Upgrading of Hdo Heavy Products

This application claims priority to U.S. Provisional Application No. 63/568,918, filed Mar. 22, 2024, the content of which is hereby incorporated by reference in its entirety.

Bioreforming processes can produce aromatic hydrocarbons and other useful compounds from biomass feedstocks such as cellulose, hemicellulose and lignin. For instance, cellulose and hemicellulose can be used as feedstock for various bioreforming processes, including aqueous phase reforming (APR) and hydrodeoxygenation (HDO)-catalytic reforming processes that, when integrated with hydrogenation, can convert cellulose and hemicellulose into an array of products, including hydrogen, liquid fuels, aromatics, kerosene, diesel fuel, lubricants, and fuel oils, among others. In addition, catalytic acid condensation (AC) can be used to convert oxygenates (e.g., generated by HDO) into hydrocarbons.

The HDO products represent a range of conversion products, from highly converted paraffins to completely unconverted feed (e.g., sugar in the biomass). The least desirable products from HDO (e.g., the heavy components) may not represent a large amount of the total products but generally have the highest impact on subsequent acid condensation due to their significant selectivity to form coke. It has been shown that the least desirable HDO products can be selectively purged from AC by distillation since they have the lowest volatility. This approach can significantly reduce the coke yield in AC, but at the expense of significantly lower product yield.

Accordingly, there remains a need for a method and reactor system that can upgrade these undesirable HDO products and achieve lower coking in AC without the yield loss.

Described herein includes a method for producing an oxygenate product. The method may comprise:

In another aspect, the present disclosure provides a method for producing a Ccompound. The method may comprise producing an upgraded oxygenate stream according to the oxygenate production method as described herein; and reacting the upgraded oxygenate stream in the presence of a condensation catalyst to produce the Ccompound.

The present disclosure relates to processes and systems for upgrading HDO products, in particular the heavy components that causes coking on the catalysts for downstream AC reactions. In one aspect, the present disclosure provides a method for producing an oxygenate product, the method comprising:

The present method may be carried out in an HDO heavy products upgrading reactor system. An exemplary system for upgrading of HDO heavy products is shown in. The system includes components for (1) fractionating HDO product (distillation/flash) in such a way that heavier products (e.g., by composition or boiling point) are concentrated and (2) upgrading the heavier product with Hand a suitable catalyst that promotes chemistries of hydrogenation, hydrodeoxygenation, cracking, etc. such that when fed to acid condensation (AC) reactor, the selectivity to form coke is reduced without incurring significant loss of product yield. Referring to, a feed stream including products from hydrogenation reaction (HYD) is introduced to a hydrodeoxygenation (HDO) reactionto produce an intermediate stream. The intermediate streamis then separated into a light stream(i.e., the first oxygenate stream) and a heavy residual stream. The heavy residual streamis fed into the upgrading reactoralong with H. The upgraded product(i.e., second oxygenate stream), which is produced in the upgrading reactor, can then be combined with the first oxygenate streamto form an upgraded oxygenate stream(i.e., HDO product stream). The heaviest product from the HDO reactor, such as a sump composition or product taken from product vaporizer (PV) bottoms, may be fed across a standalone reactor. This extra reactor would likely be much smaller than the primary HDO reactor. Typically, a product vaporizer can be a separator operating at a given temperature and pressure (e.g., a single stage flash unit) that solely or additionally provides separation of the first oxygenate stream and the heavy residual stream. The HDO product streamis then directed back into the AC reactors.

Another exemplary system for upgrading of HDO heavy products in shown in.shows a process flow diagram (PFD) of an integrated HDO heavy products upgrading reactor. After production of an intermediate streamin HDO reactor, the intermediate streamis separated into a light stream(i.e., the first oxygenate stream) and a heavy residual stream. The heavy residual streamis fed into an HDO upgrading reactor. The upgraded product(i.e., second oxygenate stream), produced in the upgrading reactor, is then directed into an AC reactor.

An alternative implementation of the present system for upgrading HDO heavy products is shown in. In this configuration, the upgrading reaction is performed on a recycle stream to an upgrading reactor, which is installed in the same reactor vesselas the primary HDO reactor. This concept may avoid most of the challenges around heat integration and reduces total cost.

The present method includes reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream. Feed streams useful in the present method may originate from any source but are preferably derived from biomass. Biomass generally includes three major components: Cellulose, a primary sugar source for bioconversion processes, includes high molecular weight polymers formed of tightly linked glucose monomers; Hemicellulose, a secondary sugar source, includes shorter polymers formed of various sugars; and Lignin, which includes phenylpropanoic acid moieties polymerized in a complex three-dimensional structure. For lignocellulosic biomass, the overall composition will vary based on plant variety or type and is roughly 40-50% cellulose, 20-25% hemicellulose, and 25-35% lignin, by weight percent. This composition can be deconstructed using any one or more methods, including the following, either alone or in combination: (1) thermochemical treatment using mineral acid, strong base, water at autohydrolysis conditions, gas catalyst, oxidation catalyst, and/or an organic solvent (2) enzymatic hydrolysis, and more recently (3) catalytic biomass deconstruction. Regardless of the process used, the resulting product is likely to contain the desired oxygenated hydrocarbons (e.g., lignocellulosic derivatives, lignin derivatives, cellulose derivatives, and hemicellulose derivatives) suitable for use in the present method.

The feed stream may be pure materials, purified mixtures, or raw materials such as sugars and starches derived from the processing of corn, sugarcane, beet sugars, rice, wheat, algae, or energy crops. Some applicable feed streams are also commercially available and may be obtained as by-products from other processes, such as glycerol from biodiesel fuel production. The feed streams can also be intermediates formed as part of a larger process or in the same process, such as sugar alcohols produced in the initial stage of sugar hydrogenation.

In addition to the oxygenated hydrocarbons, the feed stream may also include lignin, one or more extractives, one or more ash components, or one or more organic products (e.g., lignin derivatives). Extractives will typically include terpenoids, stilbenes, flavonoids, phenolics, aliphatics, lignans, alkanes, proteinaceous materials, and other inorganic products. Ash components will typically include Al, Ba, Ca, Fe, K, Mg, Mn, P, S, Si, Zn, etc. Other organic products will typically include 4-ethyl phenol, 4-ethyl-2-methoxy phenol, 2-methoxy-4-propyl phenol, vanillin, 4-propyl syringol, vitamin E, steroids, long chain hydrocarbons, long chain fatty acids, stilbenoids, etc.

In general, the feed stream includes any oxygenated hydrocarbon having three or more carbon atoms and an oxygen-to-carbon ratio of between about 0.5:1 to about 1:1.2. In one aspect, the oxygenated hydrocarbon has 3 to 12 carbon atoms or 3 to 6 carbon atoms. In another aspect, the oxygenated hydrocarbon has more than 12 carbon atoms. Non-limiting examples of preferred oxygenated hydrocarbons include monosaccharides, disaccharides, trisaccharides, polysaccharides, oligosaccharides, sugars, sugar alcohols, sugar degradation products, alditols, hemicelluloses, cellulosic derivatives, lignocellulosic derivatives, lignin derivatives, hemicellulose derivatives, starches, organic acids, polyols, and the like. Preferably, the oxygenated hydrocarbon includes polysaccharides, oligosaccharides, trisaccharides, disaccharides, monosaccharides, sugar, sugar alcohols, sugar degradation products, and other polyhydric alcohols. More preferably, the oxygenated hydrocarbon is a trisaccharide, a disaccharide, a sugar, such as glucose, fructose, sucrose, maltose, lactose, mannose or xylose, or a sugar alcohol, such as arabitol, crythritol, glycerol, isomalt, lactitol, maltitol, mannitol, sorbitol, xylitol, arabitol, or glycol. The oxygenated hydrocarbons may also include alcohols derived by the hydrogenation of the foregoing.

Alternatively, the feed stream may include oxygenated hydrocarbons solvated by a solvent. Non-limiting examples of solvents include organic solvents, such as ionic liquids, acetone, ethanol, 4-methyl-2-pentanone, and other oxygenated hydrocarbons; dilute acids, such as acetic acid, oxalic acid, hydrofluoric acid; bioreforming solvents; and water. The solvents may be from external sources, recycled, or generated in-situ, such as in-situ generated oxygenated compounds.

To produce the intermediate stream, the oxygenated hydrocarbon is combined with water to provide an aqueous feed stream having a concentration effective for causing the formation of the desired reaction products. The water-to-carbon ratio on a molar basis may be from 0.5:1 to 100:1, including ratios such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 25:1, 50:1, 75:1, 100:1, and any ratios there between. The feed stream may also be characterized as a solution having at least 1.0 weight percent (wt %) of the total stream as an oxygenated hydrocarbon. For instance, the solution may include one or more oxygenated hydrocarbons, with the total concentration of the oxygenated hydrocarbons in the solution being at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or greater by weight, including any percentages between, and depending on the oxygenated hydrocarbons used. In one embodiment, at least some of the oxygenated hydrocarbons have four or more carbon atoms. In such embodiments the feed stream includes at least about 1%, 5%, 10%, 20%, 30%, 40%, 50%, or 60%, 70%, 80%, or 90% by weight of oxygenated hydrocarbons having four or more carbon atoms. Exemplary oxygenated hydrocarbons having four or more carbon atoms are sugars, such as glucose, fructose, sucrose or xylose, or sugar alcohols, such as sorbitol, mannitol, glycerol or xylitol. Water-to-carbon ratios and percentages outside of the above stated ranges are also included.

The oxygenated hydrocarbons may be any water-soluble oxygenated hydrocarbon having one or more carbon atoms and at least one oxygen atom (COhydrocarbons). In one embodiment, the “oxygenated hydrocarbon” may include carbohydrates (e.g., monosaccharides, disaccharides, oligosaccharides, polysaccharides, and starches), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols and other polyhydric alcohols (e.g., diols, triols, polyols), and/or sugar degradation products (e.g., hydroxymethyl furfural (HMF), levulinic acid, formic acid, furfural, etc.). In one embodiment, the oxygenated hydrocarbon comprises polysaccharides, disaccharides, monosaccharides, cellulose derivatives, lignin derivatives, hemicellulose, sugars, sugar alcohols or a mixture thereof. In another embodiment, the oxygenated hydrocarbon comprises a COhydrocarbon, or a COhydrocarbon. In yet another embodiment, the COhydrocarbon comprises a sugar alcohol, sugar, monosaccharide, disaccharide, alditol, cellulosic derivative, lignocellulosic derivative, glucose, fructose, sucrose, maltose, lactose, mannose, xylose, arabitol, erythritol, glycerol, isomalt, lactitol, malitol, mannitol, sorbitol, xylitol, or a mixture thereof. In another embodiment, the oxygenated hydrocarbon further comprises recycled COhydrocarbon.

The term “hydrodeoxygenation catalyst” (HDO catalyst) refers to a catalyst that catalyzes a process that removes oxygen from oxygen-containing compounds in the presence of hydrogen. Suitable HDO catalysts and processes include, for example, those described in WO 2014/152370 and WO/2023/064565, all of which are incorporated herein by reference.

In some embodiments, the HDO catalyst is composed of a heterogeneous catalyst having one or more materials capable of catalyzing a reaction between hydrogen and a feedstock solution to remove one or more of the oxygen atoms from the feedstock solution to produce one or more oxygenate. In some embodiments, the HDO catalyst is composed of one or more metal adhered to a support and may include, without limitation, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof. The HDO catalyst may include these elements alone or in combination with one or more promoters, such as Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, TI, and combinations thereof. In some embodiments, the HDO catalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W or Mo. In some embodiments, the HDO catalyst includes Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In some embodiments, the HDO catalyst includes Fe, Re and at least Cu or one Group VIIIB transition metal. In some embodiments, the metal of the HDO catalyst comprises Pd, W, Mo, Ni, Pt, Ru, or a combination thereof. In some embodiments, the HDO catalyst comprises a promoter. As an example, the promoter of the deoxygenation catalyst can comprise Sn, W, or a combination thereof. The support may include a nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacids, kieselguhr, hydroxyapatite, or a mixture thereof. In some embodiments, the support comprises zirconia.

The aqueous feed stream is reacted with hydrogen in the presence of the HDO catalyst at temperatures, pressures, and weight hourly space velocities effective to produce the desired oxygenate products. The specific oxygenates produced will depend on various factors, including the feedstock solution, reaction temperature, reaction pressure, water concentration, hydrogen concentration, the reactivity of the catalyst, and the flow rate of the feedstock solution as it affects the space velocity (the mass/volume of reactant per unit of catalyst per unit of time), gas hourly space velocity (GHSV), and weight hourly space velocity (WHSV). For example, an increase in flow rate, and thereby a reduction of the feed stream exposure to the HDO catalyst over time, will limit the extent of the reactions that may occur, thereby causing increased yield for higher level di- and tri-oxygenates, with a reduction in ketone, alcohol, and cyclic ether yields.

In general, the reaction may include a temperature gradient to allow partial deoxygenation of the oxygenated hydrocarbon at temperatures below the caramelization point of a feedstock, from which the aqueous feed stream is generated. Including a temperature gradient helps prevent the oxygenated hydrocarbons in the feed stream from condensing (e.g., caramelizing) on the catalyst and creating a substantial pressure drop across the reactor, which can lead to inoperability of the reactor. The caramelization point, and therefore the required temperature gradient, will vary depending on the feedstock. In one embodiment, the temperature gradient is from about 170° C. to 300° C. or between about 200° C. to 290° C. In another embodiment, a temperature gradient is not employed.

Operating pressures up to about 2000 psig can be used to help maintain the carbon backbone, minimize the amount of light organic acids and ketones that are formed, and increasing the product selectivity towards alcohols. By increasing operating pressures, the thermodynamics of the reaction favors alcohols to ketones and organic acids, thereby shifting the product selectivity, maintaining the carbon backbone, and improving product yields. Light organic acids are particularly undesirable products as they are highly corrosive. Producing fewer light organic acids provides more flexibility with regards to materials of construction of a reactor system because corrosion is less of an issue.

The reaction temperature and pressures are preferably selected to maintain at least a portion of a feedstock, from which the aqueous feed stream is generated, in the liquid phase at the reactor inlet. It is recognized, however, that temperature and pressure conditions may also be selected to more favorably produce the desired products in the vapor-phase. In general, the reaction should be conducted at process conditions wherein the thermodynamics of the proposed reaction are favorable. For instance, the minimum pressure required to maintain a portion of the feedstock in the liquid phase will likely vary with the reaction temperature. As temperatures increase, higher pressures will generally be required to maintain the feedstock in the liquid phase, if desired. Pressures above that required to maintain the feedstock in the liquid phase (i.e., vapor-phase) are also suitable operating conditions.

In condensed phase liquid reactions, the pressure within the reactor must be sufficient to maintain the reactants in the condensed liquid phase at the reactor inlet. For liquid phase reactions, the reaction temperature should be greater than about 100° C., or 120° C., or 150° C., or 180° C., or 200° C., and less than about 300° C., or 290° C., or 270° C., or 250° C., or 220° C. The reaction pressure should be greater than about 70 psig, or 145 psig, or 300 psig, or 500 psig, or 750 psig, or 1050 psig, and less than about 2000 psig, or 1950 psig, or 1900 psig, or 1800 psig. In one embodiment, the reaction temperature is between about 120° C. and 300° C., or between about 200° C. and 300° C., or between about 270° C. and 290° C., and the reaction pressure is between about 145 and 1950 psig, or between about 1000 and 1900 psig, or between about 1050 and 1800 psig.

For vapor phase reactions, the reaction should be carried out at a temperature where the vapor pressure of the oxygenated hydrocarbon is at least about 0.1 atm, preferably higher (e.g., 350 psi), and the thermodynamics of the reaction are favorable. This temperature will vary depending upon the specific oxygenated hydrocarbon compound used, but is generally greater than about 100° C., or 120° C., or 250° C., and less than about 600° C., or 500° C., or 400° C. for vapor phase reactions. In one embodiment, the reaction temperature is between about 120° C. and about 500° C., or between about 250° C. and about 400° C.

In general, the HDO reaction should be conducted under conditions where the residence time of the aqueous feed stream over the catalyst is appropriate to generate the desired products. For example, the WHSV for the reaction may be at least 0.01 gram of oxygenated hydrocarbon per gram of catalyst per hour (g/g-hr). In some embodiments, the WHSV for the HDO reaction is 0.01 to about 40.0 g/g-hr, such as about 0.05 to about 40.0, about 1.0 to about 40.0, about 5.0 to about 40.0, or about 1.0 to about 20.0 g/g-hr. The WHSV can be, for example, about 0.05, 0.1, 0.25, 0.5, 0.75, 1.0, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, or 40 g/g-hr.

In some embodiments, the amount of hydrogen fed to the HDO reaction ranges from 0-2400%, 5-2400%, 10-2400%, 15-2400%, 20-2400%, 25-2400%, 30-2400%, 35-2400%, 40-2400%, 45-2400%, 50-2400%, 55-2400%, 60-2400%, 65-2400%, 70-2400%, 75-2400%, 80-2400%, 85-2400%, 90-2400%, 95-2400%, 98-2400%, 100-2400%, 200-2400%, 300-2400%, 400-2400%, 500-2400%, 600-2400%, 700-2400%, 800-2400%, 900-2400%, 1000-2400%, 1100-2400%, or 1150-2400%, or 1200-2400%, or 1300-2400%, or 1400-2400%, or 1500-2400%, or 1600-2400%, or 1700-2400%, or 1800-2400%, or 1900-2400%, or 2000-2400%, or 2100-2400%, or 2200-2400%, or 2300-2400%, based on the total number of moles of the oxygenated hydrocarbon(s) in the feedstock, including all intervals between. The hydrogen may be external hydrogen or recycled hydrogen. The term “external H” refers to hydrogen that does not originate from the feedstock solution but is added to the reactor system from an external source. The term “recycled H” refers to unconsumed hydrogen, which is collected and then recycled back into the reactor system for further use.

The present method further includes fractionating the intermediate stream into a first oxygenate stream and a heavy residual stream. The chemical composition of the oxygenate product streams may be characterized by H: Cratio (H/C). As used herein, the term “H:Cratio” is based on the amount of carbon, oxygen and hydrogen in the feed, and is calculated as follows: H:C=H−2O/C, where H represents the number of hydrogen atoms, O represents the number of oxygen atoms, and C represents the number of carbon atoms. Water and molecular hydrogen (diatomic hydrogen, H) are excluded from the calculation. The H:Cratio applies both to individual components and to mixtures of components but is not valid for components which contain atoms other than carbon, hydrogen, and oxygen. For mixtures, the C, H, and O are summed over all components exclusive of water and molecular hydrogen. In some embodiments, the H:Cratio may be controlled or modulated by varying the hydrodeoxygenation catalyst and operating conditions (e.g., temperature, pressure, WHSV, feed source selection and concentration).

In some embodiments, the intermediate stream has a H/Cof 1.6 or less. For example, the H/Cof the intermediate stream can be less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.1, or less than 1.0. The H/Cof the intermediate stream can be at least 0.5, at least 0.8, at least 0.9, at least 1.0, at least 1.1, at least 1.2, at least 1.3, at least 1.4 or at least 1.5. In some embodiments, the intermediate stream comprises a H: Cfrom 0.8 to 1.5, from 1.0 to 1.5, from 1.1 to 1.5, or from 1.2 to 1.5.

The intermediate stream can be fractionated into the first oxygenate stream and the heavy residual stream by known technologies, including but not limited to distillation or phase separation. In some embodiments, the fractionation is carried out by distillation.

The first oxygenate stream includes a first pool of COhydrocarbons, which are compounds having 1 or more carbon atoms and between 1 and 3 oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxy carboxylic acids, carboxylic acids, diols, triols, and mixtures thereof. In some embodiments, the COhydrocarbons have from 1 to 7 carbon atoms, such as from 1 to 6 carbon atoms, or from 2 to 6 carbon atoms, or from 3 to 6 carbon atoms.

Exemplary alcohols in the deoxygenation product streammay include, without limitation, primary, secondary, linear, branched or cyclic Calcohols, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanonol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomers thereof.

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

Exemplary aldehydes may include, without limitation, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal, and isomers thereof.

Exemplary carboxylic acids may include, without limitation, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isomers and derivatives thereof, including hydroxylated derivatives, such as 2-hydroxybutanoic acid and lactic acid.

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

Exemplary triols may include, without limitation, glycerol, 1,1,1 tris (hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane, hexanetriol, and isomers thereof. Exemplary furans and furfurals include, without limitation, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methyl furan, 2-ethyl-tetrahydrofuran, 2-ethyl furan, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethyl furan, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl) ethanol, hydroxymethyltetrahydrofurfural, and isomers thereof.

The first oxygenate stream may have a H:Cratio between 0.5 and 2.0. For example, the H/Cof the first oxygenate stream can be from 0.5 to 1.8, from 0.8 to 1.8, from 1.0 to 1.8, from 1.0 to 1.6, or from 1.2 to 1.6.

The heavy residual stream can include water, unreacted components of the feed stream, and/or products of the hydrodeoxygenation reaction. For example, the heavy residual stream can be a mixture of water and at least one component selected from sugar alcohols, poly-oxygenates, diols, hydroxy cyclic ethers, and dioxygenates. The heavy residual stream may include Ccompounds, such as C, C, C, Cor Ccompounds. The heavy residual stream may include aromatic compounds, nonaromatic compounds, or both.

On average, the heavy residual stream may have an increased content of higher molecular weight compounds (e.g., with greater number of carbon and/or oxygen atoms) than the first oxygenate stream. As a result, the heavy residual stream may be separated from the first oxygenate stream due to the differences in their physical properties, such as boiling point, density, or viscosity. In some embodiments, the heavy residual stream has a boiling point that is higher than a boiling point of the first oxygenate stream. The difference in boiling points may be utilized to fractionate the intermediate stream in the first oxygenate stream and the heavy residual stream.

The heavy residual stream may have an H/Cthat is lower than the H/Cof the first oxygenate stream. In some embodiments, the heavy residual stream has a H/Cof 1.3 or less. For example, the H/Cof the heavy residue stream can be from 0.5 to 1.2, from 0.8 to 1.1, or from 0.8 to 1.0.

In some embodiments, the heavy residual stream has a water content of less than 25% by weight. The water content can be less than 23%, less than 22%, less than 21%, less than 20%, less than 18%, less than 18%, or less than 17% by weight. The water content can be at least 0.5%, at least 2%, at least 5%, at least 10%, at least 12%, or at least 15%. In some embodiments, the heavy residual stream has a water content of about 0.5% to about 20% by weight.

The present method further comprises reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a second oxygenate stream comprising a second pool of COhydrocarbons. The upgrading catalyst may catalyze an upgrading reaction of the heavy residual stream, which including hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof. As a result of the upgrading reaction, the compounds in the heavy residual stream can be transformed to other products that cause less coking for the subsequent AC reaction.

In some embodiment, the upgrading catalyst can be a hydrodeoxygenation catalyst, as described above. In some embodiments, the hydrodeoxygenation catalyst for producing the intermediate stream is a first hydrodeoxygenation catalyst and the upgrading catalyst is a second hydrodeoxygenation catalyst. The first and second hydrodeoxygenation catalysts can be identical or different. In some embodiments, the first and second hydrodeoxygenation catalysts are identical.

In some embodiments, the upgrading catalyst is heterogeneous and contains palladium, molybdenum, and tin. In some embodiments, the upgrading catalyst may also include tungsten. The upgrading catalyst may also contain another Group VIII transition metal (i.e., Pt, Ni, Co, Rh, Ir, Ru, Fc, Os, etc.) as a substitute or supplement for the palladium, and/or be disposed on an acidic support.

In some embodiments, loading of the palladium or other Group VIII transition metal is in the range of from 0.05 wt % to 5.0 wt %, based on the total weight of the upgrading catalyst. The content of palladium can be, for example, 0.075%, 0.10%, 0.20%, 0.50%, 0.75%, 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, or 5.00% by weight. In some embodiments, the upgrading catalyst comprises from greater than 0.05 wt % to less than 5.0 wt % palladium, based on the total weight of the catalyst.

In some embodiments, loading of the molybdenum is in the range of from 0.05 wt % to 10 wt %, based on the total weight of the upgrading catalyst. The content of molybdenum can be, for example, 0.075%, 0.10%, 0.20%, 0.50%, 0.75%, 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 6.00%, 8.50%, or 10.0% by weight. In some embodiments, the upgrading catalyst comprises from greater than 0.05 wt % to less than 10.0 wt % molybdenum, based on the total weight of the catalyst.

In some embodiments, loading of the tin is in the range of from 0.0125 wt % to 5 wt %, based on the total weight of the upgrading catalyst. The content of tin can be, for example, 0.025%, 0.050%, 0.075%, 0.10%, 0.20%, 0.50%, 0.75%, 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, or 5.00% by weight. In some embodiments, the upgrading catalyst comprises from greater than 0.0125 wt % to less than 5.0 wt % tin, based on the total weight of the catalyst.

In some embodiments, loading of the tungsten is in the range of from 0.1 wt % to 20 wt %, based on the total weight of the upgrading catalyst. The content of tungsten can be, for example, 0.20%, 0.50%, 0.75%, 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, or 5.00% by weight. In some embodiments, the upgrading catalyst comprises from greater than 0.1 wt % to less than 20 wt % tungsten, based on the total weight of the catalyst.

The atomic ratio of the palladium to molybdenum can be in the range of from 0.25:1 to 10:1, including but not limited to 0.50:1, 1:1, 2.5:1, 5:1, and 7.5:1. The atomic ratio of the tin to molybdenum can be in the range of about 0.125:1 to 10:1, including but not limited to 0.5:1, 1:1, 2.5:1, 5:1, and 7.5:1. The atomic ratio of palladium to tin can be in the range of about 0.125:1 to 10:1, including but not limited to 0.5:1, 1:1, 2.5:1, 5:1, and 7.5:1. If an alternative Group VIII transition metal is employed, the atomic ratio can be that of palladium above. In some embodiments, the catalyst is adhered to a tungsten-modified support, and the combination of the catalyst materials is from 0.30 wt % to 18 wt % of the support. In some embodiments, the catalyst is adhered to a tungsten-modified acidic support, with the combination of the catalyst materials from 0.30 wt % to 18 wt % of the support.