Process for reforming heavy aromatic streams - Patents.com

Abstract

Heavy aromatic compounds (C 11+ ) to C 6~8 Processes, catalysts, and reactor systems for the reforming of aromatic compounds are disclosed. Processes, catalysts, and reactor systems for the production of aromatic compounds and liquid fuels from oxygenated hydrocarbons, such as carbohydrates, sugars, sugar alcohols, and sugar degradation products, are also disclosed.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 255,817, filed October 14, 2021, the contents of which are hereby incorporated by reference in their entirety. [Background technology]

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

[0003] Bioreforming processes can produce aromatic hydrocarbons from biomass feedstocks such as cellulose, hemicellulose, and lignin. For example, cellulose and hemicellulose can be used as feedstocks for a variety of bioreforming processes, including aqueous phase reforming (APR) and hydrodeoxygenation (HDO)-catalytic reforming processes, which, when integrated with hydrogenation, can convert cellulose and hemicellulose into a number of products, including hydrogen, liquid fuels, aromatics, kerosene, diesel fuel, lubricants, and fuel oils, among others. APR and HDO methods and techniques are described in U.S. Pat. Nos. 6,699,457, 6,964,757, 6,964,758, and 7,618,612 (all to Cortright et al., entitled "Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons"); U.S. Pat. No. 6,953,873 (to Cortright et al., entitled "Low-Temperature Hydrocarbon Production from Oxygenated Hydrocarbons"); and U.S. Pat. Nos. 7,767,867 and 7,989,664 and U.S. Application No. 2011 / 0306804 (all to Cortright, entitled "Methods and Systems for Generating Polyols").Various APR and HDO methods and techniques are described in U.S. Pat. Nos. 8,053,615, 8,017,818, and 7,977,517, as well as U.S. patent application Ser. Nos. 13 / 163,439, 13 / 171,715, 13 / 163,142, and 13 / 157,247, all by Cortright and Blommel and entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"; U.S. patent application Ser. No. 2009 / 0211942, by Cortright, entitled "Catalysts and Methods for Reforming Oxygenated Compounds"; U.S. patent application Ser. No. 2010 / 0076233, by Cortright et al., entitled "Synthesis of Liquid Fuels from No. PCT / US2008 / 056330 (by Cortright and Blommel, entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"); and commonly owned, co-pending International Patent Application No. PCT / US2006 / 048030 (by Cortright et al., entitled "Catalyst and Methods for Reforming Oxygenated Compounds"), all of which are incorporated herein by reference.

[0004] In some cases, the light end (e.g., C 5- compounds) and heavy hydrocarbon products (e.g., C 11+) represent a significant fraction of the condensate product streams produced by bioreforming processes. However, the product value of these streams is typically low compared to other products such as aromatics (e.g., benzene, toluene, xylenes). Currently, there is a need in the art to upgrade the light ends and heavy hydrocarbon product streams to increase the product value of each stream. Summary of the Invention

[0005] In one aspect, the disclosure provides a process for producing and separating aromatic hydrocarbons from a hydrocarbon feed stream. The hydrocarbon feed stream may include a plurality of non-aromatic and aromatic hydrocarbons. The non-aromatic hydrocarbons may include paraffins, olefins, naphthenes, or combinations thereof, and the aromatic hydrocarbons may include aryls, fused aryls, polycyclic compounds, or combinations thereof. The process may include fractionating the hydrocarbon feed stream using a series of distillation columns to separate an aromatic product stream and a heavy hydrocarbon stream from the hydrocarbon feed stream. The aromatic product stream may include C6 aromatics, C7 aromatics, C8 aromatics, or combinations thereof. The heavy hydrocarbon stream may include C 11+ The process may include contacting a heavy hydrocarbon stream with a hydrogenation catalyst in the presence of hydrogen to produce hydrogenated C 11+ generating a hydrogenated C stream; 11+ The stream is contacted with at least one conversion catalyst to form a C 11+ and dealkylating at least a portion of the compounds to produce a reformate stream. The process may further include feeding the reformate stream to a series of distillation columns.

[0006] In some embodiments, the fractionation step of the process uses a first distillation column to fractionate the hydrocarbon feed stream into C 5- Stream and C 6+ and separating the C stream from the hydrocarbon feed stream using a second distillation column.6+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into a C 6~8 Step 3: Using a third distillation column, 9+ Stream to C 9~10 and fractionating the crude oil into a C20 hydrocarbon stream and a heavy hydrocarbon stream. 5- The method further comprises recycling the stream to the at least one conversion catalyst.

[0007] In some embodiments, the fractionation step of the process uses a first distillation column to fractionate the hydrocarbon feed stream into C 7- Stream and C 8+ and separating the C stream from the hydrocarbon feed stream using a second distillation column. 8+ The stream is divided into an aromatic product stream and a C 9+ a third distillation column is used to fractionate the aromatic product stream into a C8 compound, the aromatic product stream comprising C8 compounds; 9+ Stream to C 9~10 and fractionating the crude oil into a C20 hydrocarbon stream and a heavy hydrocarbon stream. 7- The process further comprises recycling the stream to at least one conversion catalyst. 9~10 The stream is recycled to at least one conversion catalyst to produce a C 9~10 C in the stream 9~10 The method further comprises the step of dealkylating at least a portion of the compound.

[0008] In some embodiments, the heavy hydrocarbon stream in the process comprises at least one polynuclear aromatic (PNA). The conversion of PNA during hydrogenation can be, for example, at least 70%. In some embodiments, the hydrogenation C of the process 11+ The stream is hydrogenated C 11+ Contains less than 5 wt.% polynuclear aromatic compounds based on the total weight of the stream.

[0009] In some embodiments, hydrogenated C 11+ The stream contains tetralin. Hydrogenation C 11+ The streams are divided into C 11+ The heavy hydrocarbon stream containing compound may comprise a weight fraction of tetralin that is at least 10 wt % greater than the weight fraction of tetralin in the heavy hydrocarbon stream containing compound.

[0010] In some embodiments, hydrogenated C 11+ The stream contains decalin. Hydrogenation C 11+ The streams are divided into C 11+ The heavy hydrocarbon stream may comprise a weight fraction of decalin that is at least 10 wt % greater than the weight fraction of decalin in the heavy hydrocarbon stream containing compound.

[0011] In some embodiments, the process further comprises, prior to the fractionation step, catalytically reacting the feed stream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream, and catalytically reacting the deoxygenated product stream with at least one conversion catalyst to produce a hydrocarbon feed stream.

[0012] In another aspect, the disclosure provides a process comprising catalytically reacting a feed stream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream. The process may further comprise catalytically reacting the deoxygenated product stream with at least one conversion catalyst to produce a condensation product stream comprising non-aromatic and aromatic hydrocarbons, wherein the non-aromatic hydrocarbons comprise paraffins, olefins, naphthenes, or combinations thereof, and the aromatic compounds comprise aryls, fused aryls, polycyclic compounds, or combinations thereof. The process may further comprise fractionating the condensation product stream using a series of distillation columns to separate the aromatic product stream and the heavy hydrocarbon stream from the condensation product stream, wherein the aromatic product stream comprises C6 aromatics, C7 aromatics, C8 aromatics, or combinations thereof, and the heavy hydrocarbon stream comprises C6 aromatics, C7 aromatics, C8 aromatics, or combinations thereof. 11+ The process may further include the step of recycling at least a portion of the heavy hydrocarbon stream to the deoxygenation catalyst.

[0013] In some embodiments, the oxygenated hydrocarbon comprises a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol, a sugar degradation product, a cellulose derivative, a hemicellulose derivative, a lignin derivative, a lignocellulose derivative, or a combination thereof.

[0014] In some embodiments, the fractionation step comprises fractionating the condensation product stream using a first distillation column to produce a C 5- Stream and C 6+ and separating the C stream from the condensation product stream using a second distillation column. 6+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into a C 6~8 Step 3: Using a third distillation column, 9+ Stream to C 9~10 and fractionating the resulting mixture into a C20 hydrocarbon stream and a C25 hydrocarbon stream.5- The stream is contacted with at least one conversion catalyst to produce, by a condensation reaction, 5- C in the stream 5- At least a portion of the compound is C 4+ The method may further include the step of converting to a compound.

[0015] In some embodiments, the fractionation step comprises fractionating the condensate stream using a first distillation column to produce a C 7- Stream and C 8+ and separating the C stream from the condensate stream using a second distillation column. 8+ The stream is divided into an aromatic product stream and a C 9+ a third distillation column is used to fractionate the aromatic product stream into a C8 compound, the aromatic product stream comprising C8 compounds; 9+ Stream to C 9~10 and fractionating the resulting mixture into a C20 hydrocarbon stream and a C25 hydrocarbon stream. 7- The stream is contacted with at least one conversion catalyst to produce, by a condensation reaction, 7- C in the stream 7- At least a portion of the compound is C 4+ In some embodiments, the process further comprises converting the compound to C. 9~10 The stream is contacted with at least one conversion catalyst to produce a conversion catalyst having a C 9~10 C in the stream 9~10 The method may further comprise the step of dealkylating at least a portion of the compound.

[0016] In some embodiments, the hydrogenation catalyst used in the present disclosure comprises at least one support and at least one metal. The metal can be, for example, Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, alloys thereof, and combinations thereof. The support can be, for example, carbon, silica, alumina, zirconia, titania, vanadia, ceria, silica-aluminate, zeolite, diatomaceous earth, hydroxyapatite, zinc oxide, chromia, or combinations thereof.

[0017] In some embodiments, the deoxygenation catalyst used in the present disclosure comprises at least one support and at least one metal. For example, the metal of the deoxygenation catalyst can comprise Pd, W, Mo, Ni, Pt, Ru, Sn, or a combination thereof. For example, the support can comprise zirconia.

[0018] In some embodiments, the conversion catalyst used in the present disclosure comprises a carbide, a nitride, a zirconia, an alumina, a silica, an aluminosilicate, a phosphate, a zeolite, a titanium oxide, a zinc oxide, a vanadium oxide, a lanthanum oxide, a yttrium oxide, a scandium oxide, a magnesium oxide, a cerium oxide, a barium oxide, a calcium oxide, a hydroxide, a heteropolyacid, an inorganic acid, an acid-modified resin, a base-modified resin, or a combination thereof. For example, the conversion catalyst may comprise a zeolite. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 illustrates an exemplary process for upgrading a hydrocarbon feed stream into a C6-8 product stream and a C9-10 product stream in accordance with some embodiments of the present disclosure. [Diagram 2] FIG. 1 illustrates an exemplary process for upgrading a hydrocarbon feed stream into a C8 product stream in accordance with some embodiments of the present disclosure. [Diagram 3] FIG. 1 illustrates an exemplary process for upgrading a hydrocarbon feed stream into a C8 product stream and a C9-10 product stream in accordance with some embodiments of the present disclosure. [Figure 4] FIG. 1 illustrates an exemplary process for converting oxygenated hydrocarbons to oxygenated compounds. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] In order that this disclosure may be more readily understood, certain terms are first defined below. Additional definitions for the following terms, as well as other terms, are set forth throughout the specification.

[0021] In this application, unless otherwise clear from the context, the term "a" may be understood to mean "at least one." As used in this application, the term "or" may be understood to mean "and / or." As used in this application, the terms "comprising" and "including" may be understood to include the listed components or steps, whether presented alone or together with one or more additional components or steps. Unless otherwise stated, the terms "about" and "approximately" may be understood to allow for standard deviations (e.g., ±10%) as understood by those of skill in the art. When ranges are provided herein, the endpoints are included. As used in this application, the term "comprise" and variations of terms such as "comprising" and "comprises" are not intended to exclude other additives, components, integers, or steps.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All definitions, as defined and used herein, should be understood to supersede dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0023] Systems and methods for converting biomass or fossil fuel derived oxygenates to hydrocarbons typically produce a distribution of products of varying value. For example, oxygenate to aromatics conversion typically produces gas, light naphtha, BTX (benzene, toluene, xylenes), mid-range aromatics (typically C9 and C10), and aromatic hydrocarbons (typically C12 and C20). 10 ), as well as the heavier C 11+ Resulting in products containing aromatics and hydrocarbons. Gasoline and C 11+The value of liquid products such as aromatics can be higher than gaseous products. In turn, the value of the BTX component is generally higher than the light gas, mid-range, and heavy aromatics. Depending on the commercial scenario, the value of the xylene products can be even higher than the mixed BTX products. Therefore, it is desirable to be able to shift the oxygenate conversion system product profile and overall yield structure from lower value products to higher value products that may be desired for a given scenario.

[0024] The present disclosure provides a method for analysing the yield structure of a hydrocarbon feedstock from non-aromatic compounds (e.g., paraffins, olefins, naphthenes) to C 6~10 In some embodiments, the present disclosure provides systems and methods for shifting aromatic compounds (e.g., C 6~10 ), particularly to increase the yield of benzene, toluene, para-xylene, ortho-xylene, and meta-xylene, light hydrocarbon streams (e.g., C 5- ) and heavy hydrocarbon streams (e.g., C 11+ ) is provided.

[0025] 1, a process 100 for upgrading a hydrocarbon feed stream 102 is described in accordance with some aspects of the present disclosure. In some embodiments, the hydrocarbon feed stream comprises non-aromatic and aromatic compounds that may be derived from a variety of original sources, including, but not limited to, oxygenates and condensation products derived from biomass, petroleum refining, thermal or catalytic cracking of hydrocarbons, coal coking, petrochemical conversion, and combinations thereof.

[0026] In some embodiments, the hydrocarbon feed stream 102 comprises 0.1 wt% to 45 wt% non-aromatic hydrocarbons, such as paraffins, olefins, naphthenes, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 0.1 wt% non-aromatic hydrocarbons, or at least 1 wt%, or at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% to less than 25 wt%, less than 30 wt%, or less than 35 wt%, or less than 40 wt%, or less than 45 wt% ... 3~30 Paraffin, C 3~30 Olefin, C 5~30 naphthenes, or combinations thereof.

[0027] As used herein, the term "paraffin" or "alkane" refers to a C 3~30 Paraffins refer to saturated straight or branched chain hydrocarbons. In some embodiments, paraffins are n H 2n+2 where n can range from 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, or 3 to 6.

[0028] As used herein, the term "olefin" or "alkene" refers to a C olefin having at least one carbon-carbon double bond. 3~30 Olefins refer to unsaturated straight or branched chain hydrocarbons. In some embodiments, olefins are C n H 2n where n can range from 3 to 30, 3 to 25, 3 to 20, 3 to 15, 3 to 10, or 3 to 6.

[0029] Examples of various paraffins and olefins include, but are not limited to, propane, propene, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, Includes undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.

[0030] As used herein, the term "naphthene" or "cycloalkane" refers to a saturated cyclic, bicyclic, or bridged cyclic hydrocarbon group. The saturated cyclic, bicyclic, or bridged cyclic (e.g., adamantane) hydrocarbon group may be substituted with one or more straight-chain or branched-chain alkyl or alkylene groups, e.g., the substituted groups may be straight-chain or branched-chain C 1~12 Alkyl, linear or branched chain C 3~12 Alkylene, linear or branched C 1~4 Alkyl, linear or branched chain C 3~4 The naphthene may be mono- or polysubstituted. In some embodiments, the naphthene may be C n H 2n where n can range from 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, or 5 to 6.

[0031] Examples of naphthenes include, but are not limited to, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, propyl-cyclohexane, butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane, pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, decalin, ethyl-decalin, pentyl-decalin, hexyl-decalin, and isomers thereof. The term "decalin" as used herein includes decalin, substituted decalin compounds (such as ethyl-decalin, pentyl-decalin, or hexyl-decalin), their isomers, and any combination thereof. For example, "decalin" can refer to pure decalin, pure substituted decalin compounds, a mixture of decalin and at least one substituted decalin compound, or a mixture of two or more substituted decalin compounds.

[0032] In some embodiments, the hydrocarbon feed stream comprises 10 wt% to 80 wt% aromatic hydrocarbons, e.g., aryl, fused aryl, polycyclic, or combinations thereof. In some embodiments, the hydrocarbon feed stream comprises at least 10 wt% aromatic hydrocarbons, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt% to less than 50 wt%, less than 55 wt%, or less than 60 wt%, or less than 65 wt%, or less than 75 wt%, or less than 80 wt% aromatics. In some embodiments, the hydrocarbon feed stream comprises a plurality of C 6~30 Aryl, C 12~30 Fused Aryl, C 12~30 polycyclic compounds, or combinations thereof.

[0033] As used herein, the term "aryl" refers to an aromatic hydrocarbon in unsubstituted (e.g., phenyl), mono-substituted, or poly-substituted form. For mono- and poly-substituted compounds, the substituents are branched C 3+ Alkyl, linear C 1+ Alkyl, branched chain C 3+ Alkylene, linear C 2+ As an example, at least one of the substituents may include a branched chain C 3+ Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 As a further example, at least one of the substituents may be a branched C 3~4 Alkyl, linear C 1~4 Alkyl, branched C 3~4 Alkylene, linear C 2~4 Examples of various aryls include, but are not limited to, benzene, toluene, xylene (dimethylbenzene), ethylbenzene, para-xylene, meta-xylene, ortho-xylene, C 9+ Aromatics include butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, decylbenzene, undecylbenzene, and their isomers.

[0034] As used herein, the term "fused aryl" or "polynuclear aromatic (PNA)" refers to bicyclic and polycyclic aromatic hydrocarbons in either unsubstituted, monosubstituted, or polysubstituted form. In the case of monosubstituted and polysubstituted compounds, the substituents are branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 Alkylene, Branched Chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, linear C 2~4 Examples of various fused aryls include, but are not limited to, naphthalene, anthracene, and their isomers.

[0035] As used herein, the term "polycyclic compound" refers to bicyclic and polycyclic hydrocarbons, either unsubstituted, monosubstituted, or polysubstituted, having at least one saturated or partially saturated ring. In the case of monosubstituted and polysubstituted compounds, the substituents are branched chain C 3~12 Alkyl, linear C 1~12 Alkyl, branched chain C 3~12 Alkylene, linear C 2~12 Alkylene, Branched Chain C 3~4 Alkyl, linear C 1~4 Alkyl, branched chain C 3~4 Alkylene, linear C 2~4 The polycyclic compounds may include, but are not limited to, tetralin (i.e., tetrahydronaphthalene), ethyl-tetralin, pentyl-tetralin, hexyl-tetralin, and isomers thereof. The term "tetralin" as used herein includes tetralin, substituted tetralin compounds (such as ethyl-tetralin, pentyl-tetralin, or hexyl-tetralin), isomers thereof, and any combination thereof. For example, "tetralin" may refer to pure tetralin, pure substituted tetralin compounds, a mixture of tetralin and at least one substituted tetralin compound, or a mixture of two or more substituted tetralin compounds.

[0036] The hydrocarbon feed stream 102 may be produced in a variety of ways. In some embodiments, the hydrocarbon feed stream 102 is produced from biomass. Methods, processes, and techniques for converting oxygenated hydrocarbons and mixtures of condensation products are described in U.S. Pat. Nos. 6,699,457, 6,964,757, 6,964,758, and 7,618,612, all to Cortright et al., entitled "Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons"; U.S. Pat. No. 6,953,873, all to Cortright et al., entitled "Low-Temperature Hydrocarbon Production from Oxygenated Hydrocarbons"; U.S. Pat. Nos. 7,767,867, 7,989,664, 8,198,486, 8,492,595, and U.S. Patent Application Publication No. 2013 / 0289302, all to Cortright, entitled "Methods and Systems for Generating Oxygenated Hydrocarbons"; Nos. 8,053,615, 8,017,818, 7,977,517, 8,362,307, 8,367,882, 8,455,705, and U.S. Patent Application Publication Nos. 2011 / 0245542 and 2013 / 0185992, all to Cortright and Blommel, entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"; U.S. Patent No. 8,231,857 to Cortright, entitled "Catalysts and Methods for Reforming Oxygenated Compounds"; U.S. Patent No. 8,350,108 to Cortright et al., entitled "Synthesis of Liquid Fuels from Biomass";No. 2011 / 0160482 to Nagaki et al., entitled "Improved Catalysts for Hydrodeoxygenation of Polyols"; U.S. Patent Application No. 2011 / 0009614 to Blommel et al., entitled "Processes and Reactor Systems for Converting Sugars to Sugar Alcohols"; International Patent Application No. PCT / US2008 / 056330 to Cortright and Blommel, entitled "Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons"; commonly owned U.S. Patent No. 8,231,857 to Cortright et al., entitled "Catalyst and Methods for Reforming Oxygenated Compounds"; and U.S. Patent Application No. 13 / 586,499 to Blank et al., entitled "Improved Catalysts for Hydrodeoxygenation of Oxygenated Compounds"; No. 10,005,700 (Beck et al., entitled "Production of Aromatics from Di- and Polyoxygenates"), all of which are incorporated herein by reference. The hydrocarbon product streams described in the above-referenced applications and patents may be suitable for use as the hydrocarbon feed stream 102 in accordance with the present application.

[0037] Additionally or alternatively, the hydrocarbon feed stream 102 may be derived from petroleum refining, thermal or catalytic cracking of hydrocarbons, coal coking, or petrochemical conversion. For example, the hydrocarbon feed stream 102 may be derived from suitable fractions from various petroleum refinery streams, e.g., as individual components or as certain boiling range fractions obtained by selective fractionation and distillation of catalytic cracking or reformed hydrocarbons.

[0038] Heavy Aromatics Upgrading (HAU): Referring again to FIG. 1, the hydrocarbon feed stream 102 is reformed to produce C 6~8 A process 100 (and corresponding system) is described for producing an aromatic product stream 104 containing aromatics and hydrocarbons, such as benzene, toluene, para-xylene, ortho-xylene, and meta-xylene. In some embodiments, the process 100 includes fractionating a hydrocarbon feed stream 102 in a distillation column 106 along with a recycled reformate stream 134 to produce a C 5- Stream 108 and C 6+ As used herein, the term “C n- " refers to a hydrocarbon compound having n or fewer carbons in the compound (e.g., 5 or fewer carbon atoms); n+ " refers to a hydrocarbon compound having n or more carbons in the compound (e.g., at least 6 carbons). 6+ Stream 110 is C 6+ Stream 110 to C 9+ Streams 114 and C 6~8 The aromatic compounds are fractionated in a second distillation column 112 to separate them into an aromatic product stream 104 containing the aromatic compounds. 9+ Stream 114 is C 9+ Stream 114 to C 9~10 Stream 118 and C 11+ The C2O is fractionated in a third distillation column 116 for separation into stream 120. 11+ Stream is also C 11+The heavy hydrocarbon stream may be referred to as a heavy hydrocarbon stream containing the compounds.

[0039] The applicant is C. 5- Stream 108, C 9~10 Stream 118, and most C 11+ Stream 120 is directly reformed over conversion catalyst 130 to produce C 5- Condensation reaction of stream 108 and C 9~10 Stream 118 and C 11+ Dealkylation of stream 120 provides additional C 6~8 However, it was found that aromatic compounds such as naphthalene could be formed. 11+ It was also found that some PNA compounds in stream 120 were minimally to completely unreactive on conversion catalyst 130. 6~8 or C 9~10 It is desirable to convert polycyclic hydrocarbons (e.g., tetralin) and cycloalkanes (decalin) to products to maximize the yield of the process 100. Applicants have found that polycyclic hydrocarbons (e.g., tetralin) and cycloalkanes (decalin) are reactive with the conversion catalyst 130 to produce the desired C 6~8 or C 9~10 It has further been found that PNA compounds (e.g., naphthalene) can be converted to products that are subsequently reformed over the conversion catalyst 130 to produce increased concentrations of C 6~8 Aromatic and C 9~10 Methods are provided for converting compounds into reactive polycyclic hydrocarbons (eg, tetralin) and cycloalkanes (decalin), which may produce the desired compounds.

[0040] In some embodiments, C 11+ Stream 120 is contacted with hydrogenation catalyst 122 in the presence of hydrogen to form hydrogenated C 11+Stream 128. In some embodiments, the hydrogenation catalyst 122 is disposed in the hydrogenation reactor 124. The hydrogenation reaction may be carried out in any reactor of suitable design, including continuous flow, batch, semi-batch or multi-system reactors, without limitations on design, size, geometry, flow rate, etc. The hydrogenation reactor 124 may also use a fluidized catalyst bed system, a swing bed system, a fixed bed system, a moving bed system, or a combination of the foregoing. The reactions of the present disclosure are typically carried out at steady-state equilibrium using a continuous flow system. Hydrogen may be provided to the hydrogenation reactor 124 by a hydrogen source 126, which may be a hydrogen-containing reservoir (e.g., a pressurized tank), a hydrogen-containing recycle stream from an upstream or downstream process unit, or a combination thereof. The hydrogenation reaction may be carried out at a temperature of 5°C to 700°C, 10°C to 500°C, 100°C to 450°C, or 200°C to 400°C. In some embodiments, the hydrogenation reaction may be carried out at a pressure of from 0 psig to 5000 psig, from 500 psig to 3000 psig, from 750 psig to 2000 psig, or from 800 psig to 1400 psig.

[0041] In some embodiments, a hydrogenation catalyst 122 suitable for the reactor system of the process 100 includes a hydrogenation catalyst 122 having one or more active metals and one or more supports (e.g., in a hydrogenation reactor 124 as shown in FIG. 1). Suitable active metals include, but are not limited to, Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, alloys thereof, and combinations thereof, 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. In some embodiments, the metal of the hydrogenation catalyst is Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, alloys thereof, or combinations thereof. In some embodiments, the hydrogenation catalyst further includes at least one promoter. For example, the promoter can be Ag, Au, Cr, Zn, Mn, Mg, Ca, Cr, Sn, Bi, Mo, W, B, P, alloys thereof, or combinations thereof.

[0042] The hydrogenation catalyst may also include any one of several supports, depending on the desired functionality of the catalyst. Exemplary supports include transition metal oxides, oxides formed from one or more metalloids, and reactive nonmetals (e.g., carbon). Non-limiting examples of supports include, but are not limited to, carbon, silica, alumina, zirconia, titania, vanadia, ceria, silica-aluminate, zeolites, diatomaceous earth, hydroxyapatite, zinc oxide, chromia, and mixtures thereof.

[0043] In some embodiments, hydrogenated C 11+ Stream 128 is hydrogenated C 11+ % PNA compound based on the total weight of stream 128. In some embodiments, the hydrogenated C 11+ Stream 128 is hydrogenated C 11+ Stream 128 contains less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% PNA compounds based on the total weight of stream 128.

[0044] In some embodiments, hydrogenated C 11+ The conversion of the PNA (e.g., naphthalene) compounds in stream 128 is at least 50%, or at least 55%, or at least 60%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%. As used herein, the conversion of a particular reactant is

[0045]

number

[0046] In some embodiments, hydrogenated C 11+ The weight fraction of tetralin in stream 128 is C11+ At least 10% greater than the weight fraction of tetralin in stream 120. In some embodiments, the hydrogenated C 11+ The weight fraction of tetralin in stream 128 is C 11+ At least 15% greater than the weight fraction of tetralin in stream 120, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0047] In some embodiments, hydrogenated C 11+ The weight fraction of decalin in stream 128 is C 11+ The weight fraction of decalin in stream 120 is at least 10% greater than the weight fraction of decalin in stream 120. 11+ The weight fraction of decalin in stream 128 is C 11+ At least 15% greater than the weight fraction of decalin in stream 120, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0048] In some embodiments, the process 100 comprises reacting hydrogenated C2H2O4 with 1,2-dichloroethane at a temperature, pressure, and weight hourly space velocity effective to induce condensation and dealkylation reactions to produce the reformate stream 134. 11+ Stream 128 and C 5- The method includes contacting the stream 108 with a conversion catalyst 130. 11+ The compound is C 10- may be dealkylated over conversion catalyst 130 to produce a compound, C 5- The compound is converted to C by condensation reaction. 4+ In this way, C 5- Stream 108 and C 11+ Stream 120 is the C in the aromatic product stream 1046~8 The compounds may be modified to increase their yield.

[0049] Without being limited to any particular theory, it is believed that the conversion catalyst 130 promotes reactions according to the present disclosure that generally include a series of steps including (a) dehydration of any oxygenates to alkenes, (b) oligomerization of alkenes, (c) cracking reactions (e.g., dealkylation), (d) cyclization of larger alkenes to form aromatics, (e) alkane isomerization, (f) hydrogen transfer reactions to form alkanes. The reactions may also include a series of steps including (1) aldol condensation to form β-hydroxyketones or β-hydroxyaldehydes, (2) dehydration of β-hydroxyketones or β-hydroxyaldehydes to form conjugated enones, (3) hydrogenation of conjugated enones to form ketones or aldehydes that may participate in further condensation reactions or conversion to alcohols or hydrocarbons, and (4) hydrogenation of carbonyls to alcohols or vice versa. Other condensation reactions may occur in parallel, including aldol condensations, Prins reactions, ketonization of acids, and Diels-Alder condensations.

[0050] The conversion catalyst 130 is generally a catalyst capable of forming a longer chain compound by linking two olefins or oxygen-containing species with a new carbon-carbon bond and converting the resulting compound to a hydrocarbon, alcohol or ketone. The conversion catalyst 130 is generally a catalyst capable of forming a longer chain compound by linking two olefins or oxygen-containing species with a new carbon-carbon bond and converting the resulting compound to a hydrocarbon, alcohol or ketone. 11+Aromatics and hydrocarbons can also be dealkylated. The conversion catalyst can include, but is not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof. The conversion catalyst can include the above alone or in combination with modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The conversion 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 and combinations thereof to provide metal functionality. In some embodiments, the conversion catalyst comprises a metal that is 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. In some embodiments, the conversion catalyst comprises at least one metal. For example, the conversion catalyst may comprise at least Ni. In some embodiments, the conversion catalyst comprises a modifier that is Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, or combinations thereof.

[0051] In certain embodiments, the conversion catalyst may include, but is not limited to, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48), titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropolyacids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof. The conversion catalyst may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof to provide metal functionality.

[0052] The conversion catalyst 130 may be free-standing (i.e., the catalyst does not require another material to act as a support) or may require a separate support suitable for suspending the catalyst in the reactant stream. In certain embodiments, the support is selected from the group consisting of alumina, silica, and zirconia. In other embodiments, the catalyst system may include a binder to aid in forming the catalyst into the desired catalytic shape, especially when the conversion catalyst is a powder. Applicable forming processes include extrusion, pelleting, oil dripping, or other known processes. Zinc oxide, alumina, and peptizer may also be mixed together and extruded to produce a formed material. After drying, the material is calcined at a temperature appropriate for the formation of the catalytically active phase, which typically requires temperatures in excess of 350° C. Other catalyst supports may include those described in more detail below.

[0053] In some embodiments, the conversion catalyst comprises a zeolite. The conversion catalyst may comprise one or more zeolite structures, including silica-alumina cage-like structures. Zeolites are crystalline microporous materials with well-defined pore structures. Zeolites contain active sites, usually acid sites, that may be produced within the zeolite framework. The strength and concentration of the active sites may be tailored to a particular application. Examples of zeolites suitable for condensing secondary alcohols and alkanes may include aluminosilicates, optionally modified with cations such as Ga, In, Zn, Mo, and mixtures of such cations, as described, for example, in U.S. Pat. No. 3,702,886, which is incorporated herein by reference. As recognized in the art, the structure of a particular zeolite or zeolites may be altered to provide different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain different amounts of aromatic and cyclic hydrocarbons.

[0054] Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5 and its conventional preparation are described in U.S. Pat. No. 3,702,886, Re. 29,948 (high silica ZSM-5), U.S. Pat. No. 4,100,262 and U.S. Pat. No. 4,139,600, all of which are incorporated herein by reference. Zeolite ZSM-11 and its conventional preparation are described in U.S. Pat. No. 3,709,979, also incorporated herein by reference. Zeolite ZSM-12 and its conventional preparation are described in U.S. Pat. No. 3,832,449, also incorporated herein by reference. Zeolite ZSM-23 and its conventional preparation are described in U.S. Pat. No. 4,076,842, also incorporated herein by reference. Zeolite ZSM-35 and its conventional preparation are described in U.S. Patent No. 4,016,245, which is incorporated herein by reference. Another preparation of ZSM-35 is described in U.S. Patent No. 4,107,195, the disclosure of which is incorporated herein by reference. ZSM-48 and its conventional preparation are taught by U.S. Patent No. 4,375,573, which is incorporated herein by reference. Other examples of zeolite catalysts are described in U.S. Patent Nos. 5,019,663 and 7,022,888, which are also incorporated herein by reference. An exemplary conversion catalyst is ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Re, Ni, Sn, or a combination thereof.

[0055] As described in U.S. Pat. No. 7,022,888, the conversion catalyst may be a bifunctional pentasil zeolite catalyst containing at least one metal element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolite may have strong acid sites and may be used with reactant streams containing oxygenated hydrocarbons at temperatures below 580° C. The bifunctional pentasil zeolite may have a ZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of multiple five-membered oxygen rings (i.e., pentasil rings). In one embodiment, the zeolite has a ZSM-5 type structure.

[0056] Alternatively, solid acid catalysts such as alumina modified with phosphate, chloride, silica, and other acidic oxides can be used in the process. Also, sulfated zirconia, phosphated zirconia, titania zirconia, or tungstated zirconia can provide the necessary acidity. Re and Pt / Re catalysts are also useful for promoting the condensation reaction. Re is sufficiently acidic to promote acid-catalyzed condensation. In certain embodiments, acidity can also be added to the activated carbon by the addition of sulfate or phosphate salts.

[0057] The condensation reaction may take place in condensation reactor 132. Condensation reactor 132 may have any reactor of suitable design, including continuous flow, batch, semi-batch or multi-system reactors, without limitation as to design, size, geometry, flow rate, etc. Reactor 132 may also use a fluidized catalyst bed system, a swing bed system, a fixed bed system, a moving bed system, or a combination of the foregoing. Reactions of the present disclosure are typically carried out at steady-state equilibrium using a continuous flow system. Hydrogen may be provided to 132, but this is not shown in FIG. 1.

[0058] The specific C generated 4+ Compound (C 6~8aromatic compounds) and C 10- Compound (C 9~10 The condensation rate (e.g., condensation product, etc.) depends on a variety of factors including, but not limited to, the type of oxygenated compound in the reactant stream, the condensation temperature, the condensation pressure, the reactivity of the catalyst, and the flow rate of the reactant stream since it affects the space velocity, GHSV (gas hourly space velocity), LHSV (liquid hourly space velocity), and WHSV (weight hourly space velocity). In certain embodiments, the reactant stream contacts the conversion catalyst at a WHSV appropriate to produce the desired hydrocarbon products. In one embodiment, the WHSV is at least 0.1 grams of reactant per gram of catalyst per hour. In another embodiment, the WHSV is between 0.1 and 10.0 g / g hr, including WHSVs of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g / g hr and increments therebetween.

[0059] In certain embodiments, the condensation reaction is carried out in the condensation reactor 132 at a temperature and pressure where the thermodynamics of the proposed reaction are favorable. The condensation temperature is generally greater than 80° C., or 100° C., or 125° C., or 150° C., or 175° C., or 200° C., or 225° C., or 250° C., and less than 500° C., or 450° C., or 425° C., or 375° C., or 325° C., or 275° C. For example, the condensation temperature 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 is typically greater than 0 psig, or 10 psig, or 100 psig, or 200 psig, and less than 2000 psig, or 1800 psig, or 1600 psig, or 1500 psig, or 1400 psig, or 1300 psig, or 1200 psig, or 1100 psig, or 1000 psig, or 900 psig, or 700 psig. For example, the condensation pressure can be greater than 0.1 psig, or between 0 and 1500 psig, or between 0 and 1200 psig.

[0060] The condensation reaction of the present disclosure is 4~30 Non-aromatic hydrocarbons and C 6~30 Aromatic hydrocarbons, such as linear or branched C4~30 Alkanes, linear or branched C 4~30 Alkenes, optionally with straight or branched chain alkyl groups 5~30 Cycloalkane, C with optional straight or branched chain alkene group 5~30 Cycloalkene, optionally with linear or branched alkanes or alkenes 6~30 C with aryl, optional straight or branched chain alkane or alkene 12~30 C with fused aryl, optionally straight or branched chain alkanes or alkenes 12~30 Polycyclic compounds, linear or branched chain C 4~30 Alcohol, linear or branched C 4~30 Ketones, linear or branched C 4~30 They can be used in the production of furans and mixtures thereof, advantageously with a high proportion of aryls and a low proportion of alkanes.

[0061] In some embodiments, the reformate stream 134 produced by the conversion catalyst 130 is recycled to the distillation column 106. The reformate stream 134 may optionally be combined with the hydrocarbon feed stream 102 before being fed to the distillation column 106.

[0062] C 5- Stream 108 and Hydrogenated C 11+ By feeding stream 128 to a conversion catalyst 130, the process 100 produces a high concentration of C 6~10 Aromatics, low concentration C 4+ In particular, the use of the above process 100 provides the advantage of producing paraffins and PNA compounds with a carbon fraction (CF) of 50% or more of the hydrocarbon feed stream 102. 6~10 aryl yield, PNA yield of 5% or less of the CF of the hydrocarbon feed stream 102, and C of 25% or less of the CF of the aqueous feed carbon 4+ In certain embodiments, the C 6~10The aryl yield may be 55 wt% or more, 60% or more, or 65% or more CF of the hydrocarbon feed stream 102. In certain embodiments, the PNA yield is less than 5% CF, or less than 4% CF, or less than 3% CF, or less than 2% CF, or less than 1% CF of the hydrocarbon feed stream 102. 4+ The alkane yield is 25% CF or less, 20% CF or less, 15% CF or less, or less than 10% CF of the hydrocarbon feed stream 102.

[0063] As used herein, the terms "carbon fraction" and "CF", which may be used interchangeably, may be calculated by dividing the mass of carbon of a component (e.g., the mass of carbon in an aryl) by the mass of carbon in the feedstock and multiplying by 100. Alternatively, %CF may be reported as feedstock carbon percentage, carbon percentage, or other similar terminology.

[0064] Xylene only (NBX): Referring to FIG. 2, the hydrocarbon feed stream 102 is reformed to produce an aromatic product stream 204 containing C aromatics and hydrocarbons, such as para-xylene, ortho-xylene, and meta-xylene, as well as a C 9~10 A process 200 is described for producing a product stream 218. 9~10 A range of hydrocarbons and aromatics have uses other than making other aromatics, such as solvents, paints, resins, pesticides and uses in oil drilling. 9~10 Product stream 218 may include or be processed to produce products such as Aromatic 100 solvent (ARO100) or Aromatic 150 solvent (ARO150).

[0065] In some embodiments, the process 200 fractionates the hydrocarbon feed stream 102 in a distillation column 206 along with a recycled reformate stream 234 to produce a C 7- Streams 208 and C 8+ C.8+ Stream 210 is a 8+ Stream 210 to C 9+ The aromatic product stream 204 is fractionated in a second distillation column 212 to separate the aromatic product stream 204 containing C8 compounds and the aromatic product stream 214 containing C8 compounds. 9+ Stream 214 is C 9~10 Streams 218 and C 11+ Stream 220 is fractionated in third distillation column 216 to separate the condensed olefins.

[0066] In some embodiments, C 11+ Stream 220 is contacted with hydrogenation catalyst 122 in the presence of hydrogen to form hydrogenated C 11+ The hydrogenation catalyst 122, hydrogenation reactor 124, and operating conditions described in process 100 produce hydrogenated C 11+ Suitable for use in process 200 to produce stream 228.

[0067] In some embodiments, hydrogenated C 11+ Stream 228 is hydrogenated C 11+ % PNA compound based on the total weight of stream 228. In some embodiments, the hydrogenated C 11+ Stream 228 is hydrogenated C 11+ It contains less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% PNA compounds based on the total weight of stream 228.

[0068] In some embodiments, hydrogenated C 11+ The conversion of PNA (e.g., naphthalene) compounds in stream 228 is at least 50%, or at least 55%, or at least 60%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%.

[0069] In some embodiments, hydrogenated C 11+The weight fraction of tetralin in stream 228 is C 11+ At least 10% greater than the weight fraction of tetralin in stream 220. In some embodiments, the hydrogenated C 11+ The weight fraction of tetralin in stream 228 is C 11+ At least 15% greater than the weight fraction of tetralin in stream 220, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0070] In some embodiments, hydrogenated C 11+ The weight fraction of decalin in stream 228 is C 11+ The weight fraction of decalin in stream 220 is at least 10% greater than the weight fraction of decalin in stream 220. 11+ The weight fraction of decalin in stream 228 is C 11+ At least 15% greater than the weight fraction of decalin in stream 220, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0071] In some embodiments, the process 200 comprises reacting hydrogenated C2H2O4 with 1,2-dichloroethane at a temperature, pressure, and weight hourly space velocity effective to induce condensation and dealkylation reactions to produce a reformate stream 234. 11+ Stream 228, C 7- Stream 208, and C 9~10 The step of contacting the stream 218 with a conversion catalyst 130 includes contacting the stream 218 with a conversion catalyst 130. 11+ and C 9~10 The compound is dealkylated over the conversion catalyst 130 to give C 10- The compound C can be produced. 7- The compound is converted to C by condensation reaction. 4+In this way, C 7- Stream 208, C 9~10 Stream 218, and C 11+ Stream 220 may be reformed to increase the yield of C8 compounds in aromatic product stream 204. The conversion catalyst 130, condensation reactor 132, and operating conditions described in process 100 are suitable for use in process 200 to produce reformate stream 234.

[0072] In some embodiments, the reformate stream 234 produced by the conversion catalyst 130 is recycled to the distillation column 206. The reformate stream 234 may optionally be combined with the hydrocarbon feed stream 102 before being fed to the distillation column 206.

[0073] Hydrogenation C 11+ Stream 228, C 7- Stream 208, and C 9~10 By feeding stream 218 to conversion catalyst 130, process 200 converts the high concentration of C aromatics into the low concentration of C 4+ In particular, the use of the above process 200 provides the advantage of producing C8 aryl yields at 35% or more carbon fraction (CF) of the hydrocarbon feed stream 102, PNA yields at 5% or less CF of the hydrocarbon feed stream 102, and C8 aryl yields at 35% or less CF of the aqueous feed carbon. 4+ In certain embodiments, the C8 aryl yield may be 40 wt% or more, 45% or more CF, 50% or more CF, or 60% or more CF of the hydrocarbon feed stream 102. In certain embodiments, the PNA yield is less than 5% CF, or less than 4% CF, or less than 3% CF, or less than 2% CF, or less than 1% CF of the hydrocarbon feed stream 102. In certain embodiments, the C8 aryl yield may be 40 wt% or more, 45% or more CF, or 50% or more CF, or 60% or more CF of the hydrocarbon feed stream 102. In certain embodiments, the C8 aryl yield may be less than 5% CF, or less than 4% CF, or less than 3% CF, or less than 2% CF, or less than 1% CF of the hydrocarbon feed stream 102. 4+ The alkane yield is 30% CF or less, 25% CF or less, or 20% CF or less of the hydrocarbon feed stream 102.

[0074] Xylene-Synthetic Aromatic Kerosene (Xylene-SAK): Referring to FIG. 3, the hydrocarbon feed stream 102 is reformed to produce an aromatics product stream 304 containing C aromatics and hydrocarbons, such as para-xylene, ortho-xylene, and meta-xylene, as well as a C 9~10 A process 300 for producing a product stream 318 is described.

[0075] In some embodiments, the process 300 fractionates the hydrocarbon feed stream 102 in a distillation column 306 along with a recycled reformate stream 334 to produce a C 7- Streams 308 and C 8+ C. 8+ Stream 310 is a 8+ Stream 310 to C 9+ The aromatic product stream 304 is fractionated in a second distillation column 312 to separate the aromatic product stream 304 containing C8 compounds. 9+ Stream 314 is C 9~10 Streams 318 and C 11+ The stream is fractionated in a third distillation column 316 to separate stream 320. 9~10 The stream is collected as product stream 318.

[0076] In some embodiments, C 11+ Stream 320 is contacted with hydrogenation catalyst 122 in the presence of hydrogen to form hydrogenated C 11+ The hydrogenation catalyst 122, hydrogenation reactor 124, and operating conditions described in process 100 produce hydrogenated C 11+ Suitable for use in process 300 to produce stream 328.

[0077] In some embodiments, hydrogenated C 11+ Stream 328 is hydrogenated C 11+ % PNA compound based on the total weight of stream 328. In some embodiments, the hydrogenated C 11+ Stream 328 is hydrogenated C11+ Contains less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% PNA compounds based on the total weight of stream 328.

[0078] In some embodiments, hydrogenated C 11+ The conversion of PNA (e.g., naphthalene) compounds in stream 328 is at least 50%, or at least 55%, or at least 60%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%.

[0079] In some embodiments, hydrogenated C 11+ The weight fraction of tetralin in stream 328 is C 11+ At least 10% greater than the weight fraction of tetralin in stream 320. 11+ The weight fraction of tetralin in stream 328 is C 11+ At least 15% greater than the weight fraction of tetralin in stream 320, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0080] In some embodiments, hydrogenated C 11+ The weight fraction of decalin in stream 328 is C 11+ At least 10% greater than the weight fraction of decalin in stream 320. 11+ The weight fraction of decalin in stream 328 is C 11+At least 15% greater than the weight fraction of decalin in stream 320, or at least 20% greater, or at least 25% greater, or at least 30% greater, or at least 35% greater to less than 40% greater, or less than 45% greater, or less than 50% greater.

[0081] In some embodiments, the process 300 comprises reacting a hydrogenated C4H2O4 with a condensation and dealkylation reaction mixture at a temperature, pressure, and weight hourly space velocity effective to induce condensation and dealkylation reactions to produce a reformate stream 334. 11+ Streams 328 and C 7- The step of contacting the stream 308 with a conversion catalyst 130. In particular, 11+ The compound is dealkylated over the conversion catalyst 130 to give C 10- The compound C can be produced. 7- The compound is converted to C by condensation reaction. 4+ In this way, C 7- Streams 308 and C 11+ Stream 320 may be reformed to increase the yield of C8 compounds in aromatic product stream 304. The conversion catalyst 130, condensation reactor 132, and operating conditions described in process 100 are suitable for use in process 300 to produce reformate stream 334.

[0082] In some embodiments, the reformate stream 334 produced by the conversion catalyst 130 is recycled to the distillation column 306. The reformate stream 334 may optionally be combined with the hydrocarbon feed stream 102 before being fed to the distillation column 306.

[0083] Hydrogenation C 11+ Streams 328 and C 7- By feeding stream 308 to conversion catalyst 130, process 300 produces a high concentration of C 8~10 Aromatics, low concentration C 4+ In particular, the use of the above process 300 provides the advantage of producing paraffins and PNA compounds with a carbon fraction (CF) of 35% or more of the hydrocarbon feed stream 102.8~10 aryl yield, PNA yield of 5% or less of the CF of the hydrocarbon feed stream 102, and C of 25% or less of the CF of the aqueous feed carbon 4+ In certain embodiments, the C 8~10 The aryl yield may be 40 wt% or more, 45% or more CF, 50% or more CF, or 60% or more CF of the hydrocarbon feed stream 102. In certain embodiments, the PNA yield is less than 5% CF, or less than 4% CF, or less than 3% CF, or less than 2% CF, or less than 1% CF of the hydrocarbon feed stream 102. 4+ The alkane yield is 25% CF or less, 20% CF or less, or 15% CF or less of the hydrocarbon feed stream 102.

[0084] Biomass feedstock: 4, a process 400 for producing a hydrocarbon feed stream 102 derived from biomass is illustrated. The process 400 further includes a step for upgrading the hydrocarbon feed stream 102 into an aromatic product stream 404.

[0085] As used herein, the term "biomass" refers to, without limitation, organic matter produced by plants (e.g., leaves, roots, seeds and stems), as well as microbial and animal metabolic waste. Common sources of biomass include: (1) agricultural wastes such as corn stalks, straw, seed husks, sugarcane meal, bagasse, nut shells, and manure from cattle, poultry, and hogs; (2) woody materials such as wood or bark, sawdust, timber debris, and mill scraps; (3) municipal waste such as wastepaper and yard clippings; and (4) energy crops such as poplar, willow, switchgrass, alfalfa, prairie bluestem, corn, soybeans, and the like.

[0086] Various sugar processing methods are well known in the art and are commercially practiced on a large scale to produce sugar liquor from biomass. For example, in processes using sugar cane, the sugar cane is typically washed, crushed or spread, and clarified with lime to isolate and obtain an aqueous biomass-derived intermediate feed stream rich in sucrose, fructose, and glucose. In processes using sugar beet, the sugar beet is similarly washed, sliced, extracted, and clarified to isolate and obtain an aqueous biomass-derived intermediate feed stream rich in sucrose, fructose, and glucose. For processes involving grain, the grain is washed and then processed to obtain wet-milled starch (corn) or dry-milled / floured starch (corn, wheat, barley, sorghum grain). The isolated sugar liquor may be adjusted to obtain a desired sugar concentration, for example, concentrated or diluted with water to obtain a feed solution 10. Generally, suitable concentrations are in the range of about 5% to about 70%, with a range of about 40% to 70% being more common in industrial applications.

[0087] For raw feedstocks of lignocellulosic biomass, the biomass feedstock may be degraded from complex biopolymers to sugars and soluble oxygenates to form the feedstock solution 10. In one embodiment, raw lignocellulosic feedstock (e.g., corn stover) undergoes decomposition by dilute acid thermochemical pretreatment, pH adjustment with bases such as ammonium hydroxide, lime, sodium hydroxide or potassium hydroxide, and enzymatic hydrolysis to form soluble sugars. Optional pre-conversion methods include fractionation of the feedstock at harvest, fractionation by sieving, chemical pretreatment to leach out undesirable components, fermentative pretreatment such as treatment with white rot fungi, mechanical methods such as steam explosion, roasting, or pelleting. Alternative means of decomposition include autohydrolysis (hot water only), alkali (e.g., ammonia, sodium hydroxide, potassium hydroxide), oxidation (e.g., hydrogen peroxide, oxygen, air), organosolv (e.g., ethanol, acetic acid, catalyst derived solvents), and thermochemical pretreatment with ionic liquids. The processing step of lignocellulosic biomass may also include additional processing to obtain chopped, shredded, compressed, pulverized or otherwise processed biomass of a size suitable for conversion.

[0088] In some embodiments, the feedstock solution 10 may be formed using one or more of the processes described above and may be derived from one or more of the biomass sources described above. The feedstock solution may be made from biomass by any means now known or developed in the future, or may simply be a by-product of other processes. The feedstock solution may also be referred to as a feed stream for the processes as described herein.

[0089] In some embodiments, the feedstock solution comprises one or more oxygenated hydrocarbons. The term "oxygenated hydrocarbons" refers to water-soluble hydrocarbons containing three or more carbon atoms and two or more oxygen atoms, such as carbohydrates (e.g., monosaccharides, disaccharides, oligosaccharides, polysaccharides, and starches), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols (e.g., diols, triols, and polyols), and sugar degradation products (e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, and furfural), each of which is referred to herein as 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+ ), and the term "monoxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and one oxygen atom (i.e., C 2+ O1), and the term "dioxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and two oxygen atoms (i.e., C 2+ O2), and the term "polyoxygenate" refers to a hydrocarbon molecule that contains two or more carbon atoms and three or more oxygen atoms (i.e., C 2+ O 3+ )

[0090] In addition to oxygenated hydrocarbons, the feedstock may also include lignin, one or more extractives, one or more ash components, or one or more organic species (e.g., lignin derivatives). Extractives include terpenoids, stilbenes, flavonoids, phenols, aliphatics, lignans, alkanes, proteinaceous matter, amino acids, and other inorganic products. Ash components include Al, Ba, Ca, Fe, K, Mg, Mn, P, S, Si, Zn, and the like. Other organic species include 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, vanillin, 4-propylsyringol, vitamin E, steroids, long chain hydrocarbons, long chain fatty acids, stilbenoids, and the like. In some embodiments, the feedstream as described herein includes oxygenated hydrocarbons, and the oxygenated hydrocarbons include monosaccharides, disaccharides, oligosaccharides, polysaccharides, sugar alcohols, sugar degradation products, cellulose derivatives, hemicellulose derivatives, lignin derivatives, lignocellulose derivatives, or combinations thereof.

[0091] 4, feed solution 10 is contacted with deoxygenation catalyst 12 in the presence of hydrogen to produce a deoxygenation product stream 18 comprising a mixture of one or more oxygenates. The hydrogen may be provided from a hydrogen source 14, which may be a reservoir containing hydrogen (e.g., a pressurized tank) or an upstream process unit that produces hydrogen. In some embodiments, deoxygenation catalyst 12 is disposed in a deoxygenation reactor 16.

[0092] The deoxygenated product stream 18 has a H:C ratio of 0.5 to less than 2, or between 0.8 and 1.8, or between 1 and 1.6, or between 1.2 and 1.6. eff In some embodiments, the ratio of H:C eff The ratio is at least 0.5, or at least 0.6, or at least 0.7, or at least 0.8, or at least 0.9, or at least 1, or at least 1.1, or at least 1.2 but less than 1.3, or less than 1.4, or less than 1.5, or less than 1.6, or less than 1.8, or less than 1.9, or less than 2.0.

[0093] As used herein, the term "H:C eff The "carbon to hydrogen ratio" is based on the amounts of carbon, oxygen and hydrogen in the feedstock and is calculated as follows:

[0094]

number

[0095] In some embodiments, the deoxygenated product 18 stream is a C 2 O 3 , which is a compound having one or more carbon atoms and between one and three oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxycarboxylic acids, carboxylic acids, diols, and triols. 1+ O 1~3 In some embodiments, C 1+ O 1~3 The hydrocarbons have 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms. 1+ O 1~3 In addition to hydrocarbons, the deoxygenated product stream 18 may include hydrocarbons that do not have oxygen elements.

[0096] Exemplary alcohols in the deoxygenated product stream 18 include, but are not limited to, primary, secondary, linear, branched, or cyclic C alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof. 1+ It may contain alcohol.

[0097] Exemplary ketones can include, without limitation, hydroxyketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, methylglyoxal, butanedione, pentanedione, diketohexane, and isomers thereof.

[0098] Exemplary aldehydes can include, without limitation, hydroxyaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof.

[0099] Exemplary carboxylic acids can include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, 2-hydroxybutanoic acid, and lactic acid and their isomers and derivatives, including hydroxylated derivatives.

[0100] Exemplary diols can include, without limitation, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof.

[0101] 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-furanmethanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methylfuran, 2-ethyl-tetrahydrofuran, 2-ethylfuran, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethylfuran, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.

[0102] In some embodiments, the deoxygenation catalyst 12 comprises a heterogeneous catalyst having one or more materials capable of catalyzing the reaction of hydrogen with the feedstock solution 10 to remove one or more of the oxygen atoms from the feedstock solution to produce one or more oxygenates. In some embodiments, the deoxygenation catalyst 12 comprises one or more metals attached to a support, which may include, but are not limited to, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof. The deoxygenation catalyst may include these elements alone or in combination with one or more promoters, such as Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof. In one embodiment, the deoxygenation catalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W, or Mo. In yet another embodiment, the deoxygenation catalyst comprises Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In another embodiment, the catalyst comprises Fe, Re, and at least Cu or one group VIIIB transition metal. In some embodiments, the metal of the deoxygenation catalyst comprises Pd, W, Mo, Ni, Pt, Ru, or a combination thereof. In some embodiments, the deoxygenation catalyst comprises a promoter. By way of example, the promoter of the deoxygenation catalyst may comprise Sn, W, or a combination thereof. The support may be any one of the supports described herein, including nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacid, diatomaceous earth, hydroxyapatite, and mixtures thereof. In some embodiments, the support comprises zirconia.

[0103] The deoxygenation temperature may range from 80° C. to 300° C. In some embodiments, the reaction temperature is between about 120° C. to 600° C., or between about 200° C. to 280° C., or between about 220° C. to 260° C. The deoxygenation pressure may range from 72 psig to 1300 psig. In some embodiments, the deoxygenation pressure ranges from 72 to 1200 psig, or from 145 to 1200 psig, or from 200 to 725 psig, or from 365 to 700 psig, or from 600 to 650 psig.

[0104] In some embodiments, the WHSV of the deoxygenation reaction ranges from 0.1 grams of oxygenated hydrocarbon per gram of catalyst per hour (g / g-hr) to 40 g / g-hr. In some embodiments, the WHSV is at least 0.25, at least 0.5, at least 0.75, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9, at least 2.0, at least 2.1, at least 2.2, at least 2.3, at least 2.4, at least 2.5, at least 2.6, at least 2.7, at least 2.8, at least 2.9, at least 3.0, at least 3.1, at least 3.2, at least 3.3, at least 3.4, at least 3.5, at least 3.6, at least 3.7, at least 3.8, at least 3.9, at least 4.0, at least 4.1, at least 4.2, at least 4.3, at least 4.4, at least 4.5, at least 4.6, at least 4.7, at least 4.8, at least 4.9, at least 5.0, at least 5.1, at least 5.2, at least 5.3, at least 5.4, at least 5.5, at least 5.6, at least 5.7, at least 5.8, at least 5.9, at least 6.0, at least 6.1, at least 6.2, at least 6.3, at least 6.4, at least 6.5, at least 6.6, at least 6.7, at least 6.8, at least 6.9, at least 7.0, at at least 3.2, at least 3.3, at least 3.4, at least 3.5, at least 3.6, at least 3.7, at least 3.8, at least 3.9, at least 4.0, at least 4.1, at least 4.2, at least 4.3, at least 4.4, at least 4.5, at least 4.6, at least 4.7, at least 4.8, at least 4.9, at least 5.0 to less than 6, less than 7, less than 8, less than 9, less than 10, less than 11, less than 12, less than 13, less than 14, less than 15, less than 20, less than 25, less than 30, less than 35, or less than 40 g / g hr.

[0105] In some embodiments, the amount of hydrogen supplied to the deoxygenation reactor 16 is between 0 and 2400%, between 5 and 2400%, between 10 and 2400%, between 15 and 2400%, between 20 and 2400%, between 25 and 2400%, between 30 and 2400%, between 35 and 2400%, between 40 and 2400%, between 45 ... %, 50~2400%, 55~2400%, 60~2400%, 65~2400%, 70~2400%, 75~2400%, 80~2400%, 85~2400%, 90~2400%, 95~2400%, 98~2400%, 100~2400%, 200~2400%, 300~2400%, 400~2400 %, 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%, 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 or recycled hydrogen. The term "external H2" refers to hydrogen that does not originate from the feed solution but is added to the reactor system from an external source. The term "recycled H2" refers to unconsumed hydrogen that is collected and then recycled back into the reactor system for further use.

[0106] In some embodiments, the product stream 18 passes through a three-phase separator 20 to separate the product stream 18 into a non-condensable gas stream 22, an organic product stream 24, and an aqueous product stream 26. The non-condensable gas stream 22 may consist of hydrogen, carbon dioxide, methane, ethane, and propane. The non-condensable gases may be removed and combusted to create process heat (i.e., heat to drive the reaction in the deoxygenation reactor) or sent to a separation system where hydrogen may be recovered for recycling back to the hydrogen stream 14. The aqueous product stream 26, containing the partially deoxygenated hydrocarbons, may be recycled back to the inlet of the deoxygenation reactor 16. An aqueous purge stream 28, which contains some monooxygenates (e.g., alcohols), may be used to prevent the accumulation of water in the reactor system. The aqueous purge stream 28 may be combined with the organic product stream 24 or may be discarded from the process.

[0107] In some embodiments, the oxygenate-containing organic product stream 24 is a stream that is 4+ with a conversion catalyst 130 at a temperature, pressure, and weight hourly space velocity effective to induce a condensation reaction to convert the compound into a condensate product stream 30 comprising the compound. 4+ The compound is C 4~30 Non-aromatic hydrocarbons and C 6~30 Aromatic hydrocarbons, such as linear or branched C 4~30 Alkanes, linear or branched C 4~30 Alkenes, optionally with straight or branched chain alkyl groups 5~30 Cycloalkane, C with optional straight or branched chain alkene group 5~30 Cycloalkene, optionally with linear or branched alkanes or alkenes 6~30 C with aryl, optional straight or branched chain alkane or alkene 12~30 C with fused aryl, optionally straight or branched chain alkanes or alkenes 12~30 Polycyclic compounds, linear or branched chain C 4~30 Alcohol, linear or branched C 4~30 Ketones, linear or branched C4~30 It may comprise one or more of furans and mixtures thereof.

[0108] In some embodiments, the condensation product stream 30 may pass through a three-phase separator 32 to separate the condensation product stream 30 into an acid condensation gas stream 34, an organic stream 102, and an aqueous stream 38. The organic stream 102 and the aqueous stream 38 are separated by density differences, while the acid condensation gas stream 34, including non-condensable gases, is recycled to the acid condensation reactor 132 to generate additional C 4+ In some embodiments, aqueous stream 38 is discarded from the process or is further processed in a downstream process unit.

[0109] In some embodiments, the organic stream 102 may form or may be similar in composition to the hydrocarbon feed stream 102 described in processes 100-300. In some embodiments, the process 400 includes fractionating the organic stream 102 in a first distillation column 406 to separate the organic stream 102 into a first distillate stream 408 and a first bottoms stream 410. In some embodiments, the first distillate stream 408 is a C 7- Compound or C 5- The first bottom stream 410 comprises 8+ Compound or C 6+ Contains compounds.

[0110] The process 400 further includes fractionating the first bottoms stream 410 in a second distillation column 412 to separate the first bottoms stream 410 into a second distillate stream 404 and a second bottoms stream 414. The second distillate stream 404 may be collected as a product stream and may contain C8 compounds or C 6~8 The second bottom stream 414 contains either 9+ The process 400 includes fractionating the second bottoms stream 414 in a third distillation column 416 to separate the second bottoms stream 414 into C 9~10a third distillate stream 418 containing the compound and C 11+ The method further includes separating a third bottom stream 420 comprising the compound.

[0111] C 11+ Rather than hydrogenating the compounds over a hydrogenation catalyst, process 400 includes recycling the third bottoms stream 420 to the deoxygenation catalyst 12. Applicants have surprisingly found that the deoxygenation catalyst 12 can recycle the C from the third bottoms stream 420 while maintaining acceptable conversion. 11+ It has been found that it is possible to dealkylate compounds and simultaneously deoxygenate water-soluble sugars and oxygenates in the feed solution 10.

[0112] In some embodiments, the process comprises reacting a C 2 -CO 3 -N 2 O 4 mixture at a temperature, pressure, and weight hourly space velocity effective to induce condensation and dealkylation reactions to produce a reformate stream 134. 7- Compound or C 5- a first distillate stream 408 containing the compound and C 9~10 The method further comprises contacting the third distillate stream 418 containing the compounds with a conversion catalyst 130. 9~10 A third distillate stream 418 containing the compounds is collected as a product stream rather than being recycled back to the conversion catalyst 130 .

[0113] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All definitions, as defined and used herein, should be understood to supersede dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0114] The present invention has been described in terms of one or more preferred embodiments, and it should be understood that aside from what has been expressly stated, many equivalents, alternatives, variations, and modifications are possible and are within the scope of the invention. EXAMPLES

[0115] The following examples will enable those skilled in the art to more readily understand the principles of the present disclosure. The following examples are offered by way of illustration and are not intended to be limiting in any way.

[0116] Comparative Example 1: Baseline setup using sorbitol feedstock A feed solution consisting of 50 wt% sorbitol in water was reacted over Pd-Mo-Sn-W ZrO2 HDO catalyst to produce a mixture of oxygenates. 140 grams of HDO catalyst was loaded into two 1 inch OD Inconel reactors connected in series. Prior to the intake of the feedstock, the HDO catalyst was reduced in situ with hydrogen at 400°C and 1050 psig. The feed solution was reacted over the HDO catalyst at 1800 psig and a weight hourly space velocity (WHSV) of 0.8 grams of feed solution per gram of catalyst per hour. The first HDO reactor had an inlet temperature of 232°C and an outlet temperature of 254°C. The second HDO reactor had an inlet temperature of 264°C and an outlet temperature of 295°C. Hydrogen was co-fed to the HDO reactors at a rate of 2550 ml / min. A 7.5 g / min aqueous recycle of product from the HDO product stream was sent back to the HDO inlet.

[0117] The mixture of oxygenates produced from the HDO reactor was then reacted over Ni-modified ZSM-5 conversion catalyst to produce a mixed aromatic feed stream. 165 grams of Ni-modified ZSM-5 catalyst was loaded into a 1 inch OD Inconel lead reactor and 150 grams of Ni-modified ZSM-5 catalyst was loaded into a 1 inch OD Inconel lagged reactor. Regeneration was performed continuously with the reactors swinging from lagged to lead in the order of regeneration. Prior to taking in the feed, the conversion catalyst was reduced in situ under nitrogen at 100 psig and 400°C. The mixture of oxygenates was reacted over the conversion catalyst at 100 psig. The lead and lagged AC reactors had inlet temperatures of 410°C and outlet temperatures of 405°C. Hydrogen from the HDO reactor was separated and sent to and co-fed to the AC reactor. 1-3 g / min of aqueous recycle from the AC product stream was recycled back to the lead AC reactor. 3000 mL / min of steam recycle from the AC product stream was recycled back to the AC reactor.

[0118] AC product stream, AC product stream, C 6- Stream and C 7+ The light end products are then sent to a distillation column configured to separate the light end products into a C stream for further upgrading to aromatics. 6- The stream was recycled back to the AC catalyst. 7+ The stream was collected as product.

[0119] [Table 1]

[0120] Four gravimetric checks were performed on all product streams to compile a net yield profile. Table 1 summarizes the carbon yield profile, which was the average of the gravimetric checks.

[0121] [Example 1] HAU with Sorbitol Feedstock Using the same reaction conditions outlined in Comparative Example 1, a feed solution consisting of 50 wt% sorbitol in water was reacted over Pd-Mo-Sn-W ZrO2HDO catalyst and Ni-modified ZSM-5 conversion catalyst.

[0122] The first distillation column separates the acid condensation product stream into C 5- Stream and C 6+ For further upgrading to produce increased concentrations of aromatics, 5- The stream was recycled back to the AC catalyst. The second distillation column was 6+ Stream to C 6~8 Stream and C 9+ The third distillation column was the C 9+ Stream to C 9~10 Stream and C 11+ separated into streams. 9~10 The stream was collected as the product stream.

[0123] C 11+ The stream was contacted with a commercially available nickel oxide hydrogenation catalyst (KL6560, having 18% Ni, available from CRI catalysts) to produce hydrogenated C 11+ 10 grams of hydrogenation catalyst was loaded into a ½ inch OD Inconel reactor. Prior to the intake of the feedstock, the hydrogenation catalyst was reduced in situ with hydrogen at 400° C. and 1050 psig. 11+ The stream was reacted over a hydrogenation catalyst at 600 psig. The hydrogenation reactor had an inlet temperature of 170° C. and an outlet temperature of 100° C. Hydrogen was co-fed to the hydrogenation reactor at a rate of 150 mL / min. Hydrogen C was used for dealkylation. 11+ The stream was recycled back to the AC catalyst.

[0124] [Table 2]

[0125] Table 2 includes the composition of the materials entering the hydrogenation reactor and the composition of the effluent. As mentioned, PNAs (e.g., naphthalene) are minimally reactive on the conversion catalyst, while tetralin and decalin are C 10- The hydrogenation catalyst is based on the percentage of feed carbon and is easily dealkylated to aromatics and hydrocarbons. 11+ It was effective in reducing the concentration of PNA in the stream from 13.02% to 4.11%.

[0126] [Table 3]

[0127] Four weight checks were performed on all product streams to gather a net yield profile. The net yield profile was the average of the weight checks. Table 3 summarizes the carbon yield profile for the HAU configuration and compares the carbon yield profile to the baseline configuration. 10+ The carbon once captured by aromatics and PNAs (e.g., naphthalene) was redistributed to higher value products including saturated compounds such as paraffins and naphthenes, and unsaturated compounds such as aromatics and olefins.

[0128] Comparative Example 2: Baseline setup with conditioned ethanol feedstock A feed solution consisting of 41.2 wt% ethyl acetate, 27.7 wt% deionized water, and 31.1 wt% 190 proof ethanol was reacted over a Ni-modified ZSM-5 conversion catalyst to produce a mixed aromatic feed stream. 165 grams of Ni-modified ZSM-5 catalyst were loaded into a 1 inch OD Inconel lead reactor and 150 grams of Ni-modified ZSM-5 catalyst were loaded into a 1 inch OD Inconel lug reactor. Regeneration was performed continuously with the reactor swinging from lug to lead in the regeneration sequence. Prior to taking in the feed, the conversion catalyst was reduced in situ under nitrogen at 100 psig and 400°C. The oxygenate mixture was reacted in the AC reactor in a lug to lead configuration. The reaction pressure was 200 psig and occurred at a WHSV of 0.25 grams of feed solution per gram of catalyst per hour. The LAG AC reactor had an inlet temperature of 405° C. and an outlet temperature of 435° C. The Lead AC reactor had inlet and outlet temperatures of 450° C. No hydrogen was co-fed to the reactors. Approximately 1 g / min of aqueous recycle from the AC product stream was recycled back to the Lead AC reactor. 2700 mL / min of steam recycle from the AC product stream was recycled back to the LAG AC reactor.

[0129] AC product stream, AC product stream, C 6- Stream and C 7+ The light end products are then sent to a distillation column configured to separate the light end products into a C stream for further upgrading to aromatics. 6- The stream was recycled back to the AC catalyst. 7+ The stream was collected as product.

[0130] [Table 4]

[0131] Four gravimetric checks were performed on all product streams to compile a net yield profile. Table 4 summarizes the carbon yield profile that was the average of the gravimetric checks.

[0132] [Example 2] HAU with tailored ethanol feedstock Using the same reaction conditions outlined in Comparative Example 2, 41.2 wt. % ethyl acetate, 27.7 wt. % deionized water, and 31.1 wt. % 190 proof ethanol were reacted over a Ni-modified ZSM-5 conversion catalyst to produce a mixed aromatic feed stream.

[0133] The first distillation column separates the acid condensation product stream into C 5- Stream and C 6+ For further upgrading to produce increased concentrations of aromatics, 5- The stream was recycled back to the AC catalyst. The second distillation column was 6+ Stream to C 6~8 Stream and C 9+ The third distillation column was the C 9+ Stream to C 9~10 Stream and C 11+ separated into streams. 9~10 The stream was collected as the product stream.

[0134] C 11+ The stream was contacted with a commercially available nickel oxide hydrogenation catalyst (KL6560, having 18% Ni, available from CRI catalysts) to produce hydrogenated C 11+ 10 grams of hydrogenation catalyst was loaded into a ½ inch OD Inconel reactor. Prior to the intake of the feedstock, the hydrogenation catalyst was reduced in situ with hydrogen at 400° C. and 1050 psig. 11+ The stream was reacted over a hydrogenation catalyst at 600 psig. The hydrogenation reactor had an inlet temperature of 130° C. and an outlet temperature of 105° C. Hydrogen was co-fed to the hydrogenation reactor at a rate of 150 mL / min. Hydrogen C was used for dealkylation. 11+ The stream was recycled back to the AC catalyst.

[0135] [Table 5]

[0136] Table 5 contains the composition of the material entering the hydrogenation reactor and the composition of the effluent. The hydrogenation catalyst was selected from the group consisting of C, C2H3, C1H4, C2H5, C1H6, C1H7, C1H8, C1H9, C1H10, C1H11, C1H12, C1H13, C1H14, C1H15, C1H16, C1H17, C1H18, C1 11+ It was effective in reducing the concentration of PNA in the stream from 13.02% to 4.11%. The hydrogenation catalyst was also effective in increasing the concentration of tetralin and decalin, which are readily dealkylated over the conversion catalyst.

[0137] [Table 6]

[0138] Four weight checks were performed on all product streams to gather a net yield profile. The net yield profile was the average of the weight checks. Table 6 summarizes the carbon yield profile for the HAU configuration and compares the carbon yield profile to the baseline configuration. 10+ The carbon once captured by aromatics and PNAs (e.g., naphthalene) was redistributed to higher value products including saturated compounds such as paraffins and naphthenes, and unsaturated compounds such as aromatics and olefins.

[0139] [Example 3] NBX with tailored ethanol feedstock Using the same reaction conditions outlined in Comparative Example 2, 41.2 wt. % ethyl acetate, 27.7 wt. % deionized water, and 31.1 wt. % 190 proof ethanol were reacted over a Ni-modified ZSM-5 conversion catalyst to produce a mixed aromatic feed stream.

[0140] The first distillation column separates the acid condensation product stream into C 7- Stream and C 8+ The crude oil was then separated into the C stream for further upgrading to produce increased concentrations of aromatics. 7-The stream was recycled back to the AC catalyst. The second distillation column was 8+ Stream to C8 stream and C 9+ The third distillation column was C 9+ Stream to C 9~10 Stream and C 11+ The C stream was used for dealkylation. 9~10 The stream was recycled back to the AC catalyst.

[0141] C 11+ The stream was contacted with a commercially available nickel oxide hydrogenation catalyst (KL6560, having 18% Ni, available from CRI catalysts) to produce hydrogenated C 11+ 10 grams of hydrogenation catalyst was loaded into a ½ inch OD Inconel reactor. Prior to the intake of the feedstock, the hydrogenation catalyst was reduced in situ with hydrogen at 400° C. and 1050 psig. 11+ The stream was reacted over a hydrogenation catalyst at 600 psig. The hydrogenation reactor had an inlet temperature of 130° C. and an outlet temperature of 105° C. Hydrogen was co-fed to the hydrogenation reactor at a rate of 150 mL / min. Hydrogen C was used for dealkylation. 11+ The stream was recycled back to the AC catalyst. A C8 stream containing xylenes was collected as the net product stream.

[0142] [Table 7]

[0143] Table 7 includes the composition of the material entering the hydrogenation reactor and the composition of the effluent. The hydrogenation catalyst was selected from the group consisting of C, C2H, C3H, C4H, C5H, C6H, C7H, C8H, C9H, C10H, C11H, C12H, C13H, C14H, C15H, C16H, C17H, C18H, C19H, C20H, C21H 11+ It was effective in reducing the concentration of PNA in the stream from 44.37% to 7.4%. The hydrogenation catalyst was also effective in increasing the concentration of tetralin and decalin, which are readily dealkylated over the conversion catalyst.

[0144] [Table 8]

[0145] Four weight checks were performed on all product streams to gather a net yield profile. The net yield profile was the average of the weight checks. Table 8 summarizes the carbon yield profile for the NBX configuration and compares the carbon yield profile with the HAU configuration and the baseline configuration. 10+ The carbon once captured by aromatics and PNAs (e.g., naphthalene) was redistributed to higher value products including saturated compounds such as paraffins and naphthenes, and unsaturated compounds such as aromatics and olefins.

[0146] [Example 5] Xylene-SAK with conditioned ethanol feedstock Using the same reaction conditions outlined in Comparative Example 2, 41.2 wt. % ethyl acetate, 27.7 wt. % deionized water, and 31.1 wt. % 190 proof ethanol were reacted over a Ni-modified ZSM-5 conversion catalyst to produce a mixed aromatic feed stream.

[0147] The first distillation column separates the acid condensation product stream into C 7- Stream and C 8+ Then, the C 7- The stream is recycled back to the AC catalyst. The second distillation column is 8+ Stream to C8 stream and C 9+ The third distillation column is the C 9+ Stream to C 9~10 Stream and C 11+ C8 stream and C 9~10 The stream is collected as the net product stream.

[0148] C 11+ The stream was contacted with a commercially available nickel oxide hydrogenation catalyst (KL6560, having 18% Ni, available from CRI catalysts) to produce hydrogenated C11+ 10 grams of hydrogenation catalyst was loaded into a ½ inch OD Inconel reactor. Prior to the intake of the feedstock, the hydrogenation catalyst was reduced in situ with hydrogen at 400° C. and 1050 psig. 11+ The stream was reacted over a hydrogenation catalyst at 600 psig. The hydrogenation reactor had an inlet temperature of 130° C. and an outlet temperature of 105° C. Hydrogen was co-fed to the hydrogenation reactor at a rate of 150 mL / min. Hydrogen C was used for dealkylation. 11+ The stream was recycled back to the AC catalyst.

[0149] [Table 9]

[0150] Four weight checks were performed on all product streams to gather a net yield profile. The net yield profile was the average of the weight checks. Table 9 summarizes the carbon yield profile for the xylene-SAK configuration and compares the carbon yield profile to the HAU configuration, the NBX configuration, and the baseline configuration. 10+ The carbon once captured by aromatics and PNAs (e.g., naphthalene) was redistributed to higher value products including saturated compounds such as paraffins and naphthenes, and unsaturated compounds such as aromatics and olefins.

[0151] Thus, the present disclosure provides a method for diversifying the yield structure of a hydrocarbon feedstock from non-aromatic compounds (e.g., paraffins, naphthenes) to C 6~10 In some embodiments, the present disclosure provides systems and methods for shifting aromatic compounds (e.g., C 6~10 ), particularly to increase the yield of benzene, toluene, para-xylene, ortho-xylene, and meta-xylene, light hydrocarbon streams (e.g., C 5- ) and heavy hydrocarbon streams (e.g., C 11+ ) is provided.

[0152] Although the present invention has been described in some detail with reference to certain specific embodiments, those skilled in the art will appreciate that the present invention may be used in alternative embodiments to those described, which are presented for purposes of illustration and not limitation, and therefore the scope of the appended claims should not be limited to the description of the embodiments contained herein.

[0153] For completeness, various aspects of the invention are set forth in the following numbered clauses.

[0154] Clause 1. A process for producing and separating aromatic hydrocarbons from a hydrocarbon feed stream comprising a plurality of non-aromatic and aromatic hydrocarbons, wherein the non-aromatic hydrocarbons comprise one or more of paraffins, olefins, naphthenes, or combinations thereof, and the aromatic compounds comprise one or more of aryls, fused aryls, polycyclic compounds, or combinations thereof, the process comprising: (i) fractionating the hydrocarbon feed stream using a series of distillation columns to separate an aromatic product stream and a heavy hydrocarbon stream from the hydrocarbon feed stream, wherein the aromatic product stream comprises at least one of C aromatics, C aromatics, C aromatics, or combinations thereof, and the heavy hydrocarbon stream comprises C aromatics. 11+ comprising a compound; (ii) contacting the heavy hydrocarbon stream with a hydrogenation catalyst in the presence of hydrogen to produce a hydrogenated C 11+ generating a stream; (iii) Hydrogenation C 11+ The stream is contacted with at least one conversion catalyst to produce a conversion catalyst having a C 11+ dealkylating at least a portion of the compounds to produce a reformate stream, the reformate stream being fed to the series of distillation columns of step (i); A process including.

[0155] Clause 2. Step (i) A first distillation column is used to fractionate the hydrocarbon feed stream into C 5- Stream and C 6+ separating the stream from the hydrocarbon feed stream; A second distillation column is used to produce C 6+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into a C 6~8 comprising a compound; A third distillation column was used to produce C 9+ Stream to C 9~10 and fractionating the mixture into a heavy hydrocarbon stream and a heavy hydrocarbon stream. 2. The process of claim 1, further comprising:

[0156] Article 3.C 5- 3. The process of claim 2, further comprising recycling the stream to the at least one conversion catalyst.

[0157] Article 4.C 6~8 3. The process of claim 2, wherein the stream comprises at least one of benzene, toluene, xylene, or combinations thereof.

[0158] Clause 5. Step (i) A first distillation column is used to fractionate the hydrocarbon feed stream into C 7- Stream and C 8+ separating the stream from the hydrocarbon feed stream; A second distillation column is used to produce C 8+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into streams, wherein the aromatic product stream comprises C8 compounds; A third distillation column was used to produce C 9+ Stream to C 9~10 and fractionating the mixture into a heavy hydrocarbon stream and a heavy hydrocarbon stream. 2. The process of claim 1, further comprising:

[0159] Article 6.C 7- 6. The process of claim 5, further comprising recycling the stream to the at least one conversion catalyst.

[0160] Article 7.C 9~10 The stream is recycled to at least one conversion catalyst to produce C 9~10 6. The process of clause 5, further comprising the step of dealkylating at least a portion of the compound.

[0161] Clause 8. The process of clause 1, wherein the hydrogenation catalyst comprises at least one support and at least one metal.

[0162] Clause 9. The process of clause 8, wherein the at least one support comprises at least one of carbon, silica, alumina, zirconia, titania, vanadia, ceria, silica-aluminate, zeolite, diatomaceous earth, hydroxyapatite, zinc oxide, chromia, and combinations thereof.

[0163] Clause 10. The process of clause 8, wherein the metal comprises at least one of Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, alloys thereof, and combinations thereof.

[0164] Clause 11. The process of clause 8, wherein the hydrogenation catalyst further comprises at least one promoter.

[0165] Clause 12. The process of clause 11, wherein the promoter comprises at least one of Ag, Au, Cr, Zn, Mn, Mg, Ca, Cr, Sn, Bi, Mo, W, B, P, and alloys or combinations thereof.

[0166] Clause 13. The process of clause 1, wherein the conversion catalyst comprises at least one of a carbide, a nitride, a zirconia, an alumina, a silica, an aluminosilicate, a phosphate, a zeolite, a titanium oxide, a zinc oxide, a vanadium oxide, a lanthanum oxide, a yttrium oxide, a scandium oxide, a magnesium oxide, a cerium oxide, a barium oxide, a calcium oxide, a hydroxide, a heteropoly acid, an inorganic acid, an acid-modified resin, a base-modified resin, and combinations thereof.

[0167] Clause 14. The process of clause 1, wherein the conversion catalyst comprises at least one metal, the metal comprising at least one of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof.

[0168] Clause 15. The process of clause 1, wherein the conversion catalyst comprises at least one modifier, the modifier comprising at least one of Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof.

[0169] Clause 16. The process of clause 1, wherein the heavy hydrocarbon stream in step (ii) comprises at least one polynuclear aromatic (PNA), and the conversion of the PNA during hydrogenation is at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%.

[0170] Article 17. Hydrogenation C 11+ The stream is hydrogenated C 11+ 13. The process of claim 1, wherein the stream contains less than 5 wt.% polynuclear aromatics, or less than 4 wt.%, or less than 3 wt.%, or less than 2 wt.%, or less than 1 wt.%, based on the total weight of the stream.

[0171] Article 18. Hydrogenation C 11+ The stream contains tetralin and is hydrogenated C 11+ The streams are divided into C 11+2. The process of claim 1, comprising a weight fraction of tetralin that is at least 10 wt% greater than the weight fraction of tetralin in the stream, or at least 20 wt% greater, or at least 30 wt% greater, or at least 40 wt% greater, or at least 50 wt% greater.

[0172] Article 19. Hydrogenation C 11+ The stream comprises decalin and is hydrogenated C 11+ The streams are divided into C 11+ 2. The process of claim 1, comprising a weight fraction of tetralin that is at least 10 wt% greater than the weight fraction of tetralin in the stream, or at least 20 wt% greater, or at least 30 wt% greater, or at least 40 wt% greater, or at least 50 wt% greater.

[0173] Clause 20. Before step (i) catalytically reacting a feedstream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream; catalytically reacting the deoxygenated product stream with at least one conversion catalyst to produce a hydrocarbon feed stream; 2. The process of claim 1, further comprising:

[0174] Article 21. (i) catalytically reacting a feedstream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream; (ii) catalytically reacting the deoxygenated product stream with at least one conversion catalyst to produce a condensation product stream comprising non-aromatic and aromatic hydrocarbons, wherein the non-aromatic hydrocarbons comprise one or more of paraffins, olefins, naphthenes, or combinations thereof, and the aromatic compounds comprise one or more of aryls, fused aryls, polycyclic compounds, or combinations thereof; (iii) fractionating the condensation product stream using a series of distillation columns to separate an aromatic product stream and a heavy hydrocarbon stream from the condensation product stream, wherein the aromatic product stream comprises at least one of C aromatics, C aromatics, C aromatics, or combinations thereof, and the heavy hydrocarbon stream comprises C aromatics. 11+ comprising a compound; (iv) recycling at least a portion of the heavy hydrocarbon stream to the deoxygenation catalyst of step (i); A process including.

[0175] Clause 22. The process of clause 21, wherein the oxygenated hydrocarbons comprise one or more of monosaccharides, disaccharides, oligosaccharides, polysaccharides, sugar alcohols, sugar degradation products, cellulose derivatives, hemicellulose derivatives, lignin derivatives, lignocellulose derivatives, and combinations thereof.

[0176] Clause 23. Step (iii) A first distillation column is used to fractionate the condensate stream to produce C 5- Stream and C 6+ Separating the stream from the condensate stream; A second distillation column is used to produce C 6+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into a C 6~8 comprising a compound; A third distillation column was used to produce C 9+ Stream to C 9~10 and fractionating the mixture into a heavy hydrocarbon stream and a heavy hydrocarbon stream. 22. The process of claim 21, further comprising:

[0177] Article 24.C 5- The stream is contacted with at least one conversion catalyst to produce, by a condensation reaction, 5- At least a portion of the compound is C 4+ 24. The process of claim 23, further comprising converting to a compound.

[0178] Article 25.C 6~8 24. The process of claim 23, wherein the stream comprises at least one of benzene, toluene, xylene, or combinations thereof.

[0179] Clause 26. Step (iii) A first distillation column is used to fractionate the condensate stream to produce C 7- Stream and C 8+ Separating the stream from the condensate stream; A second distillation column is used to produce C 8+ The stream is divided into an aromatic product stream and a C 9+ fractionating the aromatic product stream into streams, wherein the aromatic product stream comprises C8 compounds; A third distillation column was used to produce C 9+ Stream to C 9~10 and fractionating the mixture into a heavy hydrocarbon stream and a heavy hydrocarbon stream. 22. The process of claim 21, further comprising:

[0180] Article 27.C 7- The stream is contacted with at least one conversion catalyst to produce, by a condensation reaction, 7- At least a portion of the compound is C 4+ 27. The process of claim 26, further comprising converting to a compound.

[0181] Article 28.C 9~10 The stream is contacted with at least one conversion catalyst to form a C 9~10 27. The process of clause 26, further comprising the step of dealkylating at least a portion of the compound.

[0182] Clause 29. The process of clause 21, wherein the deoxygenation catalyst comprises at least one support and at least one metal.

[0183] Clause 30. The process of clause 29, wherein at least one support comprises zirconia.

[0184] Clause 31. The process of clause 29, wherein the at least one metal comprises Pd, W, or a combination thereof.

[0185] Clause 32. The process of clause 29, wherein the deoxygenation catalyst comprises a promoter.

[0186] Clause 33. The process of clause 32, wherein the promoter comprises Sn, W, or a combination thereof.

[0187] Clause 34. The process of clause 21, wherein the conversion catalyst comprises a zeolite.

[0188] Clause 35. The process of clause 21, wherein the conversion catalyst comprises at least one metal.

[0189] Clause 36. The process of clause 35, wherein the metal is Ni. [Explanation of symbols]

[0190] 10 Raw material solution 12 Deoxygenation catalyst 14 Hydrogen Source 16 Deoxygenation Reactor 18 Deoxygenated Product Stream 20 3 phase separator 22 Non-condensable gas streams 24 Organic Product Stream 26 Aqueous Product Stream 28 Aqueous Purge Stream 30 Condensation product stream 34 Acid condensation gas stream 32 3 phase separator 38 Aqueous Stream 100 Processes 102 Hydrocarbon feed streams, organic streams 104 Aromatic Product Stream 106 Distillation Tower 108 C 5- stream 110 C 6+ stream 112 Second Distillation Tower 114 C 9+ stream 116 Third Distillation Tower 118 C 9~10 stream 120 C 11+ stream 122 Hydrogenation catalyst 124 Hydrogenation Reactor 126 Hydrogen Source 128 Hydrogenated C 11+ stream 130 Conversion Catalyst 132 Condensation Reactor 134 Reformate Stream 200 processes 204 Aromatic Product Stream 206 Distillation Tower 208 C 7- stream 210 C 8+ stream 212 Second Distillation Tower 214 C 9+ stream 216 Third Distillation Tower 218 C 9~10 stream 220 C 11+ stream 228 Hydrogenation C 11+ stream 234 Reformate Stream 300 processes 304 Aromatic Product Stream 306 Distillation Tower 308 C 7- stream 310C 8+ stream 312 Second Distillation Tower 314 C 9+ stream 316 Third Distillation Tower 318 C 9~10 stream 320C 11+ stream 328 Hydrogenation C11+ stream 334 Reformate Stream 400 processes 404 Second distillate stream, aromatic product stream 406 First Distillation Tower 408 First distillate stream 410 First Bottom Stream 412 Second Distillation Tower 414 Second Bottom Stream 416 Third Distillation Tower 418 Third distillate stream 420 Third Bottom Stream

Claims

1. 1. A process for producing and separating aromatic hydrocarbons from a hydrocarbon feed stream comprising a plurality of non-aromatic hydrocarbons and aromatic hydrocarbons, wherein the non-aromatic hydrocarbons comprise paraffins, olefins, naphthenes, or combinations thereof, and the aromatic hydrocarbons comprise aryls, fused aryls, polycyclic compounds, or combinations thereof, the process comprising: (i) fractionating said hydrocarbon feed stream using a series of distillation columns to separate an aromatic product stream and a heavy hydrocarbon stream from said hydrocarbon feed stream, wherein said aromatic product stream is a C ６ aromatic, C ７ aromatic, C ８ aromatics, or combinations thereof, and the heavy hydrocarbon stream is C １１＋ a compound comprising: (ii) contacting the heavy hydrocarbon stream with a hydrogenation catalyst in the presence of hydrogen to form a hydrogenated C １１＋ generating a stream; (iii) The hydrogenated C １１＋ The stream is contacted with at least one conversion catalyst to form the C １１＋ dealkylating at least a portion of the compounds to produce a reformate stream, said reformate stream being fed to said series of distillation columns of step (i); A process involving:

2. Step (i) A first distillation column is used to fractionate the hydrocarbon feed stream to produce a C ５－ Stream and C ６＋ separating a stream from said hydrocarbon feed stream; A second distillation column is used to separate the C ６＋ the aromatic product stream and C ９＋ fractionating the aromatic product stream into a C ６～８ a compound comprising: A third distillation column is used to separate the C ９＋ Stream to C ９～１０ fractionating said heavy hydrocarbon stream into a heavy hydrocarbon stream; 10. The process of claim 1 further comprising:

3. Said C ５－ 3. The process of claim 2, further comprising recycling a stream to the at least one conversion catalyst.

4. Step (i) A first distillation column is used to fractionate the hydrocarbon feed stream into C ７－ Stream and C ８＋ separating a stream from said hydrocarbon feed stream; A second distillation column is used to separate the C ８＋ the aromatic product stream and C ９＋ fractionating the aromatic product stream into a C ８ a compound comprising: A third distillation column is used to separate the C ９＋ Stream to C ９～１０ fractionating said heavy hydrocarbon stream into a heavy hydrocarbon stream; 10. The process of claim 1 further comprising:

5. Said C ７－ 5. The process of claim 4, further comprising recycling a stream to the at least one conversion catalyst.

6. Said C ９～１０ 4. Recycle the stream to the at least one conversion catalyst to form the C ９～１０ C in the stream ９～１０ 5. The process of claim 4, further comprising the step of dealkylating at least a portion of the compound.

7. the hydrogenation catalyst comprises at least one support and at least one metal; the at least one support comprises at least one of carbon, silica, alumina, zirconia, titania, vanadia, ceria, silica-aluminate, zeolite, diatomaceous earth, hydroxyapatite, zinc oxide, chromia, and combinations thereof; 10. The process of claim 1, wherein the at least one metal comprises Fe, Ru, Co, Pt, Pd, Ni, Re, Cu, alloys thereof, or combinations thereof.

8. the conversion catalyst comprises a zeolite and at least one metal; 10. The process of claim 1, wherein the metal comprises 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.

9. 2. The process of claim 1, wherein the heavy hydrocarbon stream in step (ii) comprises at least one polynuclear aromatic (PNA), and the conversion of the PNA during hydrogenation is at least 70%.

10. The hydrogenation C １１＋ The hydrogenated C stream １１＋ 10. The process of claim 1, wherein the stream contains less than 5 wt.% polynuclear aromatic compounds based on the total weight of the stream.

11. The hydrogenation C １１＋ The hydrogenated C stream comprises tetralin. １１＋ The streams are divided into C １１＋ 10. The process of claim 1, comprising a weight fraction of tetralin that is at least 10 wt% greater than the weight fraction of tetralin in the heavy hydrocarbon stream containing compound.

12. The hydrogenation C １１＋ the stream comprises decalin, and １１＋ The streams are divided into C １１＋ 10. The process of claim 1, comprising a weight fraction of decalin that is at least 10 wt% greater than the weight fraction of decalin in the heavy hydrocarbon stream containing compound.

13. Before step (i), catalytically reacting a feedstream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream; catalytically reacting said deoxygenated product stream with said at least one conversion catalyst to produce said hydrocarbon feed stream; 10. The process of claim 1 further comprising:

14. (i) catalytically reacting a feedstream comprising water and oxygenated hydrocarbons with a deoxygenation catalyst in the presence of hydrogen to produce a deoxygenated product stream; (ii) catalytically reacting the deoxygenated product stream with at least one conversion catalyst to produce a condensation product stream comprising non-aromatic hydrocarbons and aromatic hydrocarbons, wherein the non-aromatic hydrocarbons comprise paraffins, olefins, naphthenes, or combinations thereof, and the aromatic compounds comprise aryls, fused aryls, polycyclic compounds, or combinations thereof; (iii) fractionating the condensation product stream using a series of distillation columns to separate an aromatic product stream and a heavy hydrocarbon stream from the condensation product stream, wherein the aromatic product stream is a C ６ aromatic, C ７ aromatic, C ８ aromatics, or combinations thereof, and the heavy hydrocarbon stream is C １１＋ a compound comprising: (iv) recycling at least a portion of said heavy hydrocarbon stream to said deoxygenation catalyst of step (i); A process involving:

15. 15. The process of claim 14, wherein the oxygenated hydrocarbon comprises a monosaccharide, a disaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol, a sugar degradation product, a cellulose derivative, a hemicellulose derivative, a lignin derivative, a lignocellulose derivative, or a combination thereof.

16. Step (i) catalytically reacting said feedstream, comprising water and oxygenated hydrocarbons, with said deoxygenation catalyst in the presence of hydrogen to produce a product stream; separating the product stream into a gaseous product stream, an organic product stream, and an aqueous product stream, wherein the organic product stream is utilized as the deoxygenated product stream; 15. The process of claim 14, comprising:

17. The process of claim 16, wherein the aqueous product stream is recycled to the feed stream.

18. Step (iii) is A first distillation column is used to fractionate the condensation product stream to obtain C ５－ Stream and C ６＋ separating the stream from the condensation product stream; A second distillation column is used to separate the C ６＋ the aromatic product stream and C ９＋ fractionating the aromatic product stream into a C ６～８ a compound comprising: A third distillation column is used to separate the C ９＋ Stream to C ９～１０ fractionating said heavy hydrocarbon stream into a heavy hydrocarbon stream; 15. The process of claim 14, comprising:

19. Said C ５－ the stream is contacted with the at least one conversion catalyst to produce the C ５－ C in the stream ５－ At least a portion of the compound is C ４＋ 20. The process of claim 18, further comprising converting to a compound.

20. Step (iii) is A first distillation column is used to fractionate the condensate stream to produce C ７－ Stream and C ８＋ separating a stream from the condensed stream; A second distillation column is used to separate the C ８＋ the aromatic product stream and C ９＋ fractionating the aromatic product stream into a C ８ a compound comprising: A third distillation column is used to separate the C ９＋ Stream to C ９～１０ fractionating said heavy hydrocarbon stream into a heavy hydrocarbon stream; 15. The process of claim 14, further comprising:

21. Said C ７－ the stream is contacted with the at least one conversion catalyst to produce the C ７－ C in the stream ７－ At least a portion of the compound is C ４＋ 21. The process of claim 20, further comprising converting to a compound.

22. Said C ９～１０ contacting the stream with the at least one conversion catalyst to form the C ９～１０ C in the stream ９～１０ 21. The process of claim 20, further comprising the step of dealkylating at least a portion of the compound.

23. 15. The process of claim 14, wherein the deoxygenation catalyst comprises at least one support and at least one metal.

24. The process of claim 23, wherein the at least one metal comprises Pd, W, Mo, Ni, Pt, Ru, or a combination thereof.

25. The process of claim 23, wherein the deoxygenation catalyst further comprises a promoter, the promoter comprising Sn, W, or a combination thereof.

26. The process of claim 23, wherein the at least one support comprises nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacid, diatomaceous earth, hydroxyapatite, or a combination thereof.

27. The process of claim 23, wherein the at least one support comprises zirconia.

28. The process of claim 23, wherein the deoxygenation catalyst comprises Pd, Mo, Sn, and W, and zirconia.

29. The process of claim 14, wherein step (i) is carried out at a temperature of 80°C to 300°C and a pressure of 72 psig to 1300 psig (496.4 kPa to 8963.2 kPa).

30. The process of claim 14, wherein the deoxygenation catalyst dealkylates the C 11+ compounds of the recycled heavy hydrocarbon stream and simultaneously deoxygenates the oxygenated hydrocarbons of the feed stream.

31. The conversion catalyst comprising: Zeolite and At least one metal Including, 15. The process of claim 14, wherein the at least one metal comprises 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.

32. The process of claim 31, wherein the at least one metal comprises Ni.

33. The process of claim 14, wherein the condensation product stream comprises C4-30 non-aromatic hydrocarbons and C6-30 aromatic hydrocarbons.

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