System and method for generating high-purity aromatics from a mixed aromatic feedstock stream.

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 of related applications This application claims priority to U.S. Provisional Application No. 63 / 255,812, filed on 14 October 2021, the contents of which are thus incorporated in their entirety by reference. [Background technology]

[0002] Aromatic hydrocarbons, particularly benzene, toluene, and xylene, are important industrial products used to produce a wide range of chemicals, fibers, plastics, and polymers, including styrene, phenol, aniline, polyester, and nylon. Typically, such aromatic hydrocarbons are produced from petroleum raw materials using well-established refining or chemical processes. More recently, there has been growing interest in obtaining aromatic hydrocarbons from alternative resources such as biomass, synthesis gas, and natural gas. [Overview of the Initiative]

[0003] In one embodiment, the present disclosure provides a method for separating aromatic compounds from a mixed aromatic feedstock stream. The method is (i) C 7~10 A step of producing a product stream by contacting a mixed aromatic feed stream containing aromatics with an aromatic treatment catalyst, wherein the aromatic treatment catalyst may include a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feed stream may contain more than 1 wt% of non-aromatic components relative to the total weight of the mixed aromatic feed stream. The mixed aromatic feed stream is C 12+ The product does not need to contain aromatics substantially. The method may further include (ii) fractional distillation of the product stream to separate the 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, an amount of phenol from 10 ppm to 10 wt%, and / or an amount of oxygenates from 10 ppm to 10 wt%. In some embodiments, the mixed aromatic feed stream has a bromine number of at least 1 mg Br2 / g of mixed aromatic feed to less than 100 mg Br2 / g of mixed aromatic feed. 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 contains C9~ 10 aromatics.

[0005] In some embodiments, step (ii) of the method comprises feeding a product stream containing C8 aromatics to a first distillation column that fractionates the product stream to separate a C 7- stream from a C 8+ stream. The C 7- stream may be fed to a second distillation column that fractionates the C 7- stream into a C 6- stream and a C7 stream. In some embodiments, at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

[0006] In some embodiments, step (ii) further comprises feeding the C 8+ stream to a third distillation column that fractionates the C 8+ stream into a C8 stream and a C 9+ stream. The C8 stream may contain C8 aromatics. The C 9+ stream may be fed to a fourth distillation column that fractionates the C 9+ stream into a C 9~10 stream and a C 11+ stream. The C 9~10 stream may be recycled and combined with the mixed aromatic feed stream.

[0007] In some embodiments, the method may further include (iii) providing at least a portion of the C8 stream to an isomer recovery process unit to generate a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, and (iv) contacting the raffinate stream with an isomerization catalyst to generate an isomerized product stream. The isomerized product stream may contain at least one xylene isomer. At least a portion of the isomerized product stream may be combined with a product stream generated from the aromatic treatment catalyst in step (i).

[0008] In some embodiments, at least a portion of the isomerization product stream is combined with a C8 stream that enters an isomer recovery process unit.

[0009] In some embodiments, C 8+ At least a portion of the stream is combined with the C8 stream that enters the isomer recovery process unit.

[0010] In some embodiments, step (ii) of the method involves fractional distillation of the product stream into C7 stream, C8 stream, and C 9~10 A step of separating the streams, wherein the C8 stream is supplied to the isomer recovery process unit, and the C7 stream is recycled and combined with the mixed aromatic feedstock stream, C 9~10 The process includes a step in which the stream is recycled and combined with a mixed aromatic feedstock stream.

[0011] In some embodiments, step (ii) involves fractional distillation of the product stream into C7 stream, C8 stream, and C 9+ A step of separating the streams, wherein the C8 stream is supplied to the isomer recovery process unit, and the C7 stream is recycled and combined with the mixed aromatic feedstock stream, C 9+ The process includes a step in which the stream is recovered as a product.

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

[0013] The aromatic treatment catalyst in this method may include an acid catalyst. The acid catalyst may include aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, sulfated zirconia, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, sulfated carbon, phosphated carbon, acidic resins, heteropoly acids, tungstate heteropoly acids, inorganic acids, or combinations 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 method is carried out at a temperature of 200°C to 600°C. In some embodiments, step (i) of the method is carried out at a pressure of 100 psig to 1500 psig. In some embodiments, step (i) of the method is carried out at a weight-space velocity (WHSV) of 0.1 to 10 feedstock mass / catalyst mass / time. In some embodiments, step (i) of the method includes supplying hydrogen in an amount of at least 0.1 moles of hydrogen per mole of mixed aromatic feedstock, for example, at least 1 mole of hydrogen per mole of mixed aromatic feedstock.

[0015] In other embodiments, the Disclosure provides a method for generating and separating aromatic compounds from a mixed aromatic feedstock stream. The method involves (i) contacting an aqueous hydrocarbon feedstock containing water and one or more oxygenates with a condensation catalyst, C 4+ The step may include generating a condensation product stream containing the compound. 4+ Compounds include, for example, C 4+ Alcohol, C4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ The method may include cycloalkenes, aryls, or condensed aryls. The method may further include (ii) fractional distillation of the condensation product stream to produce a light stream and a heavy stream. In some embodiments, the light stream contains azeotropic non-aromatic impurities of benzene or toluene, and the heavy stream is substantially free of azeotropic non-aromatic impurities of benzene or toluene. The method may include (iii) recycling the light stream into a condensation catalyst, and (iv) distilling the heavy stream into C 7+ The method may further include the step of fractionally distilling a mixed aromatic feedstock containing aromatics. The method may further include the step of contacting the mixed aromatic feedstock stream with an aromatic treatment catalyst to produce a product stream. The aromatic treatment catalyst may include a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof.

[0016] In some embodiments, step (iv) is C 7+ A blend of aromatics containing aromatics is used as raw material for C 7~10 Streams and C 11+ The process further includes the step of fractionating into streams. In some embodiments, step (iv) is C 7+ A blend of aromatics containing aromatics is used as raw material for C 9~10 Streams and C 11+ The process further includes the step of fractionating into streams. 7~10 Stream or C 9~10 The stream can come into contact with the aromatic treatment catalyst.

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

[0018] In another aspect, the present disclosure provides a method for generating and separating xylene isomers. The method is (i) C 7+ The method comprises the steps of (ii) contacting a mixed aromatic feed stream containing aromatics with an aromatic treatment catalyst to produce a product stream containing C8 aromatics at an increased concentration compared to the mixed aromatic feed stream, wherein the aromatic treatment catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. 7- Streams and C 8+ (iii) Using a distillation column, C 8+ Streams C8 streams and C 9+ The method may further include the step of fractional distillation into streams. The method may further include the steps of (iv) providing at least a portion of the C8 stream to an isomer recovery process unit to produce a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer. In some embodiments, C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit.

[0019] In yet another aspect, the present disclosure provides a method for generating and separating xylene isomers. The method is (i) C 7+ A method comprising the steps of (ii) contacting a mixed aromatic feed stream containing aromatics with an aromatic treatment catalyst to produce a product stream containing C8 aromatics at an increased concentration compared to the mixed aromatic feed stream, wherein the catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. 7- Streams and C 8+(iii) Using a distillation column, C 8+ Streams C8 streams and C 9+ The method may further include the step of fractional distillation into streams. The method may further include (iv) providing at least a portion of the C8 stream to an isomer recovery process unit to produce a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer. In some embodiments, at least a portion of the isomerized product stream is combined with the C8 stream before entering the isomer recovery process unit.

[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 bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit.

[0022] In some embodiments, before step (i), the method is A water-based hydrocarbon raw material containing water and one or more oxygenated materials is brought into contact with a condensation catalyst, C 4+ A step of generating a condensation product stream containing a compound, C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ Steps containing cycloalkenes, aryls, or condensed aryls, The condensation product stream is fractionally distilled, C 6- Stream to C 7+ Steps to separate from the stream, C 6-Steps to recycle the stream into a condensation catalyst, C 7+ Stream to C 7~10 Streams and C 11+ A step of fractional distillation into streams, C 7~10 The stream forms a mixed aromatic feed stream, step Includes, C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit. [Brief explanation of the drawing]

[0023] [Figure 1] This is a schematic diagram of an aromatic purification system according to some embodiments of the present disclosure. [Figure 2] This is a schematic diagram of a process configured to convert oxygenated hydrocarbons to form a mixed aromatic feedstock stream according to some embodiments of the present disclosure. [Modes for carrying out the invention]

[0024] To facilitate understanding of this disclosure, certain terms are first defined below. Additional definitions of the following terms and other terms are provided throughout this specification.

[0025] In this application, unless otherwise clearly stated in the context, the term “one (a)” may be understood to mean “at least one.” In this application, the term “or” may be understood to mean “and / or.” In this application, the terms “comprising” and “including” may be understood to encompass 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 a standard deviation (e.g., ±10%), as understood by those skilled in the art. Where a range is provided herein, the endpoint is included. In this application, the terms “comprise” and variations 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 those generally understood by those skilled in the art to which this invention belongs. It should be understood that any definitions used herein, when defined and used herein, take precedence over dictionary definitions, definitions in documents incorporated by reference, and / or the ordinary meanings of the defined terms.

[0027] This 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 having high purity, for example, at least 98.5%, or at least 99%, or at least 99.5%, or at least 99.9%.

[0028] The systems and methods provided offer various advantages. For example, processing a mixed aromatic feedstock stream typically requires separation steps, such as extraction, to produce high-purity aromatics. In some embodiments, the systems and methods provided obtain high-purity aromatics without performing extraction techniques to remove impurities from the feedstock 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 isomer recovery process unit (e.g., adsorption or crystallization) integrated with an isomerization step and distillation. Crystallization and adsorption processes require a considerable amount of energy, in the form of heat and electricity, to separate the xylene isomers from intermediate products. In one aspect of the present disclosure, systems and methods are provided to reduce the energy load of separation by allowing a portion of the intermediate stream to enter the 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, remarkably, maintains acceptable product purity despite bypassing the purification step.

[0029] In another aspect of this disclosure, systems and methods are provided for generating mixed aromatic feedstock streams that are free or substantially free of azeotropic non-aromatic impurities of benzene, toluene, and combinations thereof. As used herein, the term “substantially free” means less than 1% (w / w) of a particular compound or mixture of compounds in a particular stream. In some embodiments, the mixed aromatic feedstock stream contains less than 1% (w / w), less than 0.5% (w / w), or less than 0.1% (w / w) of azeotropic non-aromatic impurities of benzene, toluene, and combinations thereof. By feeding a mixed aromatic feedstock stream that is free or substantially free of azeotropic non-aromatic impurities onto a transalkylation and / or dealkylation catalyst, aromatic products with higher purity and yield compared to mixed aromatic streams containing non-aromatic impurities can be obtained.

[0030] As used herein, the term “azeotropic non-aromatic impurities” refers to non-aromatic species that cannot be separated from the desired product by distillation, or that can only be separated with great difficulty. Azeotropic non-aromatics vary depending on the desired product and may include hydrocarbons, oxygenates, sulfur-containing species, and nitrogen-containing species. The benzene azeotropic range is defined here as all components (including benzene) having a standard boiling point greater than or equal to methylcyclopentane (standard boiling point 71.8°C) and less than or equal to the standard boiling point of 1,3-dimethylcyclopentane and cis (standard boiling point 91°C). Exemplary azeotropic non-aromatic impurities of benzene include, but are not limited to, methylcyclopentane, cyclohexane, methylcyclopentene, C7 paraffins, and C7 olefins.

[0031] The azeotropic range of toluene is defined here as all components (including toluene) that have a retention time greater than 1,3-dimethylcyclopentane, cis (boiling point 91°C), and less than trans-1,2-dimethylcyclohexane (boiling point 123°C).

[0032] Referring to Figure 1, the aromatic purification system 10 is described according to certain aspects of the present disclosure. For clarity and brevity, equipment for controlling temperature and flow within the aromatic purification system 10 has been omitted from the drawings. However, it should be understood that the aromatic purification system 10 may include various equipment for controlling temperature (e.g., heat exchangers, combustion heaters, coolers, electric heaters, or combinations thereof for heating or cooling the process stream), even if omitted from the drawings. The aromatic purification system 10 may also include equipment for controlling the fluid velocity, including, but not limited to, pumps, valves, compressors, blowers, or combinations thereof for regulating the fluid flow throughout the system 10.

[0033] In some embodiments, the aromatic purification system 10 includes an aromatic treatment reactor 12 having an inlet that fluidly connects the aromatic treatment reactor 12 to a mixed aromatic feed stream 14. A pump may be configured within the mixed aromatic feed stream 14 to transport the mixed aromatic feed stream 14 from a mixed aromatic feed source 16, such as a reservoir or upstream process unit, to the aromatic treatment reactor 12. In some embodiments, the mixed aromatic feed stream 14 is further defined below as C7 stream 36 and C 9~10 It is optionally combined with Stream 46.

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

[0035] In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains 0.1 wt% to 45 wt% of non-aromatic hydrocarbons, such as paraffins, olefins, naphthenes, naphtheno-olefins, or combinations thereof. In some embodiments, the hydrocarbon feedstock stream contains at least 0.1 wt% of 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%. In some embodiments, the hydrocarbon feedstock stream contains C 3~30 Paraffin, C 3~30 Olefin, C 5~30 Includes naphthenes or combinations thereof.

[0036] As used herein, the terms “paraffin” or “alkane” are C 3~30 This refers to saturated straight-chain or branched-chain hydrocarbons. In some embodiments, paraffin is C n H 2n+2 It has a general formula where n can be in the range of 3-30, 3-25, 3-20, 3-15, 3-10, or 3-6.

[0037] As used herein, the terms “olefin” or “alkene” mean a carbon having at least one carbon-carbon double bond. 3~30 This refers to unsaturated straight-chain or branched-chain hydrocarbons. In some embodiments, olefins are C n H 2n It has a general formula where n can be in the range of 3-30, 3-25, 3-20, 3-15, 3-10, or 3-6.

[0038] Examples of various paraffins and olefins are, 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, This includes undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecane, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosane, uneicosane, uneicosane, doeicosane, doeicosane, trieicosane, trieicosane, tetraeicosane, tetraeicosane, and their isomers.

[0039] In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains at least 0.1 wt% of 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% of olefins.

[0040] As used herein, the terms “naphthene” or “cycloalkane” refer to saturated cyclic, bicyclic, or crosslinked cyclic hydrocarbon groups. Saturated cyclic, bicyclic, or crosslinked cyclic (e.g., adamantane) hydrocarbon groups may be substituted with one or more linear or branched alkyl or alkylene groups, for example, linear or branched C 1~12 Alkyl, linear, or branched C 3~12 Alkylene, straight-chain or branched-chain C1 1~4 Alkyl, linear, or branched C 3~4It may contain alkylenes. The naphthene may be monosubstituted or polysubstituted. In some embodiments, the naphthene is C n H 2n It has a general formula where n can be in the range of 5-30, 5-25, 5-20, 5-15, 5-10, or 5-6.

[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 their isomers.

[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 crosslinked cyclic hydrocarbon group having a monosubstituted or polysubstituted olefin in the hydrocarbon group. In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains at least 0.1 wt% of 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% of naphtheno-olefins.

[0044] In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains 10 wt% to 80 wt% of aromatic hydrocarbons, such as aryls, condensed aryls, polycyclic compounds, or combinations thereof. In some embodiments, the hydrocarbon feedstock stream contains at least 10 wt% of 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% of aromatics. In some embodiments, the hydrocarbon feedstock stream contains multiple C 6~30 Ariel, C 12~30 Condensed aryl, C 12~30 This includes polycyclic compounds, or combinations thereof.

[0045] As used herein, the terms “aryl” and “aromatic” refer to aromatic hydrocarbons in their unsubstituted (phenyl), monosubstituted, or polysubstituted forms. In the case of monosubstituted and polysubstituted compounds, the substituted group is branched C. 3+ Alkyl, linear C 1+ Alkyl, branched chain C 3+Alkylene, straight-chain C 2+ It may include alkylene, or a combination thereof. As an example, at least one of the substituted groups is branched-chain C 3+ Alkyl, straight-chain C 1~12 Alkyl, branched-chain C 3~12 Alkylene, straight-chain C 2~12 It includes alkylene, or a combination thereof. As a further example, at least one of the substituted groups is branched C 3~4 Alkyl, straight-chain C 1~4 Alkyl, branched C 3~4 Alkylene, straight-chain C 2~4 It includes alkylene, or a combination thereof. Examples of various aryls include, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, para-xylene, meta-xylene, ortho-xylene, C 9+ Aromatic, 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 contains 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 contains at least 10 ppm of 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% based on the total weight of the feed stream.

[0047] As used herein, the terms “condensed aryl” or “polynuclear aromatic (PNA)” refer to bicyclic and polycyclic aromatic hydrocarbons in any form: unsubstituted, monosubstituted, or polysubstituted. In the case of monosubstituted and polysubstituted compounds, the substituted group is a branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, straight chain C 2~12 Alkylene, branched chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, straight chain C 2~4 This may include alkylenes or combinations thereof. Examples of various condensed aryls include, but are not limited to, naphthalenes, anthracenes, and their isomers.

[0048] As used herein, the term “polycyclic compound” refers to any bicyclic and polycyclic hydrocarbon having at least one saturated or partially saturated ring, in any unsubstituted, monosubstituted, or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted group is a branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, straight chain C 2~12 Alkylene, branched chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, straight chain C 2~4 This may include alkylenes 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 their isomers.

[0049] In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 has a bromine value of at least 1 mg Br2 / g to less than 100 Br2 / g. In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 has a bromine value greater than 1 mg Br2 / g, or at least 5 mg Br2 / g, or at least 10 mg Br2 / g, or at least 15 mg Br2 / g, or at least 20 mg Br2 / g, or at least 25 mg Br2 / g, or at least 30 mg Br2 / g, or at least 40 mg Br2 / g, or at least 50 mg Br2 / g, or less than 60 mg Br2 / g, or less than 70 mg Br2 / g, or less than 80 mg Br2 / g, or less than 90 mg Br2 / g, or less than 100 mg Br2 / g. The bromine value is a measure of aliphatic unsaturation in the feedstock. The bromine value can be determined using known methods such as ASTM D1159.

[0050] In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains oxygenated material in an amount of 10 ppm to less than 10 wt% of the total weight of the feedstock stream. In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 contains at least 10 ppm of oxygenated material relative to the total weight of the feedstock stream, 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 7 wt%, or less than 8 wt%, or less than 9 wt%, or less than 10 wt% of oxygenated material.

[0051] As used herein, the term "C n+ " refers to hydrocarbon compounds that have n or more carbon atoms (for example, at least 7 carbon atoms) in the compound, and the term "C" refers to hydrocarbon compounds that have n or more carbon atoms in the compound. n- " refers to hydrocarbon compounds having n or fewer carbon atoms (e.g., fewer than 7 carbon atoms) in the compound. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is C 7+ Contains aromatic hydrocarbons. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is C 7~10 aromatic, C 8~10 Aromatic, or C 9~10 It consists of aromatics. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is C 11+ It does not contain or substantially contains heavy aromatic compounds. In some embodiments, the mixed aromatic feedstock stream 14 or the combined mixed aromatic feedstock stream 15 does not contain or substantially contains azeotropic impurities of benzene, toluene, or combinations thereof.

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

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

[0054] The aromatic treatment reactor 12 includes an aromatic treatment catalyst 22 configured to modify the mixed aromatic feed stream 14 to produce a product stream having an increased concentration of C8 aromatics compared to the aromatic feed stream 14 or the combined aromatic feed stream 15. Suitable aromatic treatment catalysts 22 include, but are not limited to, transalkylation catalysts, dealkylation catalysts, hydrocracking catalysts, or combinations thereof. In some embodiments, the aromatic treatment catalyst 22 may consist of a bifunctional, acidic metal-containing catalyst. The aromatic treatment 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, heteropoly acids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof.

[0055] In some embodiments, the aromatic treatment catalyst 22 may contain 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. The aromatic treatment catalyst 22 may also contain 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, in order to provide metallic functionality.

[0056] In some embodiments, the aromatic treatment reactor 12 operates as a gas-phase reactor, into which an optional hydrogen and aromatic feedstock stream 14 is introduced and flowed downward over the fixed bed of the aromatic treatment catalyst 22. Alternatively, the aromatic treatment reactor 12 operates as a radial or upward-flow reactor. In other embodiments, the reactor 12 operates as a fixed trickle-bed reactor, into which an optional hydrogen and combined aromatic feedstock stream is introduced and flowed downward over the fixed bed of the catalyst 22. Although the hydrogen conduit 18 and combined aromatic stream 15 are shown in parallel flow in Figure 1, it should be understood that counterflow orientations are also possible.

[0057] In some embodiments, the aromatic treatment reactor 12 operates at temperatures of 200°C to 600°C, 250°C to 550°C, or 300°C to 500°C. In some embodiments, the pressure of the aromatic treatment reactor 12 is in the range of atmospheric pressure to 1500 psig. In some embodiments, the reactor 12 operates at a weight space velocity (WHSV) of 0.1 to 10 feedstock mass / catalyst mass / time or 0.5 to 8 WHSV.

[0058] The product stream 24 exits the aromatic treatment reactor 12 through a reactor outlet that is cooled to condense the aromatics, and is transported to a separator 25 that removes unreacted hydrogen and non-condensable compounds from the product stream 24. Cooling of stream 24 at the reactor outlet can be carried out using one or more heat exchangers. A portion of the unreacted hydrogen can be optionally recycled through a gas outlet 29 and combined with the hydrogen stream 18. Recycling of unreacted hydrogen can be achieved using a gas transport device such as a compressor or blower. The liquid product stream 27 from the 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 execution details.

[0059] In one embodiment, the liquid product stream 27 from the separator 25 is directed toward the first distillation column 26. A pump may be configured within the liquid product stream 27 to facilitate the transport of the liquid product stream 27, and a heat exchanger may be configured within the liquid product stream 27 to control the temperature of the liquid product stream entering the first distillation column 26. Valves may be placed within the product stream 27 to regulate the flow. The first distillation column 26 directs the liquid product stream 27 toward the first distillation column 26. 7- Stream 28 and C 8+ The product is fractionally distilled into stream 30. Figure 1 shows the first distillation column 26 as a single column, but the liquid product stream 27 is C 7- Stream 28 and C 8+ It should be understood that fractional distillation into Stream 30 can be carried out across multiple distillation columns.

[0060] In some embodiments, C 7- Stream 28 is C 7- Stream 28 to C 6- It is supplied to a second distillation column 32 which fractionates into stream 34 and C7 stream 36. In some embodiments, C 6- Stream 34 is collected or discarded from the process. 6- Stream 34 produces the product C 6- To isolate it from stream 34, it may optionally be further processed in an aromatic purification unit. For example, C 6- Stream 34 uses benzene and C 6- To isolate it from stream 34, it may be subjected to further distillation, crystallization, or adsorption. In some embodiments, C 6- At least a portion of stream 34 is recycled to an upstream process unit, such as an acid condensation catalyst, to produce more C8 aromatics or other desired aromatics.

[0061] In some embodiments, at least a portion of the C7 stream 36 is recycled and combined with the mixed aromatic feed stream 14 to form a combined mixed aromatic feed stream 15, so that the C7 stream 36 can react further on the aromatic treatment catalyst 22. In addition or alternatively, at least a portion of the C7 stream 36 may be collected or discarded from the process. The collected or discarded portion of the C7 stream 36 may optionally be further processed in an aromatic purification unit to isolate the product from the C7 stream 36. For example, the C7 stream 36 may be subjected to further distillation, crystallization, or adsorption to isolate toluene from the C7 stream 36.

[0062] In some embodiments, C is discharged from the first distillation column 26. 8+ Stream 30 is supplied to the third distillation column 38. The third distillation column 38 is C 8+ Stream 30 to C8 Stream 40 and C 9+ The fractional distillation is carried out in stream 42. In some embodiments, C 8+ A portion of stream 30 is combined with the C8 stream 40 coming from the third distillation column 38, 8+ At least a portion of stream 30 optionally bypasses the third distillation column 38. The bypass stream offers several advantages. First, bypassing the third distillation column 38 reduces the overall system energy load by decreasing the flow rate of material passing through the distillation column 38, thereby reducing operating costs. Furthermore, the applicant has found, surprisingly and unexpectedly, that incorporating the bypass stream reduces operating costs while still maintaining an acceptable product purity despite bypassing the distillation column 38.

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

[0064] In some embodiments, the C8 stream 40 is supplied to an isomer recovery process unit 50. The isomer recovery process unit 50 is configured to produce a xylene isomer stream 52 and a raffinate stream 54 containing unrecovered C8 compounds. An exemplary isomer recovery process unit 50 includes, but is not limited to, a crystallization unit, an adsorption unit, or a combination thereof, configured to selectively purify xylene isomers from the C8 stream 40. The isomer recovery process unit 50 may be configured to purify para-xylene, ortho-xylene, or meta-xylene from the C8 stream 40.

[0065] In some embodiments, a raffinate stream 54 containing unrecovered C8 compounds is supplied to an isomerization reactor 56. Pumps and valves may be configured within the raffinate stream 54 to regulate the flow of raffinate to the isomerization reactor 56. The isomerization reactor 56 includes an isomerization catalyst 58 configured to produce an isomerization product stream containing increased concentrations of the 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 that fluid-couples the isomerization reactor 56 to a hydrogen stream 59. A gas transport device may be configured within the hydrogen stream 59 to transport hydrogen from a hydrogen source 57, such as a reservoir or 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 consists of alumina, silica, aluminosilicate, zeolite (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 thereof, and combinations thereof to provide metallic functionality. The isomerization reactor 56 can be operated as a fixed trickle bed reactor or as a slurry reactor. In some embodiments, the isomerization reactor 56 is operated at a temperature of 100°C to 500°C, a pressure of atmospheric pressure to 1500 psig, and a WHSV of 0.1 to 10 feedstock mass / catalyst mass / time.

[0067] In some embodiments, at least a portion of the isomerization product stream 60 exits through a reactor outlet that is cooled to condense the product and is transported to a separator 61 that removes unreacted hydrogen and non-condensable compounds from the isomerization product stream 60. Cooling of the isomerization product stream 60 can be performed using one or more heat exchangers. Some or all of the unreacted hydrogen can be optionally recycled through a gas outlet 63 and combined with a hydrogen stream 59. Recycling of unreacted hydrogen can be achieved by using a gas transport device such as a compressor or blower. The liquid product stream 65 from the separator 61 is transported to a first distillation column 26 for fractional distillation. In some embodiments, the liquid product stream 65 from the separator 61 is optionally recycled before being transported to the first distillation column 26 and combined with a liquid product stream 27 from the separator 25.

[0068] In some embodiments, at least a portion of the isomerized product 60 is optionally recycled and combined with the C8 stream 40 coming out of the third distillation column 38. For example, a portion of the liquid product stream 65 may be separated into stream 62, which is then transported and combined with the C8 stream 40. The bypass stream 62 offers several advantages. As described above, bypassing distillation columns 26, 32, and 38 reduces the overall system energy load by reducing the flow rate of material passing through the distillation columns, thereby reducing operating costs. Furthermore, the applicant has found, surprisingly and unexpectedly, that incorporating the bypass stream 62 reduces operating costs while still maintaining an acceptable product purity despite bypassing distillation columns 26, 32, and 38. For example, when operating with one or both of the 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 the xylene stream 52.

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

[0070] In some embodiments, the raw material solution source 104 includes a raw material solution containing water-soluble sugars derived from biomass. As used herein, the term “biomass” refers, 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 waste such as corn stalks, straw, seed hulls, sugarcane meal, bagasse, nut shells, and manure from livestock, poultry, and pigs; (2) woody materials such as wood or bark, sawdust, timber scraps, and mill scrap; (3) general waste such as paper waste and garden grass; and (4) energy crops such as poplar, willow, switchgrass, alfalfa, prairie blue stems, corn, and soybeans.

[0071] Various sugar processing methods are well known in the art and are carried out on a large scale and commercially to produce sugar solutions from biomass. For example, in processes using sugarcane, sugarcane is generally washed, crushed or diffused and clarified with lime in order to isolate and obtain an aqueous biomass-derived intermediate raw material stream rich in sucrose, fructose, and glucose. In processes using sugar beets, sugar beets are similarly washed, sliced, extracted, and clarified in order to isolate and obtain an aqueous biomass-derived intermediate raw material stream rich in sucrose, fructose, and glucose. For processes involving grains, the grains are washed and then processed to obtain wet-ground starch (corn) or dry-ground / powdered starch (corn, wheat, barley, sorghum grains). The isolated sugar solutions may be adjusted to obtain a desired sugar concentration, for example, by concentrating or diluting with water to obtain a raw material solution 104. Generally, the appropriate concentration range is approximately 5% to 70%, with the range of approximately 40% to 70% being more common in industrial applications.

[0072] For raw lignocellulose biomass raw materials, the biomass feedstock can be broken down from complex biopolymers into sugars and soluble oxygenated products to form a raw material solution 104. In one embodiment, raw lignocellulose raw material (e.g., corn leaves and stalks) is broken down 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 at harvest of the raw material, fractionation by sieving, chemical pretreatment to leach undesirable components, fermentative pretreatment such as treatment with white rot fungi, and mechanical methods such as steam explosion, roasting, or pellet formation. Alternatives to decomposition include autohydrolysis (hot water only), alkalis (e.g., ammonia, sodium hydroxide, potassium hydroxide), oxidation (e.g., hydrogen peroxide, oxygen, air), organosolves (e.g., ethanol, acetic acid, catalyst-derived solvents), and thermochemical pretreatment with ionic liquids. The processing steps for lignocellulose biomass may also include additional processing to obtain biomass that has been chopped, shredded, compressed, powdered, or processed to a size suitable for conversion.

[0073] In some embodiments, the raw material solution 104 may be formed using one or more of the processes described above, or it may originate from one or more of the biomass sources described above. The raw material solution may be produced from biomass by any means currently known or to be developed in the future, or it may simply be a byproduct of other processes.

[0074] In some embodiments, the raw material solution contains one or more oxygenated hydrocarbons. The term “oxygenated hydrocarbon” 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 decomposition products (e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, and furfural), each of which is referred to herein as C3+ O 2+ This is expressed as follows. As used herein, the term “oxygenated compound” or “oxygenated product” means a molecule having two or more carbon atoms and one or more oxygen atoms (i.e., C 2+ O 1+ The term "monooxygenated molecule" refers to a hydrocarbon molecule containing two or more carbon atoms and one oxygen atom (i.e., C 2+ The term "dioxygenated molecule" refers to a hydrocarbon molecule containing two or more carbon atoms and two oxygen atoms (i.e., C1). 2+ The term "polyoxygenated" refers to hydrocarbon molecules (i.e., C2) that contain two or more carbon atoms and three or more oxygen atoms. 2+ O 3+ ) refers to.

[0075] In addition to oxygenated hydrocarbons, the raw materials may also include lignin, one or more extracts, one or more ash components, or one or more organic species (e.g., lignin derivatives). Extracts include terpenoids, stilbenes, flavonoids, phenols, aliphatics, lignans, alkanes, protein-like substances, amino acids, and other inorganic products. Ash components include Al, Ba, Ca, Fe, K, Mg, Mn, P, S, Si, Zn, etc. 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, etc.

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

[0077] Generally, hydrogenation reactions are carried out at hydrogenation temperatures between approximately 80°C and 350°C and hydrogenation pressures between approximately 50 psig and 5000 psig. The hydrogen used in the reaction may include situ hydrogen produced from other reactions occurring sequentially or in parallel within the reactor, external H2, recycled H2, or a combination thereof.

[0078] In some embodiments, the starting material solution 104 contains a carboxylic acid that can be hydrogenated. The degree to which the carboxylic acid starting material 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 per mole of carboxylic acid groups in the starting material. Generally, the reaction should be carried out under conditions where the residence time of the carboxylic acid starting material on the catalyst is appropriate for producing the desired oxygenate. For example, the residence time can be established between 0.01 and 30, or between 0.05 and 10, or at a weight-space velocity (WHSV) between 0.1 and 5.

[0079] Referring again to Figure 2, the raw material solution 104 comes into contact with the deoxygenation catalyst 108 in the presence of hydrogen to produce a deoxygenation product stream 110 containing 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 0.8 to 1.8, or 1 to 1.6, or 1.2 to 1.6. eff It may include a ratio. In some embodiments, 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 to 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 ratio is calculated based on the amounts of carbon, oxygen, and hydrogen in the raw materials, as follows:

[0081]

number

[0082] In some embodiments, the deoxygenation product stream 110 is a compound having one or more carbon atoms and one to three oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxycarboxylic acids, carboxylic acids, diols, and triols. 1+ O 1~3 Contains hydrocarbons. In some embodiments, C 1+ O 1~3 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 deoxygenation product stream 110 may contain hydrocarbons that do not contain the element oxygen.

[0083] Exemplary alcohols in the deoxygenation product stream 110 include, but are not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methylcyclopentanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and their isomers, including primary, secondary, linear, branched, or cyclic C alcohols. 1+May contain alcohols. Exemplary ketones may include, but are not limited to, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butan-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentan-2,3-dione, pentan-2,4-dione, hexanone, cyclohexanone, 2-methylcyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, and their isomers. Exemplary aldehydes may include, but are not limited to, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and their isomers. 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, including their isomers and derivatives, and their 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 their isomers. The exemplary triols may include, but are not limited to, glycerol, 1,1,1-tris(hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane, hexanetriol, and their isomers.Exemplary furans and furfurals include, but are not limited to, 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 their isomers.

[0084] In some embodiments, the deoxygenation catalyst 108 consists of a heterogeneous catalyst having one or more materials that can catalyze the reaction between hydrogen and the raw material solution 104 to extract one or more oxygen atoms from the raw material solution to produce one or more oxygenates. In some embodiments, the deoxygenation catalyst 108 consists of one or more metals attached to a support, and may include, but is 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 individually 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 yet another embodiment, the catalyst comprises Fe, Re, and at least Cu or one group VIIIB transition metal. The support may be any one of the supports further described below, including nitrides, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropoly acids, diatomaceous earth, hydroxyapatite, and mixtures thereof.

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

[0086] In some embodiments, the WHSV of the deoxygenation reaction is in the range of 0.1 grams of oxygenated hydrocarbons (g / g-hr) per gram of catalyst per hour 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, and less 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 supplied to the deoxygenation reactor 102 is 0-2400%, 5-2400%, 10-2400%, 15-2400%, 20-2400%, 25-2400%, 30-2400%, 35-2400%, 40-2400%, and 45-240% of the total number of moles of oxygenated hydrocarbons in the raw material. 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 The ranges are 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%, and include all intervals between these ranges. Hydrogen can be external or recycled hydrogen. The term "external H2" refers to hydrogen that is not derived from the raw material solution but is added to the reactor system from an external source. The term "recycled H2" refers to unused 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 gas may be removed and sent to a separation system in which hydrogen can be recovered for recycling back into the hydrogen stream 106, or it may be burned to produce process heat (i.e., heat to drive reactions in the deoxygenation reactor). The aqueous product stream 116, containing partially deoxygenated hydrocarbons, may be recycled back into the inlet of the deoxygenation reactor 102. An aqueous purge stream 118, containing some monooxygenated substances (e.g., alcohols), may be used to prevent water accumulation in the reactor system. The aqueous purge stream 118 may be combined with the organic product stream 114 or discarded from the process.

[0089] In some embodiments, the organic product stream 114 containing oxygenated material passes through a condensation reactor 120 containing a condensation catalyst 122. The oxygenated material undergoes a condensation reaction catalyzed by the condensation catalyst 122, resulting in C 4+The condensation product containing the compound is converted to stream 124. Although not limited to any particular theory, condensation reactions are generally considered to consist of a series of steps including (a) dehydration from an oxygenated product to an alkene, (b) oligomerization of the alkene, (c) cracking reaction, (d) cyclization of a larger alkene to form an aromatic, (e) alkane isomerization, and (f) hydrogen transfer reaction to form an alkane. The reaction may also consist of a series of steps including (1) aldol condensation to form a β-hydroxyketone or β-hydroxyaldehyde, (2) dehydration of the β-hydroxyketone or β-hydroxyaldehyde to form a conjugated enone, (3) hydrogenation of the conjugated enone to form a ketone or aldehyde that may be involved in further condensation reactions or conversion to an alcohol or hydrocarbon, and (4) hydrogenation from a carbonyl to an alcohol or vice versa. Other condensation reactions, including aldol condensation, Prince reaction, acid ketonation, and Diels-Alder condensation, may occur in parallel.

[0090] Condensation catalysts 122 are generally catalysts that can form longer-chain compounds by linking two oxygen-containing species or other functionalized compounds (e.g., olefins) with a new carbon-carbon bond, thereby converting the resulting compounds into hydrocarbons, alcohols, or ketones. 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, heteropoly acids, 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. Condensation catalysts 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, in order to provide metallic 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, heteropoly acids, 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, in order to provide metallic functionality.

[0092] The condensation catalyst 122 may be self-supporting (i.e., the catalyst does not require another material to act as a support) or may require a separate support suitable for suspending the catalyst in the reactant stream. In certain embodiments, the support 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 help form the catalyst into a desired catalytic shape. Applicable formation processes include extrusion, pelletization, oil dropping, or other known processes. Zinc oxide, alumina, and a gelatinizer may also be mixed together and extruded to produce a formed material. After drying, this material is calcined at a temperature suitable for forming a catalytically active phase, typically requiring temperatures above 350°C. Other catalyst supports may include those described in more detail below.

[0093] Condensation catalysts may include one or more zeolite structures, including a silica-alumina cage-like structure. Zeolites are crystalline microporous materials with a distinct pore structure. Zeolites contain active sites, usually acidic sites, that can be produced within the zeolite framework. The intensity and concentration of the active sites can be tailored to specific applications. 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. Patent No. 3,702,886, incorporated herein by reference. As is recognized in the art, the structure of a particular one or more zeolites may be modified to yield different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain varying 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 preparations are all described in U.S. Patent No. 3,702,886, Re. 29,948 (High Silica ZSM-5), U.S. Patent No. 4,100,262, and U.S. Patent No. 4,139,600, all of which are incorporated herein by reference. Zeolite ZSM-11 and its conventional preparations are also described in U.S. Patent No. 3,709,979, which is also incorporated herein by reference. Zeolite ZSM-12 and its conventional preparations are also described in U.S. Patent No. 3,832,449, which is also incorporated herein by reference. Zeolite ZSM-23 and its conventional preparations are also described in U.S. Patent No. 4,076,842, which is also incorporated herein by reference. Zeolite ZSM-35 and its conventional preparations 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 preparations are taught in U.S. Patent No. 4,375,573, which is incorporated herein by reference. Other examples of zeolite catalysts are described in U.S. Patent No. 5,019,663 and U.S. Patent No. 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. Patent No. 7,022,888, the condensation catalyst may be a bifunctional pentasylzeolite catalyst comprising at least one metallic element from the group consisting 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 consisting of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolite may have strongly acidic moieties and can be used with a reactant stream containing oxygenated hydrocarbons at temperatures below 580°C. The bifunctional pentasylzeolite may have a ZSM-5, ZSM-8, or ZSM-11 type crystalline structure consisting of numerous five-membered oxygen rings (i.e., pentasyl rings). In one embodiment, the zeolite has a ZSM-5 type structure.

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

[0097] The specific C that is generated 4+ The compound is not limited and depends on various factors, including the type of oxygenated compound in the reactant stream, condensation temperature, condensation pressure, catalyst reactivity, and the flow rate of the reactant stream, as these affect space velocity, GHSV, LHSV, and WHSV. In certain embodiments, the reactant stream is in contact with the condensation catalyst at a WHSV suitable for producing the desired hydrocarbon product. In one embodiment, the WHSV is at least 0.1 grams of volatile (C) in the reactant stream per gram of catalyst per hour. 2+ O 1~3) is an oxygenated product. In another embodiment, the WHSV is between 0.1 and 10.0 g / g hr, including WHSV of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 g / g hr and increments between them.

[0098] In a particular embodiment, the condensation reaction is carried out at a temperature and pressure where the thermodynamics of the proposed reaction are favorable. Volatile C 2+ O 1~3 For oxygenates, the reaction may take place at a temperature where the vapor pressure of the volatile oxygenate is at least 0.1 atm (preferably higher). The condensation temperature varies depending on the specific composition of the oxygenated compound. Generally, the condensation temperature is above 80°C, or 100°C, or 125°C, or 150°C, or 175°C, or 200°C, or 225°C, or 250°C, and below 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. Condensation pressure is generally 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, 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 described herein is C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ Cycloalkenes, aryl compounds, condensed aryl compounds, polycyclic compounds, C 4+ Alcohol, C 4+ Ketones, C 4+It can be used in the production of furans and their mixtures, with a favorably high proportion of aryls and a low proportion of alkanes. In particular, the use of the above mixtures of oxygenated furans yields aryls with a carbon fraction (CF) of 50% or more of the aqueous raw material carbon and C20% or less of the aqueous raw material carbon. 4+ This yields an alkane yield. In certain embodiments, the aryl yield may be 55 wt% or more of the aqueous raw material carbon, 60% or more of CF, or 65% or more of CF. In certain embodiments, C 4+ The alkane yield is 15% or less CF, 10% or less CF, or 5% or less CF of the aqueous starting material carbon. In certain other embodiments, the product is C 1~3 It may also contain alkanes, total C 1+ The alkane yield is 20% or less CF, 15% or less CF, 10% or less CF, or 5% or less CF of the aqueous raw material carbon.

[0100] As used herein, the terms "carbon fraction" and "CF," which may be used interchangeably, can be calculated by dividing the mass of carbon in the 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 technical terms.

[0101] In a particular embodiment, the aryl yield is 55% or more of the aqueous raw material carbon CF, and C 4+ The alkane yield is CF of 15% or less of the aqueous raw material carbon. In another embodiment, the aryl yield is CF of 60% or more of the aqueous raw material carbon, and C 4+ The alkane yield is CF of 10% or less of the aqueous raw material carbon. In a further embodiment, the aryl yield is CF of 55% or more of the aqueous raw material carbon, and C 1+ The alkane yield is CF of 15% or less of the aqueous raw material carbon. In other embodiments, the aryl yield is CF of 60% or more of the aqueous raw material carbon, and C 1+ The alkane yield is CF of 10% or less of the aqueous raw material carbon.

[0102] C 4+Alkanes and C 4+ Alkenes have 4 to 30 carbon atoms (C 4+ Alkanes and C 4+ Alkenes), branched or straight-chain alkanes or alkenes C 4+ Alkanes and C 4+ Alkenes are, respectively, C 4~9 , C 7~14 , C 12~24 Alkanes and alkenes may also be included, C 4~9 The fraction is for gasoline, C 7~16 The fraction is for jet fuel, C 11~24 The fractions are used for diesel fuel and other industrial applications such as chemicals. Various C 4+ Alkanes and C 4+ Examples of alkenes 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, octen, 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene This includes dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecane, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosane, uneicosane, uneicosane, doeicosane, doeicosane, trieicosane, trieicosane, tetraeicosane, tetraeicosane, and their isomers.

[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 group is branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+This may include alkylenes, phenyls, or combinations thereof. For example, at least one of the substituted groups may be branched C. 3~12 Alkyl, linear C 1~12 Alkyl, branched C 3~12 Alkylene, straight chain C 1~12 Alkylene, straight chain C 2~12 This includes alkylenes, phenyls, or combinations thereof. As a further example, at least one of the substituted groups is branched C. 3~4 Alkyl, linear C 1~4 Alkyl, branched C 1~4 Alkylene, straight chain C 1~4 Alkylene, straight chain C 2~4 Contains alkylene, phenyl, or a combination thereof. Desired C 5+ Cycloalkanes and C 5+ Examples of cycloalkenes 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, and their isomers.

[0104] Aryls generally consist of unsubstituted (phenyl), monosubstituted, or polysubstituted aromatic hydrocarbons. In the case of monosubstituted and polysubstituted compounds, the substituted group is branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ This may include alkylenes, phenyls, or combinations thereof. For example, at least one of the substituted groups may be branched C. 3+ Alkyl, linear C 1~12 Alkyl, branched C 3~12 Alkylene, straight chain C 2~12 This includes alkylenes, phenyls, or combinations thereof. As a further example, at least one of the substituted groups is branched C. 3~4 Alkyl, linear C 1~4 Alkyl, branched C3~4 Alkylene, straight chain C 2~4 Includes alkylenes, phenyls, or combinations thereof. Examples of various aryls are, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, paraxylene, metaxylene, orthoxylene, C 9+ This includes aromatic compounds, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, and their isomers.

[0105] Condensed aryl compounds generally consist of bicyclic and polycyclic aromatic hydrocarbons in unsubstituted, monosubstituted, or polysubstituted forms. In the case of monosubstituted and polysubstituted compounds, the substituted group is branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ This may include alkylenes, phenyls, or combinations thereof. For example, at least one of the substituted groups may be branched C. 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4 Alkylene, straight chain C 2~4 This includes alkylenes, phenyls, or combinations thereof. Examples of various condensed aryls include, but are not limited to, naphthalenes, anthracenes, and their isomers.

[0106] Polycyclic compounds generally consist of bicyclic and polycyclic hydrocarbons in unsubstituted, monosubstituted, or polysubstituted forms. Polycyclic compounds generally contain condensed aryl groups, 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 group is branched C 3+ Alkyl, linear C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ This may include alkylenes, phenyls, or combinations thereof. For example, at least one of the substituted groups may be branched C. 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4Alkylene, straight chain C 2~4 This includes alkylenes, phenyls, or combinations thereof. Examples of various condensed aryls include, but are not limited to, tetrahydronaphthalene and decahydronaphthalene, as well as their isomers.

[0107] C 4+ Alcohols can also be cyclic, branched, or linear, and have 4 to 30 carbon atoms. Generally, C 4+ Alcohol is, formula R 1 It can be a compound that follows the -OH group, R 1 This is branch C 4+ Alkyl, linear C 4+ Alkyl, branched C 4+ Alkylene, straight chain C 4+ Alkylene, substitution C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloalkenes, unsubstituted C 5+ The member is selected from cycloalkenes, aryls, phenyls, or combinations thereof. Desired C 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 their isomers.

[0108] C 4+ Ketones can also be cyclic, branched, or linear, and have 4 to 30 carbon atoms. Generally, C 4+ Ketones are,

[0109] [ka] (In the formula, R 3 and R 4 Independently, branch C 3+ Alkyl, linear C 1+Alkyl, branched C 3+ Alkylene, straight chain C 2+ Alkylene, substitution C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloalkenes, unsubstituted C 5+ It may be a compound that follows the pattern (a member selected from cycloalkenes, aryls, phenyls, or combinations thereof). Desired C 4+ Examples of ketones 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 their isomers.

[0110] In some embodiments, C 4+ The condensation product stream 124 containing compounds can be fractionated into various product streams such as gasoline, jet fuel (kerosene), diesel fuel, and aromatics. The condensation product stream 124 can pass through a three-phase separator 126 to separate it 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 difference, while the acid condensation gas stream 128 containing non-condensable gases is recycled to the acid condensation reactor 120 for additional carbon dioxide. 4+ The compound is produced. In some embodiments, a gas transport device, such as a blower or compressor, is configured within 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 within the acid condensation gas stream 128. In some embodiments, the aqueous stream 132 is discarded from the process or further processed in a downstream process unit.

[0111] In some embodiments, the organic stream 130 is fractionally distilled 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 a combination thereof. As described, removing azeotropic contaminants of benzene and / or toluene before processing on the transalkylation and / or dealkylation catalyst 22 results in surprising and unexpected advantages such as higher purity and yield of the desired aromatic product.

[0112] In some embodiments, the distillation column 136 is configured to produce a heavy stream 140 that is free or substantially free of azeotropic non-aromatic impurities of benzene. The distillation column 136, through the light product stream 138, produces an organic stream 130 containing benzene, azeotropic non-aromatic impurities of benzene, and a lighter product. 6- By fractional distillation into streams, azeotropic non-aromatic impurities of benzene can be removed. Distillation column 136 passes organic stream 130 to C 7+ The heavy product stream 140 containing the compound can be further fractionated.

[0113] In some embodiments, the distillation column 136 is configured to produce a heavy stream 140 that is free of or substantially free of toluene azeotropic non-aromatic impurities. The distillation column 136, through the light product stream 138, distills the organic stream 130 containing toluene, toluene azeotropic non-aromatic impurities, and a lighter product. 7- or C 8- By fractional distillation into streams, azeotropic non-aromatic impurities of toluene can be removed. Distillation column 136 passes organic stream 130 to C 8+ or C 9+ The heavy product stream 140 containing the compound can be further fractionated.

[0114] In some embodiments, the heavy product stream 140 is C 7+ compound, C 8+The heavy product stream 140, which contains compounds or C9+ compounds, is fractionally distilled in a distillation column 142 to separate it into a mixed aromatic feed stream 16 and a heavy product feed stream 144. In some embodiments, the distillation column 142 distills the heavy product stream 140 into C 7+ Mixed aromatic feedstock streams 16 and C containing compounds 11+ It is configured to fractionally distill into a heavy product feed stream 144 containing the compound. In some embodiments, the mixed aromatic feed stream 16 is 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 compound is included. The mixed aromatic feedstock stream 16 can be used as the inlet feedstock for the process shown in Figure 1.

[0115] In some embodiments, the heavy stream 144 is kerosene (e.g., C for jet fuel applications). 11~14 ), diesel fuel applications (for example, C 12~24 ), and lubricating oil or fuel oil (for example, C 25+ It can be further separated for use as a fraction. Alternatively, the heavy stream 144 can be cracked to produce additional fractions for use in gasoline, kerosene, aromatic, and / or diesel fractions.

[0116] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. It should be understood that any definitions used herein, when defined and used herein, take precedence over dictionary definitions, definitions incorporated by reference in other documents, and / or the ordinary meanings of the defined terms.

[0117] The present invention is described in relation to one or more preferred embodiments, and it should be understood that many equivalents, substitutions, modifications, and improvements are possible and fall within the scope of the invention, apart from those explicitly stated. [Examples]

[0118] The following embodiments will enable those skilled in the art to more readily understand the principles of the present disclosure. The following embodiments are presented for illustrative purposes only and are not intended to limit the scope of this disclosure.

[0119] Example 1: Production of high-purity aromatics from mixed aromatic feedstocks C7~C 10 A mixed aromatic feedstock stream (MAF) containing aromatics and substantially lacking benzene azeotropic non-aromatic impurities was treated with a nickel-containing ZSM-5 catalyst at 375°C, 100 psig, at a hydrogen-to-hydrocarbon ratio of approximately 4, and a gravimetric space velocity of 1. The feedstock contained less than 0.1% benzene, while the product contained 7.04 wt% benzene relative to the total weight of the product stream. The potential purity of benzene was estimated by dividing the amount of benzene by the total amount of benzene azeotropes (including benzene) and multiplying by 100. The benzene azeotropic range is defined here as all components (including benzene) with retention times greater than and greater than methylcyclopentane (standard boiling point 71.8°C), and less than and greater than 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%. Since the supplied raw materials did not contain substantial amounts of benzene, the purity of benzene in the supplied raw materials could not be estimated.

[0120] Comparative Example 1: Benzene production from mixed aromatic feedstock containing azeotropic impurities C4~C 10MAF containing aromatics and substantial benzene azeotropic non-aromatic contaminants was treated 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, but compared to the product of Example 1, approximately 10 times more benzene azeotropic contaminants are still present in the product of Comparative Example 1, demonstrating the advantage of eliminating azeotropic contaminants in the feedstock.

[0121] Example 2: Production of high-purity aromatics from a mixed aromatic feedstock stream C9~C 10 MAF containing aromatics and lacking substantial benzene or toluene azeotropic non-aromatic contaminants was treated 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 here, when measured by gas chromatograph (GC), includes 1,3-dimethylcyclopentane, cis (boiling point 91 °C), and exceeds this, including trans 1,2-dimethyl-cyclohexane (boiling point 123 °C), and is defined as all components (including toluene) having a retention time less than this. Detectable components other than toluene were not found within this boiling range using this analysis, showing an estimated toluene purity of approximately 100%.

[0122] Comparative Example 2: Aromatic generation from a mixed aromatic feed stream containing azeotropic impurities MAF was produced. 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 C4~C produced lower yields of aromatics. 10 MAF is not suitable for use with this invention.

[0123] Example 3: Production of high-purity aromatics from a mixed aromatic feedstock stream MAF was generated. 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 components mainly having six or fewer carbon atoms including benzene. The overhead product was recycled to the aromatization section. Surprisingly, by recycling the light product to the reaction section, the total yield of aromatics increased. Then, the dehexanized aromatics were distilled to remove heavy components generally containing 11 or more carbon atoms. The resulting C7 - C 10 MAF is suitable for use with this invention to produce pure benzene.

[0124] Example 4: Production of MAF from aqueous hydrocarbon streams An aqueous mixture of oxygenates was treated with 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. The light stream consisted of C3 - C6 components that were recycled back to the condensation catalyst. The heavy stream was fractionated to mainly C7 - C 10 Aromatic MAF was generated. Representative MAF products are shown in Table 1.

[0125]

Table 1

[0126] Example 5: Production of mixed xylene from mixed aromatic feedstock MAF from Example 4 containing substantial xylene azeotropic non-aromatic impurities was treated with a transalkylation catalyst at 344 °C, 430 psig, at a hydrogen-to-hydrocarbon ratio of approximately 3.8, and a weight hourly space velocity of 3.3. The product was separated into benzene-rich, toluene-rich, xylene-rich, C9 aromatic-rich, and C 10+Fractional distillation was performed into an aromatic-rich stream. The toluene and C9 aromatic streams were recycled back to the transalkylation catalyst to maximize xylene production. The xylene-rich stream was sent to an isomer recovery process unit to produce a raffinate stream containing a para-xylene isomer stream and unrecovered C8 compounds. The raffinate stream was processed with an isomerization catalyst at 340°C, 150 psig, with a hydrogen-to-hydrocarbon ratio of approximately 1.5 and a gravimetric 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 para-xylene production rate of >99.7% from the isomer recovery process unit at a rate of 457 kilograms per month.

[0127] [Table 2]

[0128] Example 6: Production of benzene from mixed aromatic feedstock The benzene-rich stream, generated in the same manner as in Example 4, was further treated on a transalkylation catalyst at 375°C, 40 psig, with a hydrogen-to-hydrocarbon ratio of approximately 0.4 and a gravimetric space velocity of 1. The product stream was fractionally distilled to recover a purified benzene stream with >99.9% purity having the product composition shown in Table 3.

[0129] [Table 3]

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

[0131]

Table 4

[0132] Example 8: Production of high-purity para-xylene from mixed aromatic feedstock C5 - C 10 MAF containing aromatics and substantially xylene - azeotropic non - aromatic impurities was fractionated to remove C5 - C6 compounds. C7 - C 10 The resulting MAF containing aromatics was treated with a transalkylation catalyst at 360 °C, 430 psig, at a hydrogen - to - hydrocarbon ratio of approximately 3.6, and a weight hourly space velocity of 2.7. The production of para - xylene was increased by diverting a fraction of the isomerization product stream to fractionation and combining it with the C8 stream before entering the isomer recovery process unit. 150 grams per minute were diverted and 20 grams per minute were fractionated. The resulting para - xylene production increased from 457 kilograms per month to 830 kilograms per month. The composition of a representative para - xylene product is shown in Table 5, and the results from different processes are shown in Table 6.

[0133]

Table 5

[0134]

Table 6

[0135] The present invention has been described in considerable detail with reference to certain embodiments, but those skilled in the art will understand that the invention can be used in alternative embodiments of the described embodiments, which are presented for purposes of illustration and not limitation. Accordingly, the scope of the appended claims should not be limited to the descriptions 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 method for separating aromatic compounds from a mixed aromatic feedstock stream, (I C 7~10 A step of generating a product stream by contacting a mixed aromatic feed stream containing aromatic hydrocarbons with an aromatic treatment catalyst, The aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feedstock stream contains more than 1 wt% of non-aromatic components relative to the total weight of the mixed aromatic feedstock stream, and the mixed aromatic feedstock stream is C 12+ Steps that are substantially free of aromatics, (ii) A step of separating aromatic compounds from the product stream by fractional distillation of the product stream. A method that includes this.

[0138] Clause 2. The method according to Clause 1, wherein the mixed aromatic feedstock stream contains 0.1 wt% to 45 wt% of olefins relative to the total weight of the mixed aromatic feedstock stream.

[0139] Clause 3. The method according to Clause 1, wherein the mixed aromatic feedstock stream contains 0.1 wt% to 25 wt% naphthenes relative to the total weight of the mixed aromatic feedstock stream.

[0140] Clause 4. The method according to Clause 1, wherein the mixed aromatic feedstock stream contains 0.1 wt% to 40 wt% of naphthenoolefins relative to the total weight of the mixed aromatic feedstock stream.

[0141] Clause 5. The method according to Clause 1, wherein the mixed aromatic feedstock stream has a bromine value of at least 1 mg Br2 / g mixed aromatic feedstock to less than 100 mg Br2 / g mixed aromatic feedstock.

[0142] Clause 6. The method according to Clause 1, wherein the mixed aromatic feedstock stream contains phenol in an amount of 10 ppm to 10 wt% relative to the total weight of the mixed aromatic feedstock stream.

[0143] Clause 7. The method according to Clause 1, wherein the mixed aromatic feedstock contains oxygenated material in an amount of 10 ppm to 10 wt% ppm relative to the total weight of the mixed aromatic feedstock stream.

[0144] Clause 8.C 7~10 The method according to Clause 1, wherein the aromatic hydrocarbon includes benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, naphthalene, or a combination thereof.

[0145] Clause 9. Step (ii) further includes the step of fractionating the product stream to separate the C8 stream from the product stream of step (i), The method is (iii) The step of providing at least a portion of the C8 stream to an isomer recovery process unit to generate a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, (iv) A step of contacting a raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer, and at least a portion of the isomerized product stream is combined with the product stream produced from the aromatic treatment catalyst in step (i), and The method described in Clause 1, further including the method described in Clause 1.

[0146] Clause 10. Mixed aromatic feedstock stream is C 9~10 The method according to Clause 1, including aromatic compounds.

[0147] Clause 11. The method according to Clause 9, wherein at least a portion of the isomerization product stream is recycled and combined with a C8 stream that enters an isomer recovery process unit.

[0148] Clause 12. The method according to Clause 1, wherein the mixed aromatic feedstock stream does not contain azeotropic impurities of benzene, toluene, and combinations thereof.

[0149] Clause 13. Step (ii) is to fractionally distill the product stream containing the C8 aromatic by C8 distillation. 7- Stream to C 8+ The method according to Clause 1, further comprising the step of supplying to a first distillation column for separation from the stream.

[0150] Clause 14.C 7- The stream is C 7- Stream to C 6- The method according to Clause 13, supplied to a second distillation column that fractionates into a stream and a C7 stream.

[0151] The method according to Clause 14, wherein at least a portion of the C7 stream is recycled and combined with a mixed aromatic feedstock stream.

[0152] Clause 16.C 8+ The method according to Clause 9, wherein at least a portion of the stream is recycled and combined with C8 aromatics that enter an isomer recovery process unit.

[0153] Clause 17. Step (ii) is C 8+ The stream, C 8+ Streams C8 streams and C 9+ The method according to Clause 13, further comprising the step of supplying a stream to a third distillation column for fractional distillation, wherein the C8 stream contains a C8 aromatic compound.

[0154] Clause 18.C 9+ The stream is C 9+ Stream to C 9~10 Streams and C 11+ It is supplied to the fourth distillation column, which fractionates into streams, C 9~10 The method according to Clause 17, wherein the stream is recycled and combined with a mixed aromatic feedstock stream.

[0155] Clause 19. Step (ii) involves fractional distillation of the product stream into C7 stream, C8 stream, and C 9~10A step of separating the streams, wherein the C8 stream is supplied to the isomer recovery process unit, and the C7 stream is recycled and combined with the mixed aromatic feedstock stream, C 9~10 The method according to Clause 9, further comprising the step of recycling the stream and combining it with a mixed aromatic feedstock stream.

[0156] Clause 20. Step (ii) involves fractional distillation of the product stream into C7 stream, C8 stream, and C 9+ A step of separating the streams, wherein the C8 stream is supplied to the isomer recovery process unit, and the C7 stream is recycled and combined with the mixed aromatic feedstock stream, C 9+ The method according to Clause 9, further comprising the step of recovering the stream as a product.

[0157] Clause 21. The method according to Clause 9, wherein the isomer recovery process unit includes an adsorption unit.

[0158] Clause 22. The method according to Clause 9, wherein the isomer recovery process unit includes a crystallization unit.

[0159] Clause 23. The method according to Clause 1, wherein the aromatic treatment catalyst comprises an acid catalyst.

[0160] Clause 24. The method according to Clause 23, wherein the acid catalyst is selected from aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, zirconia sulfate, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination thereof.

[0161] Clause 25. The method according to 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 according to Clause 1, wherein step (i) is performed at a temperature of 200°C to 600°C.

[0163] Clause 27. The method according to Clause 1, wherein step (i) is performed at a pressure of 100 psig to 1500 psig.

[0164] Clause 28. The method according to Clause 1, wherein step (i) is performed at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time.

[0165] Clause 29. The method according to Clause 1, wherein step (i) includes supplying hydrogen in an amount of at least 0.1 moles of hydrogen per mole of mixed aromatic feedstock.

[0166] Clause 30. The method according to Clause 1, wherein step (1) includes supplying hydrogen in an amount of at least 1 mole of hydrogen per mole of mixed aromatic feedstock.

[0167] Clause 31. A method for generating and separating aromatic compounds from a mixed aromatic feedstock stream, (i) Contacting an aqueous hydrocarbon raw material containing water and one or more oxygenated materials with a condensation catalyst, C 4+ A step of generating a condensation product stream containing a compound, C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ A step comprising a cycloalkene, aryl, or condensed aryl, (ii) A step of fractionally distilling the condensation product stream to produce a light stream and a heavy stream, wherein the light stream contains azeotropic non-aromatic impurities of benzene or toluene, and the heavy stream is substantially free of azeotropic non-aromatic impurities of benzene or toluene. (iii) A step of recycling the light stream into a condensation catalyst, (iv) Heavy streams, C 7+ A step of fractional distillation into a mixed aromatic feedstock containing aromatics, (v) A step of contacting a mixed aromatic feed stream with an aromatic treatment catalyst to produce a product stream, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. A method that includes this.

[0168] Clause 32. Step of fractionating the product stream to separate the C8 stream from the product stream, A step of providing at least a portion of the C8 stream to an isomer recovery process unit to generate a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds. A step of contacting a raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer, and at least a portion of the isomerized product stream is combined with a product stream produced from an aromatic treatment catalyst. The method described in Clause 31, which further includes the method described in Clause 31.

[0169] Clause 33. Step (iv) C 7+ Stream to C 7~10 Streams and C 11+ A step of fractionating into streams, C 7~10 The method according to clause 31, further comprising the step of bringing the stream into contact with an aromatic treatment catalyst.

[0170] Clause 34. C9+ stream from step (iv)9~10 Streams and C 11+ A step of fractionating into streams, C 9~10 The method according to clause 31, further comprising the step of bringing the stream into contact with the catalyst.

[0171] Clause 35. The method according to Clause 32, wherein at least a portion of the isomerization product stream is recycled and combined with a C8 stream that enters an isomer recovery process unit.

[0172] The method according to Clause 31, further comprising the step of 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 C 8+ From Stream to C 7- The method according to clause 32, further comprising the step of supplying to a first distillation column for fractional distillation into streams.

[0174] Clause 38.C 7- The stream, C 7- Stream to C 6- The method according to clause 37, further comprising the step of supplying to a second distillation column that fractionates into a stream and a C7 stream.

[0175] Clause 39.C7 At least a portion of the stream is recycled and C 7+ The method described in Clause 38, in combination with the Stream.

[0176] Clause 40.C 8+ The method according to Clause 37, wherein at least a portion of the stream is recycled and combined with C8 aromatics that enter an isomer recovery process unit.

[0177] Clause 41.C 8+ The stream, C 8+ Streams C8 streams and C 9+The method according to Clause 37, further comprising the step of supplying a stream to a third distillation column for fractional distillation, wherein the C8 stream contains a C8 aromatic compound.

[0178] Clause 42.C 9+ The stream is C 9+ Stream to C 9~10 Streams and C 11+ It is supplied to the fourth distillation column, which fractionates into streams, C 9~10 The method according to Clause 41, wherein the stream is recycled and combined with a mixed aromatic feedstock stream.

[0179] Clause 43. The product streams are fractionated into C7 stream, C8 stream, and C 9~10 A step to separate the streams, wherein the C8 stream is supplied to the isomer recovery process unit, and the C7 stream is recycled, and C 7+ Combined with stream, C 9~10 The stream is recycled, C 7+ The method of Clause 32, further including steps, which are combined with the stream.

[0180] Clause 44. The method according to Clause 32, wherein the isomer recovery process unit includes an adsorption unit.

[0181] Clause 45. The method according to Clause 32, wherein the isomer recovery process unit includes a crystallization unit.

[0182] Clause 46. The method according to Clause 31, wherein the aromatic treatment catalyst includes an acid catalyst.

[0183] Clause 47. The method according to Clause 31, wherein the acid catalyst is selected from aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, zirconia sulfate, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, and combinations thereof.

[0184] Clause 48. The method according to 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, their alloys and combinations.

[0185] The method according to Clause 49, wherein step (iv) is carried out at a temperature of 200°C to 600°C and a pressure of 100 psig to 1500 psig, and at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time.

[0186] Article 50. A method for producing and separating xylene isomers, (I C 7+ A step of contacting a mixed aromatic feed stream containing aromatics with an aromatic treatment catalyst to produce a product stream containing C8 aromatics at an increased concentration compared to the mixed aromatic feed stream, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. (ii) Using a distillation column, the product stream is converted to C 7- Streams and C 8+ The step of fractional distillation into streams, (iii) Using a distillation column, C 8+ Streams C8 streams and C 9+ The step of fractional distillation into streams, (iv) The step of providing at least a portion of the C8 stream to an isomer recovery process unit to generate a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, (v) A step of contacting a raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer. Includes, C 8+ A method wherein at least a portion of the stream bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit.

[0187] Clause 51. The method according to Clause 50, wherein the xylene isomer is selected from paraxylene, orthoxylene, or metaxylene.

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

[0189] Clause 53. The method according to Clause 50, wherein the mixed aromatic feedstock stream is substantially free of azeotropic impurities of benzene, toluene, and combinations thereof.

[0190] Clause 54.C 7- The stream is C 7- Stream to C 6- The method according to clause 50, supplied to a distillation column that fractionates into a stream and a C7 stream.

[0191] The method according to Clause 54, wherein at least a portion of the Clause 55.C7 stream is recycled and combined with a mixed aromatic feedstock stream.

[0192] Clause 56.C 9+ The stream is C 9+ Stream to C 9~10 Streams and C 11+It is supplied to the distillation column that fractionates into streams, C 9~10 The method according to Clause 50, wherein the stream is recycled and combined with a mixed aromatic feedstock stream.

[0193] Clause 57. The method according to Clause 50, wherein the isomer recovery process unit includes an adsorption unit.

[0194] Clause 58. The method according to Clause 50, wherein the isomer recovery process unit includes a crystallization unit.

[0195] Clause 59. The method according to Clause 50, wherein the aromatic treatment catalyst comprises an acid catalyst.

[0196] Clause 60. The method according to Clause 59, wherein the acid catalyst is selected from aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, zirconia sulfate, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination thereof.

[0197] Clause 61. The method according to 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 according to Clause 50, wherein step (i) is performed at a temperature of 200°C to 600°C.

[0199] Clause 63. The method according to Clause 50, wherein step (i) is performed at a pressure of 100 psig to 1500 psig.

[0200] Clause 64. The method according to Clause 50, wherein step (i) is performed at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time.

[0201] Clause 65. Before step (i), A condensation catalyst is brought into contact with an aqueous hydrocarbon raw material containing water and one or more oxygenated materials, C 4+ A step of generating a condensation product stream containing a compound, C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ Steps containing cycloalkenes, aryls, or condensed aryls, The condensation product stream is fractionally distilled and C 6- Stream to C 7+ Steps to separate from the stream, C 6- Steps to recycle the stream into a condensation catalyst, C 7+ Stream to C 7~10 Streams and C 11+ A step of fractionating into streams, C 7~10 The stream forms a mixed aromatic feedstock stream, step The method described in Clause 50, including the method described in Clause 50.

[0202] Article 66. A method for producing and separating xylene isomers, (I C 7+ A step of contacting a mixed aromatic feed stream containing aromatics with an aromatic treatment catalyst to produce a product stream containing C8 aromatics at an increased concentration compared to the mixed aromatic feed stream, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. (ii) Using a distillation column, the product stream is converted to C 7- Streams and C 8+The step of fractional distillation into streams, (iii) Using a distillation column, C 8+ Streams C8 streams and C 9+ The step of fractional distillation into streams, (iv) The step of providing at least a portion of the C8 stream to an isomer recovery process unit to generate a raffinate stream containing a xylene isomer stream and unrecovered C8 compounds, (v) A step of contacting a raffinate stream with an isomerization catalyst to produce an isomerization product stream, wherein the isomerization product stream contains at least one xylene isomer, At least a portion of the isomerization product stream is combined with the C8 stream before entering the isomer recovery process unit, and A method that includes this.

[0203] Clause 67. The method according to Clause 66, wherein the xylene isomer includes paraxylene, orthoxylene, or metaxylene.

[0204] Clause 68.C 8+ The method according to Clause 66, wherein at least a portion of the stream bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit.

[0205] Clause 69. The method according to Clause 66, wherein the mixed aromatic feedstock stream is substantially free of azeotropic impurities of benzene, toluene, and combinations thereof.

[0206] Clause 70.C 7- The stream is C 7- Stream to C 6- The method according to Clause 66, supplied to a distillation column that fractionates into a stream and a C7 stream.

[0207] The method according to Clause 70, wherein at least a portion of the C7 stream is recycled and combined with a mixed aromatic feedstock stream.

[0208] Clause 72.C 9+ The stream is C 9+ Stream to C 9~10 Streams and C 11+ It is supplied to the distillation column that fractionates into streams, C 9~10 The method according to Clause 66, wherein the stream is recycled and combined with a mixed aromatic feedstock stream.

[0209] Clause 73. The method according to Clause 66, wherein the isomer recovery process unit includes an adsorption unit.

[0210] Clause 74. The method according to Clause 66, wherein the isomer recovery process unit includes a crystallization unit.

[0211] Clause 75. The method according to Clause 66, wherein the aromatic treatment catalyst comprises an acid catalyst.

[0212] Clause 76. The method according to Clause 75, wherein the acid catalyst is selected from aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, zirconia sulfate, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination thereof.

[0213] Clause 77. The method according to 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 according to Clause 66, wherein step (i) is performed at a temperature of 200°C to 600°C.

[0215] Clause 79. The method according to Clause 66, wherein step (i) is performed at a pressure of 100 psig to 1500 psig.

[0216] The method according to Clause 80, wherein step (i) is performed at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time.

[0217] Clause 81. Before step (i), A water-based hydrocarbon raw material containing water and one or more oxygenated materials is brought into contact with a condensation catalyst, C 4+ A step of generating a condensation product stream containing a compound, C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ A step comprising a cycloalkene, aryl, or condensed aryl, The condensation product stream is fractionally distilled and C 6- Stream to C 7+ Steps to separate from the stream, C 6- The steps include recycling the stream into a condensation catalyst, C 7+ Stream to C 7~10 Streams and C 11+ A step of fractionating into streams, C 7~10 The stream forms a mixed aromatic feedstock stream, and Includes, C 8+ The method according to Clause 66, wherein at least a portion of the stream bypasses the distillation column in step (iii) and is combined with the C8 stream before entering the isomer recovery process unit. It should be noted that the present invention also includes the following embodiments. [Aspect 1] A method for separating aromatic compounds from a mixed aromatic feedstock stream, (I C 7~10 A step of generating a product stream by contacting a mixed aromatic feed stream containing aromatic hydrocarbons with an aromatic treatment catalyst, The aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feedstock stream contains more than 1 wt% of non-aromatic components relative to the total weight of the mixed aromatic feedstock stream, and the mixed aromatic feedstock stream contains C 12+ Steps that are substantially free of aromatics, (ii) A step of fractional distillation of the product stream to separate aromatic compounds from the product stream. A method that includes this. [Aspect 2] With respect to the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream is, 0.1 wt% to 45 wt% olefin, 0.1 wt% to 25 wt% naphthenes, 0.1 wt% to 40 wt% naphthenoolefin, Phenol in amounts of 10 ppm to 10 wt%, and / or Oxygenated substances in amounts of 10 ppm to 10 wt% The method according to embodiment 1, including the method described in embodiment 1. [Aspect 3] The mixed aromatic feedstock stream contains at least 1 mg Br 2 / The aforementioned mixed aromatic supply raw material g~100mg Br 2 The method according to embodiment 1, wherein the bromine value of the mixed aromatic feedstock is less than g. [Aspect 4] The mixed aromatic feedstock stream is substantially free of azeotropic impurities of benzene, toluene, and combinations thereof, or the mixed aromatic feedstock stream is C 9~10 The method according to embodiment 1, comprising an aromatic compound. [Aspect 5] Step (ii) is C 8 The product stream containing aromatics is fractionated by distilling the product stream into C 7- Stream to C 8+ The method according to embodiment 1, comprising the step of supplying to a first distillation column that separates from the stream. [Aspect 6] Said C 7- The stream is C 7- Stream to C 6- Streams and C 7 The method according to embodiment 5, supplied to a second distillation column that fractionates into streams. [Aspect 7] Said C 7 The method according to embodiment 6, wherein at least a portion of the stream is recycled and combined with the mixed aromatic feedstock stream. [Aspect 8] Step (ii) is C 8+ The stream is, C 8+ Stream to C 8 Streams and C 9+ A step of supplying to a third distillation column for fractional distillation in a stream, the C 8 The stream is C 8 The method according to embodiment 5, further comprising the step of including an aromatic compound. [Aspect 9] Said C 9+ The stream is C 9+ Stream to C 9~10 Streams and C 11+ It is supplied to a fourth distillation column that fractionates into streams, and the C 9~10 The method according to embodiment 8, wherein the stream is recycled and combined with the mixed aromatic feedstock stream. [Aspect 10] (iii) C 8 At least a portion of the stream is fed to an isomer recovery process unit, and the xylene isomer stream and unrecovered C 8 The steps include generating a raffinate stream containing the compound, (iv) A step of contacting the raffinate stream with an isomerization catalyst to generate an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer, and at least a portion of the isomerized product stream is combined with the product stream generated from the aromatic treatment catalyst in step (i), and The method according to embodiment 8, further comprising: [Aspect 11] At least a portion of the isomerization product stream enters the isomer recovery process unit C 8 The method according to embodiment 10, which is combined with a stream. [Aspect 12] Said C 8+ At least a portion of the stream enters the isomer recovery process unit C 8 The method according to embodiment 10, which is combined with a stream. [Aspect 13] Step (ii) involves fractional distillation of the product stream to obtain C 7 Stream, C 8 Streams, and C 9~10 A step of separating the stream, wherein C 8 The stream is supplied to the isomer recovery process unit, and the C 7 The stream is recycled and combined with the mixed aromatic feedstock stream, and the C 9~10 The method according to embodiment 10, comprising the step of recycling a stream and combining it with the mixed aromatic feedstock stream. [Aspect 14] Step (ii) involves fractional distillation of the product stream, C 7 Stream, C 8 Streams, and C 9+ A step of separating the stream, wherein C 8 The stream is supplied to the isomer recovery process unit, and the C 7 The stream is recycled and combined with the mixed aromatic feedstock stream, and the C 9+ The method according to embodiment 10, comprising the step of recovering the stream as a product. [Aspect 15] The method according to embodiment 10, wherein the isomer recovery process unit includes an adsorption unit or a crystallization unit. [Aspect 16] The method according to embodiment 1, wherein the aromatic treatment catalyst comprises an acid catalyst comprising aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, sulfated zirconia, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, sulfated carbon, phosphated carbon, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination thereof, and 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. [Aspect 17] The method according to embodiment 1, wherein step (i) is performed at a temperature of 200°C to 600°C, a pressure of 100 psig to 1500 psig, or a weight-space velocity (WHSV) of 0.1 to 10 feedstock mass / catalyst mass / time, or step (i) includes supplying hydrogen in an amount of at least 0.1 mol of hydrogen per mol of mixed aromatic feedstock. [Aspect 18] A method for generating and separating aromatic compounds from a mixed aromatic feedstock stream, (i) Contacting an aqueous hydrocarbon raw material containing water and one or more oxygenated materials with a condensation catalyst, C 4+ A step of generating a condensation product stream containing a compound, wherein C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ A step comprising a cycloalkene, aryl, or condensed aryl, (ii) A step of fractionally distilling the condensation product stream to produce a light stream and a heavy stream, wherein the light stream contains azeotropic non-aromatic impurities of benzene or toluene, and the heavy stream is substantially free of azeotropic non-aromatic impurities of benzene or toluene. (iii) A step of recycling the light stream into the condensation catalyst, (iv) The heavy stream is C 7+ A step of fractional distillation into a mixed aromatic feedstock containing aromatics, (v) A step of contacting the mixed aromatic feed stream with an aromatic treatment catalyst to produce a product stream, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. A method that includes this. [Aspect 19] Step (iv) is C 7+ The mixed aromatic feedstock containing aromatics is (A)C 7~10 Streams and C 11+ Stream or (B)C 9~10 Streams and C 11+ A step of fractionating into streams, wherein C 7~10 Stream or C 9~10 The method according to embodiment 18, further comprising the step of bringing the stream into contact with the aromatic treatment catalyst. [Aspect 20] The method according to embodiment 18, wherein step (iv) is performed at a temperature of 200°C to 600°C and a pressure of 100 psig to 1500 psig, and at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time. [Aspect 21] A method for generating and separating xylene isomers, (I C 7+ A mixed aromatic feedstock stream containing aromatics is brought into contact with an aromatic treatment catalyst, and the concentration of C is increased compared to the mixed aromatic feedstock stream. 8 A step of generating a product stream containing aromatics, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. (ii) Using a distillation column, the product stream is converted to C 7- Streams and C 8+ The step of fractional distillation into streams, (iii) Using a distillation column, C 8+ Stream to C 8 Streams and C 9+ The step of fractional distillation into streams, (iv) C 8 At least a portion of the stream is fed to an isomer recovery process unit, and the xylene isomer stream and unrecovered C 8 The steps include generating a raffinate stream containing the compound, (v) A step of contacting the raffinate stream with an isomerization catalyst to generate an isomerization product stream, wherein the isomerization product stream contains at least one xylene isomer, and at least a portion of the isomerization product stream is brought into contact with the isomerization catalyst before entering the isomer recovery process unit. 8 Steps and A method that includes this. [Aspect 22] The method according to embodiment 21, wherein the xylene isomer stream includes para-xylene, ortho-xylene, or meta-xylene. [Aspect 23] Said C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and enters the isomer recovery process unit before C 8 The method according to embodiment 21, which is combined with a stream. [Aspect 24] Before step (i), A water-based hydrocarbon raw material containing water and one or more oxygenated materials is brought into contact with a condensation catalyst, C 4+ A step of generating a condensation product stream containing a compound, wherein C 4+ The compound is C 4+ Alcohol, C 4+ Ketones, C 4+ Alkane, C 4+ Alken, C 5+ Cycloalkanes, C 5+ Steps containing cycloalkenes, aryls, or condensed aryls, The condensation product stream is fractionally distilled and C 6- Stream to C 7+ Steps to separate from the stream, Said C 6- A step of recycling the stream into the condensation catalyst, Said C 7+ Stream to C 7~10 Streams and C 11+ A step of fractionating into streams, wherein C 7~10 The stream forms the mixed aromatic feed stream, step Includes, Said C 8+ At least a portion of the stream bypasses the distillation column in step (iii) and enters the isomer recovery process unit before C 8 The method according to embodiment 21, which is combined with a stream. [Explanation of Symbols]

[0218] 10 Aromatic Purification Systems 12 Aromatic treatment reactor 14. Mixed aromatic feedstock stream 15 Combined mixed aromatic feedstock streams 16 Mixed aromatic feedstock sources 18 Hydrogen Stream 20 Hydrogen supply sources 22 Aromatic treatment catalysts 24. Product Stream 25 Separator 26. First distillation column 27 Liquid product stream 28 C 7- stream 29 Gas outlet 30 C 8+ Stream, detour stream 32 Second distillation column 34 C 6- stream 36 C7 Stream 38. Third distillation column 40 C8 Stream 42 C 9+ stream 44 The 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 supply sources 58 Isomerization catalysts 59 Hydrogen Stream 60 Isomerization Product Stream 61 Separator 62 Bypass Stream 63 Gas outlet 65 Liquid Product Stream 100 Systems 102 Hydrogenated Deoxygenation (HDO) Reactor 104 Raw material solution supply source 106 Hydrogen supply sources 108 Deoxygenation catalyst 110 Deoxygenation product stream 112 Non-condensable gas stream 111 3 phase separator 114 Organic Product Stream 116 Aqueous Product Stream 118 Water-based 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 Water-based Stream 134 Purge Stream 136 Distillation Column 138 Light product stream 140 Heavy Product Stream 142 Distillation column 144 Heavy Product Supply Raw Material Stream

Claims

1. A method for generating and separating xylene isomers, (i) C ７＋ A mixed aromatic feedstock stream containing aromatics is brought into contact with an aromatic treatment catalyst, and the concentration of C is increased compared to the mixed aromatic feedstock stream. ８ A step of generating a product stream containing aromatics, wherein the aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. (ii) Using a distillation column, the product stream is converted to C ７－ Streams and C ８＋ The step of fractional distillation into streams, (iii) Using a distillation column, the C ８＋ Stream to C ８ Streams and C ９＋ The step of fractional distillation into streams, (iv) At least a part of the C ８ stream is fed to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream containing un-recovered C ８ compounds, and (v) A step of contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream contains at least one xylene isomer. Includes, Before at least a portion of the isomerization product stream enters the isomer recovery process unit, C ８ Combined with stream, Said C ８＋ At least a portion of the stream bypasses the distillation column in step (iii) and enters the isomer recovery process unit before C ８ A method that combines with a stream.

2. The method according to claim 1, wherein the xylene isomer is selected from paraxylene, orthoxylene, or metaxylene.

3. Before step (i), A condensation catalyst is brought into contact with an aqueous hydrocarbon raw material containing water and one or more oxygenated materials, C ４＋ A step of generating a condensation product stream containing a compound, wherein the oxygenated product is a molecule having two or more carbon atoms and one or more oxygen atoms, and the C ４＋ The compound is C ４＋ Alcohol, C ４＋ Ketones, C ４＋ Alkane, C ４＋ Alken, C ５＋ Cycloalkanes, C ５＋ Steps containing cycloalkenes, aryls, or condensed aryls, The condensation product stream is fractionally distilled and C ６－ Stream to C ７＋ Steps to separate from the stream, Said C ６－ A step of recycling the stream into the condensation catalyst, Said C ７＋ Stream to C ７～１０ Streams and C １１＋ A step of fractionating into streams, the C ７～１０ The stream forms a mixed aromatic feed stream, step The method according to claim 1, including the method described in claim 1.

4. With respect to the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream is, 0.1 wt% to 45 wt% olefin, 0.1 wt% to 25 wt% naphthenes, 0.1 wt% to 40 wt% naphthenoolefin, Phenol in amounts of 10 ppm to 10 wt%, and / or Oxygenated substances in amounts of 10 ppm to 10 wt% Includes, The method according to claim 1, wherein the oxygenated product is a molecule having two or more carbon atoms and one or more oxygen atoms.

5. The mixed aromatic feedstock stream contains at least 1 mg Br ２ / The above mixed aromatic supply raw material g to 100 mg Br ２ The method according to claim 1, wherein the bromine value is less than g of the mixed aromatic feedstock.

6. The mixed aromatic feed stream is C ９～１０ The method according to claim 1, comprising an aromatic compound.

7. Said C ７－ The stream is C ７－ Stream to C ６－ Streams and C ７ The method according to claim 1, supplied to a distillation column for fractional distillation into streams.

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

9. Said C ９＋ The stream is C ９＋ Stream to C ９～１０ Streams and C １１＋ It is supplied to a distillation column that fractionates into streams, and the C ９～１０ The method according to claim 1, wherein the stream is recycled and combined with the mixed aromatic feedstock stream.

10. The method according to claim 1, wherein at least a portion of the isomerization product stream is combined with the product stream generated from the aromatic treatment catalyst in step (i).

11. Said C ７－ Stream to C ６－ Streams and C ７ The step of fractional distillation into streams, Said C ９＋ Stream to C ９～１０ Streams and C １１＋ A step of fractionating into streams, the C ７ Stream and the C ９～１０ The method according to claim 10, further comprising the step of recycling the stream and combining it with the mixed aromatic feedstock stream.

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

13. The method according to claim 1, wherein the isomer recovery process unit includes an adsorption unit or a crystallization unit.

14. The method according to claim 1, wherein the aromatic treatment catalyst comprises an acid catalyst comprising aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, sulfated zirconia, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination 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. The method according to claim 1, wherein step (i) is carried out at a temperature of 200°C to 600°C, a pressure of 689 kPa to 10342 kPa (100 psig to 1500 psig), or at a weight-space velocity (WHSV) of 0.1 to 10 feedstock mass / catalyst mass / time, or step (i) comprises supplying hydrogen in an amount of at least 0.1 mol of hydrogen per mol of mixed aromatic feedstock.

16. A method for separating aromatic compounds from a mixed aromatic feedstock stream, (i) C ７～１０ A mixed aromatic feedstock stream containing aromatic hydrocarbons is brought into contact with an aromatic treatment catalyst, ８ A step of generating a product stream containing aromatics, The aromatic treatment catalyst includes a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feedstock stream contains more than 1 wt% of non-aromatic components relative to the total weight of the mixed aromatic feedstock stream, and the mixed aromatic feedstock stream contains less than 1% (w / w), (a) C １２＋ A step comprising (b) an aromatic compound and azeotropic impurities of benzene and toluene, (ii) A step of separating aromatic compounds from the product stream by fractional distillation, (ii-a) C ８ The product stream containing aromatics is obtained by fractional distillation of the product stream. ８＋ From Stream to C ７－ The process of supplying the stream to a distillation column for separation, and (ii-b) C ８＋ At least a portion of the stream is C ８＋ The aforementioned portion of the stream is C ８ Streams and C ９＋ A process of supplying to a distillation column for fractional distillation in a stream, the C ８ The stream is C ８ Processes including aromatics Steps including, (iii) C ８ At least a portion of the stream is fed to an isomer recovery process unit, and the xylene isomer stream and unrecovered C ８ A step of generating a raffinate stream containing a compound, wherein C ８＋ At least a portion of the stream bypasses the distillation column of process (ii-b) and enters the isomer recovery process unit before C ８ Steps combined with streams, (iv) A method comprising the steps of 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 at least a portion of the isomerized product stream is combined with the product stream produced from the aromatic treatment catalyst in step (i).

17. With respect to the total weight of the mixed aromatic feed stream, the mixed aromatic feed stream is, 0.1 wt% to 45 wt% olefin, 0.1 wt% to 25 wt% naphthenes, 0.1 wt% to 40 wt% naphthenoolefin, Phenol in amounts of 10 ppm to 10 wt%, and / or Oxygenated substances in amounts of 10 ppm to 10 wt% Includes, The method according to claim 16, wherein the oxygenated product is a molecule having two or more carbon atoms and one or more oxygen atoms.

18. The mixed aromatic feedstock stream contains at least 1 mg Br ２ / The above mixed aromatic supply raw material g to 100 mg Br ２ The method according to claim 16, wherein the bromine value is less than g of the mixed aromatic supply raw material.

19. The mixed aromatic feed stream is C ９～１０ The method according to claim 16, comprising an aromatic compound.

20. Said C ７－ The stream is C ７－ Stream to C ６－ Streams and C ７ The method according to claim 16, supplied to a distillation column for fractional distillation in stream.

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

22. Said C ９＋ The stream is C ９＋ Stream to C ９～１０ Streams and C １１＋ It is supplied to a distillation column that fractionates into streams, and the C ９～１０ The method according to claim 16, wherein the stream is recycled and combined with the mixed aromatic feedstock stream.

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

24. Step (ii) fractionates the product stream to obtain a C ７ stream, a C ８ stream, and a C ９～１０ stream, wherein the C ８ stream is supplied to the isomer recovery process unit, the C ７ stream is recycled and combined with the mixed aromatic feed stream, and the C ９～１０ stream is recycled and combined with the mixed aromatic feed stream, the method according to claim 16, comprising the step.

25. Step (ii) fractionates the product stream to separate a C ７ stream, a C ８ stream, and a C ９＋ stream, wherein the C ８ stream is fed to the isomer recovery process unit, the C ７ stream is recycled and combined with the mixed aromatic feed stream, and the C ９＋ stream is recovered as a product, the method according to claim 16, comprising the step.

26. The method according to claim 16, wherein the isomer recovery process unit includes an adsorption unit or a crystallization unit.

27. The method according to claim 16, wherein the aromatic treatment catalyst comprises an acid catalyst comprising aluminosilicate, aluminosilicate tungstate, silica-alumina phosphate, aluminum phosphate, amorphous silica-alumina, zirconia, sulfated zirconia, zirconia tungstate, tungsten carbide, molybdenum carbide, titania, acidic alumina, alumina phosphate, alumina tungstate, silica phosphate, silica tungstate, titania tungstate, tungstate phosphate, niobia, carbon sulfate, carbon phosphate, acidic resin, heteropoly acid, tungstate heteropoly acid, inorganic acid, or a combination 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. The method according to claim 16, wherein step (i) is carried out at a temperature of 200°C to 600°C, a pressure of 689 kPa to 10342 kPa (100 psig to 1500 psig), or a weight-space velocity (WHSV) of 0.1 to 10 feedstock mass / catalyst mass / time, or step (i) comprises supplying hydrogen in an amount of at least 0.1 mol of hydrogen per mol of mixed aromatic feedstock.

29. A method for generating and separating aromatic compounds from a mixed aromatic feedstock stream, (i) Contacting an aqueous hydrocarbon raw material containing water and one or more oxygenated materials with a condensation catalyst, C ４＋ A step of generating a condensation product stream containing a compound, wherein the oxygenated product is a molecule having two or more carbon atoms and one or more oxygen atoms, and the C ４＋ The compound is C ４＋ Alcohol, C ４＋ Ketones, C ４＋ Alkane, C ４＋ Alken, C ５＋ Cycloalkanes, C ５＋ A step comprising a cycloalkene, aryl, or condensed aryl, (ii) A step of fractionally distilling the condensation product stream to produce a light stream and a heavy stream, wherein the light stream contains azeotropic non-aromatic impurities of benzene or toluene, and the heavy stream contains less than 1% (w / w) of azeotropic non-aromatic impurities of benzene or toluene. (iii) A step of recycling the light stream into the condensation catalyst, (iv) The heavy stream is C ７＋ The mixed aromatic feedstock containing aromatics is fractionated, and the mixed aromatic feedstock is C ７～１０ Streams and C １１＋ The step of splitting the stream, (v) C above ７～１０ The steps include: separating the aromatic compound by subjecting at least a portion of the stream to the method of claim 1; A method that includes this.

30. The method according to claim 29, wherein step (iv) is carried out at a temperature of 200°C to 600°C and a pressure of 689 kPa to 10342 kPa (100 psig to 1500 psig), and at a weight-space velocity (WHSV) of 0.1 to 10 feed material mass / catalyst mass / time.

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