Production of renewable jet from catalytic pyrolysis feedstocks.

Abstract

The present invention provides a method comprising preparing a renewable jet fuel blendstock by: a) feeding biomass, a catalyst, and optionally a transport fluid to a fluid bed reactor of a catalytic pyrolysis process maintained at reactive conditions to produce a raw fluid product stream containing renewable aromatic compounds; b) feeding the raw fluid product stream of a) to a solids separation and stripping system to produce separated solids and a fluid product stream; c) feeding the fluid product stream of b) to a fractionation system to recover a fraction boiling between 180°C and 300°C; d) hydrogenating at least a portion of the fraction produced in c) with hydrogen at hydrogenation conditions to produce a hydrogenated fraction containing naphthenes suitable as a jet fuel blendstock; and e) optionally recovering the naphthene-containing jet fuel blendstock from the hydrogenated fraction of d) in a product recovery system.

Description

[Technical field]

[0001] The present invention relates to an improved catalytic pyrolysis process. In particular, the present invention relates to a process for producing renewable aviation fuel blendstocks and chemicals from renewable feedstocks via catalytic pyrolysis and hydrogenation of a naphthalene-rich oil phase, the chemicals, fuel blendstocks, and fuel compositions produced thereby. [Background technology]

[0002] Modern refineries convert crude oil through numerous unit operations and conversion reactions into several individual streams, including diesel, jet fuel, and gasoline blend stocks, which are stored in separate tanks and then blended together in calculated proportions to produce the various grades of "finished" fuel grades used in cars, trucks, and airplanes.

[0003] There are additional laws in the United States that require gasoline, jet, and diesel fuels to contain renewable origin blendstocks between certain minimum and maximum levels. Currently, these limits are set by Congress through the Renewable Fuels Standards (RFS). The RFS mandates that 21 billion gallons of advanced biofuels must be produced by 2022. Some of these advanced biofuels will be fungible transportation fuels, e.g., biomass-derived gasoline, jet fuel, and diesel. Efforts to produce such fuels from biomass to meet this mandate are ongoing, and it is recognized that there will be a strong demand for gasoline, jet, and diesel fuels that are economically produced from biomass. The primary renewable origin gasoline blendstock used in the United States to meet gasoline blending requirements is ethanol, produced primarily from corn or sugar fermentation. A small but growing contribution to the nation's renewable gasoline pool is so-called "second generation" cellulosic ethanol, made from non-food biomass, e.g., corn stover.

[0004] As stated in a US DOE Office of Energy Efficiency and Renewable Energy (EERE) report released in September 2020 (Non-Patent Document 1), the global 106 billion gallon (21 billion gallon domestic) commercial jet fuel market is estimated to more than double by 2050. This market could consume hundreds of millions of tons of biomass per year, which is consistent with the current biomass availability in the United States (340 million tons per year). Cost-competitive sustainable aviation fuels (SAF) are recognized as a key part of addressing this market growth. Renewable and / or waste carbon can provide a pathway to jet fuels that are low-cost, have low air pollution from combustion, and produce less soot. Key to this fuel pathway is sourcing the three SAF blendstocks - isoalkanes, cycloalkanes, and high-performance molecules - from low-cost renewable sources. When sourcing from waste carbon, there are often additional benefits, such as cleaner water if sourcing carbon from wet sludge, or less waste going to landfill if sourcing carbon from municipal solid waste. Additionally, the current price of SAF is higher than petroleum-based Jet A fuel. Fuel prices are a hurdle, as fuel represents 20%-30% of an airline's operating costs.

[0005] For civil or commercial aircraft, there are two main grades of jet fuel: Jet A-1 and Jet A. Both grades of jet fuel are kerosene type fuels, the difference between them is that Jet A-1 meets a maximum freezing point requirement of -47°C while Jet A meets a maximum freezing point requirement of -40°C. There is another grade of jet fuel: Jet B, used in very cold climates, is a wide cut fuel covering fractions from naphtha and kerosene and meets a maximum freezing point requirement of -50°C.

[0006] Jet fuel consists of n-alkanes, isoalkanes, cycloalkanes, and aromatics, with 5 to 16 carbon atoms. Aromatics do not burn as cleanly as alkanes, resulting in higher particulate emissions and lower specific energy. n-alkanes, while acceptable, do not meet flow and handleability properties, limiting their blending potential. Isoalkanes have high specific energy, good thermal stability, and low freezing point. Cycloalkanes provide complementary value to isoalkanes, allowing the fuel to meet density requirements and offering the same functional benefits as aromatics by potentially providing the seal swell capability currently offered from aromatics. Combining isoalkanes with cycloalkanes could add value to the fuel by achieving high specific energy and energy density and minimizing emissions characteristics.

[0007] Cycloalkanes include a diverse range of molecules and properties and are divided into three classes: monocyclic, fused bicyclic, and strained molecules. Each of these cycloalkane classes has a higher energy density than typical Jet A fuels. Nominally, the average Jet A fuel is approximately 25 / 7 / 0 wt% (weight %) monocyclic / fused bicyclic / strained cycloalkanes. Monocyclic alkanes can have densities, freezing points, flash points, and specific energies that exceed the requirements of conventional fuels. A process for producing cyclohexane from benzene derived from renewable sources is the subject of U.S. Pat. Nos. 5,993,333 and 5,943,623.

[0008] The condensed bicyclic alkanes in Jet A fuel are naphthenes, e.g., decalin (C 10 H 18 ), which is composed of naphthalene (C 10H8), often with additional carbons and branches of various alkyl lengths. These condensed bicyclic alkanes are characterized by high energy density, specific energy similar to that of average Jet A, and good thermal stability. Decalin and monocyclic alkanes have shown expansion capabilities similar to those of aromatic-containing Jet A fuels, and therefore may replace the aforementioned aromatic concentration minimum. Tricyclic and tetracyclic substances, such as phenanthrene, pyrene, chrysene, and fluoranthene, are potential sources of polycyclic paraffins that could become part of jet fuel blends. There is currently no method to produce condensed polycyclic aromatic compounds from renewable materials that meets economic and environmental requirements.

[0009] In January 2020, ASTM approved a Fast Track Annex to D4054 (Figure 9) that meets stringent compositional and performance requirements for conventional jet fuels and limits blending levels with Jet A or Jet A-1 to a maximum of 10%. The compositional requirements include restrictions on the types of hydrocarbons in the blend. Cycloparaffin concentrations must be less than 30 wt.% and aromatic compositions must be less than 20 wt.%. Additionally, tetralins and indanes (C9H 10 ) must have a composition of less than 6% by weight (or less than 30% by weight aromatics).

[0010] Biomass pyrolysis has been developed as an alternative to provide renewable fuels and fuel blendstocks. The product of biomass pyrolysis is a complex and unstable bio-oil, the composition of which varies significantly depending on the feedstock and pyrolysis conditions, and which contains hundreds of compounds, including excessive oxygenates. Generally, bio-oil contains 20% to 40% by weight oxygen and a small percentage (%) of sulfur-containing materials. Hydroprocessing of bio-oil is required to make the oil suitable as a blendstock or sole fuel, including hydrodeoxygenation (HDO), hydrodesulfurization (HDS), and hydrogenation of olefins. While hydroprocessing is well developed for petroleum feedstocks that contain little oxygen, the challenge of hydroprocessing bio-oil is more substantial. To date, the preferred method for hydroprocessing bio-oil is a multi-stage system requiring high pressure hydrogen, precious metal catalysts, and multiple unit operations (see, for example, Non-Patent Document 2, available electronically at http: / / www.osti.gov / bridge).

[0011] Catalytic pyrolysis of biomass has been developed as an improved thermal method for upgrading biomass to chemicals and fuels. The method involves the conversion of biomass in the presence of a catalyst in a fluidized bed reactor. The catalyst is usually an acidic microporous crystalline material, usually a zeolite. The zeolite is effective in upgrading the primary pyrolysis products of biomass cracking, converting them to aromatics, olefins, CO, CO2, charcoal, coke, water, and other useful materials. The aromatics include benzene, toluene, xylenes (collectively BTX), and naphthalene, among other aromatics. The olefins include ethylene, propylene, and smaller amounts of higher molecular weight olefins. The BTX aromatics are desirable products due to their high value and ease of transport. Toluene and xylenes are particularly desirable as gasoline components due to their high octane ratings and energy density. The heavier aromatics are suitable precursors for jet and diesel fuels. When produced under proper conditions, the products of catalytic pyrolysis have a very low oxygen content.

[0012] Patent Document 3 describes the isolation of a naphthalene-rich oil phase from a biomass catalytic pyrolysis process. No mention is made of hydrotreating or hydroprocessing the naphthalene-rich oil phase or other materials containing polynuclear aromatic compounds.

[0013] Prior publications have demonstrated the effectiveness of hydrotreating coal extracts containing similar bicyclic naphthalenic and substituted naphthalenic structures to produce streams suitable for use as jet fuel. This application discloses a hydrogenation process to produce a jet fuel additive or blendstock derived almost entirely from renewable feedstocks, such as loblolly pine from the southeastern United States or other similar biomass sources.

[0014] There are various techniques developed to convert biomass-derived feedstocks to jet fuel, such as alcohol dehydration, oil hydrogenation, gasification, and sugar conversion. All of these techniques involve multiple processing steps to create jet fuel from renewable fuels, and one-step catalytic pyrolysis of woody biomass to create jet fuel precursors has not been described. Many such methods are described in detail in Wang, et al., "Solid-based feedstocks are converted to biomass-derived intermediates through gasification, converted to alcohols through biochemical or thermochemical methods, converted to sugars through biochemical methods, and converted to bio-oil through pyrolysis methods." Wang points out that "bio-oil is a mixture of oxygenated organic species containing carbons ranging from C1 to C21 and above." None of the methods considered by Wang can directly convert solid feedstocks to very low oxygen content materials to produce renewable jet fuel or jet fuel blendstocks, requiring only the removal of residual heteroatoms, e.g., S, N, and O, and saturation of certain aromatic moieties.

[0015] Zhang et al., in Non-Patent Document 4, describe a multi-step process for producing renewable jet fuel, which involves catalytic pyrolysis of wood, followed by catalytic alkylation of the resulting aromatics with ionic liquid catalyst and light (C2-C4) olefins in a batch mode at 25°C-80°C for 20-240 min, and hydrogenation of the resulting alkylated aromatics with 5 wt% Pd / activated carbon catalyst at 120-200°C for 6 h.

[0016] US Pat. Nos. 4,399,403, 4,443, 4,513, 4,671, 4,721, 4,893, 5,103, 5,146, 5,152, 5,163, 5,171, 5,211, 5,221, 5,352, 5,361, 5,376, 5,47

[0017] In light of current commercial practices and technical disclosures, there is a need for a simple and economical method for producing renewable jet fuel blendstocks or fuels that meet technical and regulatory limitations by using a single-step catalytic pyrolysis of biomass. The present invention provides such a method and the resulting jet fuel blend compositions and chemicals. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] U.S. Pat. No. 1,076,7127 [Patent Document 2] U.S. Pat. No. 10,822,562 [Patent Document 3] US Patent Application Publication No. 2020 / 0165527 [Patent Document 4] U.S. Patent No. 8,277,643 [Patent Document 5] U.S. Patent No. 8,864,984 [Patent Document 6] U.S. Patent No. 9,790,179 [Patent Document 7] U.S. Patent No. 10,370,601 [Non-patent literature]

[0019] [Non-Patent Document 1] “Sustainable Aviation Fuel: Review of Technical Pathways,” [Non-Patent Document 2] S. Jones et al., “Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-oil Pathway,” PNNL-23053, November 2013 [Non-Patent Document 3] WC Wang et al., “Review of Biojet Fuel Conversion Technologies,” Technical Report NREL / TP-5100-66291, July 2016 [Non-Patent Document 4] Zhang et al., “Production of jet and diesel biofuels from renewable lignocellulosic biomass,” 2015, Applied Energy 150, p. 128-137 Summary of the Invention [Means for solving the problem]

[0020] (Summary of the invention) Various aspects of the present invention include the production of jet fuel blendstocks and chemicals from renewable feedstocks via catalytic pyrolysis and hydrogenation or other processes of selected catalytic pyrolysis products. The present invention provides this in an economical and improved manner.

[0021] In a first aspect, the present invention provides an improved process for preparing a renewable jet fuel blendstock, the process comprising the steps of: feeding a mixture containing renewable aromatics to a fractionation system to recover fractions, such as a fraction boiling at or above 180° C. at atmospheric conditions and a fraction boiling at or below 180° C. at atmospheric conditions, hydrotreating at least a portion of the recovered fraction of step a) boiling at or above 180° C. at atmospheric conditions to produce a hydrogenated fraction, and recovering a renewable fuel blendstock from the hydrogenated fraction of step b) in a product recovery system.

[0022] More specifically, the present invention comprises the steps of: a) feeding biomass, a catalyst composition, and a transport fluid to a fluidized bed reactor of a catalytic pyrolysis process maintained at reactive conditions to produce a feed fluid product stream; b) feeding the feed fluid product stream of step a) to a solids separation and stripping system to produce separated solids and a fluid product stream; c) feeding the fluid product stream of step b) into a fractionation system to recover a fraction above 180°C; preferably a fraction boiling between 180°C and 350°C; more preferably a fraction boiling between 180°C and 320°C, and even more preferably a fraction boiling between 200°C and 300°C; d) hydrogenating at least a portion of the product stream produced in step c) with hydrogen under hydrogenation conditions to produce a hydrogenated fraction; e) recovering a naphthenes-containing fuel, such as jet fuel blendstock, from the hydrogenated fraction of step d) in a product recovery system.

[0023] The boiling ranges given in this invention refer to the boiling ranges under modest pressure operation, typically at or near atmospheric pressure, for example 0.1 MPa.

[0024] (Glossary) As used herein, the term "biomass" has its customary meaning in the art and refers to any renewable organic source of energy or chemicals. Its main components can be: (1) trees (wood) and all other vegetation; (2) agricultural products and wastes (corn stover, fruits, garbage ensilage, etc.); (3) algae and other marine plants; (4) metabolic wastes (compost, sewage), and (5) cellulosic and carbonaceous municipal wastes. Examples of biomass materials are described, for example, in Huber, GW et al, "Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering," Chem. Rev. 106, (2006), pp. 4044-4098.

[0025] Biomass is conventionally defined as living or recently dead biological material that can be used as fuel or converted for industrial production. The criterion for biomass is that the material should have recently entered the carbon cycle, so that the release of carbon in a combustion process does not result in a net increase in carbon entering the carbon cycle averaged over a reasonably short period of time (for this reason, fossil fuels such as peat, lignite and coal are not considered biomass by this definition, because they contain carbon that has not been added to the carbon cycle for a long time, and therefore their combustion results in a net increase in atmospheric carbon dioxide). Most commonly, biomass refers to plant matter cultivated for use as biofuel, but it also includes plant or animal matter used to produce fiber, chemicals or heat. Biomass may also include biodegradable waste or by-products that can be burned as fuel or converted into chemicals, including municipal waste, vegetable waste (biodegradable waste consisting of garden or park waste, e.g., grass or flower clippings and hedge trimmings), agricultural by-products including animal waste, food processing waste, sewage sludge, and black liquor from wood pulp or algae. Biomass excludes organic material that has been converted by geological processes into substances such as coal, oil shale, or petroleum. Biomass is widely and typically grown from plants including miscanthus, spurge, sunflower, switchgrass, hemp, corn (maize), poplar, willow, sugarcane, and oil palm (palm oil), with roots, stems, leaves, seed coats, and fruits all potentially useful. Processing of raw materials for introduction into a processing unit may vary depending on the requirements of the unit and the form of the biomass. Biomass contains carbon dioxide in amounts significantly greater than those found in fossil fuels as determined by ASTM method D 6866-06. 14 It can be distinguished from fossil carbon by the presence of C.

[0026] The biomass used in the method of the present invention may most preferably be a solid material selected from among wood, forestry waste, corn stover, agricultural solid waste, municipal solid waste, digestate, food waste, animal waste, carbohydrates, lignocellulosic materials, xylitol, glucose, cellobiose, hemicellulose, lignin, and combinations thereof.

[0027] The term "renewable" refers to a material derived from biomass; preferably containing at least 50% by mass C derived from biomass, or at least 80% by mass C derived from biomass, and typically 90-100% by mass C derived from biomass.

[0028] The term "naphthalene-rich oil" obtained from biomass conversion in catalytic pyrolysis as used herein includes naphthalene, methylnaphthalenes (e.g., 1-methylnaphthalene, 2-methylnaphthalene, etc.), dimethylnaphthalenes (e.g., 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,5-dimethylnaphthalene, etc.), ethylnaphthalenes, other polyaromatic compounds (e.g., anthracene, 9,10-dimethylanthracene, pyrene, phenanthrene, etc.), and aromatic and polyaromatic compounds containing heteroatoms (e.g., oxygen, sulfur, nitrogen, etc.). Naphthalene-rich oil is a stream that typically boils in the temperature range of about 180°C to about 575°C. This stream is obtained from biomass conversion in a catalytic pyrolysis process.

[0029] The naphthalene-rich fraction contains at least 25% by weight, or at least 35% by weight, or at least 40% by weight, or between 25% and 90% by weight, or between 35% and 80% by weight, or between 40% and 75% by weight of the sum of naphthalene, substituted naphthalenes, naphthalenols, methyl naphthalenols, and naphthalenediols, at least 3% by weight, or at least 5% by weight, or at least 6% by weight, or between 3% and 15% by weight, or between 5% and 10% by weight, or between 6% and 8% by weight of xylenols, and less than 15% by weight, or less than 10% by weight, or less than 5% by weight, or between 0.01% by weight and 20% by weight, or between 1% by weight and 15% by weight, or between 5% by weight and 13% by weight of the sum of phenanthrene, anthracene, and other materials.

[0030] The term "off-gas" as used herein includes H2, CO, CO2, N2, and hydrocarbons containing 1 to 6 carbon atoms (e.g., methane, ethane, ethylene, propane, propylene, n-butane, isobutane, isobutene, 1-butene, 2-butene, pentane, pentene, hexane, hexene, etc.).

[0031] The term "tar" as used herein refers to a stream that typically boils in the temperature range of about 310° C. to about 575° C., and the stream is usually dark brown or black in color, bituminous and viscous.

[0032] As used herein, the term "aromatic compound(s)" refers to one or more compounds containing one or more aromatic groups, such as hydrocarbons containing single aromatic ring systems (e.g., benzyl, phenyl, etc.) and fused polycyclic aromatic ring systems (e.g., naphthyl, 1,2,3,4-tetrahydronaphthyl, etc.). Examples of aromatic compounds include benzene, phenol, benzenediols, benzenetriols, toluene, cresols, methoxybenzene, methylbenzenediols, ethylbenzene, xylenes, styrene, 2,3-dihydrobenzofuran, methylbenzenemethanol, dimethylphenols, ethylphenols, dimethylbenzenediols, ethylcatechol, resorcinol monoacetate, benzofuran, 3,4-dihydroxyethylbenzene, phorone, ethyltoluenes, propylbenzenes, trimethylbenzenes, benzene-1-ethyl-4-methoxy, phenol-2,3,6-trimethyl, phenol-4-ethyl-2-methoxy, α-methylstyrene, methylstyrenes, 1-propenylbenzene, 2-propenylbenzene, indane, 2,3-dihydro-1H-inden-5-ol, 1,2-indanediol, 3-hydroxy-2-methylbenzoic acid methyl, 4-(2-propenyl)-phenol, (2e)-3-Phenylprop-2-enal, indene, phenol-2-(2-propynyl), methylbenzofurans, 1H-indenol, 2-methylbenzothiophene, 1-methyl-4-propylbenzene, 1-methyl-4-(propan-2-yl)benzene, 4-isopropylbenzyl alcohol, 5-isopropyl-2-methylphenol, carvacrol, 2,3,5,6-tetramethyl-1,4-benzenediol, 1,2,3,4-tetrahydronaphthalene, Phthalene, methylindanes, 2,4-dimethylstyrene, 1-ethenyl-4-ethylbenzene, 2-methyl-1-propenylbenzene, 2,3-dihydro-5-methyl-1H-indene, 5-methoxyindane, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, benzene, (1-methyl-2-cyclopropen-1-yl), 1-methylindene, 2-methylindene, 3-methylindene, 4-methylindene, 1,2-dihydronaphthalene, 1,4-Dihydronaphthalene, 5,8-dihydro-1-naphthalenol, 2-methyl-1-indanone, 2,3-dimethylbenzofuran, naphthalene, naphthalenols, pentamethylbenzene, methyltetralins, 2,2-dimethylindane, 1H-indene 1-ethyl-2,3-dihydro, dimethylindenes, ethylindenes, dihydromethylnaphthalenes, methylnaphthalenes, methylnaphthols, 1-phenylcyclohexene, ethylnaphthalenes, dimethylnaphthalenes, biphenyl, acenaphthene, dibenzofuran, 2-(1-methylethyl)naphthalene, trimethylnaphthalenes, trimethylazulene, 3-methyl-1,1-biphenyl, fluorene, 2-phenanthrenyl-1,2,3,4-tetrahydro, 9H-fluorene-1-methyl -, 9H-fluorene-2-methyl, 9H-fluorene-4-methyl, anthracene, phenanthrene, 3-phenanthrol, methylanthracenes, 2,6-dimethylphenanthrene, 2-phenylnaphthalene, pyrene, 1-benzylnaphthalene, 7H-benzo-[c]-fluorene, 11H-benzo-[b]-fluorene, 1-methyl-7-isopropylphenanthrene, 1,4-dimethyl-2-phenylnaphthalene, chrysene, aniline, pyridine, pyrrole.

[0033] Single and / or multiple ring aromatic compounds may be produced in some embodiments. Aromatic compounds include single and multiple ring compounds containing heteroatom substituents, i.e., phenols, cresols, benzofurans, anilines, indoles, etc. Renewable aromatic compounds are the above materials prepared from renewable resources, e.g., biomass.

[0034] As used herein, the term "naphthenes" includes compounds having at least one saturated paraffin ring, such as those of the general formula C, including cyclopentane, cyclohexane, and cycloheptane. n H 2nalkylated cycloparaffins such as methyl-, ethyl-, dimethyl-, propyl-, trimethyl-, and butyl-cyclohexanes, cyclopentanes, and cycloheptanes, and polycyclic cycloparaffins such as decalin, alkylated decalins, tetralin, and alkylated tetralins.

[0035] As used herein, the terms "olefin" or "olefinic compound" (also known as "alkene") have their usual meaning in the art and refer to any unsaturated hydrocarbon containing one or more pairs of carbon atoms linked by a double bond. Olefins include both cyclic and acyclic (aliphatic) olefins, where the double bond is located between carbon atoms forming part of a cyclic (closed ring) group or an open chain group, respectively. Furthermore, olefins may contain any suitable number of double bonds (e.g., monoolefins, diolefins, triolefins, etc.). Examples of olefinic compounds include, but are not limited to, ethene, propene, allene (propadiene), 1-butene, 2-butene, isobutene (2-methylpropene), butadiene, and isoprene, among others. Examples of cyclic olefins include cyclopentene, cyclohexene, and cycloheptene, among others. Aromatic compounds, such as toluene, are not considered olefins; however, olefins that contain aromatic moieties are considered olefins, such as benzyl acrylate or styrene.

[0036] As used herein, the term "oxygenate" includes any organic compound that contains at least one oxygen atom in its structure, such as alcohols (e.g., methanol, ethanol, etc.), acids (e.g., acetic acid, propionic acid, etc.), aldehydes (e.g., formaldehyde, acetaldehyde, etc.), esters (e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., dimethyl ether, diethyl ether, etc.), aromatic compounds with oxygen containing substituents (e.g., phenol, cresol, benzoic acid, naphthol, etc.), cyclic ethers, acids, aldehydes, and esters (e.g., furan, furfural, etc.).

[0037] As used herein, the terms "phenolic oil" and "oxygenated oil" include aromatic compounds having oxygen-containing substituents (e.g., phenol, m-cresol, o-cresol, p-cresol, xylenols, etc.) and other compounds from the Bio-TCat reactor effluent that typically boil in the range of 80°C to 220°C (e.g., benzene, toluene, p-xylene, m-xylene, α-xylene, indane, indene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, ethylbenzene, styrene, cumene, propylbenzene, naphthalene, etc.). Phenolic oil and oxygenated oil are streams that typically boil in the temperature range of 80°C to 220°C.

[0038] As used herein, the terms "pyrolysis" and "pyrolyzing" have their customary meaning in the art and refer to the conversion of compounds, such as solid hydrocarbonaceous materials, to one or more other substances, such as volatile organic compounds, gases, and coke, by heat, preferably without or in the absence of the addition of molecular oxygen, i.e., O2. Preferably, the volume fraction of oxygen present in the pyrolysis reaction chamber is 0.5% or less. Pyrolysis may be carried out with or without a catalyst. "Catalytic pyrolysis" refers to pyrolysis carried out in the presence of a catalyst and may include the steps described in more detail below. Catalytic pyrolysis, which involves the conversion of biomass in a catalytic fluidized bed reactor to produce a mixture of aromatics, olefins, and various other materials, is also called catalytic fast pyrolysis (CFP), and is a particularly useful pyrolysis method. Examples of catalytic pyrolysis processes are reviewed, for example, in Huber, GW et al, “Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering,” Chem. Rev. 106, (2006), pp. 4044-4098, incorporated herein by reference. Products from the catalytic pyrolysis process may include, for example, the following materials: benzene, phenol, benzenediols, benzenetriols, toluene, cresols, methoxybenzene, methylbenzenediols, ethylbenzene, xylenes, styrene, 2,3-dihydrobenzofuran, methylbenzenemethanol, dimethylphenols, ethylphenols, dimethylbenzenediols, ethylcatechol, resorcinol monoacetate, benzofuran, 3,4-dihydroxyethylbenzene, phorone, ethyltoluenes, propylbenzenes, trimethylbenzenes, benzene-1-ethyl-4-methoxy, phenol-2,3,6-trimethyl, phenol-4-ethyl-2-methoxy, α-methylstyrene, methylstyrenes, 1-propenylbenzene, 2-propenylbenzene, indane, 2,3-dihydro-1H-inden-5-ol, 1,2-Indanediol, methyl 3-hydroxy-2-methylbenzoate, 4-(2-propenyl)-phenol, (2e)-3-phenylprop-2-enal, indene, phenol-2-(2-propynyl), methylbenzofurans, 1H-indenol, 2-methylbenzothiophene, 1-methyl-4-propylbenzene, 1-methyl-4-(propan-2-yl)benzene, 4-isopropylbenzyl alcohol, 5-isopropyl-2-methylphenol, carvacrol, 2,3,5,6-tetramethyl-1,4-benzenediol, 1,2,3,4-tetrahydronaphthalene, methylindanes, 2,4-dimethylstyrene, 1-ethenyl-4-ethylbenzene, 2-methyl 1-propenylbenzene, 2,3-dihydro-5-methyl-1H-indene, 5-methoxyindane, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, benzene, (1-methyl-2-cyclopropen-1-yl), 1-methylindene, 2-methylindene, 3-methylindene, 4-methylindene, 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, 5,8-dihydro-1-naphthalenol, 2-methyl-1-indanone, 2,3-dimethylbenzofuran, naphthalene, naphthalenols, pentamethylbenzene, methyltetralins, 2,2-dimethylindane, 1H-indene 1-ethyl-2,3-dihydro, dimethylindenes, ethylindenes, dihydromethylnaphthalenes, methylnaphthalenes, methylnaphthols, 1-phenylcyclohexene, ethylnaphthalenes, dimethylnaphthalenes, biphenyl, acenaphthene, dibenzofuran, 2-(1-methylethyl)naphthalene, trimethylnaphthalenes, trimethylazulene, 3-methyl-1,1-biphenyl, fluorene, 2-phenanthrenyl-1, 2,3,4-tetrahydro, 9H-fluorene-1-methyl-, 9H-fluorene-2-methyl, 9H-fluorene-4-methyl, anthracene, phenanthrene, 3-phenanthrol, methylanthracenes, 2,6-dimethylphenanthrene, 2-phenylnaphthalene, pyrene, 1-benzylnaphthalene, 7H-benzo-[c]-fluorene, 11H-benzo-[b]-fluorene, 1-methyl-7-isopropylphenanthrene, 1,4-Dimethyl-2-phenylnaphthalene, chrysene, aniline, pyridine, pyrrole, etc.

[0039] Hydroprocessing is the reaction of organic materials with hydrogen and includes the processes of hydrotreating, hydrogenation, and hydrocracking. As used herein, the term "hydroprocessing" refers to a relatively mild hydroprocessing method for reacting organic feed materials with hydrogen, which is used to remove at least 90% of contaminants, such as nitrogen, sulfur, and oxygen, from the organic liquid fraction. These contaminants can adversely affect the equipment, catalyst, and end product quality. Hydroprocessing also saturates a large portion of the olefinic portion of many materials into the corresponding materials, converting the olefinic portion to its paraffinic equivalent portion, e.g., 1-hexene may be saturated into hexane, and styrene may be saturated into ethylbenzene. Hydroprocessing does not significantly saturate the aromatic portion of the material, e.g., benzene, into cyclohexane, i.e., the saturation of the aromatic rings is less than 10% of the aromatic rings in the material. Hydroprocessing is performed before processes such as hydrogenation to prevent the hydrogenation catalyst from being contaminated by contaminants in the untreated feedstock. Hydrotreating is used prior to catalytic cracking or hydrocracking to reduce sulfur, improve product yields, and upgrade petroleum fractions into finished jet fuel, diesel fuel, and heating fuel oil.

[0040] Suitable hydrotreating catalysts for use in the hydrotreater are known conventional hydrotreating catalysts, including those composed of at least one Group VIII metal (i.e., iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum, preferably iron, cobalt, or nickel, more preferably cobalt and / or nickel) and at least one Group VI metal (preferably molybdenum or tungsten or both) on a high surface area support material, preferably alumina or silica or a mixture of alumina and silica. Other suitable hydrotreating catalysts include zeolite catalysts, as well as noble metal catalysts, where the noble metal is selected from one or more of rhodium, ruthenium, iridium, palladium, and platinum. It is within the scope of the process of the present invention for multiple types of hydrotreating catalysts to be used in the same reaction vessel. The Group VIII metal is typically present in an amount ranging from about 0.5 weight percent to about 20 weight percent, preferably from about 0.5 weight percent to about 10 weight percent. The Group VI metal will typically be present in an amount ranging from about 1 weight percent to 25 weight percent, preferably from about 1 weight percent to 12 weight percent. Although several exemplary catalysts for hydrotreating are described above, other hydrotreating and / or hydrodesulfurization catalysts may be used depending on the particular feedstock and desired effluent quality. Catalysts and hydrotreating conditions may be selected to achieve hydrogenation of less than 10%, or less than 5%, or less than 2%, or less than 1% of the aromatic carbon-carbon bonds in the aromatic rings in the feed to the hydrotreater.

[0041] The reaction conditions used for hydrotreating will depend in part on the particular reactor design and concentrations of the individual species selected, but reaction temperatures of 200° C. to 400° C. and hydrogen pressures of 4.0 MPa (40 bar) to 12 MPa (120 bar) are usually suitable. Advantageously, this contacting step is carried out for 0.1 hours. -1The gas to liquid volumetric ratio ("G:L ratio") in the hydrotreater at reactor operating conditions may range from 0.1 to 20:1, more typically from 0.1 to 10:1.

[0042] As used herein, the term "hydrogenation" refers to a hydroprocessing method for reacting an organic feed material with hydrogen to saturate a substantial portion of the aromatic rings in the feed mixture. Hydrogenation may convert a material having two or more aromatic rings to a material in which one or more of the aromatic rings are saturated. For example, the conversion of naphthalene to tetralin, or decalin, or a mixture of tetralin and decalin with hydrogen is a hydrogenation method. Typically, the conversion of aromatic rings in the material to yield naphthenes is at least 15%, or at least 25%, or at least 35%, or between 15% and 99%, or between 25% and 90%, or between 35% and 85% of the aromatic rings in the mixture. Typical processing conditions for hydrogenation include temperatures of at least 280°C, or at least 300°C, or at least 320°C, or between 280 and 450°C, or between 300 and 400°C, or between 320 and 350°C. Typical hydrogen pressures for the hydrogenation of aromatic rings include at least 4 MPa, or at least 6 MPa, or at least 8 MPa, or 4 to 20 MPa, or 6 to 15 MPa, or 8 to 12 MPa. Typical liquid hourly space velocities for hydrogenation are at least 0.5 h -1 , or at least 1 hour -1 , or at least 2 hours -1 , or 10 hours -1 Less than or equal to 5 hours -1 Less than or equal to 3 hours -1 Less than or equal to 0.5 hours -1 ~5 hours -1 , or 1 hour -1 ~4 hours -1 , or 2 hours -1 ~3 hours -1 where the liquid hourly space velocity is the ratio of the volume of liquid feed fed over the catalyst per hour to the volume of catalyst in the reactor. Typical hydrogen flow rates for hydrogenation are calculated based on the volume of liquid feed (m 3) H2 at least 100Nm 3 , or at least 1000Nm 3 , or at least 2000Nm 3 , or 100 to 5000 Nm 3 , or 1000~4500Nm 3 , or 2000~4000Nm 3 Typical catalysts for hydrogenation include CoMo, NiMo, Pt, Pd, Rh, Ru, or combinations thereof.

[0043] The catalyst component useful in the context of the present invention can be selected from any catalyst known in the art or as would be understood by one of ordinary skill in the art. A catalyst promotes and / or causes a reaction. Thus, as used herein, a catalyst lowers the activation energy (increases the rate) of a chemical process and / or improves the distribution of products or intermediates in a chemical reaction (e.g., shape-selective catalysis). Examples of reactions that can be catalyzed include: dehydration, dehydrogenation, hydrogenation, isomerization, oligomerization, cracking, hydrogen transfer, aromatization, cyclization, decarbonylation, decarboxylation, aldol condensation, molecular cracking and decomposition, combinations thereof, and other reactions. As would be understood by one of ordinary skill in the art, the catalyst component can be considered to be acidic, neutral, or basic. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0044] Detailed Description of the Invention In view of the above, and as a result of extensive research, it has been discovered that, through a series of sequential steps, the catalytic pyrolysis process can be economically and efficiently carried out to enhance the production of valuable fuel blendstocks and chemical products.

[0045] An embodiment of the improved method of the present invention comprises the steps of: a) feeding biomass, e.g., biomass provided from a renewable source of organic material, a catalyst composition, e.g., a catalyst composition comprising one or more crystalline molecular sieves, e.g., a catalyst composition characterized by a silica to alumina molar ratio (SAR) greater than 12 and a constraint index (CI) between 1 and 12, and a transport fluid, to a fluidized bed reactor maintained at reaction conditions, e.g., a temperature of 300° C. to 1000° C. and a pressure of 0.1 MPa to 1.5 MPa, to produce a feed fluid product stream; b) feeding the feed fluid product stream of step a) to a solids separation and stripping system to produce separated solids and a fluid product stream; c) feeding the fluid product stream of step b) to a fractionation system to recover a fraction, the fraction boiling between 180°C and 350°C, preferably the fraction boiling between 180°C and 320°C, more preferably the fraction boiling between 200°C and 310°C, d) hydrogenating at least a portion of the high boiling fraction of step c) under hydrogenation conditions to produce a hydrogenated fraction; and e) recovering a fuel blend stock, e.g., a jet fuel blend stock, from the hydrogenated fraction of step d) in a product recovery system, having less than 0.4 wt.% olefins, less than 10 parts per million (ppm) sulfur, less than 10 ppm nitrogen, and less than 1 wt.% oxygen.

[0046] An embodiment of the invention includes the new fuel blendstock recovered by step e) and mixtures thereof with a fuel, such as jet fuel or other fuel blendstock.

[0047] Hydrotreating and hydrogenation of a portion of the biomass catalytic pyrolysis products can efficiently hydrogenate the C10-C16 aromatic components to produce renewable jet fuel additives or blendstocks. The key regulatory parameter for efficient production of this material is the removal of three-ring species from the feed to the hydrogenation to avoid catalyst fouling. This is done by limiting the final boiling point of the distilled product to below 310-320°C, preferably 300-310°C, to minimize the presence of compounds such as phenanthrene, anthracene, and related compounds.

[0048] In one embodiment of the invention, the renewable fuel blendstock comprises at least 50% by weight, or at least 75% by weight, or at least 90% by weight, or between 50% and 99% by weight, or between 75% and 95% by weight of hydrocarbons having 10 to 16 carbon atoms. Another embodiment of the invention includes a mixture of the above blendstock with petroleum-derived materials in a jet fuel product. Another embodiment of the invention includes a mixture of a renewable fuel blendstock with petroleum-derived materials, such as jet fuel, where the renewable fuel blendstock comprises between 0.1% by volume and 80% by volume, or between 3% by volume and 70% by volume, or between 5% by volume and 60% by volume of jet fuel, with the remainder of the mixture comprising petroleum-derived jet fuel.

[0049] BRIEF DESCRIPTION OF THE DRAWINGS 1, 2, 3 and 4 are block flow diagrams of various aspects of the methods of the present invention.

[0050] An embodiment of the improved method of the present invention comprises the steps of: a) feeding biomass, e.g., biomass provided from a renewable source of organic material, a catalyst composition, e.g., a catalyst composition comprising one or more crystalline molecular sieves, e.g., a catalyst composition characterized by a SAR greater than 12 and a CI between 1 and 12, and a transport fluid, into a fluidized bed reactor of a catalytic pyrolysis process maintained at reaction conditions, e.g., a temperature of 300° C. to 1000° C. and a pressure of 0.1 MPa to 1.5 MPa, to produce a feed fluid product stream; b) feeding the feed fluid product stream of step a) to a solids separation and stripping system to produce a separated solids and fluid product stream; c) feeding the fluid product stream of step b) to a fractionation system to recover a fraction, the fraction boiling between 180°C and 350°C, preferably the fraction boiling between 180°C and 320°C, more preferably the fraction boiling between 200°C and 310°C, d) hydrogenating at least a portion of the fraction boiling between 180° C. and 350° C. of step c) under hydrogenation conditions to produce a hydrogenated fraction; and e) recovering in a product recovery system a chemical compound comprising tetralins, decalins, substituted tetralins or decalins, or some combination thereof, wherein the number of carbon atoms in the product comprises 10 to 16 carbon atoms.

[0051] (Details of the invention method) (Explanation of catalytic pyrolysis) Some embodiments of the invention are shown in Figure 1, where stream (1) is derived from the Bio-TCat® process. Examples of equipment and process conditions suitable for the Bio-TCat® process are described in U.S. Patents 8,277,643, 8,864,984, 9,169,442, 9,790,179, 10,370,601, 10,767,127; and 10,822,562, each of which is incorporated herein by reference. The conditions for the conversion of biomass to Bio-TCat® may include one or a combination of the following features (which are not intended to limit the broader aspects of the invention): biomass processing; catalyst composition; catalyst composition optionally containing metal; fluidized bed, circulating bed, moving bed, or riser reactor; fluidizing fluid; operating temperature in the range of 300° C. to 1000° C., or 450° C. to 800° C., or 500° C. to 650° C., and pressure in the range of 0.1 to 3.0 MPa (1 to 30 atm); and solid catalyst / biomass mass ratio of 0.1 to 40, or 2 to 20, or 3 to 10. The solid biomass may be fed to the reactor in a continuous or intermittent manner. The solid catalyst may be regenerated by an oxidation method and partly returned to the reactor. The solid catalyst may be removed from the reactor, stripped with steam to drive off organic materials and reactive gases, then regenerated by treatment with oxygen-containing gas in a fluidized bed catalyst regenerator and partially returned to the reactor. In order to reduce the proportion of non-aromatic components in the product, thereby benefiting downstream separation and conversion technologies, the reaction severity in the Bio-TCat® reactor may be increased. Ways to achieve greater reaction severity include higher reaction temperature, higher catalyst activity (which may be achieved by higher replenishment rates of fresh catalyst and removal rates of spent catalyst, or by catalyst modification (e.g., higher zeolite content, lower silica / alumina ratio, greater macro- and meso-porosity, etc.), higher pressure, or longer residence time.

[0052] Biomass may not be available in a form convenient for processing in the fluidized bed reactor of the Bio-TCat® process. While solid biomass is the preferred feed, it may contain a portion of liquid at ambient conditions. The solid biomass may be treated in any order in any of a number of ways, including cutting, chopping, chipping, shredding, grinding, grinding, sizing, drying, roasting, roasting, washing, extracting, or some combination thereof, to make it more suitable for processing and achieve the desired properties of the biomass feed in terms of size, moisture, sulfur and nitrogen impurity content, density, and metal content. Procedures may be used to reduce agglomeration and aggregation of the biomass.

[0053] After conversion in the fluidized bed reactor, the products of the Bio-TCat® process are recovered by a combination of solids separation, quenching or cooling of the hydrocarbons, gas-liquid separation, compression cooling, gas-liquid absorption, condensation of condensable compounds, or other methods known in the art to recover C4 + A mixture of hydrocarbons is produced. Distillation can be used to separate out the desired fractions by boiling point range. The desired product fraction can then be subjected to hydrotreating to remove heteroatoms, such as O, N, or S, and to saturate olefins to provide a first liquid stream.

[0054] In some embodiments, the product mixture from the catalytic pyrolysis process comprises 2-methylnaphthalene, naphthalene, indene, 1,2,4-trimethylbenzene, 1,5-dimethylnaphthalene, 2-methylindane, 1-methylanthracene, -methylstyrene, 5-methylindane, indane 3-ethyltoluene, 1-methylindene, 2-phenylnaphthalene, anthracene, 2,3-dimethylindene, 1-benzylnaphthalene, 2,6-dimethylnaphthalene, 4-ethyltoluene, 1,3-dimethylindene, 9H-fluorene, 2-methylbiphenyl, 1-methyl-4-propylbenzene, 1-methylnaphthalene, 1,7-dimethylnaphthalene, 9H-fluorene, 1-methyl-4-methylindene, 2-(1-methylethyl)naphthalene, 1H-indene 1-Ethyl-2,3-dihydro, 1-phenylcyclohexene, n-propylbenzene, 11H-benzo-[b]-fluorene, 1,4-diethylcyclohexane, 1,2,3-trimethylbenzene, 1-ethenyl-4-ethylbenzene, 1-methylindane, 2,3,5-trimethylnaphthalene, 3-methyl-1,1-biphenyl, propadienylcyclohexane, trimethylazulene, phenanthrene, 2-ethylnaphthalene, fluorene, 1,2-dihydronaphthalene, 2-methylindene, 1,2-dihydro 4-methylnaphthalene, 2,6-dimethylphenanthrene, 1-methyl-7-isopropylphenanthrene, 1,2-dihydro 3-Methylnaphthalene, 1,4,6-trimethylnaphthalene, 2-phenanthrenyl, 1,2,3,4-tetrahydro-4-methylindan, 1,2,3,4-tetrahydronaphthalene, 2,2-dimethylindan, 1,4-dihydronaphthalene, 1-methyl-4-(propan-2-yl)benzene, 1,4-dimethyl-2-phenylnaphthalene, and the oxygenates 3-phenanthrol, 1H-indenol, 1-naphthalenol (1-naphthol), 2-methyl-1-naphthol, 2-methylbenzofuran, 2-acetyl-5-norbornene, dibenzofuran, 2-naphthalenol, 7-methyl-1-naphthol, 5-isopropyl-2-methylphenol, 2,3-dihydro-1H-inden-5-ol, 5,8-dihydro-1-naphthalenol, 5-methoxyindan, 1,7,The compounds include those selected from the group consisting of 7-trimethylbicyclo[2.2.1]heptan-2-one, 2-(2-propynyl)-phenol, (2E)-3-phenylprop-2-enal (cinnamaldehyde), 2,3-dimethylbenzofuran, and 2,3,6-trimethyl-phenol, as well as combinations thereof.

[0055] (Catalyst for catalytic pyrolysis) For catalytic pyrolysis, useful catalysts include catalysts containing internal porosity selected according to pore sizes (e.g., mesoporous and pore sizes typically associated with zeolites), such as average pore sizes of less than 10 nm (1 nm equals 10 angstroms (Å)), less than 5 nm, less than 2 nm, less than 1 nm, less than 0.5 nm, or smaller. In some embodiments, catalysts having average pore sizes of 0.5 nm to 10 nm may be used. In some embodiments, catalysts having average pore sizes of 0.5 nm to 0.65 nm, or 0.59 nm to 0.63 nm may be used. In some cases, catalysts having average pore sizes of 0.7 nm to 0.8 nm, or 0.72 nm to 0.78 nm may be used.

[0056] Particularly advantageous catalyst compositions in the catalytic pyrolysis fluidized bed reactor of the present invention include crystalline molecular sieves characterized by a silica-to-alumina ratio (SAR) greater than 12 and a constraint index (CI) between 1 and 12. Non-limiting examples of these crystalline molecular sieves are those having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, or combinations thereof. In embodiments, the catalyst composition includes crystalline molecular sieves characterized by a SAR greater than 12 to 240 and a CI between 5 and 10, such as molecular sieves having the structure of ZSM-5, ZSM-11, ZSM-22, ZSM-23, or combinations thereof. The method by which CI is determined is more fully described in U.S. Patent No. 4,029,716, which is incorporated by reference for details of the method.

[0057] Without limitation, some such and other catalysts may be selected from naturally occurring zeolites, synthetic zeolites, and combinations thereof. In certain embodiments, the catalyst may be a ZSM-5 zeolite catalyst, as would be understood by one skilled in the art. In some cases, such catalysts may contain acid sites. Other types of zeolite catalysts include ferrierite, zeolite Y, zeolite beta, mordenite, MCM-22, ZSM-23, ZSM-57, SUZ-4, EU-1, ZSM-11, (S)AIPO-31, SSZ-23, and the like. In other embodiments, non-zeolite catalysts may be used; for example, WO x / ZrO2, aluminum phosphate, etc. In some embodiments, the catalyst may include metals and / or metal oxides selected from among nickel, palladium, platinum, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, copper, gallium, rare earth elements, i.e., elements 57-71, cerium, zirconium, and / or any of their oxides, or some combination thereof. Additionally, in some cases, the properties of the catalyst (e.g., pore structure, type and / or number of acid sites, etc.) may be selected to selectively produce the desired products.

[0058] The molecular sieve for use herein or catalyst composition comprising same may be heat treated at elevated temperature. This heat treatment is generally carried out by heating (typically in an oxygen-containing atmosphere, preferably air) at a temperature of at least 370°C for at least 1 minute and generally not more than 20 hours. Although pressures below atmospheric pressure may be used for the heat treatment, atmospheric pressure is preferred for convenience. The heat treatment may be carried out at a temperature up to about 925°C. The heat treated product is particularly useful in the present process.

[0059] For the catalyst compositions useful in the present invention, suitable molecular sieves may be used in combination with a carrier or binder material, such as a porous inorganic oxide carrier or a clay binder. Non-limiting examples of such binder materials include alumina, zirconia, silica, magnesia, thoria, titania, boria, and combinations thereof, generally in the form of dry inorganic oxide gels and gelatinous precipitates. Suitable clay materials include, by way of example, bentonite, diatomaceous earth, and combinations thereof. The relative proportion of suitable crystalline molecular sieves in the total catalyst composition may vary widely, with molecular sieve contents ranging from 30 weight percent to 90 weight percent by weight of the composition, more usually ranging from 40 weight percent to 70 weight percent by weight of the composition. The catalyst composition may be in the form of extrudates, beads, or flowable microspheres.

[0060] Molecular sieves for use herein or catalyst compositions containing same may have original cations which are replaced, at least in part, by ion exchange with hydrogen or hydrogen precursor cations and / or non-noble metal ions of Group VIII of the Periodic Table, i.e., nickel, iron, or cobalt, or some combination thereof, according to techniques well known in the art.

[0061] (Fraction) The effluent (1) from the catalytic pyrolysis is cooled in a heat exchanger (150), possibly producing steam, and then fed to the main fractionation column (200). A part of the stream (4) containing naphthalene and tars is recycled to the fractionation column (200), and another part is taken from the bottom of the fractionation column and sent to an additional distillation column (400) to efficiently separate the three-ring species in stream (13) from the naphthalene-rich stream (12), which may contain xylenols, so as to reach a final boiling point target of 350° C. or less, or preferably 320° C. or less, or much more preferably 310° C. or less, as mentioned above.

[0062] The final boiling point is fixed at or below 310-320°C, preferably below 300-310°C, to minimize the presence of compounds such as phenanthrene, anthracene, and related compounds.

[0063] After removal of materials boiling at or below 180°C, the mixture may contain at least 25% by weight, or at least 35% by weight, or at least 40% by weight, or between 25% and 90% by weight, or between 35% and 80% by weight, or between 40% and 75% by weight of the sum of naphthalene, substituted naphthalenes, naphthalenols, methyl naphthalenols, and naphthalenediols, at least 3% by weight, or at least 5% by weight, or at least 6% by weight, or between 3% and 15% by weight, or between 5% and 10% by weight, or between 6% and 8% by weight of xylenols, and less than 15% by weight, or less than 10% by weight, or less than 5% by weight, or between 0.01% by weight and 20% by weight, or between 1% and 15% by weight, or between 5% and 13% by weight of the sum of phenanthrene, anthracene, and other materials.

[0064] Optionally, at least a portion of streams (3) or (13), or at least a portion of the fractions remaining after removal of the fractions boiling below 310° C., or below 320° C., or below 350° C. recovered in the fractionation step, or some combination thereof, can be hydrocracked in a hydrocracking process.

[0065] 2 and 3 are conceptual block flow diagrams showing the hydrogenation of a naphthalene-rich stream to cycloalkanes with hydrogen, resulting in a stream containing less than 5%, or less than 3%, or less than 1% naphthalenic species. The design of the hydrogenation unit is readily accomplished by one familiar with the art of hydrogenation of petrochemical naphthalenic species. The reactor can incorporate features to control the exotherm of hydrogenation that are typically implemented by those skilled in the art. These features can be selected from among: 1) recycle of cooled hydrogen, 2) limiting the percentage of hydrogen added to the total mass of the feed by diluting the feed, 3) introduction of a "quench fluid" at various points within the reactor, whereby the heat of vaporization of a liquid is used to mitigate the exotherm, or some combination thereof. Such quench fluids are typically derived from the product stream either before or after removal of the more volatile components.

[0066] In Figure 2, one embodiment of a process for hydrogenation and purification of a naphthalene-rich stream is shown. A naphthalene-rich stream (12), possibly containing xylenols, e.g., derived from biomass by the process in Figure 1 or a similar process, is passed to a hydrogenation reactor (500) along with hydrogen (22). In the hydrogenation reactor, the naphthalene-rich stream is hydrogenated to tetralins, decalins, other naphthenes, and similar cycloalkane materials, and this mixture (23) is passed to a purification column (600). Any xylenols present will also be hydrogenated in this reactor to benzene, toluene, xylenes, and naphthenes. In the purification column (600), the light materials (24) are passed to a decanter / reflux drum (700) where the xylenes are recovered in stream (25) and a portion of the mixture (27) is returned to the separation column and the water fraction (26) is separated. Stream (27) typically contains tetralins, decalins, other naphthenes, as well as some xylenes and some water. A stream (28) containing purified cycloalkanes is separated and recovered as product. A slipstream of cycloalkanes (28) is returned to the separation column. By returning a portion of the heavier materials to column (600), efficiency and yields can be improved. The naphthalene-rich stream (12) may contain at least 25% by weight, or at least 35% by weight, or at least 40% by weight, or between 25% and 90% by weight, or between 35% and 80% by weight, or between 40% and 75% by weight of the sum of naphthalene, substituted naphthalenes, naphthalenols, methyl naphthalenols, and naphthalenediols, at least 3% by weight, or at least 5% by weight, or at least 6% by weight, or between 3% and 15% by weight, or between 5% and 10% by weight, or between 6% and 8% by weight of xylenols, and less than 15% by weight, or less than 10% by weight, or less than 5% by weight, or between 0.01% by weight and 20% by weight, or between 1% by weight and 15% by weight, or between 5% by weight and 13% by weight of the sum of phenanthrene, anthracene, and other materials.

[0067] In Figure 2, the hydrogenation is carried out in one step and the resulting product is fed to a distillation column to remove water from the hydrogenation of oxygen-containing two-ring species and other compounds, and xylenes resulting from deoxygenation of xylenols, which can be fed to a purification scheme as described in US2020 / 0165527. The bottoms from the distillation column (28) can be sold as a jet fuel additive or blend stock with a biomass-derived content of greater than 90%.

[0068] In FIG. 3, another embodiment of the process of the invention is shown, which includes a second hydrogenation step. A naphthalene-rich stream (12), for example from biomass by the process in FIG. 1 or other processes, is passed to a hydrogenation reactor (500) together with hydrogen (22). In the hydrogenation reactor, the naphthalene-rich stream is hydrogenated to tetralins, decalins, other naphthenes, and similar materials, and the mixture (23) is passed to a purification column (600). Any xylenols present will also be hydrogenated in this reactor (500) to a mixture of xylenes, toluene, benzene, and naphthenes. In the purification column (600), the light material (24) is passed to a decanter / reflux drum (700), where the xylenes are recovered in stream (25); a portion of the mixture (27) is returned to the separation column, and the water fraction (26) is separated. A stream (28) containing purified partially hydrogenated cycloalkanes is separated from column (600) and sent to a second hydrogenation reactor (800), while a slipstream of the cycloalkanes stream (28) is returned to the separation column. Hydrogen (29) is also sent to the second hydrogenation reactor (800), where the product is further hydrogenated and the hydrogenated product (30) is recovered.

[0069] In some cases, the hydrogenation in (500) in FIG. 3 can be divided into two steps, whereby the hydrogenation reactor (500) essentially comprises a hydrogenation operating at a lower pressure to partially hydrogenate the aromatic rings and reduce xylenols to benzene, toluene, and xylenes, and naphthalenes to naphthenes, producing a partially hydrogenated stream, and a second reactor (not shown) operating at a higher pressure to further hydrogenate the aromatics, and the hydrogenation reactor (800) is removed. In this case, the first hydrogenation can be operated in the range of 2.0-7.0 MPa with a CoMo-containing catalyst. An optional distillation can be inserted after the first hydrogenation step in (500) to remove the water of reaction as well as the xylenes. The second hydrogenation process in (500) (not shown) completes the hydrogenation of the aromatics to produce cycloalkanes, and can use a noble metal catalyst, such as Pd, or Pt, or a combination of the two. The second hydrogenation may be operated at a similar pressure to the first but at a higher pressure, in the range of 2.0-8.0 MPa. This combination of low pressure hydrogenation in (500), optional distillation (not shown), and higher pressure hydrogenation results in a product that does not require any additional purification. An alternative embodiment is to perform a distillation after the second hydrogenation step in (500).

[0070] Another embodiment of the invention is shown in Figure 4, in which tetralins or decalins or both are cracked or hydrocracked to produce a stream containing alkylated benzenes or alkylated tetralins or some combination thereof. A naphthalene-rich stream (12), such as that produced from biomass by any of the methods in Figure 1 or other methods, is passed to a hydrogenation reactor (500) along with hydrogen (22). In the hydrogenation reactor, the naphthalene-rich stream is hydrogenated to tetralins, decalins, other naphthenes, and similar materials, and the mixture (23) is passed to a purification column (600). Any xylenols present will also be hydrogenated to benzene, toluene, and xylenes in the hydrogenation reactor (500). In the purification column (600), the light materials (24) are passed to a decanter / reflux drum (700) where the xylenes are recovered in stream (25); a portion of the mixture (27) is returned to the separation column and the water fraction (26) is separated. A stream (28) containing the purified, partially hydrogenated cycloalkanes is optionally separated from the column (600) and sent to an optional second hydrogenation reactor (800), while a slipstream of the cycloalkanes stream (28) is returned to the separation column. Hydrogen (29) is also sent to the second optional hydrogenation reactor (800), where the product is further hydrogenated and a hydrogenated product (30) is recovered. Either stream (28) or stream (30) is cracked or hydrocracked (i.e., with or without hydrogen) in unit (900) to open the paraffinic cyclic molecular moieties to produce alkylated benzenes, alkylated cyclohexanes, or both as stream (32) and a gas fraction in stream (31) that may include hydrogen, methane, ethane, ethylene, propane, propylene, butanes, butenes, or mixtures thereof. Product stream (32) includes jet fuel blend streams that more closely meet the Jet Fuel A or A-1 specifications.

[0071] In any of the above cases, if the hydrogen is derived from catalytic pyrolysis of biomass, the biomass-derived content of the resulting fuel can approach 100%. In each of the embodiments shown in Figures 3-7, a portion of the unreacted hydrogen is optionally collected from the top of the hydrogenation reactor (500), or the hydrogenation reactor (800), or the separation column (600), or the reactor (900), or some combination thereof, and recycled to the hydrogenation reactor(s).

[0072] (Hydrogenation) The hydrogenation of the naphthalene-rich fraction may be carried out by contacting the liquid with H2-containing gas at a pressure of 4 MPa to 15 MPa (40 to 150 atm), preferably 6 to 12 MPa (60 to 120 atm), at a temperature of 280 to 400°C, preferably 320 to 350°C, in the presence of a solid catalyst. Solid catalysts useful in the hydrogenation process include Ni / Mo, Co / Mo, optionally deposited on oxide supports containing Fe, Cu, Zn, Ag, Pt, Pd, Ru, Rh, Ir, Mo, W, or combinations thereof, either as crystalline solids or amorphous mixtures, including oxides of Al, Si, Ti, Zr, Th, Mg, Ca, or some combination thereof. Hydrogenation may be carried out in fixed bed, trickle bed, catalytic distillation reactor, multi-tube reactor, or fluidized bed reactor, with countercurrent or cocurrent flow of feed and hydrogen.

[0073] Jet fuel is a complex mixture of hundreds of individual chemicals produced in refineries or made from various blendstocks produced elsewhere and blended at the refinery or distribution terminal. To meet technical, regulatory, and commercial requirements, several constraints must be met, including limitations on flash point, smoke point, autoignition temperature, density, freezing point (less than -47°C), limitations on aromatics content (less than 25% by weight), limitations on naphthalene content (less than 3.0% by weight), limitations on sulfur (less than 0.3% by weight), limitations on specific energy (greater than 42.8 MJ / kg), limitations on boiling range (less than 10% by weight below 205°C, the remainder between 205-300°C). It is therefore possible that two or more combinations and proportions of the various blendstocks can result in a finished jet fuel that meets all of the constraints and requirements.

[0074] (Blendstock) An embodiment of the invention is a renewable jet fuel blendstock comprising a mixture of naphthenes, aromatics, and paraffins, produced by pyrolyzing and catalytically reacting biomass in a fluidized bed reactor, quenching the product mixture by mixing with hydrocarbon liquids or by cooling, separating vapor from the quenched mixture, condensing and separating the organic phase from the vapor, separating the organic phase into a higher boiling fraction and a lower boiling fraction, hydrogenating at least a portion of the higher boiling fraction, and separating and recovering a product fraction of the renewable jet fuel blendstock boiling between 180°C and 300°C.

[0075] In one embodiment, the renewable jet fuel blendstock mixture has between 30% and 98% by weight, or between 50% and 97% by weight, or between 65% and 95% by weight naphthenes, between 3% and 50% by weight tetralins, and no more than 30% by weight, or no more than 20% by weight, or no more than 10% by weight, or no more than 5% by weight, or between 1% and 30% by weight, or between 2% and 20% by weight, or no more than 2% by weight of terpenes, as determined by mass spectrometry. % to 15% by weight, or 2% to 10% by weight of naphthalenes and alkylnaphthalenes, and 0.1% by weight or less, or 1% by weight or less, or 2% by weight or less, or 3% by weight or less, or 5% by weight or less, or 0.1% to 5% by weight, or 0.5% to 3% by weight, or 0.5% to 2% by weight of acenaphthenes, acenaphthylenes, fluorenes, phenanthrenes, and anthracenes.

[0076] In another embodiment, the renewable jet fuel blendstock has at least 30 wt%, or at least 50 wt%, or at least 65 wt%, or at least 90 wt%, or between 30 wt% and 95 wt%, or between 50 wt% and 95 wt%, or between 65 wt% and 95 wt% saturates and no more than 55 wt%, or no more than 40 wt%, or no more than 30 wt%, or no more than 7 wt%, or between 2 wt% and 75 wt%, or between 3 wt% and 40 wt%, or It may contain 4% to 26% by weight of mono-aromatic compounds, 12% or less, or 9% or less, or 5% or less, or 3% or less, or 0.5% to 20% by weight, or 1% to 12% by weight, or 2% to 7% by weight of diaromatic compounds, and 0.5% or less, or 0.3% or less, or 0.2% or less, or 0.01% to 0.5% by weight, or 0.1% to 0.3% by weight of tri-aromatic compounds.

[0077] Another embodiment of the invention is a renewable fuel blendstock or processing feedstock comprising a mixture of aromatics and naphthenes, produced by pyrolyzing and catalytically reacting biomass in a fluidized bed reactor, quenching the product mixture by mixing with hydrocarbon liquids or by cooling, separating vapor from the quenched mixture, condensing and separating the organic phase from the vapor, separating the organic phase into a higher boiling fraction and a lower boiling fraction, hydrogenating at least a portion of the higher boiling fraction, recovering condensable products therefrom, and separating the condensed products into a fraction boiling below 180°C, a fraction boiling between 180°C and 300°C, and a fraction boiling above about 300°C.The fraction boiling between 180°C and 300°C contains at least 75% by weight, or at least 85% by weight, or at least 90% by weight, or between 75% and 99.9% by weight, or between 85% and 99% by weight naphthenes, less than 20% by weight, or less than 15% by weight, or less than 10% by weight, or between 1% and 20% by weight, or between 5% and 10% by weight of the sum of benzene, toluene, and xylenes, and less than 3% by weight, or less than 2% by weight, or less than 1% by weight of benzene, toluene, and xylenes. 0.001% by weight to 3% by weight, or 0.01% by weight to 2% by weight of naphthalenes, less than 0.4% by weight, or less than 0.1% by weight, or less than 100 ppm by weight, or less than 25 ppm by weight, or 1 ppm by weight to 1000 ppm by weight, or 2 ppm by weight to 25 ppm by weight of olefins, and less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight, or 0.01 ppm by weight m to 5 ppm by weight of tricyclic aromatic compounds, less than 0.4% by weight, or less than 0.1% by weight, or less than 100 ppm by weight, or less than 25 ppm by weight, or 1 ppm by weight to 1000 ppm by weight, or 2 ppm by weight to 25 ppm by weight of olefins, less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight, or 0.01 ppm by weight to 5 ppm by weight, and m, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm to 10 ppm by weight, or 0.01 ppm to 5 ppm by weight of nitrogen, and less than 1% by weight, or less than 0.1% by weight, or less than 0.01% by weight, or less than 100 ppm by weight, or less than 1 ppm by weight, or 0.01 ppm to 1000 ppm by weight, or 0.01 ppm to 10 ppm by weight of oxygen.The lower boiling fraction may contain at least 50%, or at least 60%, or at least 65% by volume of benzene, toluene, and xylenes combined; less than 15%, or less than 10%, or less than 6% by volume of C9 or higher aromatics; less than 2%, or less than 1%, or less than 0.5% by volume of paraffins; less than 0.4%, or less than 0.1%, or less than 100 ppm by weight, or less than 25 ppm by weight of olefins; less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight of sulfur; less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight of nitrogen; and less than 1%, or less than 0.1%, or less than 0.01%, or less than 100 ppm by weight, or less than 10 ppm by weight, or less than 1 ppm by weight of oxygen.

[0078] (Fuel Blend) Another embodiment of the invention includes a mixture of a renewable fraction of the inventive process boiling between 180° C. and 300° C. with a petroleum-derived material, such as jet fuel. In some embodiments, the renewable fraction of the inventive process product boiling between 180° C. and 300° C. comprises 0.1% to 90% by volume, or 1% to 70% by volume, or 1% to 50% by volume, or 1% to 20% by volume, or 0.1% to 10% by volume, or at least 0.1% by volume, or at least 5% by volume, or at least 10% by volume, or at least 20% by volume, with the remainder of the mixture comprising conventional petroleum-derived jet fuel.

[0079] In one embodiment, a fuel blending system can be used to combine petroleum-derived jet fuel with at least a portion of the renewable biomass-derived blendstock of the present method to produce a renewable jet fuel composition. The renewable jet fuel blend composition can include petroleum-derived jet fuel in an amount of at least 80% by volume, or at least 85% by volume, or at least 90% by volume, or at least 95% by volume, and / or up to 96% by volume, or up to 98% by volume, or up to 99% by volume, or up to 99.5% by volume; or between 80% by volume and 99.5% by volume, or between 90% by volume and 98% by volume, and a renewable blendstock fraction in an amount of at least 0.1% by volume, or at least 0.5% by volume, or at least 1% by volume, or at least 5% by volume, or no more than 20% by volume, or no more than 15% by volume, or no more than 10% by volume, or no more than 5% by volume, or between 0.1% by volume and 20% by volume, or between 1% by volume and 10% by volume.

[0080] In a further aspect, the present invention provides a jet fuel blend comprising 0.1% to 90% by volume, or 1% to 70% by volume, or 1% to 50% by volume, or 1% to 20% by volume, or 0.1% to 10% by volume, or at least 0.1% by volume, or at least 5% by volume, or at least 10% by volume, or at least 20% by volume of a renewable fuel blendstock as set forth in any of the claims, with the remainder of the jet or diesel fuel blend comprising petroleum derived jet or diesel fuel.

[0081] The renewable jet fuel composition may have sulfur or aromatics, with a sulfur content of less than 0.3 wt%, or less than 0.2 wt%, or less than 0.1 wt%, or between 0.01 wt% and 0.3 wt%, or between 0.1 wt% and 0.25 wt%, and an aromatics content of less than 60 wt%, or less than 50 wt%, or less than 25 wt%, or less than 20 wt%, or less than 15 wt%, or between 5 wt% and 60 wt%, or between 5 wt% and 50 wt%, or between 10 wt% and 60 wt%, or between 20 wt% and 60 wt%, or between 20 wt% and 40 wt%, or between 20 wt% and 30 wt%.

[0082] In a further aspect, the present invention provides a renewable jet fuel blend stock mixture having from 30% to 98%, or from 50% to 97%, or from 65% to 95% naphthenes, from 3% to 50% tetralins, and from 30% or less, or from 20% or less, or from 10% or less, or from 5% to 30%, or from 2% to 20% by weight of terpenes, as determined by mass spectrometry. %, or 2% to 15% by weight, or 2% to 10% by weight of naphthalenes and alkylnaphthalenes, and 0.1% by weight or less, or 1% by weight or less, or 2% by weight or less, or 3% by weight or less, or 5% by weight or less, or 0.1% to 5% by weight, or 0.5% to 3% by weight, or 0.5% to 2% by weight of the total of acenaphthenes, acenaphthylenes, fluorenes, phenanthrenes, and anthracenes.

[0083] The invention may further be characterized by one or any combination of the following features: petroleum-derived jet fuel in an amount of at least 80% by volume, or at least 85% by volume, or at least 90% by volume, or at least 95% by volume, and / or at most 96% by volume, or at most 98% by volume, or at most 99% by volume, or at most 99.5% by volume; or in an amount between 80% by volume and 99.5% by volume, or between 90% by volume and 98% by volume; and a renewable blendstock fraction of at least 0.1% by volume, or at least 0.5% by volume, or at least 1% by volume, or at least 5% by volume, or no more than 20% by volume, or no more than 15% by volume, or no more than 10% by volume, or no more than 5% by volume; in an amount of 0.1% to 20% by volume, or 1% to 10% by volume; sulfur in an amount of less than 0.3% by weight, or less than 0.2% by weight, or less than 0.1% by weight, or 0.01% to 0.3% by weight, or 0.1% to 0.25% by weight; or aromatics in an amount of less than 60% by weight, or less than 50% by weight, or less than 25% by weight, or less than 20% by weight, or less than 15% by weight, or 5% to 60% by weight, or 5% to 50% by weight, or 10% to 60% by weight, or 20% to 60% by weight, or 20% to 40% by weight, or 20% to 30% by weight, or some combination thereof.

[0084] In a further aspect, the present invention provides a renewable distillate fuel blendstock having at least 30 wt%, or at least 50 wt%, or at least 65 wt%, or at least 90 wt%, or between 30 wt% and 95 wt%, or between 50 wt% and 95 wt%, or between 65 wt% and 95 wt% saturates and no more than 55 wt%, or no more than 40 wt%, or no more than 30 wt%, or no more than 7 wt%, or between 2 wt% and 75 wt%, or 3% to 40%, or 4% to 26% by weight of mono-aromatic compounds; 12% or less, or 9% or less, or 5% or less, or 3% or less, or 0.5% to 20% by weight, or 1% to 12% by weight, or 2% to 7% by weight of diaromatic compounds; and 0.5% or less, or 0.3% or less, or 0.2% or less, or 0.01% to 0.5% by weight, or 0.1% to 0.3% by weight of tri-aromatic compounds.

[0085] In another aspect, the present invention provides a renewable distillate fuel blendstock having at least 75 wt%, or at least 85 wt%, or at least 90 wt%, or between 75 wt% and 99.9 wt%, or between 85 wt% and 99 wt% naphthenes, less than 20 wt%, or less than 15 wt%, or less than 10 wt%, or between 1 wt% and 20 wt%, or between 5 wt% and 10 wt% benzene, toluene, and xylenes, and less than 3 wt%, or less than 2 wt% benzene, toluene, and xylenes. naphthalenes of less than 0.4% by weight, or less than 0.1% by weight, or less than 100 ppm by weight, or less than 25 ppm by weight, or 1 ppm by weight to 1000 ppm by weight, or 2 ppm by weight to 25 ppm by weight, and olefins of less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight. or 0.01 ppm by weight to 5 ppm by weight of tricyclic aromatic compounds, less than 0.4 ppm by weight, or less than 0.1 ppm by weight, or less than 100 ppm by weight, or less than 25 ppm by weight, or 1 ppm by weight to 1000 ppm by weight, or 2 ppm by weight to 25 ppm by weight of olefins, less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight, or 0.01 ppm by weight to 5 ppm by weight, It contains less than 10 ppm by weight, or less than 5 ppm by weight, or less than 2 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight, or 0.01 ppm by weight to 5 ppm by weight, and less than 1% by weight, or less than 0.1% by weight, or less than 0.01% by weight, or less than 100 ppm by weight, or less than 1 ppm by weight, or 0.01 ppm by weight to 1000 ppm by weight, or 0.01 ppm by weight to 10 ppm by weight.

[0086] The following examples demonstrate the present invention and its applicability. The present invention is capable of other different embodiments, and its several details can be modified in various obvious respects, without departing from the spirit and scope of the present invention. Therefore, the examples should be regarded as illustrative in nature, and not as limiting. Unless otherwise indicated, all parts and percentages are by weight, and all temperatures are given uncorrected in degrees Celsius.

[0087] The entire disclosures of all applications, patents and publications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein, as well as co-pending U.S. Provisional Application (Attorney Docket No. PET-3515-V01), are hereby incorporated by reference in their entirety for all jurisdictions where such incorporation is permitted.

[0088] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preferred specific embodiments set forth above are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

[0089] (Examples 1 to 3) Several samples of the organic liquid product obtained from the operation of the catalytic pyrolysis Bio-TCat pilot plant (T-Cat8) using loblolly pine as feedstock were distilled to obtain various fractions based on boiling ranges 204+, 204-320, 204-300 (all in °C), where 204+ means all material boiling at or above 204°C, and where "+" indicates that all material boiling above this temperature is included in the fraction.

[0090] The compositions of the different fractions determined by GC-MS are summarized in Table 1.

[0091] [Table 1]

[0092] (Examples 4 to 7) The 204-300° C. cut was selected as the feed for producing renewable jet fuel; analytical results for the 204-300° C. cut and products are in Table 3.

[0093] Hydrogenation experiments were carried out in a 33cc downflow packed bed reactor unit with selected feeds. The reactor unit was equipped with separate feed and product recovery sections. The catalyst was a commercial NiMo / Al2O3 catalyst that was fully sulfided in-situ before hydrogenation was started. The reactor effluent was depressurized and sent to an H2 stripper. The gas fraction was collected at the top of the stripper and analyzed via online gas chromatography. The liquid fraction was collected from the bottom of the stripper and analyzed offline. After the process was lined out to steady state, product collection and analysis was started.

[0094] Four hydrogenation runs were performed. The experimental parameters for the tests are shown in Table 2. A comparison of the product characterization data with that of the Jet A-1 specification is shown in Table 3. Detailed analytical data for the hydrogenation products is shown in Table 4.

[0095] [Table 2]

[0096] [Table 3]

[0097] [Table 4A]

[0098] [Table 4B]

[0099] [Table 4C]

[0100] Examples 4-7 show the synthesis of renewable jet fuel blend components from a portion of the product of a catalytic pyrolysis process in a conventional hydroprocess at temperatures ranging from 330-340° C. and 90-120 bar. g The results show that the product can be produced in excellent yields at hydrogen pressures in the range of 120 bar. The sulfur content and freezing point of the product are all well within the Jet A-1 specification. The aromatics content is within the Jet A-1 specification (less than 25%) at both conditions, and the maximum pressure in Example 4 is 120 bar. g In this case, naphthalenes are within the Jet A specification (less than 3%).

[0101] All of the product mixtures exhibit maximum boiling points above the Jet A-1 specification, but also show that 97% of the material boils within the Jet A-1 specification. The heavier materials can be removed by simple distillation, for example, by the methods shown in Figures 5, 6, or 7.

[0102] The densities of the product mixtures all exceed the Jet A-1 specification, so these materials cannot be used directly as jet fuel but must be blended. However, the higher density allows the fuel blend to contain more low density paraffins, such as normal alkanes, 2- and 3-methylalkanes, 2,2-dimethylalkanes, and alkylpentanes and hexanes, all with carbon numbers between 10 and 16.

[0103] The aromatics content of the blendstock can also be an advantage in jet fuel blending, for example the more aromatic products from Examples 5 and 6 can be good blendstocks for low aromatics jet fuel stocks, and the products from Examples 4 and 7 could be blended with jet fuel that is already high in aromatics to bring the aromatics content down below the 25% limit.

[0104] When numerical lower limits and numerical upper limits are recited herein, ranges from any lower limit to any upper limit are contemplated.

Claims

1. 1. A method comprising preparing a renewable jet fuel blendstock by the steps of: a) feeding biomass, catalyst, and optionally a transport fluid to a fluidized bed reactor of a catalytic pyrolysis process maintained at reactive conditions to produce a feedstock fluid product stream containing renewable aromatic compounds; b) feeding the feed fluid product stream of a) to a solids separation and stripping system to produce separated solids and a fluid product stream; c) feeding the fluid product stream of b) to a fractionation system to recover a fraction boiling between 180°C and 300°C; d) hydrogenating at least a portion of the fraction produced in c) with hydrogen under hydrogenation conditions to produce a hydrogenated fraction containing naphthalenes suitable as a jet fuel blendstock; e) optionally recovering a naphthenes-containing jet fuel blendstock from the hydrogenated fraction of d) in a product recovery system.

2. 10. The method of claim 1, wherein the biomass is wood, forestry waste, corn stover, agricultural solid waste, municipal solid waste, digestate, food waste, animal waste, carbohydrates, lignocellulosic material, xylitol, glucose, cellobiose, hemicellulose, lignin, or a combination thereof.

3. 10. The method of claim 1, wherein the renewable aromatic compounds comprise benzene, toluene, indane, indene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, trimethylbenzene, ethylbenzene, styrene, cumene, n-propylbenzene, xylene, naphthalene, methylnaphthalene, anthracene, methylanthracene, 9,10-dimethylanthracene, pyrene, phenanthrene, dimethylnaphthalene, ethylnaphthalene, 1-indenol, acenaphthalene, phenol, cresol, benzofuran, naphthalenol, methylnaphthalenol, dimethylnaphthalenol, aniline, indole, or a combination thereof.

4. 2. The method of claim 1, wherein the renewable aromatic compounds in a) comprise a minimum of 25% by volume of naphthalene, substituted naphthalenes, naphthalenols, methylnaphthalenols, and naphthalenediols, a minimum of 3% by weight of xylenols, and less than 15% by weight of the sum of phenanthrene, anthracene, and other materials.

5. 10. The process of claim 1, wherein at least a portion of the fluid product stream of b) is hydrotreated to remove heteroatoms.

6. 2. The method of claim 1, wherein the catalyst for hydrogenation in d) comprises at least one Group VIII metal and at least one Group VI metal supported on alumina, silica, silica-alumina, a mixture of alumina and silica; or the catalyst is a zeolite catalyst or a noble metal catalyst wherein the noble metal is one or more of rhodium, ruthenium, iridium, palladium, and platinum, or a combination thereof.

7. 2. The process of claim 1, wherein the hydrogenation in d) is carried out at a reaction temperature of 200° C. to 400° C. and a hydrogen pressure of 4.0 MPa to 12 MPa.

8. The liquid hourly space velocity during hydrogenation is 0.1 h －１ and the gas to liquid volume ratio at reactor operating conditions is 0.1 to 20:

1.

9. 10. The process of claim 1, wherein the hydrogenated fraction in d) suitable as jet fuel blendstock comprises a minimum of 50 wt. % hydrocarbons having 10 to 16 carbon atoms.

10. 10. The method of claim 9, wherein the hydrogenated fraction comprises tetralins, decalins, or substituted tetralins or decalins.

11. 11. The method of claim 10, wherein the hydrogenated fraction comprises 30% to 98% by weight of naphthenes, 3% to 50% by weight of tetralins, up to 30% by weight of naphthalenes and alkylnaphthalenes, and up to 0.1% by weight of the sum of acenaphthenes, acenaphthylenes, fluorenes, phenanthrenes, and anthracenes.

12. 10. The method of claim 1, wherein the fluid product stream of b) is fed to a quench vapor / liquid separation system utilizing hydrocarbon quenching or cooling to produce a liquid phase stream comprising oxygenates, C9+ aromatics, and entrained char, coke, ash, catalyst fines, and a vapor phase stream comprising carbon monoxide, carbon dioxide, hydrogen, olefins, and aromatics, wherein the aromatics of the vapor phase stream comprise benzene, toluene, xylenes, phenols, naphthols, benzofuran, ethylbenzene, styrene, naphthalene, methylnaphthalene, or combinations thereof, prior to fractionation in c).

13. 10. The method of claim 1, further comprising separating the tricyclic species in fraction c) and recycling said species to the pyrolysis in a).

14. 10. The method of claim 1, further comprising: conducting d) as a first hydrogenation over a CoMo-containing catalyst at 2.0 to 7.0 MPa to produce a partially hydrogenated stream of partially hydrogenated aromatic rings; and conducting a second hydrogenation of the aromatic compounds to reduce xylenols to benzene, toluene, and xylenes, and reduce naphthalenes to naphthenes and produce alkanes over a noble metal catalyst containing Pd, or Pt, or a combination thereof, at a pressure of 2.0 to 8.0 MPa, higher than the pressure of the first hydrogenation.

15. 10. A jet fuel blendstock produced by the method of claim 1.

16. 10. A jet fuel blendstock produced by the method of claim 9.

17. 12. A jet fuel blendstock produced by the method of claim 11.