1+Exemplary ketones may include, but are not limited to, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, and isomers thereof. Exemplary aldehydes may include, but are not limited to, hydroxyaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof. Exemplary carboxylic acids may include, but are not limited to, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, 2-hydroxybutanoic acid, and lactic acid, and their isomers and derivatives, including hydroxylated derivatives. Exemplary diols may include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof. Exemplary triols can include, without limitation, glycerol, 1,1,1 tris(hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane, hexanetriol, and isomers thereof.Exemplary furans and furfurals include, without limitation, furan, tetrahydrofuran, dihydrofuran, 2-furanmethanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methylfuran, 2-ethyl-tetrahydrofuran, 2-ethylfuran, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethylfuran, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furonic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.

[0084] In some embodiments, the deoxygenation catalyst 108 comprises a heterogeneous catalyst having one or more materials capable of catalyzing the reaction of hydrogen with the feed solution 104 to remove one or more of the oxygen atoms from the feed solution to produce one or more oxygenates. In some embodiments, the deoxygenation catalyst 108 comprises one or more metals attached to a support, which may include, but are not limited to, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof. The deoxygenation catalyst may include these elements alone or in combination with Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof. In one embodiment, the deoxygenation catalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W, or Mo. In yet another embodiment, the deoxygenation catalyst comprises Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, or Ru. In another embodiment, the catalyst comprises Fe, Re, and at least Cu or one Group VIIIB transition metal. The support can be any one of the supports further described below, including nitrides, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, and mixtures thereof.

[0085] The deoxygenation temperature may range from 80° C. to 300° C. In some embodiments, the reaction temperature is between about 120° C. to 600° C., or between about 200° C. to 280° C., or between about 220° C. to 260° C. The deoxygenation pressure may range from 72 psig to 1300 psig. In some embodiments, the deoxygenation pressure ranges between 72 psig to 1200 psig, or 145 psig to 1200 psig, or 200 psig to 725 psig, or 365 psig to 700 psig, or 600 psig to 650 psig.

[0086] In some embodiments, the WHSV of the deoxygenation reaction ranges from 0.1 grams of oxygenated hydrocarbon per gram of catalyst per hour (g / g-hr) to 40 g / g-hr. In some embodiments, the WHSV is at least 0.25, at least 0.5, at least 0.75, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, at least 2.7, at least 2.8, at least 2.9, at least 3.0, at least 3.1, at least 3.2, at least 3.3, at least 3.4, at least 3.5, at least 3.6, at least 3.7, at least 3.8, at least 3.9, at least 4.0, at least 4.1, at least 4.2, at least 4.3, at least 4.4, at least 4.5, at least 4.6, at least 4.7, at least 4.8, at least 4.9, at least 5.0, at least 5.1, at least 5.2, at least 5.3, at least 5.4, at least 5.5, at least 5.6, at least 5.7, at least 5.8, at least 5.9, at least 6.0, at least 6.1, at least 6.2, at least 6.3, at least 6.4, at least 6.5, at least 6.6, at least 6.7, at least 6.8, at least 6.9, at least 7.0, at at least 3.2, at least 3.3, at least 3.4, at least 3.5, at least 3.6, at least 3.7, at least 3.8, at least 3.9, at least 4.0, at least 4.1, at least 4.2, at least 4.3, at least 4.4, at least 4.5, at least 4.6, at least 4.7, at least 4.8, at least 4.9, at least 5.0 to less than 6, less than 7, less than 8, less than 9, less than 10, less than 11, less than 12, less than 13, less than 14, less than 15, less than 20, less than 25, less than 30, less than 35, or less than 40 g / g hr.

[0087] In some embodiments, the amount of hydrogen fed to the deoxygenation reactor 102 is between 0 and 2400%, between 5 and 2400%, between 10 and 2400%, between 15 and 2400%, between 20 and 2400%, between 25 and 2400%, between 30 and 2400%, between 35 and 2400%, between 40 and 2400%, between 45 ... 0%, 50~2400%, 55~2400%, 60~2400%, 65~2400%, 70~2400%, 75~2400%, 80~2400%, 85~2400%, 90~2400%, 95~2400%, 98~2400%, 100~2400%, 200~2400%, 300~2400%, 400~240 0%, 500-2400%, 600-2400%, 700-2400%, 800-2400%, 900-2400%, 1000-2400%, 1100-2400%, or 1150-2400%, or 1200-2400%, or 1300-2400%, or 1400-2400%, or 1500-2400%, or 1600-2400%, or 1700-2400%, or 1800-2400%, or 1900-2400%, or 2000-2400%, or 2100-2400%, or 2200-2400%, or 2300-2400%, inclusive of all intervals therebetween. The hydrogen can be external or recycled. 2 " refers to hydrogen that does not originate from the feed solution but is added to the reactor system from an external source. The term "recycled H 2 " refers to unconsumed hydrogen that is collected and then recycled back into the reactor system for further use.

[0088] In some embodiments, the product stream 110 passes through a three-phase separator 111 to separate the product stream 110 into a non-condensable gas stream 112, an organic product stream 114, and an aqueous product stream 116. The non-condensable gas stream 112 may consist of hydrogen, carbon dioxide, methane, ethane, and propane. The non-condensable gases may be removed and combusted to create process heat (i.e., heat to drive the reaction in the deoxygenation reactor) or sent to a separation system where hydrogen may be recovered for recycling back into the hydrogen stream 106. The aqueous product stream 116 containing the partially deoxygenated hydrocarbons may be recycled back to the inlet of the deoxygenation reactor 102. An aqueous purge stream 118 containing some monooxygenates (e.g., alcohols) may be used to prevent the accumulation of water in the reactor system. The aqueous purge stream 118 may be combined with the organic product stream 114 or may be discarded from the process.

[0089] In some embodiments, the organic product stream 114 containing oxygenates is passed through a condensation reactor 120 containing a condensation catalyst 122. The oxygenates are converted to C by a condensation reaction catalyzed by the condensation catalyst 122. 4+The condensation reaction is converted to a condensation product stream 124 containing the compounds. Without being limited to any particular theory, the condensation reaction is generally believed to consist of a series of steps including (a) dehydration of oxygenates to alkenes, (b) oligomerization of alkenes, (c) cracking reactions, (d) cyclization of larger alkenes to form aromatics, (e) alkane isomerization, (f) hydrogen transfer reactions to form alkanes. The reaction may also consist of a series of steps including (1) aldol condensation to form β-hydroxyketones or β-hydroxyaldehydes, (2) dehydration of β-hydroxyketones or β-hydroxyaldehydes to form conjugated enones, (3) hydrogenation of conjugated enones to form ketones or aldehydes that may participate in further condensation reactions or conversion to alcohols or hydrocarbons, and (4) hydrogenation of carbonyls to alcohols or vice versa. Other condensation reactions may occur in parallel, including aldol condensations, Prins reactions, ketonization of acids, and Diels-Alder condensations.

[0090] Condensation catalyst 122 is generally a catalyst capable of forming a longer chain compound by linking two oxygen-containing species or other functionalized compounds (e.g., olefins) with a new carbon-carbon bond and converting the resulting compound to a hydrocarbon, alcohol, or ketone. Condensation catalysts may include, but are not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof. Condensation catalysts may include the above alone or in combination with modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The condensation catalyst may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof to provide metal functionality.

[0091] In certain embodiments, the condensation catalyst may include, but is not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof. The condensation catalyst may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof to provide metal functionality.

[0092] The condensation catalyst 122 may be free-standing (i.e., the catalyst does not require another material to act as a carrier) or may require a separate carrier suitable for suspending the catalyst in the reactant stream. In certain embodiments, the carrier is selected from alumina, silica, or zirconia. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system may include a binder to aid in forming the catalyst into the desired catalyst shape. Applicable forming processes include extrusion, pelleting, oil dripping, or other known processes. Zinc oxide, alumina, and peptizer may also be mixed together and extruded to produce a formed material. After drying, the material is calcined at a temperature appropriate for the formation of the catalytically active phase, which typically requires temperatures in excess of 350° C. Other catalyst supports may include those described in more detail below.

[0093] The condensation catalyst may include one or more zeolite structures, including silica-alumina cage-like structures. Zeolites are crystalline microporous materials with well-defined pore structures. Zeolites contain active sites, usually acid sites, that can be produced within the zeolite framework. The strength and concentration of the active sites can be tailored to a particular application. Examples of zeolites suitable for condensing secondary alcohols and alkanes may include aluminosilicates, optionally modified with cations such as Ga, In, Zn, Mo, and mixtures of such cations, as described, for example, in U.S. Pat. No. 3,702,886, which is incorporated herein by reference. As recognized in the art, the structure of a particular zeolite or zeolites may be altered to provide different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain different amounts of aromatic and cyclic hydrocarbons.

[0094] Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5 and its conventional preparation are described in U.S. Pat. No. 3,702,886, Re. 29,948 (high silica ZSM-5), U.S. Pat. No. 4,100,262 and U.S. Pat. No. 4,139,600, all of which are incorporated herein by reference. Zeolite ZSM-11 and its conventional preparation are described in U.S. Pat. No. 3,709,979, also incorporated herein by reference. Zeolite ZSM-12 and its conventional preparation are described in U.S. Pat. No. 3,832,449, also incorporated herein by reference. Zeolite ZSM-23 and its conventional preparation are described in U.S. Pat. No. 4,076,842, also incorporated herein by reference. Zeolite ZSM-35 and its conventional preparation are described in U.S. Patent No. 4,016,245, which is incorporated herein by reference. Another preparation of ZSM-35 is described in U.S. Patent No. 4,107,195, the disclosure of which is incorporated herein by reference. ZSM-48 and its conventional preparation are taught by U.S. Patent No. 4,375,573, which is incorporated herein by reference. Other examples of zeolite catalysts are described in U.S. Patent Nos. 5,019,663 and 7,022,888, which are also incorporated herein by reference. An exemplary condensation catalyst is ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Re, Ni, Sn, or a combination thereof.

[0095] As described in U.S. Pat. No. 7,022,888, the condensation catalyst may be a bifunctional pentasil zeolite catalyst containing at least one metal element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolite may have strong acid sites and may be used with reactant streams containing oxygenated hydrocarbons at temperatures below 580° C. The bifunctional pentasil zeolite may have a ZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of multiple five-membered oxygen rings (i.e., pentasil rings). In one embodiment, the zeolite has a ZSM-5 type structure.

[0096] Alternatively, solid acid catalysts such as alumina modified with phosphate, chloride, silica, and other acidic oxides can be used in the process. Also, sulfated zirconia, phosphated zirconia, titania zirconia, or tungstated zirconia can provide the necessary acidity. Re and Pt / Re catalysts also convert oxygenates to C. 5+ Hydrocarbons and / or C 5+ It is useful for promoting condensation to monooxygenates. Re is sufficiently acidic to promote acid-catalyzed condensation. In certain embodiments, acidity can also be added to the activated carbon by the addition of sulfates or phosphates.

[0097] The specific C generated 4+ The compounds will depend on a variety of factors including, but not limited to, the type of oxygenated compound in the reactant stream, the condensation temperature, the condensation pressure, the reactivity of the catalyst, and the flow rate of the reactant stream since this affects the space velocity, GHSV, LHSV, and WHSV. In certain embodiments, the reactant stream is contacted with the condensation catalyst at a WHSV appropriate to produce the desired hydrocarbon products. In one embodiment, the WHSV is at least 0.1 grams of volatility (C) in the reactant stream per gram of catalyst per hour. 2+ O 1~3In another embodiment, the WHSV is between 0.1 and 10.0 g / g hr, including WHSVs of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g / g hr and increments therebetween.

[0098] In certain embodiments, the condensation reaction is carried out at a temperature and pressure where the thermodynamics of the proposed reaction are favorable. 2+ O 1~3 For oxygenates, the reaction may be carried out at a temperature where the vapor pressure of the volatile oxygenate is at least 0.1 atm (preferably even higher). The condensation temperature varies depending on the specific composition of the oxygenated compound. The condensation temperature is generally greater than 80°C, or 100°C, or 125°C, or 150°C, or 175°C, or 200°C, or 225°C, or 250°C, and less than 500°C, or 450°C, or 425°C, or 375°C, or 325°C, or 275°C. For example, the condensation temperature may be between 80°C and 500°C, or between 125°C and 450°C, or between 250°C and 425°C. The condensation pressure is typically greater than 0 psig, or 10 psig, or 100 psig, or 200 psig, and less than 2000 psig, or 1800 psig, or 1600 psig, or 1500 psig, or 1400 psig, or 1300 psig, or 1200 psig, or 1100 psig, or 1000 psig, or 900 psig, or 700 psig. For example, the condensation pressure can be greater than 0.1 atm, or between 0 and 1500 psig, or between 0 and 1200 psig.

[0099] The condensation reaction of the present disclosure is 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ Cycloalkenes, aryls, fused aryls, polycyclic compounds, C 4+ Alcohol, C. 4+ Ketone, C 4+The use of the above mixtures of oxygenates can be used in the production of furans and mixtures thereof, advantageously with a high proportion of aryls and a low proportion of alkanes. In particular, the use of the above mixtures of oxygenates can provide an aryl yield of 50% or more of carbon fraction (CF) of the aqueous feed carbon and an aryl yield of 20% or less of CF of the aqueous feed carbon. 4+ In certain embodiments, the aryl yield can be 55 wt% or more of the aqueous feed carbon, 60% or more of the CF, or 65% or more of the CF. 4+ The alkane yield is 15% CF or less, 10% CF or less, or 5% CF or less of the aqueous feed carbon. In certain other embodiments, the product is C 1~3 It may further comprise alkanes, and the total C 1+ The alkane yield is less than or equal to 20% CF, less than or equal to 15% CF, less than or equal to 10% CF, or less than or equal to 5% CF of the aqueous feed carbon.

[0100] As used herein, the terms "carbon fraction" and "CF", which may be used interchangeably, may be calculated by dividing the mass of carbon of a component (e.g., the mass of carbon in an aryl) by the mass of carbon in the feedstock and multiplying by 100. Alternatively, %CF may be reported as feedstock carbon percentage, carbon percentage, or other similar terminology.

[0101] In certain embodiments, the aryl yield is 55% or more CF of the aqueous feed carbon, 4+ The alkane yield is 15% or less of the CF of the aqueous feed carbon. In another embodiment, the aryl yield is 60% or more of the CF of the aqueous feed carbon, and 4+ The alkane yield is 10% or less of the CF of the aqueous feed carbon. In a further embodiment, the aryl yield is 55% or more of the CF of the aqueous feed carbon, and 1+ The alkane yield is 15% or less of the CF of the aqueous feed carbon. In yet another embodiment, the aryl yield is 60% or more of the CF of the aqueous feed carbon, and 1+ The alkane yield is less than 10% CF of the aqueous feed carbon.

[0102] C 4+Alkanes and C 4+ Alkenes have 4 to 30 carbon atoms (C 4+ Alkanes and C 4+ alkene), which may be branched or straight chain alkane or alkene. 4+ Alkanes and C 4+ The alkenes are C 4~9 , C 7~14 , C 12~24 It may also contain fractions of alkanes and alkenes, 4~9 The fraction is for gasoline, and C 7~16 The fraction is for jet fuel, C 11~24 The fractions are used for diesel fuel and other industrial uses such as chemicals. 4+ Alkanes and C 4+ Examples of alkenes include, but are not limited to, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene. Examples of the aryl groups include aryl, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.

[0103] C 5+ Cycloalkanes and C 5+ Cycloalkenes have 5 to 30 carbon atoms and can be unsubstituted, monosubstituted or polysubstituted. In the case of monosubstituted and polysubstituted compounds, the substituted groups are branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, linear C 2+For example, at least one of the substituted groups may include a branched C 3~12 Alkyl, linear C 1~12 Alkyl, branched C 3~12 Alkylene, linear C 1~12 Alkylene, linear C 2~12 As a further example, at least one of the substituted groups may be a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C 1~4 Alkylene, linear C 1~4 Alkylene, linear C 2~4 alkylene, phenyl or a combination thereof. 5+ Cycloalkanes and C 5+ Examples of cycloalkenes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, propyl-cyclohexane, butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane, pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, and isomers thereof.

[0104] Aryl generally consists of aromatic hydrocarbons in unsubstituted (phenyl), mono- or poly-substituted form. In the case of mono- and poly-substituted compounds, the substituted groups are branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, linear C 2+ For example, at least one of the substituted groups may include a branched C 3+ Alkyl, linear C 1~12 Alkyl, branched C 3~12 Alkylene, linear C 2~12 As a further example, at least one of the substituted groups may be a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C3~4 Alkylene, linear C 2~4 Examples of various aryls include, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, paraxylene, metaxylene, orthoxylene, C 9+ Aromatics include butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, and their isomers.

[0105] Fused aryls generally consist of bicyclic and polycyclic aromatic hydrocarbons in unsubstituted, monosubstituted or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups are branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, linear C 2+ For example, at least one of the substituted groups may include a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4 Alkylene, linear C 2~4 alkylene, phenyl or combinations thereof. Examples of various fused aryls include, but are not limited to, naphthalene, anthracene, and their isomers.

[0106] Polycyclic compounds generally consist of bicyclic and polycyclic hydrocarbons in unsubstituted, monosubstituted, or polysubstituted form. Polycyclic compounds generally contain fused aryls, but as used herein, polycyclic compounds generally have at least one saturated or partially saturated ring. In the case of monosubstituted and polysubstituted compounds, the substituted groups are branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, linear C 2+ For example, at least one of the substituted groups may include a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4Alkylene, linear C 2~4 alkylene, phenyl or combinations thereof. Examples of various fused aryls include, but are not limited to, tetrahydronaphthalene and decahydronaphthalene, and their isomers.

[0107] C 4+ The alcohols may also be cyclic, branched or straight chain and have from 4 to 30 carbon atoms. 4+ Alcohols have the formula R 1 -OH, R 1 is branch C 4+ Alkyl, linear C 4+ Alkyl, branched C 4+ Alkylene, linear C 4+ Alkylene, substituted C 5+ Cycloalkane, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloalkene, unsubstituted C 5+ A preferred C is a member selected from cycloalkene, aryl, phenyl, or a combination thereof. 4+ Examples of alcohols include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol, nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol, tetraeicosanol, or isomers thereof.

[0108] C 4+ Ketones may also be cyclic, branched or straight chain and have from 4 to 30 carbon atoms. 4+ Ketones have the formula

[0109] [ka] (In the formula, R 3 and R 4 are independently, branch C 3+ Alkyl, linear C 1+Alkyl, branched C 3+ Alkylene, linear C 2+ Alkylene, substituted C 5+ Cycloalkane, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloalkene, unsubstituted C 5+ The compound may be a compound according to the present invention, wherein the C is a member selected from cycloalkene, aryl, phenyl, or a combination thereof. 4+ Examples of ketones include, but are not limited to, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptyldecanone, octyldecanone, nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone, tetraeicosanone, or isomers thereof.

[0110] In some embodiments, C 4+ The condensation product stream 124 containing the compounds may be fractionated into various product streams such as gasoline, jet fuel (kerosene), diesel fuel, and aromatics. The condensation product stream 124 may pass through a three-phase separator 126 to separate the condensation product stream 124 into an acid condensation gas stream 128, an organic stream 130, and an aqueous stream 132. The organic stream 130 and the aqueous stream 132 are separated by density differences, while the acid condensation gas stream 128 containing the non-condensable gases is recycled to the acid condensation reactor 120 to extract additional C 4+ In some embodiments, a gas transport device, such as a blower or compressor, is configured in the acid condensation gas stream 128 to control the recycle pressure. In some embodiments, an optional purge stream 134 may also be used to manage the pressure of the recycle loop in the acid condensation gas stream 128. In some embodiments, the aqueous stream 132 is discarded from the process or is further processed in a downstream process unit.

[0111] In some embodiments, the organic stream 130 is fractionated in a distillation column 136 to separate the organic stream 130 into a light product stream 138 and a heavy product stream 140. In some embodiments, the distillation unit 136 is configured to remove azeotropic contaminants of benzene, toluene, or combinations thereof. As described, removing the azeotropic contaminants of benzene and / or toluene prior to treatment over the transalkylation and / or dealkylation catalyst 22 provides surprising and unexpected benefits, such as higher purity and yields of the desired aromatic products.

[0112] In some embodiments, distillation column 136 is configured to produce a heavy stream 140 that is free or substantially free of azeotropic non-aromatic contaminants of benzene. Distillation column 136 divides organic stream 130 with light product stream 138 into a C 20 , 25 , 30 , 35 , 40 , 45 , 50 , 60 , 70 , 80 , 90 , 100 , 110 , 120 , 130 , 140 , 150 , 160 , 170 , 180 , 190 , 200 , 210 , 220 , 230 , 240 , 250 , 360 , 380 , 390 , 400 , 500 , 650 , 700 , 850 , 900 , 1000 , 1100 , 1200 , 1300 , 1400 , 1500 , 1600 , 1700 , 1800 , 1900 , 2000 , 2100 , 2200 , 2300 , 2400 , 2500 , 3900 , 3900 , 4000 , 4000 , 5000 , 6500 , 7000 , 8500 , 9000 , 10000 , 10000 , 15000 , 16000 , 17000 , 18000 , 19000 , 6- The distillation column 136 divides the organic stream 130 into a C 7+ It may be further fractionated into a heavy product stream 140 containing the compounds.

[0113] In some embodiments, distillation column 136 is configured to produce a heavy stream 140 that is free or substantially free of toluene azeotropic non-aromatic contaminants. Distillation column 136 divides organic stream 130 with light product stream 138 into a C 20 toluene stream that contains toluene, toluene azeotropic non-aromatic contaminants, and lighter products. 7- or C 8- The toluene azeotropic non-aromatic contaminants may be removed by fractionating the organic stream 130 into a C 8+ or C 9+ It may be further fractionated into a heavy product stream 140 containing the compounds.

[0114] In some embodiments, the heavy product stream 140 is 7+ compound, C 8+ Compound, or C 9The heavy product stream 140, which contains C+ compounds, is fractionated in a distillation column 142 to separate the heavy product stream 140 into the mixed aromatics feed stream 16 and the heavy product feed stream 144. In some embodiments, the distillation column 142 divides the heavy product stream 140 into 7+ A mixed aromatic feed stream containing compounds 16 and C 11+ In some embodiments, the mixed aromatics feed stream 16 is configured to be fractionated into a heavy product feed stream 144 containing C 7+ Compound, or C 8+ Compound, or C 9+ Compound, or C 7~10 Compound, or C 8~10 Compound, or C 9~10 The mixed aromatic feed stream 16 may be utilized as an inlet feed for the process described in FIG.

[0115] In some embodiments, the heavy stream 144 may be kerosene (e.g., C for jet fuel applications). 11~14 ), diesel fuel applications (e.g., C 12~24 ), and lubricating or fuel oils (e.g., C 25+ ), or alternatively, the heavy stream 144 may be cracked to produce additional fractions for use in the gasoline, kerosene, aromatics, and / or diesel fractions.

[0116] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All definitions, as defined and used herein, should be understood to supersede dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0117] The present invention has been described in terms of one or more preferred embodiments, and it should be understood that aside from what has been expressly stated, many equivalents, alternatives, variations, and modifications are possible and are within the scope of the invention. EXAMPLES

[0118] The following examples will enable those skilled in the art to more readily understand the principles of the present disclosure. The following examples are offered by way of illustration and are not intended to be limiting in any way.

[0119] Example 1: Production of high purity aromatics from mixed aromatic feedstocks C 7 ~C 10 A mixed aromatic feed stream (MAF) containing aromatics and lacking substantial benzene azeotropic non-aromatic contaminants was treated over a nickel-containing ZSM-5 catalyst at 375°C, 100 psig, with a hydrogen to hydrocarbon ratio of approximately 4, and a weight hourly space velocity of 1. The feed contained less than 0.1% benzene, but the product contained 7.04 wt% benzene based on the total weight of the product stream. The potential purity of benzene is estimated by dividing the amount of benzene by the sum of the benzene azeotropes (including benzene) and multiplying by 100. The benzene azeotropic range is defined herein as all components (including benzene) having retention times including and above methylcyclopentane (normal boiling point 71.8°C) and below and including 1,3 dimethylcyclopentane, cis (boiling point 91°C) as measured by gas chromatography (GC). The estimated benzene purity in the product was 99.8 wt%. The feed did not contain substantial benzene, so the purity of the benzene in the feed could not be estimated.

[0120] Comparative Example 1: Benzene production from mixed aromatic feedstock containing azeotropic impurities C 4 ~C 10 MAF containing aromatics and containing substantial benzene azeotropic non-aromatic contaminants was processed under the same conditions as in Example 1. The estimated benzene purity in the product was 98%. This is substantially higher than the estimated benzene purity of 31% in the feedstock, however, approximately 10× the benzene azeotropic contaminants were still present in the product of Comparative Example 1 compared to the product of Example 1, illustrating the advantage of eliminating the azeotropic contaminants in the feedstock.

[0121] Example 2: Production of high purity aromatics from a mixed aromatic feed stream C 9 ~C 10 MAF containing aromatics and lacking substantial benzene or toluene azeotropic non-aromatic contaminants was processed under the same conditions as in Example 1, except that the pressure was increased from 200 to 250 psig and a transalkylation catalyst was used. The estimated benzene purity in the product was 99.87%. Using a method similar to that defined for determining benzene purity in Example 1, the azeotropic range of toluene is defined here as all components (including toluene) having retention times that include and exceed 1,3 dimethylcyclopentane, cis (boiling point 91° C.), and include and fall below trans 1,2-dimethyl-cyclohexane (boiling point 123° C.), as measured by gas chromatography (GC). No detectable components other than toluene were found within this boiling range using this analysis, indicating an estimated toluene purity of nearly 100%.

[0122] Comparative Example 2: Aromatics Production from a Mixed Aromatic Feed Stream Containing Azeotropic Contaminants The raw hydrocarbon product of the production process was subjected to a distillation step to remove heavy components, generally containing 11 or more carbon atoms. The resulting C 4 ~C 10 MAF is not suitable for use with this invention.

[0123] Example 3: Production of high purity aromatics from a mixed aromatic feed stream The raw hydrocarbon product of the production process was subjected to two distillation steps. In the first step, the raw hydrocarbon was distilled to produce an overhead product containing mainly components containing 6 or less carbon atoms, including benzene. The overhead product was recycled to the aromatization section. Surprisingly, by recycling the light products to the reaction section, the total yield of aromatics was increased. The dehexanedized aromatics was then distilled to remove the heavy components, generally containing 11 or more carbon atoms. The resulting C 7 ~C 10 MAF is suitable for use with the present invention to produce pure benzene.

[0124] Example 4: Production of MAF from an aqueous hydrocarbon stream The aqueous mixture of oxygenates was treated over a nickel-containing ZSM-5 condensation catalyst at 375° C., 150 psig, and a weight hourly space velocity of 0.5. The resulting condensation product was fractionated into a light stream and a heavy stream, with the light stream being recycled back to the condensation catalyst. 3 ~C 6 The heavy stream was fractionated to produce mainly C 7 ~C 10 Aromatic MAF was produced. Representative MAF products are shown in Table 1.

[0125] [Table 1]

[0126] Example 5: Production of mixed xylenes from mixed aromatic feedstock The MAF from Example 4, containing substantial xylene azeotropic non-aromatic contaminants, was treated with a transalkylation catalyst at 344° C., 430 psig, with a hydrogen to hydrocarbon ratio of approximately 3.8, and a weight hourly space velocity of 3.3. The products were benzene-rich, toluene-rich, xylene-rich, C 9 Aromatic rich, and C 10+ The aromatics-rich stream was fractionated into toluene and C 9 The aromatic stream was recycled back to the transalkylation catalyst to maximize xylene production. The xylene-rich stream was sent to an isomer recovery process unit to produce the para-xylene isomer stream and the unrecovered C 8 A raffinate stream containing the compounds was produced. The raffinate stream was treated with an isomerization catalyst at 340° C., 150 psig, with a hydrogen to hydrocarbon ratio of approximately 1.5, and a weight hourly space velocity of 3.3. An isomerization product stream was produced, which was then combined with the xylene stream and sent back to the isomer recovery process unit. This continuous operation resulted in a production rate of para-xylene of >99.7% from the isomer recovery process unit of 457 kilograms per month.

[0127] [Table 2]

[0128] Example 6: Benzene production from mixed aromatic feedstocks The benzene-rich stream produced in the same manner as in Example 4 was further processed over a transalkylation catalyst at 375° C., 40 psig, with a hydrogen to hydrocarbon ratio of approximately 0.4, and a weight hourly space velocity of 1. The product stream was fractionated to recover a purified benzene stream of >99.9% purity having the product composition shown in Table 3.

[0129] [Table 3]

[0130] Example 7: Toluene production from mixed aromatic feedstock A toluene-rich stream was produced in the same manner as in Example 4, using more optimized fractionation conditions to achieve a toluene purity of 99.8%. Rather than being recycled back to the transalkylation to maximize xylene production, the toluene-rich stream was recovered as a product having the composition as shown in Table 4.

[0131] [Table 4]

[0132] Example 8: Production of high purity para-xylene from mixed aromatic feedstock C 5 ~C 10 The MAF, which contains aromatics and substantial xylene azeotropic non-aromatic contaminants, is fractionated to produce C 5 ~C 6 The compound was removed. 7 ~C 10The resulting MAF containing aromatics was treated over a transalkylation catalyst at 360° C., 430 psig, with a hydrogen to hydrocarbon ratio of approximately 3.6, and a weight hourly space velocity of 2.7. Para-xylene production was increased by diverting a portion of the isomerization product stream for fractionation and combining it with the C8 stream before entering the isomer recovery process unit. 150 grams per minute was diverted and 20 grams per minute underwent fractionation. The resulting para-xylene production increased from 457 kilograms per month to 830 kilograms per month. A representative para-xylene product composition is shown in Table 5, and results from the different processes are shown in Table 6.

[0133] [Table 5]

[0134] [Table 6]

[0135] Although the present invention has been described in some detail with reference to certain specific embodiments, those skilled in the art will appreciate that the present invention may be used in alternative embodiments to those described, which are presented for purposes of illustration and not limitation, and therefore the scope of the appended claims should not be limited to the description of the embodiments contained herein.

[0136] For completeness, various aspects of the invention are set forth in the following numbered clauses.

[0137] Clause 1. A process for separating aromatic compounds from a mixed aromatic feed stream, comprising: (I C 7~10 contacting a mixed aromatic feed stream comprising aromatic hydrocarbons with an aromatic processing catalyst to produce a product stream; the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; The mixed aromatic feed stream comprises greater than 1 wt. % non-aromatic components based on the total weight of the mixed aromatic feed stream, and the mixed aromatic feed stream comprises 12+ being substantially free of aromatics; (ii) fractionating the product stream to separate aromatic compounds from the product stream; The method includes:

[0138] Clause 2. The method of clause 1, wherein the mixed aromatic feed stream comprises 0.1 wt% to 45 wt% olefins, based on a total weight of the mixed aromatic feed stream.

[0139] Clause 3. The method of clause 1, wherein the mixed aromatic feed stream comprises 0.1 wt% to 25 wt% naphthenes, based on a total weight of the mixed aromatic feed stream.

[0140] Clause 4. The method of clause 1, wherein the mixed aromatic feed stream comprises 0.1 wt% to 40 wt% naphtheno-olefins, based on a total weight of the mixed aromatic feed stream.

[0141] Clause 5. The mixed aromatic feed stream comprises at least 1 mg Br 2 / mixed aromatic feedstock g~100mg Br 2 2. The method of claim 1, wherein the mixed aromatic feedstock has a bromine number of less than 1 / g.

[0142] Clause 6. The method of clause 1, wherein the mixed aromatic feed stream comprises phenol in an amount between 10 ppm and 10 wt%, based on the total weight of the mixed aromatic feed stream.

[0143] Clause 7. The method of clause 1, wherein the mixed aromatic feedstock comprises oxygenates in an amount between 10 ppm and 10 wt% ppm, based on the total weight of the mixed aromatic feedstream.

[0144] Article 8.C 7~102. The method of claim 1, wherein the aromatic hydrocarbon comprises benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, naphthalene, or a combination thereof.

[0145] Clause 9. Step (ii) fractionates the product stream to produce C 8 further comprising the step of separating the stream from the product stream of step (i); The method is (iii) C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 generating a raffinate stream comprising the compounds; (iv) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, the isomerized product stream comprising at least one xylene isomer, and at least a portion of the isomerized product stream is combined with the product stream produced from the aromatics processing catalyst in step (i); 2. The method of claim 1, further comprising:

[0146] Clause 10. The mixed aromatic feed stream is 9~10 2. The method of claim 1, comprising aromatic rings.

[0147] Clause 11. At least a portion of the isomerization product stream is recycled to an isomer recovery process unit C 8 10. The method of claim 9, in combination with a stream.

[0148] Clause 12. The method of clause 1, wherein the mixed aromatic feed stream is free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0149] Clause 13. Step (ii) is 8 The aromatics-containing product stream is fractionated to produce C 7- Stream to C 8+13. The method of claim 1, further comprising the step of feeding the first distillation column to separate the first distillation column from the stream.

[0150] Article 14.C 7- The stream is C 7- Stream to C 6- Stream and C 7 14. The process of claim 13, wherein the mixture is fed to a second distillation column which fractionates the mixture into a stream.

[0151] Article 15.C 7 15. The method of claim 14, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

[0152] Article 16.C 8+ At least a portion of the stream is recycled to an isomer recovery process unit. 8 10. The method according to claim 9, wherein the aromatic is combined with

[0153] Clause 17. Step (ii) is 8+ Stream, C 8+ Stream to C 8 Stream and C 9+ a third distillation column which fractionates the mixture into a stream C 8 Stream is C 8 14. The method of claim 13, further comprising the step of:

[0154] Article 18.C 9+ The stream is C 9+ Stream to C 9~10 Stream and C 11+ The resulting mixture is fed to a fourth distillation column which fractionates the mixture into streams C 9~10 18. The method of claim 17, wherein the stream is recycled and combined with the mixed aromatic feed stream.

[0155] Clause 19. Step (ii) fractionates the product stream to produce C 7 Stream, C 8 Stream, and C 9~10A step of separating the streams, comprising: 8 The stream is fed to an isomer recovery process unit and 7 The stream is recycled and combined with the mixed aromatic feed stream and 9~10 10. The method of claim 9, further comprising the step of: recycling and combining the stream with the mixed aromatic feed stream.

[0156] Clause 20. Step (ii) fractionates the product stream to produce C 7 Stream, C 8 Stream, and C 9+ A step of separating the streams, comprising: 8 The stream is fed to an isomer recovery process unit and 7 The stream is recycled and combined with the mixed aromatic feed stream and 9+ 10. The method of claim 9, further comprising the step of recovering the stream as a product.

[0157] Clause 21. The method of clause 9, wherein the isomer recovery process unit comprises an adsorption unit.

[0158] Clause 22. The method of clause 9, wherein the isomer recovery process unit comprises a crystallization unit.

[0159] Clause 23. The method of clause 1, wherein the aromatic processing catalyst comprises an acid catalyst.

[0160] Clause 24. The method of clause 23, wherein the acid catalyst is selected from aluminosilicates, tungstated aluminosilicates, silica-alumina phosphates, aluminum phosphates, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphates, niobia, sulfated carbon, phosphated carbon, acidic resins, heteropolyacids, tungstated heteropolyacids, inorganic acids, or combinations thereof.

[0161] Clause 25. The method of clause 23, wherein the acid catalyst comprises a metal selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof.

[0162] Clause 26. The method of clause 1, wherein step (i) is carried out at a temperature between 200°C and 600°C.

[0163] Clause 27. The method of clause 1, wherein step (i) is carried out at a pressure between 100 psig and 1500 psig.

[0164] Clause 28. The method of clause 1, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of 0.1 to 10 mass of feedstock / mass of catalyst / hour.

[0165] Clause 29. The method of clause 1, wherein step (i) comprises providing hydrogen in an amount of at least 0.1 moles of hydrogen per mole of the mixed aromatic feedstock.

[0166] Clause 30. The method of clause 1, wherein step (1) comprises providing hydrogen in an amount of at least 1 mole of hydrogen per mole of the mixed aromatic feedstock.

[0167] Clause 31. A process for producing and separating aromatic compounds from a mixed aromatic feed stream, comprising: (i) contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to produce a condensation product of C 4+ generating a condensation product stream comprising the compound C; 4+ The compound is C 4+ Alcohol, C. 4+ Ketone, C 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ comprising a cycloalkene, an aryl, or a fused aryl; (ii) fractionating the condensation product stream to produce a light stream and a heavy stream, the light stream comprising benzene or toluene azeotropic non-aromatic contaminants and the heavy stream being substantially free of benzene or toluene azeotropic non-aromatic contaminants; (iii) recycling the lights stream to the condensation catalyst; (iv) separating the heavy stream into 7+ fractionating the aromatic hydrocarbons into a mixed aromatic feedstock comprising aromatic hydrocarbons; (v) contacting the mixed aromatic feed stream with an aromatic processing catalyst to produce a product stream, the aromatic processing catalyst comprising a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; The method includes:

[0168] Clause 32. Fractionating the product stream to C 8 separating the stream from the product stream; C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 generating a raffinate stream comprising the compound; contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, the isomerized product stream comprising at least one xylene isomer, and at least a portion of the isomerized product stream is combined with a product stream produced from the aromatics processing catalyst. 32. The method of claim 31 further comprising:

[0169] Clause 33. C from step (iv) 7+ Stream to C 7~10 Stream and C 11+ fractionating the mixture into a stream comprising: 7~10 32. The method of claim 31, further comprising the step of contacting the stream with an aromatic processing catalyst.

[0170] Clause 34. The C9+ stream from step (iv) is 9~10 Stream and C 11+ fractionating the mixture into a stream comprising: 9~10 32. The method of claim 31, further comprising the step of contacting the stream with a catalyst.

[0171] Clause 35. At least a portion of the isomerization product stream is recycled to an isomer recovery process unit. 8 33. The method of claim 32, in combination with a stream.

[0172] Clause 36. The method of clause 31, further comprising fractionating the product stream from step (v) to produce a benzene stream, a toluene stream, or a naphthalene stream.

[0173] Clause 37. The product stream is 8+ Stream to C 7- 33. The method of claim 32, further comprising the step of feeding the mixture to a first distillation column for fractionation into streams.

[0174] Article 38.C 7- Stream, C 7- Stream to C 6- Stream and C 7 38. The method of claim 37, further comprising the step of feeding the mixture to a second distillation column for fractionation into streams.

[0175] Article 39.C 7 At least a portion of the stream is recycled and 7+ 39. The method of claim 38, in combination with a stream.

[0176] Article 40.C 8+ At least a portion of the stream is recycled to an isomer recovery process unit. 8 38. The method of claim 37, wherein the aromatic is combined with

[0177] Article 41.C8+ Stream, C 8+ Stream to C 8 Stream and C 9+ a third distillation column which fractionates the mixture into a stream C 8 Stream is C 8 38. The method of claim 37, further comprising the step of: comprising an aromatic ring.

[0178] Article 42.C 9+ The stream is C 9+ Stream to C 9~10 Stream and C 11+ The resulting mixture is fed to a fourth distillation column which fractionates the mixture into streams C 9~10 42. The method of claim 41, wherein the stream is recycled and combined with the mixed aromatic feed stream.

[0179] Clause 43. Fractionating the product stream to C 7 Stream, C 8 Stream, and C 9~10 A step of separating the streams, comprising: 8 The stream is fed to an isomer recovery process unit and 7 The stream is recycled and 7+ Combined with the stream, C 9~10 The stream is recycled and 7+ 33. The method of claim 32, further comprising the step of: combining with the stream.

[0180] Clause 44. The method of clause 32, wherein the isomer recovery process unit comprises an adsorption unit.

[0181] Clause 45. The method of clause 32, wherein the isomer recovery process unit comprises a crystallization unit.

[0182] Clause 46. The method of clause 31, wherein the aromatic processing catalyst comprises an acid catalyst.

[0183] Clause 47. The method of clause 31, wherein the acid catalyst is selected from aluminosilicates, tungstated aluminosilicates, silica-alumina phosphates, aluminum phosphates, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphates, niobia, sulfated carbon, phosphated carbon, acidic resins, heteropolyacids, tungstated heteropolyacids, inorganic acids, and combinations thereof.

[0184] Clause 48. The method of clause 47, wherein the acid catalyst comprises a metal selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof.

[0185] Clause 49. The method of clause 31, wherein step (iv) is carried out at a temperature between 200° C. and 600° C. and a pressure between 100 psig and 1500 psig, and a weight hourly space velocity (WHSV) between 0.1 and 10 mass of feedstock / mass of catalyst / hour.

[0186] Clause 50. A process for producing and separating xylene isomers, comprising: (I C 7+ A mixed aromatic feed stream containing aromatics is contacted with an aromatic processing catalyst to produce an increased concentration of C relative to the mixed aromatic feed stream. 8 Producing a product stream comprising aromatics, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; (ii) A distillation column is used to separate the product stream into C 7- Stream and C 8+ fractionating the product into streams; (iii) Using a distillation column, 8+ Stream to C 8 Stream and C 9+fractionating the product into streams; (iv) C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 generating a raffinate stream comprising the compounds; (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, the isomerized product stream comprising at least one xylene isomer; Including, C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and is separated into C before entering the isomer recovery process unit. 8 A method for combining with a stream.

[0187] Clause 51. The method of clause 50, wherein the xylene isomer is selected from para-xylene, ortho-xylene, or meta-xylene.

[0188] Clause 52. The process of clause 50, wherein at least a portion of the isomerization product stream is combined with the product stream produced from the catalyst in step (i).

[0189] Clause 53. The method of clause 50, wherein the mixed aromatic feed stream is substantially free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0190] Article 54.C 7- The stream is C 7- Stream to C 6- Stream and C 7 51. The method of claim 50, wherein the mixture is fed to a distillation column for fractionation into streams.

[0191] Article 55.C 7 55. The method of claim 54, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

[0192] Article 56.C9+ The stream is C 9+ Stream to C 9~10 Stream and C 11+ The mixture is fed to a distillation column where it is fractionated into streams C 9~10 51. The method of claim 50, wherein the stream is recycled and combined with the mixed aromatic feed stream.

[0193] Clause 57. The method of clause 50, wherein the isomer recovery process unit comprises an adsorption unit.

[0194] Clause 58. The method of clause 50, wherein the isomer recovery process unit comprises a crystallization unit.

[0195] Clause 59. The method of clause 50, wherein the aromatic processing catalyst comprises an acid catalyst.

[0196] Clause 60. The method of clause 59, wherein the acid catalyst is selected from aluminosilicates, tungstated aluminosilicates, silica-alumina phosphates, aluminum phosphates, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphates, niobia, carbon sulfates, carbon phosphates, acidic resins, heteropolyacids, tungstated heteropolyacids, inorganic acids, or combinations thereof.

[0197] Clause 61. The method of clause 59, wherein the acid catalyst comprises a metal selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof.

[0198] Clause 62. The method of clause 50, wherein step (i) is carried out at a temperature between 200°C and 600°C.

[0199] Clause 63. The method of clause 50, wherein step (i) is carried out at a pressure between 100 psig and 1500 psig.

[0200] Clause 64. The method of clause 50, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of 0.1 to 10 mass of feedstock / mass of catalyst / hour.

[0201] Clause 65. Before step (i) contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to produce a C 4+ generating a condensation product stream comprising the compound C; 4+ The compound is C 4+ Alcohol, C. 4+ Ketone, C 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ comprising a cycloalkene, an aryl, or a fused aryl, The condensation product stream is fractionated to produce C 6- Stream to C 7+ Separating from the stream; C 6- recycling the stream to the condensation catalyst; C 7+ Stream to C 7~10 Stream and C 11+ fractionating the mixture into a stream comprising: 7~10 the stream forming a mixed aromatic feed stream. 51. The method of claim 50, comprising:

[0202] Clause 66. A process for producing and separating xylene isomers, comprising: (I C 7+ A mixed aromatic feed stream containing aromatics is contacted with an aromatic processing catalyst to produce an increased concentration of C relative to the mixed aromatic feed stream. 8Producing a product stream comprising aromatics, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; (ii) A distillation column is used to separate the product stream into C 7- Stream and C 8+ fractionating the product into streams; (iii) Using a distillation column, 8+ Stream to C 8 Stream and C 9+ fractionating the product into streams; (iv) C 8 At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C 8 generating a raffinate stream comprising the compounds; (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, the isomerized product stream comprising at least one xylene isomer; At least a portion of the isomerization product stream is treated with C prior to entering the isomer recovery process unit. 8 Steps and The method includes:

[0203] Clause 67. The method of clause 66, wherein the xylene isomer comprises para-xylene, ortho-xylene, or meta-xylene.

[0204] Article 68.C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and is separated into C before entering the isomer recovery process unit. 8 67. The method of claim 66, in combination with a stream.

[0205] Clause 69. The method of clause 66, wherein the mixed aromatic feed stream is substantially free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0206] Article 70.C7- The stream is C 7- Stream to C 6- Stream and C 7 67. The method of claim 66, wherein the mixture is fed to a distillation column which fractionates the mixture into streams.

[0207] Article 71.C 7 71. The method of claim 70, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

[0208] Article 72.C 9+ The stream is C 9+ Stream to C 9~10 Stream and C 11+ The mixture is fed to a distillation column where it is fractionated into streams C 9~10 67. The method of claim 66, wherein the stream is recycled and combined with the mixed aromatic feed stream.

[0209] Clause 73. The method of clause 66, wherein the isomer recovery process unit comprises an adsorption unit.

[0210] Clause 74. The method of clause 66, wherein the isomer recovery process unit comprises a crystallization unit.

[0211] Clause 75. The method of clause 66, wherein the aromatic processing catalyst comprises an acid catalyst.

[0212] Clause 76. The method of clause 75, wherein the acid catalyst is selected from aluminosilicates, tungstated aluminosilicates, silica-alumina phosphates, aluminum phosphates, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphates, niobia, carbon sulfates, carbon phosphates, acidic resins, heteropolyacids, tungstated heteropolyacids, inorganic acids, or combinations thereof.

[0213] Clause 77. The method of clause 75, wherein the acid catalyst comprises a metal selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof.

[0214] Clause 78. The method of clause 66, wherein step (i) is carried out at a temperature between 200°C and 600°C.

[0215] Clause 79. The method of clause 66, wherein step (i) is carried out at a pressure between 100 psig and 1500 psig.

[0216] Clause 80. The method of clause 66, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of 0.1 to 10 mass of feedstock / mass of catalyst / hour.

[0217] Clause 81. Before step (i) Contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to form a C 4+ generating a condensation product stream comprising the compound C; 4+ The compound is C 4+ Alcohol, C. 4+ Ketone, C 4+ Alkane, C 4+ Alkenes, C 5+ Cycloalkane, C 5+ comprising a cycloalkene, an aryl, or a fused aryl; The condensation product stream is fractionated to produce C 6- Stream to C 7+ Separating the stream; C 6- recycling the stream to the condensation catalyst; C 7+ Stream to C 7~10 Stream and C 11+ fractionating the mixture into a stream comprising: 7~10 forming a mixed aromatic feed stream; Including, C 8+At least a portion of the stream bypasses the distillation column in step (iii) and is separated into C before entering the isomer recovery process unit. 8 67. The method of claim 66, combined with a stream. [Explanation of symbols]

[0218] 10. Aromatic Refining System 12 Aromatics Processing Reactor 14 Mixed aromatic feed streams 15 Combined mixed aromatic feed streams 16 Mixed aromatic feedstock sources 18 Hydrogen Streams 20 Hydrogen Source 22 Aromatics Processing Catalyst 24 Product Stream 25 Separator 26 First Distillation Tower 27 Liquid Product Stream 28 C 7- stream 29 Gas outlet 30 C 8+ Stream, Diversion Stream 32 Second Distillation Tower 34 C 6- stream 36 C 7 stream 38 Third Distillation Tower 40 C 8 stream 42 C 9+ stream 44 Fourth Distillation Column 46 C 9~10 stream 48 C 11+ stream 50 Isomer Recovery Process Unit 52 Xylene Isomer Stream 54 Raffinate Stream 56 Isomerization Reactor 57 Hydrogen Source 58 Isomerization Catalyst 59 Hydrogen Stream 60 Isomerization Product Stream 61 Separator 62 Detouring Stream 63 Gas outlet 65 Liquid Product Stream 100 Systems 102 Hydrodeoxygenation (HDO) reactor 104 Raw material solution supply source 106 Hydrogen Source 108 Deoxygenation catalyst 110 Deoxygenated Product Stream 112 Non-condensable gas streams 111 3 phase separator 114 Organic Product Streams 116 Aqueous Product Stream 118 Aqueous Purge Stream 120 Condensation Reactor 122 Condensation catalyst 124 Condensation product stream 128 Acid Condensation Gas Stream 126 3 phase separator 130 Organic Stream 132 Aqueous Stream 134 Purge Stream 136 Distillation Tower 138 Light Product Streams 140 Heavy Product Stream 142 Distillation Tower 144 Heavy Product Feed Stream

Claims

1. 1. A process for producing and separating xylene isomers, comprising: (i) C ７＋ A mixed aromatic feed stream containing aromatics is contacted with an aromatic processing catalyst to produce an increased concentration of C relative to the mixed aromatic feed stream. ８ producing a product stream comprising aromatics, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; (ii) using a distillation column to distill the product stream into C ７－ Stream and C ８＋ fractionating the product into streams; (iii) using a distillation column, ８＋ Stream to C ８ Stream and C ９＋ fractionating the product into streams; (iv) the C ８ At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C ８ producing a raffinate stream comprising the compound; (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer; Including, At least a portion of the isomerization product stream is subjected to the isomer recovery process unit prior to entering the isomer recovery process unit. ８ Combined with the stream, Said C ８＋ At least a portion of the stream bypasses the distillation column in step (iii) and is removed from the C 2 O 4 stream before entering the isomer recovery process unit. ８ Combined with streams, methods.

2. 2. The method of claim 1, wherein the xylene isomer is selected from para-xylene, ortho-xylene, or meta-xylene.

3. Before step (i), contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to form a C ４＋ producing a condensation product stream comprising compounds, ４＋ The compound is C ４＋ Alcohol, C ４＋ Ketone, C ４＋ Alkanes, C ４＋ Alkene, C ５＋ Cycloalkane, C ５＋ comprising a cycloalkene, an aryl, or a fused aryl; The condensation product stream is fractionated to obtain C ６－ Stream to C ７＋ Separating from the stream; Said C ６－ recycling the stream to said condensation catalyst; Said C ７＋ Stream to C ７～１０ Stream and C １１＋ fractionating the C ７～１０ the stream forming a mixed aromatic feed stream. The method of claim 1 , comprising:

4. based on the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream 0.1 wt % to 45 wt % of an olefin; 0.1 wt % to 25 wt % naphthenes, 0.1 wt % to 40 wt % naphtheno-olefin; phenol in an amount of 10 ppm to 10 wt %, and / or Oxygenates in amounts of 10 ppm to 10 wt % The method of claim 1 , comprising:

5. 2. The mixed aromatic feed stream, comprising at least 1 mg Br ２ / g to 100 mg Br of said mixed aromatic feedstock ２ 10. The process of claim 1, wherein the mixed aromatic feedstock has a Bromine Number of less than 1000 ppm / g.

6. the mixed aromatic feed stream is ９～１０ The method of claim 1 , comprising an aromatic compound.

7. Said C ７－ The stream is ７－ Stream to C ６－ Stream and C ７ 10. The process of claim 1, wherein the molten metal is fed to a distillation column which fractionates the molten metal into streams.

8. Said C ７ 8. The method of claim 7, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

9. Said C ９＋ The stream is ９＋ Stream to C ９～１０ Stream and C １１＋ The C ９～１０ 10. The method of claim 1, wherein the stream is recycled and combined with the mixed aromatic feed stream.

10. 10. The process of claim 1, wherein at least a portion of the isomerized product stream is combined with the product stream produced from the aromatic processing catalyst in step (i).

11. Said C ７－ Stream to C ６－ Stream and C ７ fractionating the product into streams; Said C ９＋ Stream to C ９～１０ Stream and C １１＋ fractionating the C ７ Stream and said C ９～１０ 11. The method of claim 10, further comprising the step of: recycling and combining the stream with the mixed aromatic feed stream.

12. Said C ７－ Stream to C ６－ Stream and C ７ fractionating the product into streams; Said C ９＋ Stream to C ９～１０ Stream and C １１＋ fractionating the C ７ The C stream is recycled and combined with the mixed aromatic feed stream, ９＋ The method of claim 10, comprising recovering the stream as a product.

13. 10. The method of claim 1, wherein the isomer recovery process unit comprises an adsorption unit or a crystallization unit.

14. 10. The method of claim 1, wherein the aromatic processing catalyst comprises an acid catalyst comprising an aluminosilicate, tungstated aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphate, niobia, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstated heteropolyacid, inorganic acid, or combinations thereof, wherein the acid catalyst comprises a metal comprising Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, or combinations thereof.

15. 10. The process of claim 1, wherein step (i) is conducted at a temperature of from 200° C. to 600° C., a pressure of from 100 psig to 1500 psig, or a weight hourly space velocity (WHSV) of from 0.1 to 10 mass of feedstock / mass of catalyst / hour, or wherein step (i) comprises providing hydrogen in an amount of at least 0.1 mole of hydrogen per mole of mixed aromatic feedstock.

16. 1. A process for separating aromatic compounds from a mixed aromatic feed stream, comprising: (i) C ７～１０ A mixed aromatic feed stream containing aromatic hydrocarbons is contacted with an aromatic processing catalyst to form a C ８ Producing a product stream comprising aromatics, the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; the mixed aromatic feedstream comprises greater than 1 wt. % non-aromatic components, based on the total weight of the mixed aromatic feedstream, and the mixed aromatic feedstream is further characterized by: (a) C １２＋ (b) substantially free of aromatics and (c) azeotropic contaminants of benzene and toluene; (ii) fractionating the product stream to separate aromatic compounds from the product stream, (ii-a) C ８ The product stream containing aromatics is fractionated by distilling the product stream to obtain a C ８＋ Stream to C ７－ feeding the stream to a distillation column for separation; and (ii-b) the C ８＋ At least a portion of the stream is ８＋ The part of the stream is C ８ Stream and C ９＋ a distillation column for fractionating the C into a stream, ８ The stream is ８ Aromatic-containing processes and (iii) the C ８ At least a portion of the stream is subjected to an isomer recovery process unit to produce a xylene isomer stream and unrecovered C ８ generating a raffinate stream containing compounds, ８＋ At least a portion of the stream bypasses the distillation column of step (ii-b) and is separated from the C ８ a step combined with the stream; (iv) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer, and wherein at least a portion of the isomerized product stream is combined with the product stream produced from the aromatics processing catalyst in step (i).

17. based on the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream 0.1 wt % to 45 wt % of an olefin; 0.1 wt % to 25 wt % naphthenes, 0.1 wt % to 40 wt % naphtheno-olefin; phenol in an amount of 10 ppm to 10 wt %, and / or Oxygenates in amounts of 10 ppm to 10 wt % 17. The method of claim 16, comprising:

18. 2. The mixed aromatic feed stream, comprising at least 1 mg Br ２ / g to 100 mg Br of said mixed aromatic feedstock ２ 17. The method of claim 16, wherein the mixed aromatic feedstock has a Bromine Number of less than 1000 ppm / g.

19. said mixed aromatic feed stream being C ９～１０ 17. The method of claim 16, comprising an aromatic.

20. Said C ７－ The stream is ７－ Stream to C ６－ Stream and C ７ 17. The process of claim 16, wherein the condensate is fed to a distillation column that fractionates the condensate into streams.

21. Said C ７ 21. The method of claim 20, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feed stream.

22. Said C ９＋ The stream is ９＋ Stream to C ９～１０ Stream and C １１＋ The C ９～１０ 17. The method of claim 16, wherein the stream is recycled and combined with the mixed aromatic feed stream.

23. At least a portion of the isomerization product stream is fed to the isomer recovery process unit. ８ The method of claim 16, wherein the method is combined with a stream.

24. Step (ii) fractionating the product stream to obtain C ７ Stream, C ８ Stream, and C ９～１０ A step of separating the streams, ８ The stream is fed to the isomer recovery process unit, ７ The C stream is recycled and combined with the mixed aromatic feed stream, ９～１０ 17. The method of claim 16, comprising the step of recycling a stream and combining it with the mixed aromatic feed stream.

25. Step (ii) fractionating the product stream to obtain C ７ Stream, C ８ Stream, and C ９＋ A step of separating the streams, ８ The stream is fed to the isomer recovery process unit, ７ The C stream is recycled and combined with the mixed aromatic feed stream, ９＋ 17. The method of claim 16, comprising recovering the stream as a product.

26. 17. The method of claim 16, wherein the isomer recovery process unit comprises an adsorption unit or a crystallization unit.

27. 17. The method of claim 16, wherein the aromatic processing catalyst comprises an acid catalyst comprising an aluminosilicate, tungstated aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titania, tungstated phosphate, niobia, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstated heteropolyacid, inorganic acid, or combinations thereof, wherein the acid catalyst comprises a metal comprising Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, or combinations thereof.

28. 17. The method of claim 16, wherein step (i) is conducted at a temperature of from 200° C. to 600° C., a pressure of from 100 psig to 1500 psig, or a weight hourly space velocity (WHSV) of from 0.1 to 10 mass of feedstock / mass of catalyst / hour, or wherein step (i) comprises supplying hydrogen in an amount of at least 0.1 mole of hydrogen per mole of mixed aromatic feedstock.

29. 1. A process for producing and separating aromatic compounds from a mixed aromatic feed stream, comprising: (i) contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to produce a C ４＋ producing a condensation product stream comprising compounds, ４＋ The compound is C ４＋ Alcohol, C ４＋ Ketone, C ４＋ Alkanes, C ４＋ Alkene, C ５＋ Cycloalkane, C ５＋ comprising a cycloalkene, an aryl, or a fused aryl; (ii) fractionating the condensation product stream to produce a light stream and a heavy stream, wherein the light stream comprises benzene or toluene azeotropic non-aromatic contaminants, and the heavy stream is substantially free of benzene or toluene azeotropic non-aromatic contaminants; (iii) recycling the lights stream to the condensation catalyst; (iv) subjecting the heavy stream to a ７＋ a mixed aromatic feedstock containing aromatic compounds, and said mixed aromatic feedstock is fractionated into a C ７～１０ Stream and C １１＋ splitting the water into streams; (v) C above ７～１０ separating said aromatic compounds by subjecting at least a portion of said stream to the method of claim 1; A method comprising:

30. 30. The process of claim 29, wherein step (iv) is conducted at a temperature of from 200° C. to 600° C. and a pressure of from 100 psig to 1500 psig, and a weight hourly space velocity (WHSV) of from 0.1 to 10 mass of feedstock per mass of catalyst per hour.

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