Process for producing high purity aromatic compounds from mixed aromatic feed streams

Abstract

The present disclosure provides systems and methods for producing aromatic compounds in high yield from mixed aromatic feed streams. Also disclosed are systems and methods for producing aromatic compounds in high yield from oxygenated hydrocarbons, such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 255,812, filed on October 14, 2021, the contents of which are hereby incorporated by reference in their entirety.

[0003] background

[0004] Aromatic hydrocarbons, particularly benzene, toluene and xylene are important industrial commodities for the production of many chemicals, fibers, plastics and polymers including styrene, phenol, aniline, polyester and nylon. Typically, such aromatic hydrocarbons are produced from petroleum feedstocks using well-established refining or chemical processes. Recently, there has been increasing interest in providing aromatic hydrocarbons from alternative resources such as biomass, synthesis gas and natural gas. SUMMARY OF THE INVENTION

[0006] In one aspect, the present disclosure provides a method for separating aromatic compounds from a mixed aromatic feed stream. The method may include (i) subjecting a stream comprising C 7-10 A mixed aromatic feed stream of aromatic compounds is contacted with an aromatics processing catalyst to produce a product stream, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The mixed aromatic feed stream may contain greater than 1 wt% of non-aromatic components based on the total weight of the mixed aromatic feed stream. The mixed aromatic feed stream may be substantially free of C 12+ Aromatic compounds. The method may further comprise (ii) fractionating the product stream to separate the aromatic compounds from the product stream.

[0007] In some embodiments, the mixed aromatic feed stream may comprise, based on the total weight of the mixed aromatic feed stream: from 0.1 wt% to 45 wt% olefins; from 0.1 wt% to 25 wt% naphthenes; from 0.1 wt% to 40 wt% naphtheno-olefins; phenols in an amount from 10 ppm to 10 wt%; and / or oxygenates in an amount 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 mixed aromatic feed to less than 100 mg Br2 / g 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 comprises C 9-10Aromatic compounds.

[0008] In some embodiments, step (ii) of the process of the present invention comprises supplying a product stream comprising C8 aromatic compounds to a first distillation column, which fractionates the product stream to separate the C8 aromatic compounds into the first distillation column. 7- Stream and C 8+ Flow separation. C 7- The stream can be supplied to a second distillation column which converts C 7- The flow is fractionated into C 6- In some embodiments, at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

[0009] In some embodiments, step (ii) further comprises: 8+ The stream is supplied to the third distillation column, which converts C 8+ The stream is fractionated into C8 stream and C 9+ Stream. The C8 stream may contain C8 aromatic compounds. 9+ The stream can be supplied to a fourth distillation column which converts C 9+ The flow is fractionated into C 9-10 Stream and C 11+ Flow. C 9-10 The stream may be recycled and combined with the mixed aromatic feed stream.

[0010] In some embodiments, the method of the present invention may further include: (iii) subjecting at least a portion of the C8 stream to an isomer-recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds; and (iv) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream. The isomerized product stream may comprise at least one xylene isomer. At least a portion of the isomerized product stream may be combined with the product stream produced by the aromatic compound processing catalyst in step (i).

[0011] In some embodiments, at least a portion of the isomerized product stream is combined with a C8 stream that enters an isomer recovery process unit.

[0012] In some embodiments, C 8+ At least a portion of the stream is combined with the C8 stream entering the isomer recovery process unit.

[0013] In some embodiments, step (ii) of the process of the present invention comprises fractionating the product stream to separate a C7 stream, a C8 stream, and a C 9-10 stream, wherein the C8 stream is supplied to the isomer recovery process unit, the C7 stream is recycled and combined with the mixed aromatic feed stream, and the C9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0014] In some embodiments, step (ii) comprises fractionating the product stream to separate a C7 stream, a C8 stream, and a C 9+ stream, wherein the C8 stream is supplied to the isomer recovery process unit, the C7 stream is recycled and combined with the mixed aromatic feed stream, and the C 9+ The stream is recovered as product.

[0015] In some embodiments, the isomer recovery process unit comprises an adsorption unit or a crystallization unit.

[0016] The aromatic compound processing catalyst of method of the present invention can comprise acid catalyst.Acid catalyst can comprise aluminosilicate, tungstated aluminosilicate, silicon dioxide-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconium oxide, sulfated zirconium oxide, tungstated zirconium oxide, tungstated zirconia, tungstated tungstated, tungsten carbide, molybdenum carbide, titanium dioxide, acidic aluminum oxide, phosphated aluminum oxide, tungstated aluminum oxide, phosphated silicon dioxide, tungstated silicon dioxide, tungstated titanium dioxide, tungstated phosphate, niobium oxide (niobia), sulfated carbon (sulfated carbon), phosphated carbon, acidic resin, heteropolyacid, tungstated heteropolyacid, mineral acid or its combination.Acid catalyst can also comprise metal, and described metal comprises Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, its alloy or combination.

[0017] In some embodiments, step (i) of the process of the present invention is carried out at a temperature of from 200° C. to 600° C. In some embodiments, step (i) of the process of the present invention is carried out at a pressure of from 100 psig to 1500 psig. In some embodiments, step (i) of the process of the present invention is carried out at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour. In some embodiments, step (i) of the process of the present invention comprises supplying hydrogen in an amount of at least 0.1 mol of hydrogen per mol of mixed aromatic feed, such as at least 1 mol of hydrogen per mol of mixed aromatic feed.

[0018] In other aspects, the present disclosure provides a method for producing and separating aromatic compounds from a mixed aromatic feed stream. The method can include (i) contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to produce a mixture comprising C 4+ Condensation product stream of compounds. C 4+Compounds may include, for example, C 4+ Alcohol, C 4+ ketone 、 C 4+ Alkanes 、 C 4+ Olefins 、 C 5+ Cycloalkanes 、 C 5+ Cycloolefins, aryls or fused aryls. The method may further comprise (ii) fractionating the condensation product stream to produce a light stream and a heavy stream. In some embodiments, the light stream comprises azeotropic non-aromatic contaminants of benzene or toluene, and the heavy stream is substantially free of azeotropic non-aromatic contaminants of benzene or toluene. The method may further comprise (iii) recycling the light stream to the condensation catalyst, and (iv) fractionating the heavy stream into a stream comprising C 7+ A mixed aromatic feed of aromatic compounds. The method may also include (v) contacting the mixed aromatic feed stream with an aromatic compound processing catalyst to produce a product stream. The aromatic compound processing catalyst may include a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof.

[0019] In some embodiments, step (iv) further comprises adding a 7+ Fractionation of a mixed aromatic feed of aromatic compounds into C 7-10 Stream and C 11+ In some embodiments, step (iv) further comprises adding a 7+ Fractionation of a mixed aromatic feed of aromatic compounds into C 9-10 Stream and C 11+ Flow. C 7-10 Stream or C 9-10 The stream may be contacted with an aromatics processing catalyst.

[0020] In some embodiments, step (v) is carried out at a temperature of from 200°C to 600°C and a pressure of from 100 psig to 1500 psig and at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour.

[0021] In another aspect, the present disclosure provides a method for producing and separating xylene isomers. The method may include (i) making a 7+ The mixed aromatic feed stream of aromatic compounds is contacted with an aromatic processing catalyst to produce a product stream comprising an increased concentration of C8 aromatic compounds relative to the mixed aromatic feed stream, wherein the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The method may further comprise (ii) fractionating the product stream into C8 aromatic compounds using a distillation column;7- Stream and C 8+ stream, and (iii) using a distillation column to convert C 8+ The stream is fractionated into C8 stream and C 9+ The method may further comprise (iv) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds, and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer. In some embodiments, C8 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 yet another aspect, the present disclosure provides a method for producing and separating xylene isomers. The method may include (i) making a 7+ The mixed aromatic feed stream of aromatic compounds is contacted with an aromatic compound processing catalyst to produce a product stream comprising an increased concentration of C8 aromatic compounds relative to the mixed aromatic feed stream, wherein the catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof. The method may further include (ii) fractionating the product stream into C8 aromatic compounds using a distillation column; 7- Stream and C 8+ stream, and (iii) using a distillation column to convert C 8+ The stream is fractionated into C8 stream and C 9+ stream. The method may also include (iv) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds, and (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer. 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.

[0023] The xylene isomer stream may include, for example, para-xylene, ortho-xylene, or meta-xylene.

[0024] 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.

[0025] In some embodiments, prior to step (i), the method comprises:

[0026] An aqueous hydrocarbon feedstock comprising water and one or more oxygenates is contacted with a condensation catalyst to produce a hydrocarbon feedstock comprising C 4+ Condensation product stream of compounds, wherein C 4+Compounds include C 4+ Alcohol, C 4+ Ketone, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+ Cycloolefins, aryl compounds, or fused aryl compounds;

[0027] The condensation product stream is fractionated to separate C 6- Stream and C 7+ flow;

[0028] C 6- The stream is recycled to the condensation catalyst;

[0029] C 7+ The flow is fractionated into C 7-10 Stream and C 11+ flow, where C 7-10 stream to form a mixed aromatic feed stream; and

[0030] Among them 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 DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a schematic diagram of an aromatic compound purification system according to some embodiments of the present disclosure.

[0033] Figure 2 is a schematic diagram of a process configured to convert oxygenated hydrocarbons to form a mixed aromatic feed stream, according to some embodiments of the present disclosure. Detailed Description of the Invention

[0035] In order to make the present disclosure more readily understood, certain terms are first defined below. Additional definitions of the following terms and other terms are set forth throughout the specification.

[0036] In this application, unless otherwise clear from the context, the term "a" may be understood to mean "at least one / kind". As used 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 cover the components or steps listed itemized, whether presented alone or together with one or more additional components or steps. Unless otherwise stated, the terms "about" and "approximately" may be understood to allow for standard variations (e.g., ±10%), as understood by those of ordinary skill in the art. Where ranges are provided herein, the endpoints are included. As used in this application, the term "comprise" and variations of the term, such as "comprising" and "comprises", are not intended to exclude other additions, components, integers or steps.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or the ordinary meaning of the defined terms.

[0038] The present disclosure provides systems and methods for producing aromatic hydrocarbons in high yield and purity. Exemplary aromatic hydrocarbons include, but are not limited to, benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, xylene, and naphthalene. The provided systems and methods can produce aromatic compounds with high purity, for example, at least 98.5%, or at least 99%, or at least 99.5%, or at least 99.9%.

[0039] The provided system and method provide multiple advantages. For example, the processing of mixed aromatic feed streams generally requires separation steps, such as extraction, to produce high-purity aromatic compounds. In some embodiments, the provided system and method obtain high-purity aromatic compounds without the need to implement extraction techniques to remove impurities from the feed stream. Removing extraction from the separation scheme reduces energy requirements and capital costs. Some aromatic products are more difficult to separate than other products. For example, in some embodiments of the present disclosure, xylene isomers (e.g., p-xylene) can be purified using an isomer recovery process unit (e.g., adsorption or crystallization) in combination with an isomerization stage and distillation. The crystallization and adsorption processes require a large amount of energy in the form of heat and electricity to separate the xylene isomers from the intermediate products. In one aspect of the present disclosure, a system and method for reducing the energy burden of separation by allowing a portion of the intermediate stream to directly enter the isomer recovery process unit without distillation, or bypassing a portion of the distillation unit, thereby eliminating the energy associated with the bypassed distillation. This reduces the energy burden of the entire system and surprisingly maintains acceptable product purity despite bypassing the purification stage.

[0040] In another aspect of the present disclosure, systems and methods are provided for producing a mixed aromatic feed stream that is free of or substantially free of azeotropic non-aromatic contaminants of benzene, toluene, and combinations thereof. As used herein, the term "substantially free" refers to less than 1% (w / w) of a specified compound or mixture of compounds in a specified stream. In some embodiments, the mixed aromatic feed stream comprises less than 1% (w / w), or less than 0.5% (w / w), or less than 0.1% (w / w) of azeotropic non-aromatic contaminants of benzene, toluene, and combinations thereof. In the absence or substantial absence of azeotropic non-aromatic contaminants, by supplying the mixed aromatic feed stream to a transalkylation catalyst and / or a dealkylation catalyst, an aromatic product with higher purity and yield is obtained compared to a mixed aromatic stream comprising non-aromatic contaminants.

[0041] As used herein, the term "azeotropic non-aromatic contaminants" refers to non-aromatic substances that cannot be separated from the desired product by distillation or can be separated from the desired product only with great difficulty. For each desired product, the azeotropic non-aromatic compounds are different and can include hydrocarbons, oxygenates, sulfur-containing substances, and nitrogen-containing substances. The benzene azeotropic range is defined herein as all components (including benzene) having a normal boiling point equal to or greater than methylcyclopentane (normal boiling point 71.8°C) and less than or equal to cis-1,3 dimethylcyclopentane (normal boiling point 91°C). Exemplary azeotropic non-aromatic contaminants of benzene include, but are not limited to, methylcyclopentane, cyclohexane, methylcyclopentene, C7 paraffins, and C7 olefins.

[0042] The azeotropic range of toluene is defined herein as all components (including toluene) having retention times greater than and including cis-1,3 dimethylcyclopentane (bp 91°C) and less than and including trans-1,2-dimethyl-cyclohexane (bp 123°C).

[0043] Reference Figure 1 , an aromatics purification system 10 is illustrated according to some aspects of the present disclosure. For the sake of clarity and simplicity, equipment for controlling temperature and flow within the aromatics purification system 10 has been omitted from the figure. However, it should be understood that the aromatics purification system 10 may include various equipment for controlling temperature (e.g., heat exchangers, fired heaters, chillers, electric heaters, or combinations thereof for heating or cooling process streams), even though it has been omitted from the figure. The aromatics purification system 10 may include equipment for controlling the flow of fluids, including, but not limited to, pumps, valves, compressors, blowers, or combinations thereof, for regulating the flow of fluids throughout the system 10, even though it has been omitted from the figure.

[0044] In some aspects, the aromatics purification system 10 includes an aromatics processing reactor 12 having an inlet that places the aromatics processing reactor 12 in fluid communication with a mixed aromatic feed stream 14. A pump can be configured in 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 an upstream process unit, to the aromatics processing reactor 12. In some embodiments, the mixed aromatic feed stream 14 is optionally mixed with a C7 stream 36 and a C 9-10 Streams 46 are combined, which are further defined below.

[0045] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises non-aromatic compounds and aromatic compounds, which can be derived from a variety of original sources, including but not limited to biomass-derived oxygenates and condensation products, petroleum refining, thermal or catalytic cracking of hydrocarbons, coking of coal, petrochemical conversion, or combinations thereof.

[0046] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises from 0.1 wt% to 45 wt% non-aromatic hydrocarbons, such as paraffins, olefins, cycloalkanes, cycloalkanes-olefins, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 0.1 wt% non-aromatic hydrocarbons, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt%, or less than 45 wt% non-aromatic hydrocarbons. In some embodiments, the hydrocarbon feed stream comprises C 3-30 Paraffin, C 3-30 Olefins 、 C 5-30 Cycloalkanes or combinations thereof.

[0047] As used herein, the term "paraffin" or "alkane" refers to C 3-30 Saturated straight chain hydrocarbons or branched chain hydrocarbons. In some embodiments, paraffin wax has C n H 2n+2 wherein n can be in the range of from 3 to 30, from 3 to 25, from 3 to 20, from 3 to 15, from 3 to 10, or from 3 to 6.

[0048] As used herein, the term "olefin" or "alkene" refers to a C-olefin having at least one carbon-carbon double bond. 3-30 In some embodiments, the olefin has C n H 2n wherein n can be in the range of from 3 to 30, from 3 to 25, from 3 to 20, from 3 to 15, from 3 to 10, or from 3 to 6.

[0049] Examples of various paraffins and olefins include, but are not limited to, propane, propylene, 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, decamethylpentane ... Undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptadecane, heptadecane, octadecane, octadecene, nonadecane, nonadecane, eicosane, eicosene, heneicosane, heneicosene, docosane, docosene, tricosane, tricosene, tetracosane, tetracosene and their isomers.

[0050] In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises from at least 0.1 wt% olefins, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt%, or less than 45 wt% olefins.

[0051] As used herein, the term "naphthene" or "cycloalkane" refers to a saturated cyclic hydrocarbon group, a bicyclic hydrocarbon group, or a bridged cyclic hydrocarbon group. The saturated cyclic hydrocarbon group, the bicyclic hydrocarbon group, or the bridged cyclic (e.g., adamantane) hydrocarbon group may be substituted with one or more straight or branched alkyl groups or alkylene groups, for example, the substituted group may include a straight or branched C 1-12 Alkyl, linear or branched C 3-12 Alkylene, linear or branched C 1-4 Alkyl, linear or branched C 3-4 Alkylene. Cycloalkanes may be monosubstituted or polysubstituted. In some embodiments, cycloalkanes have C n H 2n wherein n can be in the range of from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, or from 5 to 6.

[0052] Examples of cycloalkanes include, but are not limited to, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, ethylcyclohexane, propylcyclohexane, butylcyclopentane, butylcyclohexane, pentylcyclopentane, pentylcyclohexane, hexylcyclopentane, hexylcyclohexane, decalin, ethyldecalin, pentyldecalin, hexyldecalin, and isomers thereof.

[0053] In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises from at least 0.1 wt% cycloalkanes, 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% cycloalkanes.

[0054] As used herein, the term "cycloalkane-olefin" refers to a saturated cyclic hydrocarbon group, a bicyclic hydrocarbon group, or a bridged cyclic hydrocarbon group having a monosubstituted olefin or a polysubstituted olefin on the hydrocarbon group. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises at least 0.1 wt% cycloalkane-olefin, 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% cycloalkane-olefin.

[0055] In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises from 10 wt% to 80 wt% aromatic hydrocarbons, such as aromatic compounds, fused aromatic compounds, polycyclic compounds, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 10 wt% aromatic hydrocarbons, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt%, to less than 50 wt%, less than 55 wt%, or less than 60 wt%, or less than 65 wt%, or less than 75 wt%, or less than 80 wt% aromatic compounds. In some embodiments, the hydrocarbon feed stream comprises more than one C 6-30 Aryl compounds, C 12-30 Fused aromatic compounds, C 12-30 Polycyclic compounds or combinations thereof.

[0056] As used herein, the terms "aryls" and "aromatics" refer to aromatic hydrocarbons in unsubstituted (phenyl), monosubstituted, or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ As an example, at least one of the substituted groups includes a branched C 3+ Alkyl, straight chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight chain C 2-12 As another example, at least one of the substituted groups includes a branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4Examples of various aromatic compounds include, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, p-xylene, m-xylene, o-xylene, C 9+ Aromatic compounds, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene and their isomers.

[0057] In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises phenols in an amount of from at least 10 ppm to less than 10 wt%, based on the total weight of the feed stream. In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises phenols in an amount of from at least 10 ppm to less than 10 wt%, based on the total weight of the feed stream. In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises phenols in an amount of from at least 10 ppm, 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.

[0058] As used herein, the term "fused aromatic compound" or "polynuclear aromatic compound (PNA)" refers to bicyclic and polycyclic aromatic hydrocarbons in unsubstituted, monosubstituted or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3-12 Alkyl, straight chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight chain C 2-12 Alkylene, branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4 Examples of various fused aryl compounds include, but are not limited to, naphthalene, anthracene, and isomers thereof.

[0059] As used herein, the term "polycyclic compound" refers to bicyclic and polycyclic hydrocarbons having at least one saturated ring or partially saturated ring, in unsubstituted, monosubstituted or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3-12 Alkyl, straight chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight chain C 2-12 Alkylene, branched C3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4 Examples of various polycyclic compounds include, but are not limited to, tetralin (ie, tetrahydronaphthalene), ethyltetralin, pentyltetralin, hexyltetralin, and isomers thereof.

[0060] In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 has a bromine number of at least 1 mg Br2 / g feed to less than 100 mg Br2 / g feed. In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 has a bromine number greater than 1 mg Br / g feed, or at least 5 mg Br / g feed, or at least 10 mg Br / g feed, or at least 15 mg Br / g feed, or at least 20 mg Br / g feed, or at least 25 mg Br / g feed, or at least 30 mg Br / g feed, or at least 40 mg Br / g feed, or at least 50 mg Br / g feed, or less than 60 mg Br / g feed, or less than 70 mg Br / g feed, or less than 80 mg Br / g feed, or less than 90 mg Br / g feed, or less than 100 mg Br / g feed. Bromine number is a measure of aliphatic unsaturation in the feed. Bromine number can be determined using known methods such as ASTM D1159.

[0061] In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises oxygenates in an amount from 10 ppm to less than 10 wt%, based on the total weight of the feed stream. In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 comprises oxygenates in an amount from at least 10 ppm, or at least 50 ppm, or at least 100 ppm, or at least 200 ppm, or at least 300 ppm, or at least 400 ppm, or at least 500 ppm, or at least 600 ppm, or at least 700 ppm, or at least 800 ppm, or at least 900 ppm, or at least 0.1 wt%, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, to less than 5 wt%, or less than 6 wt%, or less than 7 wt%, or less than 8 wt%, or less than 9 wt%, or less than 10 wt% oxygenates, based on the total weight of the feed stream.

[0062] As used herein, the term "C n+ ” refers to a hydrocarbon compound having n or more carbons (e.g., at least 7 carbons) in the compound, and the term “Cn- " refers to hydrocarbon compounds having n or fewer carbons (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 comprises C 7+ Aromatic hydrocarbons. In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 comprises C 7-10 Aromatic compounds, C 8-10 Aromatic compounds or C 9-10 In some embodiments, the mixed aromatic feed stream 14 or the combined mixed aromatic feed stream 15 is free of or substantially free of heavy aromatic compounds, such as C 11+ In some embodiments, mixed aromatic feed stream 14 or combined mixed aromatic feed stream 15 is free or substantially free of azeotropic contaminants of benzene, toluene, or a combination thereof.

[0063] If you will refer to Figure 2 As described in more detail, the mixed aromatic feed stream 14 can be produced from water-soluble sugars derived from biomass. Additionally or alternatively, the mixed aromatic feed stream 14 can be derived from a variety of raw sources, including but not limited to petroleum refining, thermal or catalytic cracking of hydrocarbons, coking or petrochemical conversion of coal.

[0064] Return Reference Figure 1 The aromatics processing reactor 12 may optionally include a hydrogen inlet that places the aromatics processing reactor 12 in fluid communication with a hydrogen stream 18. A gas delivery device may be configured in the hydrogen stream 18 to deliver hydrogen to the aromatics processing reactor 12 from a hydrogen source 20, such as a reservoir or an upstream process unit.

[0065] The aromatics processing reactor 12 includes an aromatics processing catalyst 22 configured to reform the mixed aromatic feed stream 14 to produce a product stream having an increased concentration of C8 aromatic compounds relative to the aromatic feed stream 14 or the combined aromatic feed stream 15. Suitable aromatics processing catalysts 22 include, but are not limited to, transalkylation catalysts, dealkylation catalysts, hydrocracking catalysts, or combinations thereof. In some embodiments, the aromatics processing catalyst 22 may comprise a bifunctional acidic metal-containing catalyst. The aromatics processing catalyst 22 may include, but is not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof.

[0066] In some embodiments, the aromatics processing catalyst 22 may include the above substances 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 aromatics processing catalyst 22 may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, or combinations thereof to provide metallic functionality.

[0067] In some embodiments, aromatics processing reactor 12 is operated as a gas phase reactor, wherein optional hydrogen and aromatic feed stream 14 are introduced into aromatics processing reactor 12 and allowed to flow downwardly through a fixed bed of aromatics processing catalyst 22. Alternatively, aromatics processing reactor 12 is operated as a radial reactor or an upflow reactor. In other embodiments, reactor 12 is operated as a fixed trickle bed reactor, wherein optional hydrogen and combined aromatic feed streams are introduced into reactor 12 and allowed to flow downwardly through a fixed bed of catalyst 22. Although in Figure 1 The hydrogen stream 18 and the combined aromatic stream 15 are depicted in a co-current direction, but it should be understood that a counter-current orientation can be achieved.

[0068] In some embodiments, aromatics processing reactor 12 operates at a temperature of from 200° C. to 600° C., 250° C. to 550° C., or from 300° C. to 500° C. In some embodiments, the pressure of aromatics processing reactor 12 ranges from atmospheric pressure to 1500 psig. In some embodiments, reactor 12 operates at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour, or a WHSV of 0.5 to 8.

[0069] Product stream 24 leaves aromatic compound processing reactor 12 through reactor outlet, and this reactor outlet is cooled to condense aromatic compound; And is conveyed to separator 25, and this separator 25 removes unreacted hydrogen and non-condensable compound from product stream 24. Cooling of product stream 24 can be realized using one or more heat exchangers. A portion of unreacted hydrogen can be optionally recycled and combined with hydrogen stream 18 via gas outlet 29. Recycling of unreacted hydrogen can be realized by using gas conveying device, and described gas conveying device is such as compressor or blower. Then make liquid product stream 27 from separator 25 undergo distillation, to recover multiple product fractions. The order in which fractions are recovered can be different depending on implementation details.

[0070] In one embodiment, the liquid product stream 27 from the separator 25 is directed to the first distillation column 26. A pump may be configured in the liquid product stream 27 to facilitate the transport of the liquid product stream 27, and a heat exchanger may be configured in the liquid product stream 27 to control the temperature of the liquid product stream entering the first distillation column 26. A valve may be positioned in the product stream 27 to regulate the flow. The first distillation column 26 fractionates the liquid product stream 27 into C 7- Stream 28 and C 8+ Flow 30. Although Figure 1 The first distillation column 26 is depicted as a single column, but it should be understood that the liquid product stream 27 is fractionated into C 7- Stream 28 and C 8+ Stream 30 may be carried out on a plurality of distillation columns.

[0071] In some embodiments, C 7- Stream 28 is supplied to a second distillation column 32 which converts C 7- Stream 28 is fractionated into C 6- Stream 34 and C7 stream 36. In some embodiments, C 6- Stream 34 is collected from the process or discarded. 6- Stream 34 may optionally be further processed in an aromatics purification unit to remove C 6- The products are separated in stream 34. For example, C 6- Stream 34 may undergo additional distillation, crystallization or adsorption to remove the C 6- Benzene is separated in stream 34. 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 aromatic compounds.

[0072] 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 the combined mixed aromatic feed stream 15, so that the C7 stream 36 can be further reacted over the aromatics processing catalyst 22. Additionally or alternatively, at least a portion of the C7 stream 36 can be collected or discarded from the process. The collected or discarded portion of the C7 stream 36 can optionally be further processed in an aromatics purification unit to separate products from the C7 stream 36. For example, the C7 stream 36 can undergo additional distillation, crystallization, or adsorption to separate toluene from the C7 stream 36.

[0073] In some embodiments, the C leaving the first distillation column 26 is 8+ Stream 30 is supplied to a third distillation column 38. The third distillation column 38 converts C 8+ Stream 30 is fractionated into C8 stream 40 and C 9+ Stream 42. In some embodiments, C8+ At least a portion of stream 30 optionally bypasses third distillation column 38 so that C 8+ This portion of stream 30 is combined with C8 stream 40 exiting third distillation column 38. The bypass stream provides several advantages. First, bypassing third distillation column 38 reduces the energy burden of the overall system by reducing the flux of material passing through distillation column 38, thereby reducing operating costs. Furthermore, applicants have surprisingly and unexpectedly discovered that, despite bypassing distillation column 38, incorporating the bypass stream reduces operating costs while still maintaining acceptable product purity.

[0074] In some embodiments, C 9+ Stream 42 is supplied to a fourth distillation column 44. The fourth distillation column converts C 9+ Stream 42 is fractionated into C 9-10 Stream 46 and C 11+ Stream 48. In some embodiments, C 9-10 At least a portion of stream 46 is recycled and combined with mixed aromatic feed stream 14 to form combined mixed aromatic feed stream 15, such that C 9-10 Stream 46 may be further reacted over aromatics processing catalyst 22. Additionally or alternatively, C 9-10 At least a portion of stream 46 may be collected or discarded from the process. 9-10 Stream 46 may optionally be further processed in an aromatics purification unit to remove C 9-10 The products are separated in stream 46. For example, C 9-10 Stream 46 may undergo additional distillation, crystallization, or adsorption to remove the C 9-10 Naphthalene is separated in stream 46. In some embodiments, C 11+ Stream 48 is discarded from the system or further processed in a downstream process unit. 11+ The stream is collected or further separated for diesel fuel use or as a lubricant or fuel oil. Additionally or alternatively, C 11+ The stream may be cracked, separated and recycled to the mixed aromatic feed stream or acid condensation catalyst for further processing.

[0075] 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 comprising unrecovered C8 compounds. Exemplary isomer recovery process units 50 include, but are 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 can be configured to purify para-xylene, ortho-xylene, or meta-xylene from the C8 stream 40.

[0076] In some embodiments, a raffinate stream 54 comprising unrecovered C8 compounds is supplied to an isomerization reactor 56. A pump and valve may be configured in the raffinate stream 54 to regulate the flow of the raffinate to the isomerization reactor 56. The isomerization reactor 56 includes an isomerization catalyst 58 configured to produce an isomerized product stream comprising an increased concentration of desired xylene isomers (e.g., para-xylene, o-xylene, or meta-xylene) and with minimal conversion to lighter and heavier products. The isomerization reactor 56 may optionally include a hydrogen inlet that places the isomerization reactor 56 in fluid communication with a hydrogen stream 59. A gas delivery device may be configured in the hydrogen stream 59 to deliver hydrogen to the isomerization reactor 56 from a hydrogen source 57 such as a reservoir or an upstream process unit. In some embodiments, the hydrogen sources 20 and 57 originate from the same reservoir or upstream process unit.

[0077] In some embodiments, the isomerization catalyst 58 includes aluminum oxide, silicon dioxide, aluminosilicates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), and combinations thereof. In some embodiments, the isomerization catalyst 58 includes the above substances 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 metal functionality. The isomerization reactor 56 may be operated as a fixed trickle bed reactor or as a slurry reactor. In some embodiments, the isomerization reactor 56 operates at a temperature from 100°C to 500°C, at a pressure from atmospheric to 1500 psig, and at a WHSV from 0.1 mass feed / mass cat / hr to 10 mass feed / mass cat / hr.

[0078] In some embodiments, at least a portion of the isomerized product stream 60 exits through the reactor outlet, which is cooled to condense the product; and is conveyed to a separator 61 that removes unreacted hydrogen and non-condensable compounds from the isomerized product stream 60. Cooling of the isomerized product stream 60 can be achieved using one or more heat exchangers. Some or all of the unreacted hydrogen can be optionally recycled and combined with the hydrogen stream 59 via a gas outlet 63. Recycling of the unreacted hydrogen can be achieved by using a gas conveying device, such as a compressor or a blower. The liquid product stream 65 from the separator 61 is conveyed to the first distillation column 26 for fractionation. In some embodiments, the liquid product stream 65 from the separator 61 is optionally recycled and combined with the liquid product stream 27 from the separator 25 before being conveyed to the first distillation column 26.

[0079] In some embodiments, at least a portion of the isomerized product stream 60 is optionally recycled and combined with the C8 stream 40 exiting the third distillation column 38. For example, a portion of the liquid product stream 65 can be separated into stream 62, which is then conveyed and combined with the C8 stream 40. Bypass stream 62 provides several advantages. As discussed above, bypassing distillation columns 26, 32, and 38 reduces the energy burden of the overall system by reducing the throughput of material through the distillation columns, thereby reducing operating costs. Furthermore, applicants have surprisingly and unexpectedly discovered that, despite bypassing distillation columns 26, 32, and 38, incorporating bypass stream 62 reduces operating costs while still maintaining acceptable product purity. For example, when operated in conjunction with one or both of bypass streams 30 and 60, product purities of at least 98.5%, at least 99%, or at least 99.5% can be achieved in xylene stream 52.

[0080] In some embodiments, the mixed aromatic feed stream 14 may be generated from biomass-derived oxygenated hydrocarbons. Figure 2 An exemplary system 100 for producing a mixed aromatic feed stream 14 from biomass-derived oxygenated hydrocarbons is depicted in FIG. In some embodiments, system 100 includes a hydrodeoxygenation (HDO) reactor 102 in fluid communication with a feedstock solution source 104 and a hydrogen source 106.

[0081] In some embodiments, the feedstock solution source 104 includes a feedstock solution that includes water-soluble sugars derived from biomass. As used herein, the term "biomass" refers to, but is not limited to, organic materials produced by plants (such as leaves, roots, seeds, and stems) as well as metabolic waste products of microorganisms and animals. Common sources of biomass include: (1) agricultural wastes such as corn stover, rice straw, seed hulls, sugarcane residue, bagasse, nut shells, and manure from cattle, poultry, and pigs; (2) wood materials such as wood or bark, sawdust, timber slash, and mill scrap; (3) municipal waste such as waste paper and yard clippings; and (4) energy crops such as poplar, willow, switchgrass, alfalfa, prairie bluestream, corn, soybeans, and the like.

[0082] A variety of sugar processing methods are well known in the art and are commercially implemented on a large scale for producing sugar solutions from biomass. For example, in a process using sugar cane, the sugar cane is typically washed, crushed or spread and clarified with lime to separate and provide an intermediate raw material stream rich in sucrose, fructose and glucose derived from aqueous biomass. In a process using sugar beets, the sugar beets are also washed, sliced, extracted and clarified to separate and provide an intermediate raw material stream rich in sucrose, fructose and glucose derived from aqueous biomass. For processes involving grains, the grains are washed and then processed to provide wet-milled starch (corn) or dry-milled / ground starch (corn, wheat, barley, sorghum grains). The separated sugar solution can be adjusted to obtain the desired sugar concentration, for example, the separated sugar solution can be concentrated or diluted with water to provide a raw material solution 104. Typically, a suitable concentration is in the range of about 5% to about 70%, with a range of about 40% to 70% being more common in industrial applications.

[0083] For the raw material of lignocellulosic biomass, biomass feed can be decomposed (deconstruct) into sugar and soluble oxygen-containing compounds from complex biopolymers to form raw material solution 104. In one embodiment, the original lignocellulosic raw material (such as corn stover) is decomposed to form soluble sugar by dilute acid thermochemical pretreatment, pH adjustment via alkali such as ammonium hydroxide, lime, sodium hydroxide or potassium hydroxide and enzymatic hydrolysis. Optional pre-conversion methods include fractionation when harvesting raw materials, fractionation by screening, chemical pre-processing to extract undesirable components, fermentation pre-processing such as treatment by white rot fungi, mechanical methods such as steam explosion, drying or pelletizing. Alternative means of decomposition include thermochemical pretreatment (hot water only), alkali (such as ammonia, sodium hydroxide, potassium hydroxide), oxidation (such as peroxide, oxygen, air), organic solvents (such as ethanol, acetic acid, catalytic source solvents) and ionic liquids by autohydrolysis. The processing steps of lignocellulosic biomass can also include additional processing to provide biomass that has been chopped, chopped, pressed, ground or processed into a size suitable for conversion.

[0084] In some embodiments, feedstock solution 104 can be formed using one or more of the aforementioned processes and can be derived from one or more of the aforementioned biomass sources. The feedstock solution can be made from biomass by any means now known or developed in the future, or can simply be a byproduct of another process.

[0085] In some embodiments, the feedstock solution comprises one or more oxygenated hydrocarbons. The term "oxygenated hydrocarbons" refers to water-soluble hydrocarbons containing three or more carbon atoms and two or more oxygen atoms, such as carbohydrates (e.g., monosaccharides, disaccharides, oligosaccharides, polysaccharides, and starch), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols (e.g., diols, triols, and polyols), and sugar degradation products (e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, and furfural), each of which is represented herein as C 3+ O 2+ As used herein, the term "oxygenated compound" or "oxygenate" refers to a molecule having two or more carbon atoms and one or more oxygen atoms (i.e., C 2+ O 1+ ); The term "monooxygenate" refers to a hydrocarbon molecule containing two or more carbon atoms and one oxygen atom (i.e., C 2+ O1); the term "dioxygenate" refers to a hydrocarbon molecule containing two or more carbon atoms and two oxygen atoms (i.e., C 2+ O2); and the term "polyoxygenate" refers to a hydrocarbon molecule containing two or more carbon atoms and three or more oxygen atoms (i.e., C2+ O 3+ ).

[0086] In addition to oxygenated hydrocarbons, raw materials can also include lignin, one or more extracts, one or more ash components or one or more organic substances (such as lignin derivatives). Extracts include terpenes, stilbenes, flavonoids, phenols, aliphatic compounds, lignans, alkanes, protein materials, amino acids and other inorganic products. Ash components include Al, Ba, Ca, Fe, K, Mg, Mn, P, S, Si, Zn etc. Other organic substances include 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, vanillin, 4-propyl eugenol (4-propyl syringol), vitamin E, steroids, long-chain hydrocarbons, long-chain fatty acids, stilbenes etc.

[0087] In some embodiments, the feed solution 104 is optionally hydrogenated before being converted in the hydrodeoxygenation reactor 102. For example, the feed solution can contact the hydrogenation catalyst in the reactor (now shown) at a hydrogenation temperature and a hydrogenation pressure to produce a hydrogenated product stream. A variety of processes known for hydrogenating carboxylic acids are known. Hydrogenation catalysts typically include Fe, Ru, Co, Pt, Pd, Ni, Re, Cu and alloys or combinations thereof, either alone or with a promoter, such as Ag, Au, Cr, Zn, Mn, Mg, Ca, Cr, Sn, Bi, Mo, W, B, P and alloys or combinations thereof. The hydrogenation catalyst can also include any one of several carriers, depending on the desired function of the catalyst. Such a carrier can include carbon, silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, vanadium oxide, ceria, silica-aluminate, zeolite, diatomaceous earth, hydroxyapatite, zinc oxide, magnesium oxide, chromium oxide and mixtures thereof.

[0088] Typically, the hydrogenation reaction is carried out at a hydrogenation temperature between about 80° C. and 350° C. and a hydrogenation pressure in the range of about 50 psig to 5000 psig. The hydrogen used in the reaction may include in situ hydrogen generated from other reactions occurring in series or in parallel within the reactor, external H 2 , recycled H 2 , or a combination thereof.

[0089] In some embodiments, feed solution 104 comprises carboxylic acid that can be hydrogenated.The degree that carboxylic acid feed stream is hydrogenated can be measured by the amount of the molecular hydrogen consumed during hydrogenation, and can be in the scope of 0.05 mole to 2.0 moles of molecular hydrogen that every mole of carboxylic acid group consumes in charging.Usually, reaction should be carried out under the condition that the residence time of carboxylic acid raw material on catalyst is suitable for producing required oxygenate.For example, the residence time can be between 0.01 and 30 or between 0.05 and 10 or at the weight hourly space velocity (WHSV) between 0.1 and 5 set up.

[0090] Return Reference Figure 2 , the feed solution 104 is contacted with a deoxygenation catalyst 108 in the presence of hydrogen to produce a deoxygenated product stream 110 comprising a mixture of one or more oxygenates. The deoxygenated product stream 110 may include an H:C ratio greater than or equal to 0.5 and less than 2, or from 0.8 to 1.8, or from 1 to 1.6, or from 1.2 to 1.6. eff 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.

[0091] As used herein, the term "H:C eff The "ratio" is based on the amounts of carbon, oxygen, and hydrogen in the feed and is calculated as follows: Where H represents the number of hydrogen atoms, O represents the number of oxygen atoms, and C represents the number of carbon atoms. Water and molecular hydrogen (diatomic hydrogen, H2) are excluded from the calculation. eff The ratios apply to both individual components and mixtures of components, but are not valid for components containing atoms other than carbon, hydrogen, and oxygen. For mixtures, C, H, and O are summed over all components except water and molecular hydrogen. The term "hydrogen" refers to any hydrogen atom, while the term "molecular hydrogen" is limited to diatomic hydrogen H2. In some embodiments, H:C eff The ratio can be controlled or adjusted by varying the hydrogenation catalyst and the hydrodeoxygenation catalyst and operating conditions (eg, temperature, pressure, WHSV, feed source selection and concentration).

[0092] In some embodiments, the deoxygenated product stream 110 comprises C 1+ O 1-3 Hydrocarbons are compounds having 1 or more carbon atoms and between 1 and 3 oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxycarboxylic acids, carboxylic acids, diols, and triols. 1+ O1-3 The hydrocarbons have from 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms. 1+ O 1-3 In addition to hydrocarbons, the deoxygenated product stream 110 may also contain hydrocarbons without the element of oxygen.

[0093] Exemplary alcohols in the deoxygenated product stream 110 may include, but are not limited to, primary C 1+ Alcohol, secondary C 1+ Alcohol, linear C 1+ Alcohol, branched C 1+ Alcohol or cyclic C 1+Alcohol, such as methanol, ethanol, n-propanol, isopropanol, butanol (butyl alcohol), isobutanol, butanol (butanol), amyl alcohol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and its isomer.Illustrative ketone can include but is not limited to hydroxy ketone, cyclic ketone, diketone, acetone (acetone), acetone (propanone), 2-oxopropanal, butanone, butane -2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane -2,3-dione, pentane -2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, diacetyl, pentanedione, hexanedione (diketohexane) and its isomer. Exemplary aldehydes may include but are not limited to hydroxyaldehydes, acetaldehyde, propionic acid, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, octanal, nonanal, decanal, undecanediol, dodecanal and isomers thereof. Exemplary carboxylic acids may include but are not limited to formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives such as 2-hydroxybutyric acid and lactic acid. Exemplary diols may include but are not limited to ethylene glycol, propylene glycol, 1,3-propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanal, nonanediol, decanediol, undecanediol, dodecanediol and isomers thereof. Exemplary triols may include but are not limited to glycerol, 1,1,1 tris (hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane, hexanetriol and isomers thereof. Exemplary furans and furfurals include, but are not limited to, furan, tetrahydrofuran, dihydrofuran, 2-furylmethanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methylfuran, 2-ethyl-tetrahydrofuran, 2-ethylfuran, hydroxymethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethylfuran, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.

[0094] In some embodiments, the deoxygenation catalyst 108 comprises a heterogeneous catalyst having one or more materials that can catalyze the reaction between hydrogen and the feedstock solution 104 to remove one or more oxygen atoms from the feedstock solution to produce one or more oxygen-containing compounds. In some embodiments, the deoxygenation catalyst 108 comprises one or more metals adhered 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 thereof, and combinations thereof. The deoxygenation catalyst may include these elements alone or in combination with one or more of 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 comprises Pt, Ru, Cu, Re, Co, Fe, Ni, W, or Mo. In yet another embodiment, the deoxygenation catalyst comprises Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, or Ru. In another embodiment, the catalyst comprises Fe, Re, and at least Cu or one Group VIIIB transition metal. The support may be any of the supports described further below, including nitrides, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, and mixtures thereof.

[0095] The deoxygenation temperature may be in the range of from 80° C. to 300° C. In some embodiments, the reaction temperature is between about 120° C. and 600° C., or between about 200° C. and 280° C., or between about 220° C. and 260° C. The deoxygenation pressure may be in the range of from 72 psig to 1300 psig. In some embodiments, the deoxygenation pressure is in the range of from 72 psig to 1200 psig, or from 145 psig to 1200 psig, or from 200 psig to 725 psig, or from 365 psig to 700 psig, or from 600 psig to 650 psig.

[0096] In some embodiments, the WHSV of the deoxygenation reaction ranges from 0.1 grams of oxygenated hydrocarbon per gram of catalyst per hour (g / gh) to 40 g / gh. In some embodiments, the WHSV is at least 0.25 g / gh, at least 0.5 g / gh, at least 0.75 g / gh, at least 1.0 g / gh, at least 1.1 g / gh, at least 1.2 g / gh, at least 1.3 g / gh, at least 1.4 g / gh, at least 1.5 g / gh, at least 1.6 g / gh, at least 1.7 g / gh, at least 1.8 g / gh, at least 1.9 g / gh, at least 2.0 g / gh, at least 2.1 g / gh, at least 2.2 g / gh, at least 2.3 g / gh, at least 2.4 g / gh, at least 2.5 g / gh, at least 2.6 g / gh, at least 2.7 g / gh, at least 2.8 g / gh, at least 2.9 g / gh, at least 3.0 g / gh, at least 3.1 g / gh, at least 3.2 g / gh, at least 3.3 g / gh, at least 3.4 g / gh g / gh, to less than 6 g / gh, less than 7 g / gh, less than 8 g / gh, less than 9 g / gh, less than 10 g / gh, less than 11 g / gh, less than 12 g / gh, less than 13 g / gh, less than 14 g / gh, less than 15 g / gh, less than 20 g / gh, less than 25 g / gh, less than 30 g / gh, less than 35 g / gh, or less than 40 g / gh.

[0097] In some embodiments, the amount of hydrogen supplied to the deoxygenation reactor 102 is from 0-2400%, 5%-2400%, 10%-2400%, 15%-2400%, 20%-2400%, 25%-2400%, 30%-2400%, 35%-2400%, 40%-2400%, 45%-2400%, 50%-2400%, 55%-2400%, 60%-2400%, 65%-2400%, 70%-2400%, 75%-2400%, 80%-2400%, 80%-2400%, 85%-2400%, 90%-2400%, 95%-2400%, 10 ... 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%-24 00%, 400%-2400%, 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%. %-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%, including all intervals therebetween. The hydrogen can be external hydrogen or recycled hydrogen. The term "external H2" refers to hydrogen that is not derived from the feed solution but is added to the reactor system from an external source. The term "recovered H2" refers to unconsumed hydrogen that is collected and then recycled back into the reactor system for further use.

[0098] In some embodiments, product stream 110 passes through three-phase separator 111, to separate product stream 110 into uncondensed gas stream 112, organic product stream 114 and aqueous product stream 116. Uncondensed gas stream 112 can comprise hydrogen, carbon dioxide, methane, ethane and propane. Uncondensed gas can be removed and burned to produce process heat (that is, for the heat of driving reaction in deoxygenation reactor), or is sent to separation system, in which hydrogen can be recovered for recycling back to hydrogen gas stream 106. Aqueous product stream 116 comprising partially deoxygenated hydrocarbons can be recycled back to the inlet of deoxygenation reactor 102. Aqueous purge stream (aqueous purge stream) 118 comprising some monooxygenates (for example, alcohol) can be used to prevent water from accumulating in reactor system. Aqueous purge stream 118 can be combined with organic product stream 114 or discarded from process.

[0099] In some embodiments, the organic product stream 114 comprising oxygenates is passed through a condensation reactor 120 comprising a condensation catalyst 122. The oxygenates are converted into C 4+ A condensation product stream 124 of compounds. Without being limited to any particular theory, it is believed that the condensation reaction generally consists of a series of steps involving: (a) dehydration of oxygenates to olefins; (b) oligomerization of olefins; (c) cracking reactions; (d) cyclization of larger olefins to form aromatic compounds; (e) isomerization of alkanes; (f) hydrogen transfer reactions to form alkanes. The reaction can also consist of a series of steps involving: (1) aldol condensation to form β-hydroxyketones or β-hydroxyaldehydes; (2) dehydration of β-hydroxyketones or β-hydroxyaldehydes to form conjugated enones; (3) hydrogenation of conjugated enones to form ketones or aldehydes, which can participate in further condensation reactions or be converted to alcohols or hydrocarbons; and (4) hydrogenation of carbonyl groups to alcohols, or vice versa. Other condensation reactions can occur in parallel, including aldol condensation, prins reactions, ketonization of acids, and Diels-Alder condensations.

[0100] Condensation catalyst 122 will generally be a catalyst capable of forming a longer chain compound by connecting two oxygen-containing species or other functionalized compounds (e.g., olefins) via a new carbon-carbon bond and converting the resulting compound into a hydrocarbon, alcohol, or ketone. Condensation catalysts may include, but are not limited to, carbides, nitrides, zirconium oxide, aluminum oxide, silicon dioxide, 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-mentioned substances alone or in combination with modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The condensation catalyst may also include a metal 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.

[0101] In certain embodiments, the condensation catalyst can include, but is not limited to, carbides, nitrides, zirconium oxide, aluminum oxide, silicon dioxide, 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 can 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.

[0102] The condensation catalyst 122 can be self-supporting (i.e., the catalyst does not require another material 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 zirconium oxide. 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 catalyst shape. Suitable forming processes include extrusion, pelletizing, oil dropping, or other known processes. Zinc oxide, aluminum oxide, and a peptizing agent can also be mixed together and extruded to produce a formed material. After drying, the material is calcined at a temperature suitable for forming a catalytically active phase, which generally requires a temperature in excess of 350°C. Other catalyst supports may include those described in further detail below.

[0103] Condensation catalyst can comprise one or more zeolite structures, and this zeolite structure comprises the cage structure of silicon dioxide-alumina.Zeolite is crystalline microporous material with well-defined pore structure.Zeolite comprises active site, typically acidic site, and this active site can be produced in zeolite framework.The intensity and concentration of active site can be customized for specific application.The example of suitable zeolite for making secondary alcohol and alkane condensation can comprise aluminosilicate, and it is optionally modified with the mixture of cation such as Ga, In, Zn, Mo and such cation, as described in, for example, U.S. Patent No. 3,702,886, this U.S. Patent is incorporated herein by reference.As recognized in the art, the structure of one or more specific zeolites can be changed to provide different amounts of multiple hydrocarbon species in product mixture.Depending on the structure of zeolite catalyst, product mixture can comprise various amounts of aromatic hydrocarbons and cyclic hydrocarbons.

[0104] Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48. Zeolite ZSM-5 and its conventional preparation are described in U.S. Pat. No. 3,702,886; Re. 29,948 (highly siliceous ZSM-5); U.S. Pat. Nos. 4,100,262 and 4,139,600, all of which are incorporated herein by reference. Zeolite ZSM-11 and its conventional preparation are described in U.S. Pat. No. 3,709,979, which is also incorporated herein by reference. Zeolite ZSM-12 and its conventional preparation are described in U.S. Pat. No. 3,832,449, which is incorporated herein by reference. Zeolite ZSM-23 and its conventional preparation are described in U.S. Pat. No. 4,076,842, which is incorporated herein by reference. Zeolite ZSM-35 and its conventional preparation are described in U.S. Patent No. 4,016,245, which is incorporated herein by reference. Another preparation of ZSM-35 is described in U.S. Patent No. 4,107,195, the disclosure of which is incorporated herein by reference. ZSM-48 and its conventional preparation are taught by U.S. Patent No. 4,375,573, which is incorporated herein by reference. Other examples of zeolite catalysts are described in U.S. Patent No. 5,019,663 and U.S. Patent No. 7,022,888, which are also incorporated herein by reference. An exemplary condensation catalyst is a ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Re, Ni, Sn, or a combination thereof.

[0105] As described in U.S. Patent No. 7,022,888, the condensation catalyst can be a difunctional pentasil zeolite catalyst comprising at least one metal element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, and combinations thereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolite can have strong acid sites and can be used with a reactant stream comprising an oxygenated hydrocarbon at a temperature below 580°C. The difunctional pentasil zeolite can have a ZSM-5, ZSM-8, or ZSM-11 type crystal structure consisting of a large number of 5-membered oxygen rings (i.e., pentasil rings). In one embodiment, the zeolite will have a ZSM-5 type structure.

[0106] Alternatively, solid acid catalysts such as alumina modified with phosphates, chlorides, silica and other acidic oxides can be used in the process. In addition, sulfated zirconia, phosphated zirconia, titania zirconia or tungstated zirconia can provide the necessary acidity. Re and Pt / Re catalysts can also be used to promote the condensation of oxygenates to C 5+ Hydrocarbons and / or C 5+ Monooxygenated compounds. Re is sufficiently acidic to promote acid-catalyzed condensation. In certain embodiments, acidity can also be added to the activated carbon by adding sulfates or phosphates.

[0107] The specific C 4+ The composition will depend on a variety of factors, including but not limited to the type of oxygenate in the reactant stream, the condensation temperature, the condensation pressure, the reactivity of the catalyst, and the flow rate of the reactant stream, as the flow rate of the reactant stream affects the space velocity, GHSV, LHSV, and WHSV. In certain embodiments, the reactant stream is contacted 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 matter (C 2+ O 1-3 ) oxygenates / gram of catalyst / hour. In another embodiment, the WHSV is between 0.1 g / gh and 10.0 g / gh, including WHSVs of 1 g / gh, 2 g / gh, 3 g / gh, 4 g / gh, 5 g / gh, 6 g / gh, 7 g / gh, 8 g / gh, 9 g / gh, 10 g / gh, and increments therebetween.

[0108] In certain embodiments, the condensation reaction is carried out at a temperature and pressure where the thermodynamics of the proposed reaction are favorable. 2+ O 1-3The reaction can be carried out at a temperature at which the vapor pressure of the volatile oxygenate is at least 0.1 atm (and preferably much higher). The condensation temperature will vary depending on the specific composition of the oxygenate. The condensation temperature will typically be greater than 80°C, or 100°C, or 125°C, or 150°C, or 175°C, or 200°C, or 225°C, or 250°C, and less than 500°C, or 450°C, or 425°C, or 375°C, or 325°C, or 275°C. For example, the condensation temperature can be between 80°C and 500°C, or between 125°C and 450°C, or between 250°C and 425°C. The condensation pressure will typically be greater than 0 psig, or 10 psig, or 100 psig, or 200 psig, and less than 2000 psig, or 1800 psig, or 1600 psig, or 1500 psig, or 1400 psig, or 1300 psig, or 1200 psig, or 1100 psig, or 1000 psig, or 900 psig, or 700 psig. For example, the condensation pressure may be greater than 0.1 atm, or between 0 psig and 1500 psig, or between 0 psig and 1200 psig.

[0109] The condensation reaction of the present disclosure can be used to produce C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes 、 C 5+ Cycloolefins, aromatic compounds, fused aromatic compounds, polycyclic compounds, C 4+ Alcohol, C 4+ Ketone, C 4+ Furans and mixtures thereof, advantageously having a high proportion of aromatic compounds and a low proportion of alkanes. In particular, the use of the mixture of oxygenates described above results in an aromatic compound yield greater than or equal to 50% carbon fraction (CF) of the aqueous feed carbon and C 4+ The alkane yield is less than or equal to 20% CF of the aqueous feed carbon. In certain embodiments, the aryl compound yield can be greater than or equal to 55% CF, greater than or equal to 60% CF, or greater than or equal to 65% CF of the aqueous feed carbon. In certain embodiments, C 4+ The alkane yield is less than or equal to 15% CF, less than or equal to 10% CF, or less than or equal to 5% CF of the aqueous feedstock carbon. In certain other embodiments, the product may also include C 1-3 Alkanes, of which the total C 1+ The alkane yield is less than or equal to 20% CF, less than or equal to 15% CF, less than or equal to 10% CF, or less than or equal to 5% CF of the aqueous feedstock carbon.

[0110] As used herein, the terms "carbon fraction" and "CF," which may be used interchangeably, may be calculated by dividing the mass of carbon in a component (e.g., the mass of carbon in the aryl compound) by the mass of carbon in the feed and multiplying by 100. Alternatively, % CF may be reported as a percentage of feed carbon, a percentage of carbon, or other similar nomenclature.

[0111] In certain embodiments, the yield of aryl compounds is greater than or equal to 55% CF of the aqueous feedstock carbon, and C 4+ The alkane yield is less than or equal to 15% CF of the aqueous feed carbon. In another embodiment, the aryl compound yield is greater than or equal to 60% CF of the aqueous feed carbon, and C 4+ The alkane yield is less than or equal to 10% CF of the aqueous feed carbon. In another embodiment, the aryl compound yield is greater than or equal to 55% CF of the aqueous feed carbon, and C 1+ The alkane yield is less than or equal to 15% CF of the aqueous feed carbon. In yet other embodiments, the aryl compound yield is greater than or equal to 60% CF of the aqueous feed carbon, and C 1+ The alkane yield is less than or equal to 10% CF of the aqueous feed carbon.

[0112] C 4+ Alkanes and C 4+ Olefins have from 4 to 30 carbon atoms (C 4+ Alkanes and C 4+ Alkenes), and may be branched or linear alkanes or alkenes. 4+ Alkanes and C 4+ Olefins may also include C 4-9 、C 7-14 、C 12-24 The fraction of alkanes and alkenes, of which C 4-9 The distillate points to gasoline, C 7-16 The fraction is directed towards jet fuel, and C 11-24 The fraction is targeted towards diesel fuel and other industrial applications such as chemicals. 4+ Alkanes and C 4+Examples of alkenes include, but are not limited to, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4,-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecane, decane, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptadecane, heptadecane, octadecane, octadecene, nonadecane, nonadecane, eicosane, eicosene, heneicosane, heneicosene, docosane, docosene, tricosane, tricosene, tetracosane, tetracosene and their isomers.

[0113] C 5+ Cycloalkanes and C 5+ The cycloolefins have from 5 to 30 carbon atoms and may be unsubstituted, monosubstituted or polysubstituted. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ As an example, at least one of the substituted groups includes a branched C 3-12 Alkyl, straight chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight chain C 1-12 Alkylene, straight chain C 2-12 As another example, at least one of the substituted groups includes a branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 1-4 Alkylene, straight chain C 1-4 Alkylene, straight chain C 2-4 Alkylene, phenyl or a combination thereof. Desirable C 5+ Cycloalkanes and C 5+ Examples of cycloolefins include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentane, methylcyclopentene, ethylcyclopentane, ethylcyclopentene, ethylcyclohexane, ethylcyclohexene, propylcyclohexane, butylcyclopentane, butylcyclohexane, pentylcyclopentane, pentylcyclohexane, hexylcyclopentane, hexylcyclohexane, and isomers thereof.

[0114] Aryl compounds will generally consist of aromatic hydrocarbons in unsubstituted form (phenyl), monosubstituted form, or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ As an example, at least one of the substituted groups includes a branched C 3+ Alkyl, straight chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight chain C 2-12 As another example, at least one of the substituted groups includes a branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4 Examples of various aromatic compounds include, but are not limited to, benzene, toluene, xylene (xylene), ethylbenzene, p-xylene, m-xylene, o-xylene, C 9+ Aromatic compounds, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene and their isomers.

[0115] The fused aryl compounds will generally be composed of bicyclic and polycyclic aromatic hydrocarbons in unsubstituted, monosubstituted or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ As an example, at least one of the substituted groups includes a branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4 Examples of various fused aryl compounds include, but are not limited to, naphthalene, anthracene, and isomers thereof.

[0116] Polycyclic compounds will generally consist of bicyclic and polycyclic hydrocarbons in unsubstituted, monosubstituted, or polysubstituted form. Although polycyclic compounds generally include fused aromatic compounds, as used herein, polycyclic compounds generally have at least one saturated or partially saturated ring. In the case of monosubstituted and polysubstituted compounds, the substituted groups may include branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C3+ Alkylene, straight chain C 2+ As an example, at least one of the substituted groups includes a branched C 3-4 Alkyl, straight chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight chain C 2-4 Examples of various fused aryl compounds include, but are not limited to, tetralin and decalin and their isomers.

[0117] C 4+ The alcohol may also be cyclic, branched or linear and have from 4 to 30 carbon atoms. 4+ The alcohol may be according to formula R 1 -OH compounds, where R 1 is selected from branched C 4+ Alkyl, straight chain C 4+ Alkyl, branched C 4+ Alkylene, straight chain C 4+ Alkylene, substituted C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloolefins, unsubstituted C 5+ A member of a cycloalkene, an aryl group, a phenyl group or a combination thereof. Desirable C 4+ Examples of alcohols include, but are not limited to, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, or isomers thereof.

[0118] C 4+ Ketones may also be cyclic, branched or linear and have from 4 to 30 carbon atoms. 4+ The ketone may be a compound according to the formula:

[0119]

[0120] where R 3 and R 4 are independently selected from branched C 3+ Alkyl, straight chain C 1+ Alkyl, branched C 3+ Alkylene, straight chain C 2+ Alkylene, substituted C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloolefins, unsubstituted C 5+A member of a cycloalkene, an aryl group, a phenyl group or a combination thereof. Desirable C 4+ Examples of ketones include, but are not limited to, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptadecanone, octadecanone, nonadecanone, eicosanone, heneicosanone, docosanone, tricosanone, tetracosanone, or isomers thereof.

[0121] In some embodiments, comprising C 4+ The condensation product stream 124 of the compound can be fractionated into a variety of product streams, such as gasoline, jet fuel (kerosene), diesel fuel, and aromatic compounds. The condensation product stream 124 can pass through a three-phase separator 126 to separate the condensation product stream 124 into an acid condensation gas stream 128, an organic stream 130, and an aqueous stream 132. The organic stream 130 and the aqueous stream 132 are separated by density differences, while the acid condensation gas stream 128 containing uncondensed gas is recycled to the acid condensation reactor 120 to produce additional C 4+ compounds. In some embodiments, a gas delivery device, such as a blower or compressor, is provided in the acid condensation gas stream 128 to control the recycle pressure. In some embodiments, an optional purge stream 134 can also be used to control the pressure of the recycle loop in the acid condensation gas stream 128. In some embodiments, the water stream 132 is discarded from the process or further processed in a downstream process unit.

[0122] In some embodiments, the organic stream 130 is fractionated in a distillation column 136 to separate the organic stream 130 into a light product stream 138 and a heavy product stream 140. In some embodiments, the distillation column 136 is configured to remove azeotropic contaminants of benzene, toluene, or a combination thereof. As described, removing azeotropic contaminants of benzene and / or toluene prior to processing over the transalkylation catalyst and / or dealkylation catalyst 22 provides a variety of surprising and unexpected advantages, such as higher purity and yield of the desired aromatic products.

[0123] In some embodiments, the distillation column 136 is configured to produce a heavy stream 140 that is free of or substantially free of azeotropic non-aromatic contaminants with benzene. The distillation column 136 can be configured to produce a heavy stream 140 that is free of or substantially free of azeotropic non-aromatic contaminants with benzene by fractionating the organic stream 130 into a C product stream comprising benzene, azeotropic non-aromatic contaminants with benzene, and lighter products via a light product stream 138. 6- The distillation column 136 can also fractionate the organic stream 130 into the organic streams containing C 7+ A heavy product stream 140 of compounds.

[0124] In some embodiments, the distillation column 136 is configured to produce a heavy stream 140 that is free of or substantially free of azeotropic non-aromatic contaminants with toluene. The distillation column 136 can be configured to produce a heavy stream 140 that is free of or substantially free of azeotropic non-aromatic contaminants with toluene by fractionating the organic stream 130 into a C product stream comprising toluene, azeotropic non-aromatic contaminants with toluene, and lighter products via a light product stream 138. 7- Stream or C 8- The distillation column 136 can also fractionate the organic stream 130 into the C 8+ Compound or C 9+ A heavy product stream 140 of compounds.

[0125] In some embodiments, the heavy product stream 140 is fractionated in a distillation column 142 to separate the heavy product stream comprising C 7+ Compound, C 8+ Compound or C 9+ The heavy product stream 140 of the compounds is separated into a mixed aromatic feed stream 16 and a heavy product stream 144. In some embodiments, the distillation column 142 is configured to fractionate the heavy product stream 140 into 7+ The mixed aromatic feed stream 16 of compounds and the 11+ In some embodiments, the mixed aromatic feed stream 16 comprises C 7+ Compound, or C 8+ Compound, or C 9+ Compound, or C 7-10 Compound, or C 8-10 Compound, or C 9-10 The mixed aromatic feed stream 16 can be used as Figure 1 Inlet feed for the process described in.

[0126] In some embodiments, the heavy stream 144 can also be separated and used as kerosene (e.g., C 11-14 as jet fuel), diesel fuel applications (e.g., C 12-24 ) and lubricants or fuel oils (e.g., C 25+ ). Alternatively, the heavy stream 144 may be cracked to produce additional fractions for gasoline, kerosene, aromatics, and / or diesel fractions.

[0127] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or the ordinary meaning of the defined terms.

[0128] The invention has been described in terms of one or more preferred embodiments, and it should be understood that many equivalents, alternatives, variations and modifications, besides those expressly stated, are possible and within the scope of the invention. Example

[0129] The following examples will enable those skilled in the art to more readily understand the principles of the present disclosure.The following examples are presented in an illustrative manner and are not meant to be limiting in any way.

[0130] Example 1 of the present invention: Production of high purity aromatic compounds from mixed aromatic feeds

[0131] Will include C7-C 10 A mixed aromatic feed stream (MAF) containing aromatic compounds and lacking significant amounts of benzene azeotropic non-aromatic contaminants was processed at 375° C., 100 psig, in the presence of a hydrogen to hydrocarbon ratio of about 4 and at a weight hourly space velocity of 1 over a nickel-containing ZSM-5 catalyst. Although the feed contained less than 0.1% benzene, the product contained 7.04 wt% benzene based on the total weight of the product stream. The potential purity of the benzene was estimated by dividing the amount of benzene by the total amount of benzene azeotropic material (including benzene) and multiplying by 100. The benzene azeotropic range is defined herein as all components (including benzene) greater than and including methylcyclopentane (normal boiling point 71.8° C.) and less than and including cis-1,3-dimethylcyclopentane (boiling point 91° C.) as measured by gas chromatography (GC). The estimated benzene purity in the product was 99.8 wt%. Since the feed did not contain significant amounts of benzene, the purity of the benzene in the feed could not be estimated.

[0132] Comparative Example 1: Production of Benzene from Mixed Aromatic Feeds Containing Azeotropic Contaminants

[0133] Contains C4-C 10 MAF, which is aromatic and contains a significant amount of benzene azeotropic non-aromatic contaminants, was processed under the same conditions as in Example 1. The estimated benzene purity in the product was 98%. While this is significantly higher than the estimated benzene purity of the feed of 31%, there is still approximately 10 times more benzene azeotropic contaminant in the product of Example 2 compared to the product of Example 1, demonstrating the advantage of eliminating azeotropic contaminants in the feed.

[0134] Inventive Example 2: Production of High Purity Aromatic Compounds from a Mixed Aromatic Feed Stream

[0135] Including C9-C 10A MAF containing aromatic compounds and lacking significant amounts of azeotropic non-aromatic contaminants such as benzene or toluene was processed under the same conditions as in Example 1, except that the pressure was increased from 200 psig to 250 psig and a transalkylation catalyst was used. The estimated purity of the benzene in the product was 99.87%. Using a method similar to that used to determine benzene purity in Example 1, the azeotropic range of toluene was defined herein as all components (including toluene) with a retention time greater than and including cis-1,3-dimethylcyclopentane (boiling point 91°C) and less than and including trans-1,2-dimethylcyclohexane (boiling point 123°C) as measured by gas chromatography (GC). No detectable components other than toluene were found within this boiling point range using this analysis, indicating an estimated purity of the toluene of nearly 100%.

[0136] Comparative Example 2: Production of Aromatic Compounds from a Mixed Aromatic Feed Stream Containing Azeotropic Contaminants

[0137] MAF is produced. The raw hydrocarbon product of the production process undergoes a distillation step to remove heavy components, which generally contain 11 or more carbon atoms. The resulting C4-C 10 MAF produces relatively low yields of aromatic compounds and is not suitable for use in the present invention.

[0138] Inventive Example 3: Production of High Purity Aromatic Compounds from a Mixed Aromatic Feed Stream

[0139] MAF is produced. The raw hydrocarbon product of the production process undergoes two distillation steps. In the first step, the raw hydrocarbon is distilled to produce a tower top (overhead) product, which includes components mainly containing 6 or less carbon atoms, including benzene. The overhead product is recycled to the aromatization section. Surprisingly, by recycling the light products to the reaction section, the total yield of aromatic compounds is increased. The dehexane aromatic compounds are then distilled to remove heavy components, which generally contain 11 or more carbon atoms. The resulting C7-C 10 MAF is suitable for use in the present invention to produce pure benzene.

[0140] Example 4 of the present invention: Production of MAF from aqueous hydrocarbon streams

[0141] The aqueous mixture of oxygenates was processed over a nickel-containing ZSM-5 condensation catalyst at 375°C, 150 psig and a weight hourly space velocity of 0.5. The resulting condensation product was fractionated into a light stream and a heavy stream, wherein the light stream contained C3-C6 components that were recycled back to the condensation catalyst. The heavy stream was fractionated to produce a predominantly C7-C6 component. 10 MAF of aromatic compounds. Representative MAF products are shown in Table 1.

[0142] Table 1

[0143]

[0144]

[0145] Inventive Example 5: Production of Mixed Xylenes from Mixed Aromatic Feeds

[0146] The MAF from Example 4 containing a large amount of xylene azeotropic non-aromatic contaminants was processed over a transalkylation catalyst at 344°C, 430 psig, at a hydrogen to hydrocarbon ratio of about 3.8 and at a weight hourly space velocity of 3.3. The product was fractionated into a benzene-rich stream, a toluene-rich stream, a xylene-rich stream, a C9 aromatics-rich stream, and a C 10+ A stream of aromatic compounds is shown in Table 2. The toluene stream and the C9 aromatic compound stream are recycled back to the transalkylation catalyst to maximize the xylene production. The xylene-rich stream is sent to the isomer recovery process unit to produce a para-xylene isomer stream and a raffinate stream containing unrecovered C8 compounds. The raffinate stream is processed on an isomerization catalyst at 340°C, 150 psig, a hydrogen to hydrocarbon ratio of about 1.5 and a weight hourly space velocity of 3.3. An isomerized product stream is produced, which is then combined with the xylene stream and sent back to the isomer recovery process unit again. This continuous operation results in a para-xylene productivity of over 99.7% from the isomer recovery process unit, which is 457 kg per month.

[0147] Table 2

[0148]

[0149]

[0150] * Non-aromatic components boiling between benzene and toluene (BT), non-aromatic components boiling between toluene and ethylbenzene (TE), and non-aromatic components boiling between ethylbenzene and C9 aromatic compounds (E-9).

[0151] Inventive Example 6: Production of Benzene from Mixed Aromatic Feeds

[0152] The benzene-rich stream produced in the same manner as Example 4 was further processed over a transalkylation catalyst at 375° C., 40 psig, at a hydrogen to hydrocarbon ratio of about 0.4, and at a weight hourly space velocity of 1. The product stream was fractionated to recover a purified benzene stream of >99.9% purity, with the product composition shown in Table 3.

[0153] Table 3

[0154]

[0155]

[0156] Inventive Example 7: Production of Toluene from Mixed Aromatic Feeds

[0157] A toluene-rich stream was produced under more optimized fractionation conditions in the same manner as in Example 4 to obtain a toluene purity of 99.8%. Instead of being recycled back to the transalkylation catalyst to maximize xylene production, the toluene-rich stream was recovered as a product with the composition shown in Table 4.

[0158] Table 4

[0159] Components Results (wt%) Toluene 99.80 benzene 0.00 Ethylbenzene 0.01 Xylene 0.16 Non-aromatic compounds 0.03

[0160] Inventive Example 8: Production of High Purity Paraxylene from Mixed Aromatic Feeds

[0161] Will include C5-C 10 The aromatic compounds and the non-aromatic contaminants containing a large amount of xylene azeotropy are fractionated by MAF to remove C5-C6 compounds. 10 The MAF of the aromatics was 360°C, 430 psig, with a hydrogen to hydrocarbon ratio of approximately 3.6 and a weight hourly space velocity of 2.7 over a transalkylation catalyst. Para-xylene production was increased by bypassing a portion of the isomerized product stream and combining it with the C8 stream before entering the isomer recovery process unit. 150 grams per minute was bypassed, and 20 grams per minute was fractionated. The resulting para-xylene production increased from 457 kg per month to 830 kg per month. The composition of a representative para-xylene product is shown in Table 5, and results from different processes are shown in Table 6.

[0162] Table 5

[0163]

[0164]

[0165] Table 6

[0166]

[0167] Although the present invention has been described in considerable detail with reference to certain embodiments, those skilled in the art will appreciate that the present invention can be used in alternative embodiments to 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 description of the embodiments contained herein.

[0168] For reasons of completeness, various aspects of the invention are set out in the following numbered items:

[0169] Item 1. A method for separating aromatic compounds from a mixed aromatic feed stream, the method comprising:

[0170] (i) Make it contain C 7-10 contacting a mixed aromatic feed stream of aromatic hydrocarbons with an aromatics processing catalyst to produce a product stream,

[0171] wherein the aromatic compound processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst or a combination thereof,

[0172] wherein the mixed aromatic feed stream comprises greater than 1 wt% of non-aromatic components based on the total weight of the mixed aromatic feed stream, and wherein the mixed aromatic feed stream is substantially free of C 12+ aromatic compounds; and

[0173] (ii) fractionating the product stream to separate aromatic compounds from the product stream.

[0174] Item 2. The method according to Item 1, wherein the mixed aromatic feed stream contains from 0.1 wt% to 45 wt% olefins based on the total weight of the mixed aromatic feed stream.

[0175] Item 3. The method according to Item 1, wherein the mixed aromatic feed stream contains from 0.1 wt% to 25 wt% of cycloalkanes based on the total weight of the mixed aromatic feed stream.

[0176] Item 4. The method according to Item 1, wherein the mixed aromatic feed stream contains from 0.1 wt% to 40 wt% of cycloalkane-olefins based on the total weight of the mixed aromatic feed stream.

[0177] Item 5. The method of Item 1, wherein the mixed aromatic feed stream has a bromine number of at least 1 mg Br2 / g mixed aromatic feed stream to less than 100 mg Br2 / g mixed aromatic feed stream.

[0178] Item 6. The method according to Item 1, wherein the mixed aromatic feed stream contains phenols in an amount from 10 ppm to 10 wt% based on the total weight of the mixed aromatic feed stream.

[0179] Item 7. The method according to Item 1, wherein the mixed aromatic feed stream contains oxygenates in an amount from 10 ppm to 10 wt% based on the total weight of the mixed aromatic feed stream.

[0180] Item 8. The method according to Item 1, wherein C 7-10 The aromatic hydrocarbons include benzene, toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, naphthalene, or combinations thereof.

[0181] Item 9. The method according to Item 1, wherein step (ii) further comprises fractionating the product stream to separate the C8 stream from the product stream of step (i); and

[0182] The method further comprises:

[0183] (iii) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds; and

[0184] (iv) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer, and wherein at least a portion of the isomerized product stream is combined with the product stream produced by the aromatics processing catalyst in step (i).

[0185] Item 10. The method according to Item 1, wherein the mixed aromatic feed stream comprises C 9-10 Aromatic compounds.

[0186] Item 11. A method according to Item 9, wherein at least a portion of the isomerized product stream is recycled and combined with the C8 stream entering the isomer recovery process unit.

[0187] Item 12. The method of Item 1, wherein the mixed aromatic feed stream is free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0188] Item 13. The method according to item 1, wherein step (ii) further comprises supplying the product stream comprising C8 aromatic compounds to a first distillation column, wherein the first distillation column fractionates the product stream to separate C8 aromatic compounds. 7- Stream and C 8+ flow.

[0189] Item 14. The method according to Item 13, wherein C 7- The stream is supplied to a second distillation column which converts C 7- The flow is fractionated into C 6- flow and C7 flow.

[0190] Item 15. A method according to Item 14, wherein at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

[0191] Item 16. The method according to Item 9, wherein C 8+ At least a portion of the stream is recycled and combined with the C8 aromatics entering the isomer recovery process unit.

[0192] Item 17. The method according to Item 13, wherein step (ii) further comprises: 8+ The stream is supplied to the third distillation column, which converts C8+ The stream is fractionated into C8 stream and C 9+ stream, wherein the C8 stream comprises C8 aromatic compounds.

[0193] Item 18. The method according to Item 17, wherein C 9+ The stream is supplied to the fourth distillation column, which converts C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0194] Item 19. The method according to Item 9, wherein step (ii) further comprises fractionating the product stream to separate the C7 stream, the C8 stream and the C 9-10 stream, wherein the C8 stream is supplied to the isomer recovery process unit, the C7 stream is recycled and combined with the mixed aromatic feed stream, and the C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0195] Item 20. The method according to Item 9, wherein step (ii) further comprises fractionating the product stream to separate the C7 stream, the C8 stream and the C 9+ stream, wherein the C8 stream is supplied to the isomer recovery process unit, the C7 stream is recycled and combined with the mixed aromatic feed stream, and the C 9+ The stream is recovered as product.

[0196] Item 21. The method according to Item 9, wherein the isomer recovery process unit includes an adsorption unit.

[0197] Item 22. The method according to Item 9, wherein the isomer recovery process unit includes a crystallization unit.

[0198] Item 23. The method according to Item 1, wherein the aromatic compound processing catalyst comprises an acid catalyst.

[0199] Item 24. A method according to Item 23, wherein the acid catalyst is selected from aluminosilicate, tungstate aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconium oxide, sulfated zirconium oxide, tungstate zirconium oxide, tungstate, tungsten carbide, molybdenum carbide, titanium dioxide, acidic alumina, phosphated alumina, tungstate alumina, phosphated silica, tungstate silica, tungstate titanium dioxide, tungstate phosphate, niobium oxide, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstate heteropolyacid, inorganic acid or a combination thereof.

[0200] Item 25. A method according to Item 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, an alloy thereof, or a combination thereof.

[0201] Item 26. The method according to Item 1, wherein step (i) is carried out at a temperature of from 200°C to 600°C.

[0202] Item 27. The method of Item 1, wherein step (i) is carried out at a pressure of from 100 psig to 1500 psig.

[0203] Item 28. The method according to Item 1, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour.

[0204] Item 29. The method according to Item 1, wherein step (i) comprises supplying hydrogen in an amount of at least 0.1 mol of hydrogen per mole of mixed aromatic feed.

[0205] Item 30. The method according to Item 1, wherein step (i) comprises supplying hydrogen in an amount of at least 1 mol of hydrogen per mole of mixed aromatic feed.

[0206] Item 31. A method for producing and separating aromatic compounds from a mixed aromatic feed stream, the method comprising:

[0207] (i) contacting an aqueous hydrocarbon feedstock comprising water and one or more oxygenates with a condensation catalyst to produce a hydrocarbon feedstock comprising C 4+ Condensation product stream of compounds, wherein C 4+ Compounds include C 4+ Alcohol, C 4+ Ketone, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+ Cycloolefins, aryl compounds, or fused aryl compounds;

[0208] (ii) fractionating the condensation product stream to produce a light stream and a heavy stream, wherein the light stream comprises azeotropic non-aromatic contaminants of benzene or toluene and the heavy stream is substantially free of azeotropic non-aromatic contaminants of benzene or toluene;

[0209] (iii) recycling the light stream to the condensation catalyst;

[0210] (iv) Fractionating the heavy stream into C 7+ a mixed aromatic feed stream of aromatic compounds; and

[0211] (v) contacting the mixed aromatic feed stream with an aromatics processing catalyst to produce a product stream, wherein the aromatics processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof.

[0212] Item 32. The method according to Item 31, further comprising:

[0213] fractionating the product stream to separate a C8 stream from the product stream;

[0214] subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds,

[0215] The raffinate stream is contacted with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer, wherein at least a portion of the isomerized product stream is combined with a product stream produced by the aromatics processing catalyst.

[0216] Item 33. The method according to Item 31, further comprising: 7+ The flow is fractionated into C 7-10 Stream and C 11+ flow, where C 7-10 The stream is contacted with an aromatics processing catalyst.

[0217] Item 34. The method according to Item 31, further comprising: 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where C 9-10 The stream contacts the catalyst.

[0218] Item 35. A method according to Item 32, wherein at least a portion of the isomerized product stream is recycled and combined with the C8 stream entering the isomer recovery process unit.

[0219] Item 36. The method according to Item 31 also includes fractionating the product stream from step (v) to produce a benzene stream, a toluene stream or a naphthalene stream.

[0220] Item 37. The method according to item 32 further comprises supplying the product stream to a first distillation column, wherein the first distillation column fractionates the product stream into C 7- Stream and C 8+ flow.

[0221] Item 38. The method according to Item 37 further includes: 7- The stream is supplied to the second distillation column, which converts C 7- The flow is fractionated into C6- flow and C7 flow.

[0222] Item 39. The method of Item 38, wherein at least a portion of the C7 stream is recycled and mixed with the C 7+ Flow combination.

[0223] Item 40. The method according to Item 37, wherein C 8+ At least a portion of the stream is recycled and combined with the C8 aromatics entering the isomer recovery process unit.

[0224] Item 41. The method according to Item 37, further comprising: 8+ The stream is supplied to the third distillation column, which converts C 8+ The stream is fractionated into C8 stream and C 9+ stream, wherein the C8 stream comprises C8 aromatic compounds.

[0225] Item 42. The method according to Item 41, wherein C 9+ The stream is supplied to the fourth distillation column, which converts C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0226] Item 43. The method according to Item 32 further comprises fractionating the product stream to separate the C7 stream, the C8 stream and the C 9-10 Stream, of which C8 stream is supplied to the isomer recovery process unit, and C7 stream is recycled and combined with C 7+ Flow combination, and C 9-10 The flow is recycled and 7+ Flow combination.

[0227] Item 44. A method according to Item 32, wherein the isomer recovery process unit includes an adsorption unit.

[0228] Item 45. A method according to Item 32, wherein the isomer recovery process unit includes a crystallization unit.

[0229] Item 46. The method of Item 31, wherein the aromatic compound processing catalyst comprises an acid catalyst.

[0230] Item 47. A method according to Item 31, wherein the acid catalyst is selected from aluminosilicate, tungstated aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconium oxide, sulfated zirconium oxide, tungstated zirconium oxide, tungsten carbide, molybdenum carbide, titanium dioxide, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titanium dioxide, tungstated phosphate, niobium oxide, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstated heteropolyacid, inorganic acid or a combination thereof.

[0231] Item 48. A method according to Item 47, wherein the acid catalyst comprises a metal selected from Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof, and combinations thereof.

[0232] Item 49. A method according to Item 31, wherein step (v) is carried out at a temperature of from 200°C to 600°C and a pressure of from 100 psig to 1500 psig and at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour.

[0233] Item 50. A method for producing and separating xylene isomers, the method comprising:

[0234] (i) Make it contain C 7+ contacting a mixed aromatic feed stream of aromatic compounds with an aromatic processing catalyst to produce a product stream comprising an increased concentration of C8 aromatic compounds relative to the mixed aromatic feed stream, wherein the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof;

[0235] (ii) Using a distillation column to fractionate the product stream into C 7- Stream and C 8+ flow;

[0236] (iii) Using a distillation column to 8+ The stream is fractionated into C8 stream and C 9+ flow;

[0237] (iv) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds; and

[0238] (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer,

[0239] Among them C8+ 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.

[0240] Item 51. The method according to Item 50, wherein the xylene isomer is selected from para-xylene, o-xylene or meta-xylene.

[0241] Item 52. The method of Item 50, wherein at least a portion of the isomerized product stream is combined with the product stream produced by the catalyst in step (i).

[0242] Item 53. The method of Item 50, wherein the mixed aromatic feed stream is substantially free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0243] Item 54. The method according to Item 50, wherein C 7- The stream is supplied to a distillation column which converts C 7- The flow is fractionated into C 6- flow and C7 flow.

[0244] Item 55. A method according to Item 54, wherein at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

[0245] Item 56. The method according to Item 50, wherein C 9+ The stream is supplied to a distillation column which converts C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0246] Item 57. A method according to Item 50, wherein the isomer recovery process unit includes an adsorption unit.

[0247] Item 58. A method according to Item 50, wherein the isomer recovery process unit includes a crystallization unit.

[0248] Item 59. The method according to Item 40, wherein the aromatic compound processing catalyst comprises an acid catalyst.

[0249] Item 60. A method according to Item 59, wherein the acid catalyst is selected from aluminosilicate, tungstated aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconium oxide, sulfated zirconium oxide, tungstated zirconium oxide, tungsten carbide, molybdenum carbide, titanium dioxide, acidic alumina, phosphated alumina, tungstated alumina, phosphated silica, tungstated silica, tungstated titanium dioxide, tungstated phosphate, niobium oxide, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstated heteropolyacid, inorganic acid or a combination thereof.

[0250] Item 61. A method according to Item 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, an alloy thereof, or a combination thereof.

[0251] Item 62. The method according to Item 50, wherein step (i) is carried out at a temperature of from 200°C to 600°C.

[0252] Item 63. The method of Item 50, wherein step (i) is carried out at a pressure of from 100 psig to 1500 psig.

[0253] Item 64. The method according to Item 50, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour.

[0254] Item 65. The method according to Item 50, wherein before step (i), the method comprises:

[0255] An aqueous hydrocarbon feedstock comprising water and one or more oxygenates is contacted with a condensation catalyst to produce a hydrocarbon feedstock comprising C 4+ Condensation product stream of compounds, wherein C 4+ Compounds include C 4+ Alcohol, C 4+ Ketone, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+ Cycloolefins, aryl compounds, or fused aryl compounds;

[0256] The condensation product stream is fractionated to separate C 6- Stream and C 7+ flow;

[0257] C 6- The stream is recycled to the condensation catalyst;

[0258] C7+ The flow is fractionated into C 7-10 Stream and C 11+ flow, where C 7-10 The stream forms a mixed aromatic feed stream.

[0259] Item 66. A method for producing and separating xylene isomers, the method comprising:

[0260] (i) Make it contain C 7+ contacting a mixed aromatic feed stream of aromatic compounds with an aromatic processing catalyst to produce a product stream comprising an increased concentration of C8 aromatic compounds relative to the mixed aromatic feed stream, wherein the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof;

[0261] (ii) Using a distillation column to fractionate the product stream into C 7- Stream and C 8+ flow;

[0262] (iii) Using a distillation column to 8+ The stream is fractionated into C8 stream and C 9+ flow;

[0263] (iv) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds; and

[0264] (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer;

[0265] Wherein at least a portion of the isomerized product stream is combined with a C8 stream before entering the isomer recovery process unit.

[0266] Item 67. The method according to Item 66, wherein the xylene isomers include para-xylene, o-xylene or meta-xylene.

[0267] Item 68. The method according to Item 66, wherein 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.

[0268] Item 69. The method of Item 66, wherein the mixed aromatic feed stream is substantially free of azeotropic contaminants of benzene, toluene, and combinations thereof.

[0269] Item 70. The method according to Item 66, wherein C 7- The stream is supplied to a distillation column which converts C 7- The flow is fractionated into C 6-flow and C7 flow.

[0270] Item 71. A method according to Item 70, wherein at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

[0271] Item 72. The method according to Item 66, wherein C 9+ The stream is supplied to a distillation column which converts C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

[0272] Item 73. A method according to Item 66, wherein the isomer recovery process unit includes an adsorption unit.

[0273] Item 74. A method according to Item 66, wherein the isomer recovery process unit includes a crystallization unit.

[0274] Item 75. The method of Item 66, wherein the aromatic compound processing catalyst comprises an acid catalyst.

[0275] Item 76. A method according to Item 75, wherein the acid catalyst is selected from aluminosilicate, tungstate aluminosilicate, silica-alumina phosphate, aluminum phosphate, amorphous silica alumina, zirconium oxide, sulfated zirconium oxide, tungstate zirconium oxide, tungstate carbide, molybdenum carbide, titanium dioxide, acidic alumina, phosphated alumina, tungstate alumina, phosphated silica, tungstate silica, tungstate titanium dioxide, tungstate phosphate, niobium oxide, sulfated carbon, phosphated carbon, acidic resin, heteropolyacid, tungstate heteropolyacid, inorganic acid or a combination thereof.

[0276] Item 77. A method according to Item 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, an alloy thereof or a combination thereof.

[0277] Item 78. The method according to Item 66, wherein step (i) is carried out at a temperature of from 200°C to 600°C.

[0278] Item 79. The method of Item 66, wherein step (i) is carried out at a pressure of from 100 psig to 1500 psig.

[0279] Item 80. The method according to Item 66, wherein step (i) is carried out at a weight hourly space velocity (WHSV) of from 0.1 mass feed / mass catalyst / hour to 10 mass feed / mass catalyst / hour.

[0280] Item 81. The method according to Item 66, wherein before step (i), the method comprises:

[0281] An aqueous hydrocarbon feedstock comprising water and one or more oxygenates is contacted with a condensation catalyst to produce a hydrocarbon feedstock comprising C 4+ Condensation product stream of compounds, wherein C 4+ Compounds include C 4+ Alcohol, C 4+ Ketone, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+ Cycloolefins, aryl compounds, or fused aryl compounds;

[0282] The condensation product stream is fractionated to separate C 6- Stream and C 7+ flow;

[0283] C 6- The stream is recycled to the condensation catalyst;

[0284] C 7+ The flow is fractionated into C 7-10 Stream and C 11+ flow, where C 7-10 stream to form a mixed aromatic feed stream; and

[0285] Among them 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.

Claims

1. A method for producing and separating xylene isomers, the method comprising: (i) Make it contain C 7+ contacting a mixed aromatic feed stream of aromatic compounds with an aromatic processing catalyst to produce a product stream comprising an increased concentration of C8 aromatic compounds relative to the mixed aromatic feed stream, wherein the aromatic processing catalyst comprises a transalkylation catalyst, a dealkylation catalyst, a hydrocracking catalyst, or a combination thereof; (ii) using a distillation column to fractionate the product stream into C 7- Stream and C 8+ flow; (iii) using a distillation column to separate the C 8+ The stream is fractionated into C8 stream and C 9+ flow; (iv) subjecting at least a portion of the C8 stream to an isomer recovery process unit to produce a xylene isomer stream and a raffinate stream comprising unrecovered C8 compounds; as well as (v) contacting the raffinate stream with an isomerization catalyst to produce an isomerized product stream, wherein the isomerized product stream comprises at least one xylene isomer, wherein at least a portion of the isomerized product stream is combined with the C8 stream before entering the isomer recovery process unit, and wherein the 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.

2. The process of claim 1, wherein the xylene isomer stream comprises para-xylene, ortho-xylene, or meta-xylene.

3. The method according to claim 1, wherein before step (i), the method comprises: An aqueous hydrocarbon feedstock comprising water and one or more oxygenates is contacted with a condensation catalyst to produce a hydrocarbon feedstock comprising C 4+ a condensation product stream of a compound wherein said C 4+ Compounds include C 4+ Alcohol, C 4+ Ketone, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkanes, C 5+ Cycloolefins, aryl compounds, or fused aryl compounds; The condensation product stream is fractionated to separate C 6- Stream and C 7+ flow; The C 6- The stream is recycled to the condensation catalyst; The C 7+ The flow is fractionated into C 7-10 Stream and C 11+ flow, where the C 7-10 stream to form the mixed aromatic feed stream, The oxygenate is a molecule having two or more carbon atoms and one or more oxygen atoms.

4. The method according to claim 1, in, The mixed aromatic feed stream comprises, based on the total weight of the mixed aromatic feed stream: From 0.1 wt% to 45 wt% olefins; From 0.1 wt% to 25 wt% of cycloalkanes; From 0.1 wt% to 40 wt% of cycloalkanes-olefins; and / or Phenols in amounts from 10 ppm to 10 wt%.

5. The process of claim 1 wherein the mixed aromatic feed stream has a bromine number of at least 1 mg Br2 / g of the mixed aromatic feed to less than 100 mg Br2 / g of the mixed aromatic feed.

6. The process of claim 1 wherein the mixed aromatic feed stream comprises C 9-10 Aromatic compounds.

7. The method according to claim 5, wherein the C 7- flow is supplied to the C 7- The flow is fractionated into C 6- A distillation column for the C stream and the C7 stream.

8. The process of claim 7, wherein at least a portion of the C7 stream is recycled and combined with the mixed aromatic feed stream.

9. The method according to claim 1, wherein the C 9+ The stream is supplied to the fourth distillation column, which converts the C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, where the C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

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

11. The method according to claim 10, wherein the method further comprises: The C 7- The flow is fractionated into C 6- Stream and C7 stream; and The C 9+ The flow is fractionated into C 9-10 Stream and C 11+ flow, wherein the C7 flow and the C 9-10 The stream is recycled and combined with the mixed aromatic feed stream.

12. The method according to claim 10, further comprising: The C 7- The flow is fractionated into C 6- Stream and C7 stream; and The C 9+ The flow is fractionated into C 9-10 Stream and C 11+ stream, wherein the C7 stream is recycled and combined with the mixed aromatic feed stream, and the C 9+ The stream is recovered as product.

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

14. The process of claim 1 wherein the aromatics processing catalyst comprises an acid catalyst comprising an aluminosilicate, a tungstated aluminosilicate, a silica-alumina phosphate, an aluminum phosphate, an amorphous silica alumina, a zirconium oxide, a sulfated zirconium oxide, a tungstated zirconium oxide, a tungstate zirconia, a tungstate zirconia, a tungsten carbide, a molybdenum carbide, a titania, an acidic alumina, a phosphated silica, a tungstated silica, a tungstated titania, a tungstated phosphate, a niobia, a sulfated carbon, a phosphated carbon, an acidic resin, a heteropolyacid, a tungstated heteropolyacid, an inorganic acid, or a combination thereof.

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

16. The method according to claim 1, in, The mixed aromatic feed stream comprises, based on the total weight of the mixed aromatic feed stream: From 0.1 wt% to 45 wt% olefins; From 0.1 wt% to 25 wt% of cycloalkanes; From 0.1 wt% to 40 wt% of cycloalkanes-olefins; and / or Oxygen-containing compounds in amounts from 10 ppm to 10 wt%.

17. The method of claim 1, wherein the aromatics processing catalyst comprises an acid catalyst, 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.

18. The method of claim 1, wherein the aromatics processing catalyst comprises an acid catalyst comprising phosphated alumina, tungstated alumina, or a combination thereof.

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