PYROLYSIS OIL

BACKGROUND

[0001] Catalytically cracking olefin feedstock hydrocarbons produces a multitude of hydrocarbons including C5+ alkenes; lower alkenes such as ethylene and propylene; C4 alkanes, and fuel gas. About 20-25% of the naphtha cracker product is in liquid form, which includes pyrolysis gasoline (mainly benzene, toluene, and xylene) and pyrolysis oil (which is mainly C9+ hydrocarbons). As shown in the Figure, pyrolysis gasoline (PyGas) is hydrogenated by a one- or two-stage hydrotreatment to remove diolefins, olefins, and sulfur. The hydrogenated PyGas can be blended into gasoline or fractionated to recover higher value BTX (benzene, toluene, and xylene). The raffinate or pyrolysis oil (PyOil), which contains heavier (C9+) hydrocarbons, is generally disposed as low-value fuel oil.

[0002] There currently remains a need for a catalyst and method to selectively convert C9 ₊ hydrocarbons (e.g., PyOil) to C6-C9 aromatic hydrocarbons, such as high-value

monoaromatic hydrocarbons (e.g., BTX).

BRIEF DESCRIPTION

[0003] According to an aspect, a process for converting hydrocarbons to monoaromatic hydrocarbons comprises contacting a hydrocarbon feedstock comprising C9 ₊ hydrocarbons and a supported acid catalyst in the presence of hydrogen under conditions effective to produce a hydrocarbon product comprising C6-C9 aromatic hydrocarbons, wherein the supported acid catalyst comprises a heteropolyacid and a support material, and wherein the selectivity of the CV C9 aromatic hydrocarbons is at least 70 weight percent at 25 weight percent C9 ₊ hydrocarbon conversion.

[0004] According to another aspect, a hydrocarbon product comprises C6-C9 aromatic hydrocarbons manufactured by the process, preferably wherein the C6-C9 aromatic hydrocarbons comprise, based on the total weight of the hydrocarbon product, 4 to 15 weight percent, preferably 6 to 12 weight percent, more preferably 9 to 12 weight percent of BTX, 10 to 20 weight percent, preferably 11 to 18 weight percent, more preferably 12 to 16 weight percent of ethylbenzene, 14 to 30 weight percent, preferably 15 to 28 weight percent, more preferably 22 to 27 weight percent of C9 aromatic hydrocarbons, or a combination thereof.

[0005] The above described and other features are exemplified by the following figures and detailed description. BRIEF DESCRIPTION OF THE DRAWING

[0006] The Figure is a flow diagram showing the processing of hydrocarbons.

DETAILED DESCRIPTION

[0007] It was surprisingly discovered that metalated heteropolyacids (HPA-M) having different heteroatoms such as Mo and W species can be incorporated into mesoporous SB A- 15 to provide a catalyst for the production of mono-aromatics with high selectivity from C9 ₊ pyrolysis oil. Incorporation of HPA-M on mesoporous silica created strong acid sites, which were sufficient to produce aromatics from C9 ₊ pyrolysis oil obtained from consecutive reaction of dehydrogenation and cracking. HPA-M incorporated SBA-15 was synthesized using a direct hydrothermal method to provide a catalyst superior to one obtained by wet impregnation of Si- SB A- 15 using HPA-M.

[0008] The process for converting C9 ₊ hydrocarbons to monoaromatic hydrocarbons includes contacting a hydrocarbon feedstock comprising the C9 ₊ hydrocarbons and a supported acid catalyst in the presence of hydrogen (H ₂ ) under conditions effective to produce a hydrocarbon product comprising C6-C9 aromatic hydrocarbons.

[0009] The term“C _n ” hydrocarbon wherein n is an positive integer, e.g., 1, 2, 3, 4, 5, 6,

7, 8, 9, 10, 11, 12, as used herein means a hydrocarbon having n number of carbon atom(s) per molecule. The term“C _n+ ” hydrocarbon wherein n is an positive integer, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, as used herein means a hydrocarbon having greater than n number of carbon atom(s) per molecule. The term“C _n- ” hydrocarbon wherein n is an positive integer, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, as used herein means a hydrocarbon having no more than n number of carbon atom(s) per molecule. In other words, a C9 hydrocarbon is an example of a C _n- hydrocarbon.

[0010] The hydrocarbon feedstock includes at least some amount of C9 ₊ hydrocarbons, but can vary in the amount based on the feedstock source(s). For example, the hydrocarbon feedstock can be a pyrolysis oil (PyOil). Pyrolysis oil, sometimes also called pyrolysis fuel oil (PFO), pyrolysis gasoline, or PyGas, is a mixture of hydrocarbon compounds in C5-C10 or C5- C12 boiling range (naphtha range). It can be produced from byproducts (for example

C9 ₊ hydrocarbon fractions of catalytic reforming and steam cracking for ethylene/propylene production) of processes such as catalytic reforming, steam cracking, or pyrolysis for ethylene/propylene production. Alternatively, pyrolysis oil can be a synthetic, liquid, non-fossil fuel product, produced by the pyrolysis (i.e., thermal decomposition and destructive distillation) of biomass, which is biological material derived from living or recently living organisms. When derived from a biomass, pyrolysis oil is also known as biomass pyrolysis oil, bio-oil, biocrude, biocrude oil, bioleum, wood pyrolysis oil, wood oil, liquid wood, biomass pyrolysis liquid, or pyroligeneous tar. Pyrolysis oil can also be obtained from non-biomass source through non biomass substrates such as rubber tires, thermoplastics (including post-consumer plastics), and auto fluff.

[0011] The exact characteristics and composition of the pyrolysis oil can vary depending on the method of pyrolysis performed and the nature of the feedstock. For example, the pyrolysis oil can include aliphatic hydrocarbons having five or more carbon atoms (e.g., 2- methylpentene), naphthenes, olefins, Cx aromatics such as ethylbenzene, C9 aromatics, BTX (benzene, toluene, xylenes), dicyclopentadiene (DCPD) and its derivatives (e.g.,

dihydrodicyclopentadiene, methyldicyclopentadiene, tetrahydrodicyclopentadiene,

dimethyldicyclopentadiene, hexahydro-4,7-methanoindene, or the like), polyaromatic hydrocarbons (PAHs) including C9 ₊ aromatics, for example indene and its derivatives (e.g., methylindene, octahydro-4,7-methanoindene, or the like), naphthalene and it derivatives (e.g., methylnaphthalene, dihydronaphthalene, dimethylnaphthalene, phenylnapthalene,

butyltetrahydronaphthalene, dimethyltetrahydronaphthalene, methyldecahydronaphthalene, trimethyldihydronaphthalene, or the like), or a combination comprising at least one of the foregoing. Other hydrocarbons that can be present include, but are not limited to,

methylcyclopentene, methylphenylcyclopentane, l,3-cyclohexadiene,

isopropylmethylcyclohexane, dimethyl- l,3-cyclopentadiene, phenylacetylene, styrene, ethyltoluene, allylbenzene, n-propylbenzene, oc-methylstyrene, propenylbenzene,

cyclohexylbenzene, cyclopentylbenzene, dimethylhexenyl benzene, methylhexenylbenzene, trimethylbenzenes such as mesitylene (l,3,5-trimethylbenzene), hemimellitene (1,2,3- trimethylbenzene), and pseudocumene (l,2,4-trimethylbenzene), tetramethylbenzene such as durene (l,2,4,5-tetramethylbenzene), vinyltoluene, indane, tricyclodecene, bicyclododecene, phenylbutene, tricycloundecene, methyl-tricyclodecene, methyltricycloundecene,

ethyltricyclodecene, ethyl/endo-tricyclodecane, 3-methyl-exo/endo-tricyclodecane, 2-methyl- trans-decalin, pentylbicycloheptane, biphenyl, 2-phenylnorbornene, biphenylene, acenaphthene, fluorene, phenanthrene, terphenyl, or a combination comprising at least one of the foregoing.

[0012] The hydrocarbon feedstock can include any amount of C9 ₊ hydrocarbons. For example, the hydrocarbon feedstock can include 10 to 95 wt% of the C9 ₊ hydrocarbons, or 20 to 90 wt% C9 ₊ hydrocarbons, or 30 to 85 wt% C9 ₊ hydrocarbons, or 40 to 80 wt% C9 ₊

hydrocarbons, based on the total weight of the hydrocarbon feedstock, but the amounts are not limited thereto. [0013] For example, the hydrocarbon feedstock can include C9 ₊ hydrocarbons that comprise, based on the total weight of the hydrocarbon feedstock, 35 to 55 weight percent (wt%), preferably 35 to 50 wt%, or 40 to 55 wt%, or 40 to 50 wt% of dicyclopentadiene and derivatives thereof; 10 to 30 wt%, preferably 10 to 25 wt%, or 15 to 30 wt%, or 15 to 25 wt% of indene and derivatives thereof; and 5 to 20 wt%, preferably 5 to 16 wt%, or 8 to 20 wt%, or 8 to 16 wt% of naphthalene and derivatives thereof.

[0014] The process for converting C9 ₊ hydrocarbons to monoaromatic hydrocarbons provides a hydrocarbon product that comprises C6-C9 aromatic hydrocarbons. The hydrocarbon product as produced may be a physical mixture of different aromatic hydrocarbons, for example C6-C9, or may be directly subjected to further separation, e.g. by distillation, to provide different purified product streams. Such purified product stream can include, for example, a benzene product stream, a toluene product stream, a xylene product stream, and/or an ethylbenzene product stream.

[0015] For example, the C6-C9 aromatic hydrocarbons can include, based on the total weight of the hydrocarbon product, 4 to 15 wt%, or 4 to 12 wt%, or 5 to 14 wt%, or 6 to 15 wt%, preferably 6 to 12 wt%, or 6 to 10 wt%, or 7 to 12 wt%, or 7 to 11 wt%, or 8 to 12 wt%, more preferably 9 to 12 wt% of BTX. As used herein, the term "BTX" relates to a mixture of benzene, toluene, and xylenes.

[0016] For example, the C6-C9 aromatic hydrocarbons can include, based on the total weight of the hydrocarbon product, 10 to 20 wt%, or 10 to 18 wt%, or 11 to 20 wt%, preferably 11 to 18 wt%, or 12 to 18 wt%, or 11 to 16 wt%, or 10 to 15 wt%, more preferably 12 to 16 wt% of ethylbenzene.

[0017] For example, the C6-C9 aromatic hydrocarbons can include, based on the total weight of the hydrocarbon product, 14 to 30 wt%, or 15 to 30 wt%, or 14 to 28 wt%, preferably 15 to 28 wt%, or 15 to 27 wt%, or 16 to 26 wt%, or 17 to 25 wt%, or 18 to 24 wt%, or 19 to 25 wt%, or 20 to 26 wt%, or 21 to 27 wt%, or 22 to 28 wt%, more preferably 22 to 27 wt% of C9 aromatic hydrocarbons. The C9 aromatic hydrocarbons include, for example, para-ethyltoluene, meta-ethyltoluene ortho-ethyltoluene, pseudocumene, mesitylene, hemimellitene, n- propylbenzene, indane, a combination thereof, or the like.

[0018] The process for converting the C9 ₊ hydrocarbons to monoaromatic hydrocarbons provides a hydrocarbon product that includes C6-C9 aromatic hydrocarbons and optionally C9 ₊ hydrocarbons. For example, the hydrocarbon product can include, based on the total weight of the hydrocarbon product, 30 to 60 wt%, preferably 35 to 60 wt%, or 30 to 55 wt%, more preferably 40 to 60 wt%, or 30 to 50 wt% of the C6-C9 aromatic hydrocarbons, where the C6-C9 aromatic hydrocarbons are as defined herein. For example, the hydrocarbon product can include, based on the total weight of the hydrocarbon product, 30 to 55 wt%, preferably 30 to 50 wt%, or 35 to 55 wt%, more preferably 30 to 45 wt%, or 35 to 50 wt% of the C9 ₊ hydrocarbons, where the C9 ₊ hydrocarbons are as defined herein. For example, the hydrocarbon product can include, based on the total weight of the hydrocarbon product, 30 to 60 wt% of the C6-C9 aromatic hydrocarbons, and 30 to 55 wt% of the C9 ₊ hydrocarbons.

[0019] The amount of C9 ₊ hydrocarbons in the hydrocarbon feedstock is greater than the amount of C9 ₊ hydrocarbons in the hydrocarbon product. For example, the amount of C9 ₊ hydrocarbons in the hydrocarbon product can be at least 5 wt% less, at least 10 wt% less, at least 15 wt% less, at least 20 wt% less, at least 25 wt% less, at least 30 wt% less, at least 35 wt% less, at least 40 wt% less, at least 45 wt% less, at least 50 wt% less, at least 55 wt% less, at least 60 wt% less, at least 65 wt% less, at least 70 wt% less, or at least 75 wt% less than the amount of C9 ₊ hydrocarbons in the hydrocarbon feedstock. For example, the amount of C9 ₊ hydrocarbons in the product can be 5 to 75 wt% less, 10 to 70 wt% less, 15 to 65 wt% less, 20 to 60 wt% less, 25 to 55 wt% less, 5 to 50 wt% less, 10 to 50 wt% less, 15 to 50 wt% less, 20 to 50 wt% less, 25 to 50 wt% less, 30 to 50 wt% less, or 35 to 50 wt% less than the amount of C9 ₊ hydrocarbons in the hydrocarbon feedstock.

[0020] The selectivity for the C6-C9 aromatic hydrocarbons can be at least 70 wt% at 25 wt% C9 ₊ hydrocarbon conversion, for example at least 75 wt% or 80 wt% at 25 wt% C9 ₊ hydrocarbon conversion. For example, the selectivity for the C6-C9 aromatic hydrocarbons can be at least 70 wt% at 30% C9 ₊ hydrocarbon conversion, for example at least 75 wt% or 80 wt% at 30 wt% C9 ₊ hydrocarbon conversion. For example, the selectivity for the C6-C9 aromatic hydrocarbons can be at least 70 wt% at 35 wt% C9 ₊ hydrocarbon conversion, for example at least 75 wt% or 80 wt% at 35 wt% C9 ₊ hydrocarbon conversion. The selectivity is calculated as described herein. As used herein,“C9 ₊ hydrocarbon conversion” means the percentage of C9 ₊ hydrocarbons that are converted to C9- hydrocarbons, as measured by the difference between the amount of C9 ₊ hydrocarbons in the hydrocarbon feedstock and the amount of C9 ₊ hydrocarbons in the hydrocarbon product.

[0021] The yield of the C6-C9 aromatic hydrocarbons can be at least 20 wt%, preferably at least 25%, more preferably at least 30 wt%. For example, the yield of the C6-C9 aromatic hydrocarbons can be 10 to 50 wt%, 10 to 45 wt%, 10 to 40 wt%, 10 to 35 wt%, 10 to 30 wt%, 15 to 50 wt%, 15 to 45 wt%, 15 to 30 wt%, 15 to 35 wt%, 20 to 50 wt%, 20 to 45 wt%, 20 to 40 wt%, 20 to 35 wt%, or 20 to 30 wt%. The yield is calculated as described herein. [0022] Any effective reaction conditions can be used to produce the hydrocarbon product. For example, the conditions effective to produce the hydrocarbon product can include a temperature of 300 to 450°C, or 325 to 450°C, or 350 to 450°C, or 300 to 425 °C, or 325 to 425°C, or 350 to 425°C, preferably a temperature of 350 to 400°C, or 375 to 425°C. For example, the conditions effective to produce the hydrocarbon product include a hydrogen pressure of 1,200 to 1,800 pounds per square inch (psi), or 1,200 to 1,600 psi, or 1,400 to 1,800 psi, preferably 1,400 to 1,600 psi, or 1,350 to 1,550 psi, or 1,500 to 1,700 psi, or 1,300 to 1,500 psi. For example, the conditions effective to produce the hydrocarbon product include a temperature of 300 to 450°C and a hydrogen pressure of 1,200 to 1,800 pounds per square inch psi.

[0023] In the process for converting C9 ₊ hydrocarbons to monoaromatic hydrocarbons, the supported acid catalyst can be present in an amount of 0.5 to 6 wt%, based on the total weight of the hydrocarbon feedstock. For example, the supported acid catalyst is present in an amount of 1 to 6 wt%, 1.5 to 6 wt%, 2 to 6 wt%, or 2 to 5 wt%, based on the total weight of the hydrocarbon feedstock.

[0024] The supported acid catalyst comprises a heteropolyacid and a support material. The heteropoly acids include 12-18 oxygen-linked polyvalent metal atoms. The polyvalent metal atoms, known as the peripheral atoms, surround one or more of the central atoms in a symmetrical manner. The peripheral atoms may be one or more of molybdenum, tungsten, vanadium, niobium, tantalum, or any other polyvalent metal. The central atoms are preferably silicon or phosphorus, but may alternatively comprise any one or more atoms from Groups I- VIII in the Periodic Table of elements. These can include copper, beryllium, zinc, cobalt, nickel, boron, aluminum, gallium, iron, cerium, arsenic, antimony, bismuth, chromium, rhodium, silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese nickel, platinum, thorium, hafnium, cerium, arsenic, vanadium, antimony ions, tellurium, and iodine. Suitable heteropolyacids include Keggin, Wells-Dawson, and Anderson-Evans-Perloff heteropoly acids.

[0025] Combinations or mixtures of different heteropolyacids can be used. The preferred heteropolyacid for use in the process herein is any one or more heteropolyacids based on the Keggin (Ft _n XM^C o) or Wells-Dawson (Fl _n X ₂ Mi ₈ 0 ₆₂ ) structures. Preferably, the heteropolyacid comprises silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicovanadotungstic acid, phosphovanadotungstic acid,

phosphovanadomolybdic acid, silicovanadomolybdic acid, phosphomolybdotungstic acid, silicomolybdotungstic acid, silicovanadotungstic acid, borotungstic acid, boromolybdic acid, tungstomolybdoboric acid, or a combination comprising at least one of the foregoing, more preferably l2-phosphomolybdic acid (H ₃ RMo _ΐ2 q ₄₀ ·6H ₂ q), l2-phosphotungstic acid

(H ₃ PW ₁₂ O ₄₀ 6H ₂ O), or a combination comprising at least one of the foregoing, even more preferably l2-phosphomolybdic acid.

[0026] The supported acid catalyst also includes a support material. The support material can comprise diatomaceous earth, activated carbon, montmorillonite, silica, titania, silica alumina, alumina, magnesia, niobia, zirconia, or a combination comprising at least one of the foregoing. For example, the support material can be silica, silica alumina, alumina, or a combination thereof.

[0027] The supported acid catalyst can have a surface area of 50 to 1,500 square meters per gram (m ² /g). For example, the surface area can be 100 to 1,500 m ² /g, 200 to 1,400 m ² /g, 200 to 1,200 m ² /g, 300 to 1,200 m ² /g, 250 to 1,000 m ² /g, 300 to 1,000 m ² /g, 400 to 1,000 m ² /g, 500 to 1 ,000 m ² /g, or 600 to 1 ,000 m ² /g.

[0028] The supported acid catalyst can have an average pore diameter of 0.5 to 20 nanometers (nm). For example, the average pore diameter can be 1 to 20 nm, 1 to 15 nm, 1 to 10 nm, 2 to 10 nm, 3 to 10 nm, 4 to 10 nm, 2 to 8 nm, 3 to 8 nm, 3 to 7 nm, or 3 to 6 nm. The average pore diameter can be a D50 diameter.

[0029] The supported acid catalyst can have a total pore volume of 0.1 to 3.0 milliliters per gram (mL/g). For example, the total pore volume an be 0.1 to 2.5 mL/g, 0.1 to 2.0 mL/g, 0.1 to 1.5 mL/g, 0.1 to 1.0 mL/g, 0.1 to 0.5 mL/g, 0.2 to 2.5 mL/g, 0.2 to 2.0 mL/g, 0.2 to 1.5 mL/g, 0.2 to 1.0 mL/g, 0.3 to 2.5 mL/g, 0.3 to 2.0 mL/g, 0.3 to 1.5 mL/g, 0.3 to 1.0 mL/g, 0.4 to 2.0 mL/g, 0.4 to 1.5 mL/g, 0.4 to 1.0 mL/g, 0.5 to 1.5 mL/g, 0.5 to 1.5 mL/g, or 0.5 to 1.5 mL/g.

[0030] For example, the supported acid catalyst can have a surface area of 50 to 1,500 m ² /g, an average pore diameter of 0.5 to 20 nm, and a total pore volume of 0.1 to 3.0 cm ³ /g. For example, the supported acid catalyst can have a surface area of 200 to 1,200 m ² /g, an average pore diameter of 2 to 8 nm, and a total pore volume of 0.3 to 2.0 cm ³ /g. For example, the supported acid catalyst can have a surface area of 400 to 1 ,000 m ² /g, an average pore diameter of 2 to 8 nm, and a total pore volume of 0.5 to 1.5 cm ³ /g.

[0031] The supported acid catalyst can have bimodal acidity, designated as weak acid sites and strong acid sites. For example, the weak acid site concentration can be 0.1 to 1.5 millimoles per gram (mmol/g), 0.1 to 1.0 mmol/g, 0.1 to 0.5 mmol/g, 0.2 to 1.5 mmol/g, 0.2 to 1.0 mmol/g, 0.3 to 1.5 mmol/g, 0.3 to 1.0 mmol/g, 0.4 to 1.5 mmol/g, 0.5 to 1.5 mmol/g, 0.6 to 1.5 mmol/g, 0.7 to 1.5 mmol/g, 0.8 to 1.5 mmol/g, or 0.9 to 1.5 mmol/g of the supported acid catalyst. For example, the strong acid site concentration can be 0.3 to 1.5 mmol/g, 0.3 to 1.2 mmol/g, 0.4 to 1.5 mmol/g, 0.4 to 1.4 mmol/g, 0.4 to 1.3 mmol/g, or 0.5 to 1.5 mmol/g of the supported acid catalyst.

[0032] For example, the supported acid catalyst can have a surface area of 50 to 1,500 m ² /g, an average pore diameter of 0.5 to 20 nm, a total pore volume of 0.1 to 3.0 cm ³ /g, a weak acid site concentration is 0.1 to 1.5 mmol/g, and strong acid site concentration is 0.3 to 1.5 mmol/g. For example, the supported acid catalyst can have a surface area of 50 to 1,500 m ² /g, an average pore diameter of 0.5 to 20 nm, a total pore volume of 0.1 to 3.0 cm ³ /g, a weak acid site concentration is 0.2 to 1.0 mmol/g, and strong acid site concentration is 0.5 to 1.5 mmol/g.

[0033] For example, the supported acid catalyst can have a surface area of 200 to 1,200 m ² /g, an average pore diameter of 2 to 8 nm, a total pore volume of 0.3 to 2.0 cm ³ /g, a weak acid site concentration is 0.1 to 1.5 mmol/g, and strong acid site concentration is 0.3 to 1.5 mmol/g. For example, the supported acid catalyst can have a surface area of 200 to 1,200 m ² /g, an average pore diameter of 2 to 8 nm, a total pore volume of 0.3 to 2.0 cm ³ /g, a weak acid site concentration is 0.2 to 1.0 mmol/g, and strong acid site concentration is 0.5 to 1.5 mmol/g.

[0034] For example, the supported acid catalyst can have a surface area of 400 to 1,000 m ² /g, an average pore diameter of 2 to 8 nm, a total pore volume of 0.5 to 1.5 cm ³ /g, a weak acid site concentration is 0.1 to 1.5 mmol/g, and strong acid site concentration is 0.3 to 1.5 mmol/g. For example, the supported acid catalyst can have a surface area of 400 to 1,000 m ² /g, an average pore diameter of 2 to 8 nm, a total pore volume of 0.5 to 1.5 cm ³ /g, a weak acid site concentration is 0.2 to 1.0 mmol/g, and strong acid site concentration is 0.5 to 1.5 mmol/g.

[0035] The supported acid catalyst can comprise 20 to 60 wt% of the heteropolyacid, based on the total weight of the supported acid catalyst. For example, the supported acid catalyst can have 25 to 60 wt%, 25 to 55 wt%, 30 to 55 wt%, or 30 to 50 wt% of the heteropolyacid, based on the total weight of the supported acid catalyst.

[0036] The supported acid catalyst can be prepared using any suitable method. For example, a supported acid catalyst comprising a diatomaceous earth support material can be prepared using direct hydrothermal synthesis as provided in U.S. Patent No. 4, 966,877, the entire content of which is incorporated herein by reference. Montmorillonite can be used as a support material to prepare a supported acid catalyst as provided in Endud et al., "Friedel-Crafts Acylation of Anisole over Fleteropoly Acid Supported on Porous Montmorillonite", Materials Science Forum, Vol. 846, pp. 712-716, 2016, the entire content of which is incorporated herein by reference. Activated carbon can be used as a support material as described in Badday et al., “Transesterification of crude Jatropha oil by activated carbon- supported heteropolyacid catalyst in ultrasound-assisted reactor system”, Renewable Energy, Vol. 62, pp. 10-17, 2014, the entire content of which is incorporated herein by reference.

[0037] Supported acid catalysts that comprise support materials such as silica, titania, silica alumina, alumina, magnesia, niobia, zirconia, or the like, or a combination comprising at least one of the foregoing, can be prepared by a direct hydrothermal method. The support acid catalyst can be prepared by a direct hydrothermal method using a self-assembling organic species (i.e., template surfactant) with a network-forming inorganic precursor species (i.e., support precursor), further in combination with one or more heteropoly acids. The template surfactant species act as structure-directing agents for the inorganic precursor species, which polymerize initially into a typically amorphous inorganic network with initially hexagonal, cubic, or lamellar mesoscopic order cooperatively imparted by interactions among the self- assembled surfactant and inorganic species.

[0038] The supported acid catalyst can be prepared by combining a template surfactant, an acid modifier, and a hydrate of the heteropolyacid to provide a polymer solution. A support precursor can then be added to the polymer solution and reacted with the heteropolyacid under conditions effective to produce the supported acid catalyst.

[0039] The support precursors can include silicon alkoxides, metal alkoxides, mixed- metal alkoxides, organosiliconalkoxides, metal salts, organometalalkoxides, or a combination comprising at least one of the foregoing. Each alkoxy group can have 1 to 12, or 1 to 6, or 1 to 3 carbon atoms. The support precursor can be a silica source that comprises tetraethyl orthosilicate, tetramethyl orthosilicate, sodium metasilicate, or a combination comprising at least one of the foregoing, preferably tetraethyl orthosilicate, or organically modified derivatives, which are suitable sources of silica for the preparation of silica structures. For example, the support precursors can include any of the main group, transition metals, rare-earth metals, and mixtures thereof. "Transition metal", as used herein, refers to an element designated in the Periodic Table as belonging to Group IIIB (e.g., scandium and yttrium), Group IVB (e.g., titanium, zirconium, and hafnium), Group VB (e.g., chromium, molybdenum, and tungsten), Group VIIB (e.g., manganese, technetium and rhenium), Group VIIIB (e.g., iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum), Group IB (e.g., copper, gold, and silver), and Group IIB (zinc, cadmium, and mercury).

[0040] The support precursor can be a zirconium source that comprises a zirconium Ci- ₆ alkoxide, zirconium tetrachloride, zirconium oxychloride, or the like; a titanium source that comprises a titanium Ci- ₆ alkoxide, titanium tetrachloride, titanium oxychloride, or the like; an aluminum source that comprises an aluminum Ci- ₆ alkoxide, an aluminum halide, aluminum nitrate, or the like. Other exemplary support precursors include aluminum(III) ethoxide, aluminum(III) isopropoxide, aluminum(III) n-, sec- or tert-butoxide, magnesium(II) ethoxide, niobium(V) ethoxide, titanium(IV) ethoxide, titanium(IV) propoxide, titanium(IV) isopropoxide, titanium(IV) butoxide, titanium(IV) octadecoxide, tungsten(VI) ethoxide, tungsten (VI) isopropoxide, zirconium(IV) n-propoxide, zirconium(IV) isopropoxide, zirconium(IV) butoxide, zirconium(IV) tert-butoxide, aluminum(III) silicon(IV) alkoxide, titanium(IV) silicon(IV) polyethoxide, and combinations of the foregoing alkoxide compounds.

[0041] The formation of mesoporous is influenced by the choice of template surfactants. In particular, the end groups of the surfactant species can determine the particular structure obtained. The preferred template surfactant is comprised of an amphilic block copolymer. The block copolymer surfactant can comprise a poly(alkylene oxide) block copolymer, for example poly(ethylene oxide) -poly(propylene oxide) -poly(ethylene oxide) (EO _m -PO _n -EO _m ) copolymers wherein m and n are each independently 10 to 90. The use of EO20-PO70-EO20 is preferred.

[0042] An ionic surfactant can be used, for example ammonium and alkylammonium halide salts. Specific examples of ammonium halides contain Ci _-8 alkyl groups and include, without limitation, tetramethyl ammonium halide, tetraethyl ammonium halide,

cetyltrimethylammonium halide, and cetyldimethylethylammonium halide. The halide can be fluoride, chloride, bromide, or iodide. Even more specifically, the halide is chloride or bromide. The ionic surfactant can be a combination of halide salts such as a combination of ammonium halide, tetramethyl ammonium halide, and tetraethyl ammonium halide.

[0043] The template surfactant can be a primary or secondary amine. Exemplary amines include tetra-amines such dodecylamine, Ci4-i6NH(C3H6NH)3H, or the like.

[0044] The template surfactant can be a carboxylic acid such as caproic acid, lauric acid, stearic acid, neodecanoic acid, or the like.

[0045] The preparation of the supported acid catalyst optionally can include using an acid modifier. Exemplary acid modifiers include protic acids such as hydrochloric acid, phosphoric acid, toluenesulfonic acid, or the like.

[0046] The supported acid catalyst can be prepared in a suitable solvent. Examples include water, methanol, ethanol, n-and iso-propanol, n-, sec-, and tert-butanol, or the like. A combination of two or more solvents can be used. For example, the solvent can be water.

[0047] The conditions effective to produce the supported acid catalyst can comprise a temperature of 25 to 140°C for 30 minutes to 24 hours. For example, the temperature can be 30 to 140°C, 40 to 130°C, 40 to 120°C, 40 to 110°C, 40 to 100°C, 50 to 120°C, 50 to 110°C, 50 to 100°C, 60 to 120°C, 60 to 110°C, 60 to 100°C, 70 to 120°C, 70 to 110°C, 70 to 100°C, 80 to l20°C, 80 to H0°C, or 80 to l00°C. The reaction time can be 1 to 24 hours (h), 1 to 18 h, 1 to 16 h, 1 to 12 h, 2 to 12 h, 3 to 12 h, 2 to 10 h, 2 to 8 h, 2 to 6 h, or 2 to 4 h. For example, the temperature can be 50 to l20°C for 12 to 24 hours.

[0048] The process to prepare the supported acid catalyst can further comprise calcining the supported acid catalyst at a temperature of 350 to 750°C for 3 to 12 hours in air. For example, the calcining temperature can be 400 to 700°C, 450 to 650°C, or 450 to 600°C for a time of 3 to 10 h, 3 to 8 h, or 4 to 6 h.

[0049] This disclosure is further illustrated by the following non-limiting examples.

EXAMPLES

[0050] The materials used in the Examples are presented in Table 1.

Table 1.

Physical Measurements

[0051] Pore surface area, average pore diameter, and total pore volume measurements were carried out using a Micrometries ASAP 2020 equipment (Norcross, GA, USA). Prior to the adsorption measurements, 0.05 g of the calcined catalyst sample was degassed under nitrogen flow for 3 h at 240°C. The adsorption isotherms were measured at -l96°C (liquid nitrogen temperature). The pore surface area, pore volume, and pore diameter were measured using BET or BJH adsorption calculation methods. Pore surface area can be measured according to ISO 9277 or ASTM D6556. Pore volume and pore diameter can be measured according to ISO 15901.

[0052] Acidity was measured by ammonia temperature programmed desorption (N¾- TPD) using a chemisorption unit (BELCAT system). For each analysis, 0.1 g of the calcined catalyst sample was pretreated for lh at 500°C using inert He (50 mL/min). The catalyst was then exposed to He/NH3 mixture in volume ratio of 95/5 vol% for 30 min at l00°C. Gaseous NH3 was removed by purging using He for 1 hour (h). The NH3-TPD was performed using the same flow of He at a rate of lO°C/min up to 600°C and the desorbed N¾ was monitored using a TCD detector. The temperature at which N¾ is desorbed is an estimation of acid site strength, e.g., higher the desorption temperature indicates a stronger acid site. The amount of acid sites is reported in millimoles per gram (mmol/g), based on the weight of the sample.

[0053] Gas chromatography was performed using an Agilent 5975C Gas

Chromatograph-Mass Spectrometer and quantified using an Agilent 7890 Gas Chromatograph with a flame ionization detector (FID), employing an HP Innovax capillary column (60 m) with the oven temperature programmed from 75-250°C.

Example 1. Preparation of 20% HPA-Mo-SBA-l5

[0054] Incorporation of 20 weight percent (wt%) of l2-phosphomolybdic acid

(H3PM012O40 - HPA-Mo) via the direct synthesis route was carried out using a SBA-15 synthesis procedure. In a reaction vessel, 1.92 g of P123, 40 g of deionized water, and 30 g of hydrochloric acid (4 M) were mixed together and stirred for 30 min at room temperature (ca.

23 °C) to form a polymer solution. In a separate vessel, hydrated HPA-Mo (20 wt% based on the weight of the corresponding supported acid catalyst product) was dissolved in 5 g of deionized water, and this solution was added dropwise under vigorous stirring into the polymer solution. The resulting mixture was stirred for 24 hours at room temperature (ca. 23°C), and then 4 g of tetraethyl orthosilicate (TEOS) was added into the mixture, resulting in the formation of a white precipitate during the hydrolysis of the TEOS. Following stirring for an additional 30 minutes in the ambient atmosphere, the reaction vessel containing the mixture was capped and then heated in an oven at 80°C for 24 hours without stirring. After 24 hours, the mixture was allowed to cool to room temperature (ca. 23°C), and a solid product was separated by filtration, washed with deionized water, and dried at 60°C for 3 hours and then at l00°C for 12 hours. The obtained solid was calcined in air (ambient atmosphere) at 500°C for 6 hours using a heating ramp of 2°C per minute to provide the corresponding supported acid catalyst.

Example 2. Preparation of 40% HPA-Mo-SBA-l5

[0055] The same procedure as in Example 1 was followed, except 40 wt% of HPA-Mo was used, based on the weight of the corresponding supported acid catalyst product.

Example 3. Preparation of 60% HPA-Mo-SBA-l5

[0056] The same procedure as in Example 1 was followed, except 60 wt% of HPA-Mo was used, based on the weight of the corresponding supported acid catalyst product. Example 4. Preparation of 40% HPA-W-SBA-15

[0057] The same procedure as in Example 1 was followed, except 40 wt% of 12- phosphotungstic acid (H3PW12O40 - HPA-W) was used, based on the weight of the

corresponding supported acid catalyst product.

Comparative Example 1. Preparation of HPA-Mo/SB A- 15

[0058] An HPA-Mo supported acid catalyst was prepared by the impregnation method using SBA-15 solid support. 4 g of P123 was added to 30 mL of water. After stirring for 3 hours (h), a clear solution was obtained. About 70 g of 0.28 M hydrochloric acid was added and the solution was stirred for another 2 h. Then, 9 g of TEOS was added and the resulting mixture was stirred for 24 h at 40°C and finally heated at 100°C for 48 h. The solid product was recovered by filtration, washed with water, and dried overnight at 100°C. The resulting product was calcined at 550°C for 6h to obtain Si-SBA-15 mesoporous silica.

[0059] In a reaction vessel, 1.5 g of mesoporous silica (Si-SBA-15) was combined with 0.6 g of HPA-Mo in 3.75 ml of deionized water. After 30 minutes of thorough mixing at room temperature (ca. 23°C), the reaction vessel was capped and then heated in an oven at 60°C for 3 hours and further at 100°C for 12 hours. The obtained solid was calcined in air (i.e., ambient atmosphere) at 500°C for 6 hours using a heating ramp of 2°C per minute to provide the corresponding supported acid catalyst.

Characterization and Reactivity

[0060] The surface area, pore volume, pore diameter, and acidity of the supported acid catalysts of Examples 1 to 4, Comparative Example 1, and Si-SBA-l5 are shown in Table 2.

Table 2.

*Calculated from the areas of Gaussian deconvolution bands.

[0061] Table 2 shows the results obtained for the supported acid catalysts and Si-SBA- 15. Examples 1 to 3, prepared by a direct synthesis route using HPA-Mo, showed that the surface area, pore diameter, and total pore volume decreased with increasing concentration of HPA-Mo. Example 4, prepared by a direct synthesis route using HPA-W, had a smaller surface area, pore diameter, and pore volume as compared to Example 2, even with the same concentration of heteropoly acids. Comparative Example 1, prepared by impregnation of HPA- Mo on Si-SBA-l5, had the smallest surface area, pore diameter, and pore volume among all of the supported acid catalysts. This may be related to high loadings of HPA-Mo, which may block the pores of Si-SBA-l5 support material.

[0062] Table 2 also shows the results obtained from ammonia temperature programmed desorption (NH3-TPD) measurements. The acidity of each of the supported acid catalysts of Examples 1 to 4, Comparative Example 1, and Si-SBA-15 were measured by NH3-TPD. For Si- SBA-15, only weak acid sites were observed. Examples 1 to 4 had both strong and weak acid sites. The total acidities of Examples 1 to 4 were greater than Comparative Example 1.

Increasing the concentration of heteropolyacid correlated with an increase in total acidity and strong acid sites.

[0063] The catalytic performance of Examples 1 to 4 and Comparative Example 1 was evaluated. The process conditions are summarized in Table 3.

Table 3.

[0064] The catalytic reaction was conducted in a batch autoclave reactor. A motor speed of 300 rpm was maintained throughout the reactions to sustain thorough mixing of the supported acid catalyst, feedstock, and hydrogen gas. The temperature of the reactor was closely monitored and the set point was adjusted manually as and when necessary during the startup of the reactions. However, once the required temperature was achieved and steady state operation begins, a PID controller regulated the temperature to constant. During the runs, hydrogen pressure decreased due to its consumption in the hydrogenation reactions. To maintain a constant pressure of hydrogen, a supply of hydrogen at the required pressure was continuously provided to the batch autoclave reactor. At the end of each run, the reactor was cooled to room temperature (ca. 23°C), and the resulting reaction product was weighed, filtered, and analyzed by GC.

[0065] The composition of the feedstock, which is a pyrolysis oil obtained as a by product of cracking olefin feedstocks, is shown in Table 4.

Table 4.

| Component | Amount (wt%) |

^† MAH: monoaromatic hydrocarbons

[0066] The results of the catalytic conversions are shown in Table 5 based on catalyst.

Table 5.

^† BTX: benzene, toluene, and xylenes

DC PD: dicyclopentadiene

[0067] The results obtained are presented in terms of reaction product compositions, yields (MAH Yield), and selectivities (MAH Selectivity) of monoaromatic hydrocarbons (MAH, which are the C6-C9 aromatic hydrocarbons), where all amounts are in weight percent (wt%). To account for the MAH in the hydrocarbon feedstock, the yield and selectivity are determined according to Equations 1 and 2:

MAH Yield (Wt%)— 100 X [MAHproduct MAHfeedstock]/C9+feedstock (Eq. 1)

MAH Selectivity (%) = 100 x MAH Yield (wt%) / Conversion of C9+ (wt%) (Eq. 2) wherein MAH _pr oduct is the amount of monoaromatic hydrocarbons in the reaction product;

MAHfeedstock is the amount of monoaromatic hydrocarbons in the feedstock; C9+f _e edstock is the amount of C9 ₊ hydrocarbons in the feedstock; conversion of C9 ₊ is the amount reduction (%) of C9 ₊ hydrocarbons, which is also referred to herein as %Conversion of C9 ₊ to C9- and/or C9 ₊ hydrocarbon conversion.

[0068] In case HPA-Mo incorporated on SBA-15 with different loadings, 40% HPA-Mo incorporated on SB A- 15 (E2) showed higher yield of monoaromatic hydrocarbons as compared to 20% (El) and 60% (E3) loadings, respectively. Upon introducing a different heteroatom, such as W (E4), the yield of monoaromatic hydrocarbons decreased relative to the monoaromatic hydrocarbon yields of any of the HPA-Mo-SBA-l5 catalysts (El to E3). This indicated that the Mo atom in HPA plays an important role in converting the feedstock into monoaromatic hydrocarbon compounds. The surface area, pore diameter, and pore volume of the HPA-Mo- SBA-15 catalysts (El to E3) was also higher than those of the HPA-W-SBA-15 catalyst (E4).

[0069] The selectivity for monoaromatic hydrocarbons was greatest for the 60% loading of HPA-Mo (E3), followed by the 20% loading (El). The selectivity for monoaromatic hydrocarbons was lowest from the 40% loading (E2) among the HPA-Mo-SBA-l5 catalysts (El to E3). The selectivity for monoaromatic hydrocarbons of the HPA-W-SBA-15 catalyst (E4) was less than any of El to E3.

[0070] For comparison, NiW/SiC -AhOs and NiW/Y-zeolite catalysts were evaluated under same conditions. The NiW/SiC -ApOs catalyst had both a lower monoaromatic hydrocarbons yield and lower monoaromatic hydrocarbons selectivity than El to E4. The NiW/Y-zeolite catalyst had both a lower monoaromatic hydrocarbons yield and lower monoaromatic hydrocarbons selectivity than the HPA-Mo-SBA-l5 catalysts (El to E3).

However, the conversion of indene derivatives was slightly higher for the NiW/Y-zeolite catalyst compared to El to E4. The amount non-aromatics (saturates) observed in HPA-Mo- SBA-15 catalysts (El to E3) were lower as compared to the NiW/SiC -AhOs and the NiW/Y- zeolite catalysts. For the NiW/SiC -AUCb catalyst, the conversion of dicyclopentadiene (DCPD) and total monoaromatics yield were both less than the HPA-Mo-SBA-l5 catalysts (El to E3).

[0071] On comparing the HPA loading procedures by direct synthesis and impregnation, both the yield and selectivity of monoaromatic hydrocarbons were greater for the catalysts prepared by the direct synthesis method.

[0072] This disclosure further encompasses the following aspects.

[0073] Aspect 1. A process for converting C9 ₊ hydrocarbons to monoaromatic hydrocarbons, the process comprising: contacting a hydrocarbon feedstock comprising the C9 ₊ hydrocarbons and a supported acid catalyst in the presence of hydrogen under conditions effective to produce a hydrocarbon product comprising C6-C9 aromatic hydrocarbons, wherein the supported acid catalyst comprises a heteropolyacid and a support material, and wherein the selectivity of the C6-C9 aromatic hydrocarbons is at least 70 wt% at 25 wt% C9 ₊ hydrocarbon conversion.

[0074] Aspect 2. The process of aspect 1, wherein the support material comprises diatomaceous earth, activated carbon, montmorillonite, silica, titania, silica alumina, alumina, magnesia, niobia, zirconia, or a combination comprising at least one of the foregoing, preferably silica, silica alumina, or alumina.

[0075] Aspect 3. The process of aspect 1 or 2, wherein the heteropolyacid comprises silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicovanadotungstic acid, phosphovanadotungstic acid, phosphovanadomolybdic acid, silicovanadomolybdic acid, phosphomolybdotungstic acid, silicomolybdotungstic acid, silicovanadotungstic acid, borotungstic acid, boromolybdic acid, tungstomolybdoboric acid, or a combination comprising at least one of the foregoing, preferably l2-phosphomolybdic acid, 12- phosphotungstic acid, or a combination comprising at least one of the foregoing, more preferably l2-phosphomolybdic acid.

[0076] Aspect 4. The process of any one or more of aspects 1 to 3, wherein the supported acid catalyst has one or more of: a surface area of 50 to 1,500 square meters per gram, preferably 200 to 1,200 square meters per gram, more preferably 400 to 1,000 square meters per gram; an average pore diameter of 0.5 to 20 nanometers, preferably 1 to 10 nanometers, more preferably 2 to 8 nanometers; and a total pore volume of 0.1 to 3.0 milliliters per gram, preferably 0.3 to 2.0 milliliters per gram, more preferably 0.5 to 1.5 milliliters per gram.

[0077] Aspect 5. The process of any one or more of aspects 1 to 4, wherein the supported acid catalyst comprises weak acid sites and strong acid sites, wherein the weak acid site concentration is 0.1 to 1.5 millimoles per gram, preferably 0.2 to 1.0 millimoles per gram of the supported acid catalyst, and the strong acid site concentration is 0.3 to 1.5 millimoles per gram, preferably 0.5 to 1.5 millimoles per gram of the supported acid catalyst.

[0078] Aspect 6. The process of any one or more of aspects 1 to 5, wherein the supported acid catalyst comprises 20 to 60 weight percent of the heteropolyacid, preferably 25 to 55 weight percent of the heteropolyacid, more preferably 30 to 50 weight percent of the heteropolyacid, based on the total weight of the supported acid catalyst.

[0079] Aspect 7. The process of any one or more of aspects 1 to 6, wherein the supported acid catalyst is prepared by a process comprising: combining a template surfactant, optionally an acid modifier, and a hydrate of the heteropoly acid to provide a polymer solution; and adding a support precursor to the polymer solution; adding a support precursor to the polymer solution; and reacting the support precursor and the heteropolyacid under conditions effective to produce the supported acid catalyst.

[0080] Aspect 8. The process of aspect 7, wherein the template surfactant is a block copolymer, preferably a poly(alkylene oxide) block copolymer, more preferably poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide).

[0081] Aspect 9. The process of aspect 7 or 8, wherein the support precursor comprises tetraethyl orthosilicate, tetramethyl orthosilicate, sodium metasilicate, or a combination comprising at least one of the foregoing, preferably tetraethyl orthosilicate.

[0082] Aspect 10. The process of any one or more of aspects 7 to 9, wherein the conditions effective to produce the supported acid catalyst comprise a temperature of 25 to 140°C for 30 minutes to 24 hours.

[0083] Aspect 11. The process of any one or more of aspects 7 to 10, wherein the process to prepare the supported acid catalyst further comprises calcining the supported acid catalyst at a temperature of 350 to 750°C for 3 to 12 hours in air.

[0084] Aspect 12. The process of any one or more of aspects 1 to 11, wherein the conditions effective to produce the hydrocarbon product comprise a temperature of 300 to 450°C and a hydrogen pressure of 1,200 to 1,800 pounds per square inch, preferably a temperature of 350 to 400°C and a hydrogen pressure of 1,400 to 1,600 pounds per square inch.

[0085] Aspect 13. The process of any one or more of aspects 1 to 12, wherein the supported acid catalyst is present in an amount of 0.5 to 6 weight percent, preferably 1 to 6 weight percent, more preferably 2 to 5 weight percent based on the total weight of the hydrocarbon feedstock.

[0086] Aspect 13a: The process of any one or more of the preceding aspects, wherein the hydrocarbon product comprises, based on the total weight of the hydrocarbon product, 30 to 60 weight percent, preferably 35 to 60 weight percent, more preferably 40 to 60 weight percent, based on the total weight of the C6-C9 aromatic hydrocarbons.

[0087] Aspect 13b: The process of any one or more of the preceding aspects, wherein the yield of the C6-C9 aromatic hydrocarbons is at least 20 weight percent, preferably at least 25 weight percent, more preferably at least 30 weight percent.

[0088] Aspect 14. The process of any one or more of aspects 1 to 13, wherein the C9 ₊ hydrocarbons comprise, based on the total weight of the hydrocarbon feedstock, 35 to 55 weight percent, preferably 40 to 50 weight percent of dicyclopentadiene and derivatives thereof, 10 to 30 weight percent, preferably 15 to 25 weight percent of indene and derivatives thereof, and 5 to 20 weight percent, preferably 8 to 16 weight percent of naphthalene and derivatives thereof. [0089] Aspect 15. The process of any one or more of aspects 1 to 14, wherein the C6-C9 aromatic hydrocarbons comprise, based on the total weight of the hydrocarbon product, 4 to 15 weight percent, preferably 6 to 12 weight percent, more preferably 9 to 12 weight percent of BTX, 10 to 20 weight percent, preferably 11 to 18 weight percent, more preferably 12 to 16 weight percent of ethylbenzene, and 14 to 30 weight percent, preferably 15 to 28 weight percent, more preferably 22 to 27 weight percent of C9 aromatic hydrocarbons.

[0090] Aspect 16. The process of any one or more of aspects 1 to 15, wherein the hydrocarbon product comprises, based on the total weight of the hydrocarbon product, 30 to 60 weight percent, preferably 35 to 60 weight percent, more preferably 40 to 60 weight percent of the C6-C9 aromatic hydrocarbons, and 30 to 55 weight percent, preferably 30 to 50 weight percent, more preferably 30 to 45 weight percent of the C9 ₊ hydrocarbons.

[0091] Aspect 17. The process of any one or more of aspects 1 to 16, wherein the selectivity of the C6-C9 aromatic hydrocarbons is at least 80% at 35% C9 ₊ hydrocarbon conversion.

[0092] Aspect 18. The process of any one or more of aspects 1 to 17, wherein the yield of the C6-C9 aromatic hydrocarbons is at least 20%, preferably at least 25%, more preferably at least 30%.

[0093] Aspect l8a. The process of any one or more of the preceding aspects, wherein the C6-C9 aromatic hydrocarbons comprise, based on the total weight of the hydrocarbon product, 4 to 15 weight percent, preferably 6 to 12 weight percent, more preferably 9 to 12 weight percent of BTX.

[0094] Aspect 18b. The process of any one or more of the preceding aspects, wherein the C6-C9 aromatic hydrocarbons comprise, based on the total weight of the hydrocarbon product, 10 to 20 weight percent, preferably 11 to 18 weight percent, more preferably 12 to 16 weight percent of ethylbenzene.

[0095] Aspect l8c. The process of any one or more of the preceding aspects, wherein the C6-C9 aromatic hydrocarbons comprise, based on the total weight of the hydrocarbon product, 14 to 30 weight percent, preferably 15 to 28 weight percent, more preferably 22 to 27 weight percent of C9 aromatic hydrocarbons.

[0096] Aspect 19. A hydrocarbon product comprising C6-C9 aromatic hydrocarbons manufactured by the process of any one or more of aspects 1 to 18.

[0097] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0098] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of“up to 25 wt%, or, more specifically,

5 to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of“5 wt% to 25 wt%,” etc.).“Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms“first,”“second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms“a” and“an” and“the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

“Or” means“and/or” unless clearly stated otherwise. Reference throughout the specification to “aspects”,“embodiments”,“examples”, and so forth, means that a particular element described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects. The term“a combination thereof’ is open-ended and includes one or more of the listed items, and can include other like items that are not listed.

[0099] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0100] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. Unless otherwise defined herein, the term“hydrocarbon” means a compound that includes carbon and hydrogen, optionally with 1 to 3 heteroatoms. The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH ₂ -) or propylene (-(CH ₂ ) ₃ -))· “Cycloalkylene” means a divalent cyclic alkylene group, -Cnthn-x, wherein x is the number of hydrogens replaced by cyclization(s).

“Aryl” means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent.

[0101] Unless substituents are otherwise specifically indicated, each of the foregoing groups can be unsubstituted or substituted, provided that the substituted atom’s normal valence is not exceeded, and that the substitution does not significantly adversely affect the manufacture, stability, or desired property of the compound. “Substituted” means that the compound, group, or atom is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-NO ₂ ), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), Ci _-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl, Ci _-6 haloalkyl, C _1-9 alkoxy, Ci- ₆ haloalkoxy, C _3-12 cycloalkyl, C _5-18 cycloalkenyl, CU ₁₂ aryl, C _7-13 arylalkylene (e.g., benzyl), C _7-12 alkylarylene (e.g., toluyl), C _4-12 heterocycloalkyl, C _3-12 heteroaryl, C _1-6 alkyl sulfonyl (- S(=0) ₂ -alkyl), C _6-i2 arylsulfonyl (-S(=0) ₂ -aryl), or tosyl (CH ₃ C ₆ H ₄ SO ₂ -). When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the compound or group, including those of any substituents.

[0102] While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.