UPGRADING OF HDO HEAVY PRODUCTS

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

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.

BACKGROUND

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.

SUMMARY OF THE INVENTION

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

• • (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream;
  • (ii) fractionating the intermediate stream into a first oxygenate stream comprising a first pool of C₁₊O_1-3 hydrocarbons and a heavy residual stream;
  • (iii) 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 C₁₊O_1-3 hydrocarbons, wherein the upgrading catalyst catalyzes hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream; and
  • (iv) combining at least a portion of the first oxygenate stream and at least a portion of the second oxygenate stream to form an upgraded oxygenate stream.

In another aspect, the present disclosure provides a method for producing a C₄₊ compound. 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 C₄₊ compound.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A shows an exemplary system for upgrading of HDO heavy products. FIG. 1B shows a process flow diagram (PFD) of one embodiment of integrated HDO heavy products upgrading reactors.

FIG. 2. shows an alternative implementation of HDO heavies upgrading.

FIG. 3 illustrates the relationship between purged HDO bottoms material and coking in AC.

FIG. 4 shows certain benefit of the present system for upgrading HDO heavy products.

FIG. 5 shows reactor loading diagram for upgrading catalysts testing.

FIG. 6 demonstrates breakdown of PV bottoms composites used as feedstock for testing (AP9204-1).

FIG. 7 shows composite H/C_eff of the products of PV bottoms upgrading for two standard HDO catalyst formulations (numbers on chart refer to WC #, essentially days on stream).

FIG. 8 shows composite H/C_eff of the products of PV bottoms upgrading for two semi-commercial catalyst formulations (numbers on chart refer to WC #, essentially days on stream).

FIG. 9 shows composite H/C_eff of the products of PV bottoms upgrading for two other virent catalyst formulations (numbers on chart refer to WC #, essentially days on stream).

FIG. 10 shows composite H/C_eff of the products of PV bottoms upgrading for HDO catalyst stability test (numbers on chart refer to WC #, essentially days on stream).

FIG. 11 shows composite H/C_eff of the products of PV bottoms upgrading as a function of time for HDO catalyst stability test.

FIG. 12 demonstrates residue of products from upgrading catalyst testing as a function of temperature.

FIG. 13 shows picture of feed and products from HDO catalyst upgrading testing.

FIG. 14 shows reactor loading diagram for testing the upgrading conditions.

FIG. 15 shows breakdown of PV bottoms composites used as feedstock for testing upgrading conditions.

FIG. 16 shows H/C_eff of upgrading reactor products as a function of reactor inlet temperature.

FIG. 17 shows H/C_eff of upgrading reactor products as a function of upgrading reactor WHSV.

FIG. 18 shows H/C_eff of upgrading reactor products as a function of upgrading reactor pressure.

FIG. 19 shows H/C_eff of upgrading reactor products as a function of feedstock H/C_eff (PV Bottoms)

FIG. 20 shows H/C_eff of upgrading reactor products as a function of water content of the feedstock.

DETAILED DESCRIPTION

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:

• • (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream;
  • (ii) fractionating the intermediate stream into a first oxygenate stream comprising a first pool of C₁₊O_1-3 hydrocarbons and a heavy residual stream;
  • (iii) 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 C₁₊O_1-3 hydrocarbons, wherein the upgrading catalyst catalyzes hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream; and
  • (iv) combining at least a portion of the first oxygenate stream and at least a portion of the second oxygenate stream to form an upgraded oxygenate stream.

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 FIG. 1A. 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 H₂ and 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 FIG. 1A, a feed stream including products from hydrogenation reaction (HYD) is introduced to a hydrodeoxygenation (HDO) reaction 1 to produce an intermediate stream 2. The intermediate stream 2 is then separated into a light stream 3 (i.e., the first oxygenate stream) and a heavy residual stream 4. The heavy residual stream 4 is fed into the upgrading reactor 5 along with H₂. The upgraded product 6 (i.e., second oxygenate stream), which is produced in the upgrading reactor 5, can then be combined with the first oxygenate stream 3 to form an upgraded oxygenate stream 7 (i.e., HDO product stream). The heaviest product from the HDO reactor 1, 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 1. 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 stream 7 is then directed back into the AC reactors.

Another exemplary system for upgrading of HDO heavy products in shown in FIG. 1B. FIG. 1B shows a process flow diagram (PFD) of an integrated HDO heavy products upgrading reactor. After production of an intermediate stream 2 in HDO reactor 1, the intermediate stream 2 is separated into a light stream 3 (i.e., the first oxygenate stream) and a heavy residual stream 4. The heavy residual stream 4 is fed into an HDO upgrading reactor 5. The upgraded product 6 (i.e., second oxygenate stream), produced in the upgrading reactor 5, is then directed into an AC reactor.

An alternative implementation of the present system for upgrading HDO heavy products is shown in FIG. 2. In this configuration, the upgrading reaction is performed on a recycle stream to an upgrading reactor 5, which is installed in the same reactor vessel 10 as the primary HDO reactor 1. This concept may avoid most of the challenges around heat integration and reduces total cost.

Feed Stream

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 (C₁₊O₁₊ hydrocarbons). 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 C_1-12O_1-11 hydrocarbon, or a C_1-6O_1-6 hydrocarbon. In yet another embodiment, the C_1-12O_1-11 hydrocarbon 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 C₁₊O₁₊ hydrocarbon.

HDO Catalyst and HDO Reaction

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 H₂” 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 H₂” refers to unconsumed hydrogen, which is collected and then recycled back into the reactor system for further use.

Oxygenate Products

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: C_eff ratio (H/C_eff). As used herein, the term “H:C_eff ratio” is based on the amount of carbon, oxygen and hydrogen in the feed, and is calculated as follows: H:C_eff=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, H₂) are excluded from the calculation. The H:C_eff ratio 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:C_eff ratio 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/C_eff of 1.6 or less. For example, the H/C_eff of 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/C_eff of 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: C_eff from 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 C₁₊O_1-3 hydrocarbons, 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 C₁₊O_1-3 hydrocarbons 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 stream 18 may include, without limitation, primary, secondary, linear, branched or cyclic C₁₊ alcohols, 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:C_eff ratio between 0.5 and 2.0. For example, the H/C_eff of 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 C₈₊ compounds, such as C₈, C₉, C₁₀, C₁₁ or C₁₂₊ compounds. 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/C_eff that is lower than the H/C_eff of the first oxygenate stream. In some embodiments, the heavy residual stream has a H/C_eff of 1.3 or less. For example, the H/C_eff of 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.

Upgrading Catalyst and Upgrading Reaction

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 C₁₊O_1-3 hydrocarbons. 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.

The upgrading catalyst may include a support suitable for suspending the catalyst in a reaction stream. The support should be one that provides a stable platform for the catalyst and reaction conditions. The support may take any form that is stable at the chosen reaction conditions to function at the desired levels, and specifically stable in aqueous feed stream solutions, i.e., the support is hydrothermally stable. Such supports include, without limitation, nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, zeolites, tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, iron aluminate, phosphated alumina, theta alumina, niobia, niobia phosphate, oxides of the foregoing, and mixtures thereof. Nanoporous supports such as zeolites, carbon nanotubes, or carbon fullerene may also be used.

In some embodiments, the support includes zirconia. The zirconia may be produced, for example, via precipitation of zirconium hydroxide from zirconium salts, through sol-gel processing, or any other method. The zirconia is preferably present in a crystalline form achieved through calcination of the precursor material at temperatures exceeding 400° C. and may include both tetragonal and monoclinic crystalline phases. A modifying agent may be added to improve the textural or catalytic properties of the zirconia. Such modifying agents include, without limitation, sulfate, tungstenate, phosphate, titania, silica, and oxides of Group IIIB metals, especially Ce, La, or Y.

In some embodiments, the upgrading catalyst support further includes a modifier. For example, the support can be modified by treating the support with a modifier selected from the group consist of tungsten, titania, sulfate, phosphate, or silica. In some embodiments, the upgrading catalyst includes Pd, Mo, Sn, and/or W on tungsten-modified monoclinic zirconia. In some embodiment, the upgrading catalyst includes Pd, Mo, Sn, and/or W on tungsten-modified tetragonal zirconia.

In some embodiments, the upgrading catalyst catalyzes hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream. In some embodiments, the upgrading catalyst catalyzes a hydrogenation or a hydrocracking reaction in addition to the HDO reaction of the heavy residual stream.

In some embodiments, the upgrading catalyst is a hydrogenation catalyst. The hydrogenation catalyst can comprise a support and Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, Re, Cu, alloys thereof, or a combination thereof. In some embodiments, the hydrogenation catalyst further comprises Ag, Au, Cr, Zn, Mn, Sn, Bi, Mo, W, B, P, alloys thereof, or a combination thereof. In some embodiments, the support comprises any one of the supports selected from a nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, and a mixture thereof. In some embodiments, the support is a hydrogen peroxide treated carbon. In some embodiments, the support is modified by treating the support with a modifier being silanes, alkali compounds, alkali earth compounds, or lanthanides. In some embodiments, the support comprises carbon nanotubes, carbon fullerenes, and zeolites.

In some embodiments, the upgrading catalyst is a hydrocracking catalyst. Hydrocracking catalysts are bifunctional catalyst capable of rearranging and breaking hydrocarbon chains as well as adding hydrogen to aromatics and olefins to produce naphthenes and alkanes. Hydrocracking catalysts combine an acid function and a hydrogenating function. The acid function can be carried by supports with a large surface area and having a superficial acidity, such as halogenated aluminas, zeolites, amorphous silica-aluminas, clays, or mixtures thereof. The hydrogenating function can be carried either by one or more transition metals, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and/or platinum, or by a combination of molybdenum and tungsten. The catalysts of catalytic hydrocracking can be made up of weak acid supports.

In some embodiments, the HDO reaction of aqueous feed stream with hydrogen to produce the intermediate stream is carried out in a first reactor and the upgrading reaction of the heavy residual stream is carried out in a second reactor. In some embodiments, the first and second reactors are different, such that the conditions in each reactor can be controlled independently. In some embodiments, the HDO reaction and the upgrading reaction are carried out in a single reactor. For example, the HDO catalyst and the upgrading catalyst can be the same and the HDO and upgrading reactions can be carried out in a single reactor containing such catalyst. The first and second reactors can be contained in a single reactor vessel. For example, the HDO and upgrading reactions can be carried out in the first and second reactors, respectively, which are contained in a single reactor vessel. In some embodiments, the hydrodeoxygenation catalyst and upgrading catalyst are selected independently of whether the first and second reactors are in a same reactor vessel or different reactor vessels. For example, the catalyst can be the same or different while the first and second reactors are in the same reactor vessel. Alternatively, the catalyst can be the same or different while the first and second reactors are in different reactor vessels.

In some embodiments, the second reactor has a reaction pressure from 70 psig to 2000 psig, including but not limited to, from 100 to 1800 psig, from 100 to 1500 psig, from 100 to 1200 psig, from 100 to 1000 psig, from 100 to 800 psig, or from 100 to 500 psig, The pressure can be, for example, 145 psig, 300 psig, 500 psig, 750 psig, 1000 psig, 1200 psig, 1500 psig, or 1800 psig.

In some embodiments, the second reactor has a reaction temperature from 100° C. to 300° C., including but not limited to, from 120° C. to 300° C., from 150° C. to 300° C., from 200° C. to 300° C., and from 200° C. to and 270° C. The reaction temperature in the second reactor can be, for example, 120° C., 140° C., 160° C., 180° C., 200° C., 220° C., 240° C., 260° C., or 280° C.

In some embodiments, the heavy residual stream is contacted with the upgrading catalyst at a weight hour space velocity (WHSV) of at least 0.01 grams of the oxygenated hydrocarbon per gram of upgrading catalyst (e.g., heterogeneous catalyst) per hour (g/g · hr-1 or hr-1). In some embodiments, the WHSV is from 0.01 to 40.0 hr-1, including but not limited to, 0.01, 0.025, 0.05, 0.075, 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, and 40 hr-1.

In some embodiments, the upgrading catalyst is in operation for at least 20 days without a regeneration of the catalyst, including but not limited to, at least 30 days, at least 40 days, at least 50 days, at least 60 days, at least 90 days, at least 120 days, at least 150 days, at least 180 days, at least 210 days, at least 240 days, at least 270 days, and at least 300 days. In some embodiments, the catalysts may operate for a duration of from 20 days to 300 days, from 30 days to 270 days, from 30 days to 240 days, from 30 days to 210 days, from 30 days to 180 days, from 30 days to 150 days, from 30 days to 120 days, from 30 days to 90 days, or from 30 days to 60 days without a regeneration of the catalyst.

At least a portion of the first oxygenate stream and at least a portion of the second oxygenate stream can be combined to form an upgraded oxygenate stream. In some embodiments, all of the first oxygenate stream and all of the second oxygenate stream are combined to form the upgraded oxygenate stream.

In another aspect, the present disclosure provides a method for producing a C₄₊ compound, which comprises producing the upgraded oxygenate stream according to the method as described herein and reacting the upgraded oxygenate stream in the presence of a condensation catalyst to produce the C₄₊ compound.

The C₄₊ compound comprises a member selected from the group consisting of C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene, aryl, fused aryl, and a mixture thereof. In one exemplary embodiment, the C₄₊ alkane comprises a branched or straight chain C_4-30 alkane, or a branched or straight chain C_4-9, C_7-14, C_12-24 alkane, or a mixture thereof. In another exemplary embodiment, the C₄₊ alkene comprises a branched or straight chain C_4-30 alkene, or a branched or straight chain C_4-9, C_7-14, C_12-24 alkene, or a mixture thereof. In another exemplary embodiment, the C₅₊ cycloalkane comprises a mono-substituted or multi-substituted C₅₊ cycloalkane, and at least one substituted group is a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₁₊ alkylene, a phenyl, or a combination thereof, or a branched C_3-12 alkyl, a straight chain C_1-12 alkyl, a branched C_3-12 alkylene, a straight chain C_1-12 alkylene, a phenyl, or a combination thereof, or a branched C_3-4 alkyl, a straight chain C_1-4 alkyl, a branched C_3-4 alkylene, straight chain C_1-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the C₅₊ cycloalkene comprises a mono-substituted or multi-substituted C₅₊ cycloalkene, and at least one substituted group is a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenyl, or a combination thereof, or a branched C_3-12 alkyl, a straight chain C_1-12 alkyl, a branched C_3-12 alkylene, a straight chain C₂-12 alkylene, a phenyl, or a combination thereof, or a branched C_3-4 alkyl, a straight chain C_1-4 alkyl, a branched C_3-4 alkylene, straight chain C_2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the aryl comprises an unsubstituted aryl, or a mono-substituted or multi-substituted aryl, and at least one substituted group is a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenyl, or a combination thereof, or a branched C_3-12 alkyl, a straight chain C_1-12 alkyl, a branched C_3-12 alkylene, a straight chain C₂-12 alkylene, a phenyl, or a combination thereof, or a branched C_3-4 alkyl, a straight chain C_1-4 alkyl, a branched C_3-4 alkylene, a straight chain C_2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the fused aryl comprises an unsubstituted fused aryl, or a mono-substituted or multi-substituted fused aryl, and at least one substituted group is a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenyl, or a combination thereof, or a branched C_3-4 alkyl, a straight chain C_1-4 alkyl, a branched C_3-4 alkylene, a straight chain C_2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the C₄₊ alcohol comprises a compound according to the formula R¹—OH, wherein R¹ is a branched C₄₊ alkyl, straight chain C₄₊ alkyl, a branched C₄₊ alkylene, a straight chain C₄₊ alkylene, a substituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl, or a combination thereof. In another exemplary embodiment of method of making the C₄₊ compound, the C₄₊ ketone comprises a compound according to the formula

wherein R³ and R⁴ are independently a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a substituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl, or a combination thereof.

The condensation catalyst is generally a catalyst capable of forming longer chain compounds by linking two molecules (e.g., oxygen containing species) through a new carbon-carbon bond, and converting the resulting compound to a hydrocarbon, alcohol or ketone. In some embodiments, the condensation catalyst is an acid condensation catalyst. The condensation catalyst may include, without limitation, carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, magnesium oxides, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropolyacids, inorganic acids, acid modified resins, base modified resins, and combinations thereof. The condensation catalyst may include the above alone or in combination with a modifier, such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The condensation catalyst may also include a metal, such as Cu, Ag, Au, Pt, Ni, Fc, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, to provide a metal functionality.

The condensation catalyst may be self-supporting (i.e., the catalyst does not need another material to serve as a support) or may require a separate support suitable for suspending the catalyst in the reactant stream. One particularly beneficial support is silica, especially silica having a high surface area (greater than 100 square meters per gram), obtained by sol-gel synthesis, precipitation or fuming. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system may include a binder to assist in forming the catalyst into a desirable catalyst shape. Applicable forming processes include extrusion, pelletization, oil dropping, or other known processes. Zinc oxide, alumina, and a peptizing agent may also be mixed together and extruded to produce a formed material. After drying, this material is calcined at a temperature appropriate for formation of the catalytically active phase, which usually requires temperatures in excess of 450° C.

Without being limited to any theory, the relationship between purged HDO bottoms material and coking in AC can be illustrated in FIG. 3. The baseline case where all the products from HDO are fed into AC is represented by the upper right corner of the chart. The data points shown represent the cases where the bottoms stream from the separator was not sent to AC (purged) and only the volatile overhead fractions were sent to AC. The y-axis represents as a fraction of the base case how much carbon was still being sent forward to AC (blue points only ˜20% fed to AC/80% was purged and the orange points sent ˜75% of the carbon forward/purging ˜25%). The x-axis then shows how much the rate of coking (analogous to specific productivity) decreased as an effect of not sending the bottoms stream to AC. If what was being purged was completely homogeneous, then the data points would have fallen along the 45° parity line (i.e., removing half the carbon caused the coking rate to be cut in half). The fact that the points lie above this line shows that the bottoms material which was purged led to a disproportionate decrease in AC coking. The orange points for instance represent that the bottoms material contributes around 3-4 times more coke on the AC catalyst than the lighter products do. Thus, these data demonstrate that less volatile HDO products contribute more strongly towards AC coking.

As a nonlimiting illustration, certain important advantages of the present system for upgrading HDO heavy products (such as those from PV bottoms) are shown in FIG. 4. The base case, where HDO is a single reactor, is shown in the left column. The overall H/C_eff of all the HDO products is represented by the blue circle, which has been ˜ 1.5 in many historical runs. This overall H/C_eff is composed of two subsets of HDO products, the PV bottoms (orange) and all the volatile/overhead HDO products (green). The size of the circles conveys the relative amounts of carbon in each group. There is a significant disparity between the H/C_eff of the HDO overhead products and the PV bottoms as well as their respective selectivity to form coke in the AC reactor. It is desired to increase the extent of conversion of the PV bottoms stream to avoid the excessive coking in AC that this stream will cause. In the middle column, the PV bottoms conversion is increased by simply increasing the extent of conversion in the single primary HDO reactor. An increase in conversion will also cause the overhead products to increase, which is undesired because they already are not forming much coke on the AC catalyst and the higher the H/Ceff of this stream, the lighter paraffins will be produced in the AC process resulting in lower AC liquid product (e.g., aromatic product) yield. Upgrading the PV bottoms (right column) achieves both goals. In this scenario, the PV bottoms is upgraded in a separate reactor while the HDO overhead products are unchanged, achieving the most optimal outcome for highest AC liquid product yield and lowest AC coking.

Unless otherwise clear from context, the term “a” may be understood to mean “at least one.” As used in this application, the term “or” may be understood to mean “and/or.” The terms “comprising” and “including” may be understood to encompass itemized components or steps whether presented by themselves or together with one or more additional components or steps. The term “comprise” and variations thereof, such as “comprising” and “comprises,” are not intended to exclude other additives, components, integers or steps. Unless otherwise stated, the terms “about” and “approximately” may be understood to permit standard variation (e.g., ±10%) as would be understood by those of ordinary skill in the art. Where ranges are provided herein, the endpoints are included.

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

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

EXAMPLES

Example 1: Upgrading Catalyst Testing

Reactor and Conditions Used for Catalyst Testing

A single ½″ reactor was used to test each catalyst. There was no liquid recycle and H₂ was fed once through. The reactor was loaded by volume and so the mass of each catalyst loaded varied and the feed rate was adjusted to maintain a constant WHSV for each catalyst (˜1 g of non-water components/hr/g catalyst). The reactor loading diagram is shown FIG. 5. A batch of composite PV bottoms product was used as the feedstock, AP9204-1, and a breakdown of this feedstock is shown in FIG. 6. Generally, each catalyst was run at several temperatures to assess performance. The catalysts were all tested at 1800 psig and with a high H₂ cofeed rate (˜4 mol H₂/mol C).

Testing Results

Three temperatures were tested to determine the overall H/C_eff of the products after upgrading. Two of the catalysts tested (HDO-1 and HDO-2) were the standard HDO formulation. HDO-1 was a 2% Pd loading and HDO-2 was a 1% Pd loading. FIG. 7 shows the testing results. The composite feed (PV bottoms) had a H/C_eff of ˜1.14 and the products of HDO-1 and HDO-2 catalysts showed higher H/Cerf, generally in a linear trend with temperature. Because there wasn't a clear difference in performance between these two catalysts, it suggests that these reactions are not limited by the metal content of the catalyst. Considering that a H/C_eff range of ˜1.4 to 1.8 would be desired for these products, as too high of conversion would likely result in yield losses, these results showed that relatively mild temperatures would be needed for this conversion step, in the 250-270° C. range.

After testing the standard HDO catalysts, two semi-commercial catalysts were tested for their performance. These results are shown in FIG. 8. KF-200 is a catalyst prepared by Albemarle (now Ketjen), with pgm functionality along with a proprietary support. KL6560 is a Ni-based hydrotreating catalyst. The KF-200 seemed to fall on a similar slope as the HDO-1 and HDO-2 catalysts, although possibly slightly higher in activity for the same temperatures. The KL6560 catalyst showed unusual behavior, with relatively steady product H/C_eff regardless of temperature. It is possible that KL6560 was deactivating more than the other catalysts and each weight check (WC) at higher temperature was serendipitously cancelling out the effects of the deactivation.

To test a theory that additional acid functionality on the catalyst would be beneficial, two alternative catalysts were tested. One was the DHOG catalyst, which was a Pd/Ag loaded tungstated zirconia catalyst, with tungsten providing the acidity. The other catalyst, W-HDO, was a standard HDO catalyst but made with tungstated zirconia support, same as the DHOG catalyst. The results of these two catalysts are shown in FIG. 9. Both catalysts generally produced higher conversion at lower temperatures than the standard HDO catalysts. The DHOG catalyst was more typical in its operation, with a shift in activity to lower temperatures. It showed almost no conversion at the first temperature of 225° C., indicating a potential lower limit for this reactor service, at least for this particular catalyst. The W loaded HDO catalyst (W-HDO) was more challenging to operate. Each time the temperature was increased, there was a significant increase in reaction rate and resulting over-conversion to highly paraffinic products. After collecting this high conversion datapoint, the temperatures were cooled until the significant exotherm was lost and then very slowly reheated back to the higher inlet temperature where no significant exotherm or over-conversion was encountered the subsequent time. This pattern repeated itself several times during the testing. These catalysts proved that the addition of tungsten for acidity led to significant improvement in activity of the catalyst. The compositions of the catalysts used in these tests are summarized in Table 1.

TABLE 1
Compositions of the tested catalysts.

Catalyst	Description
HDO-1	2% Pd, 2% Mo, 0.5% Sn on crushed (18 × 30) ZrO2
HDO-2	1% Pd, 1% Mo, 0.6% Sn on crushed HDO 2.2 tableted
	ZrO2 HDO 2.2: 1% Pd, 1% Mo, 0.25% Sn on ZrO2 and
	is double impregnated
KF-200	Albemarle prepared catalyst, 18 × 40 mesh granular
KL6560	commercial, Criterion, Ni based HT catalyst, crushed
DHOG	0.5% Pd, 0.5% Ag on 14 × 30 crushed tungstated zirconia
W-HDO	2% Pd, 2% Mo, 0.5% Sn on 18 × 40 crushed
	tungstated zirconia
HDO-1	2% Pd, 2% Mo, 0.5% Sn on 1.2 mm ZrO2 extrudates
Extrudates

The Stability Test

The stability of the standard HDO catalyst was also tested. For this test, the 2% Pd HDO-1 formulation was used, but was loaded on extrudates this time instead of crushed support as it was for all the previous catalysts tested. This catalyst was run at one consistent temperature for several days. The results are shown in FIG. 10 and FIG. 11. There was a significant loss in activity during the first three days of testing followed by relatively stable performance in the next three.

The Residue Test

One other aspect that was measured from these tests was the residue. The residue test qualitatively assesses the amount of fouling that may occur in the acid condensation (AC) vaporizer when the HDO products are vaporized for the AC reactor. The test involves boiling a sample of HDO product on a hot plate and measuring the amount of residue left behind as a function of the starting liquid. The results of this testing are shown in FIG. 12 for all catalysts tested. The residue of the feed is indicated on the chart at ˜0.2 wt %. All catalysts after achieving a modest amount of conversion caused a decrease in the residue of the products, generally getting to essentially 0 at higher conversion. The three catalysts with some added acidity (KF-200, DHOG, and W-HDO) all showed an increase in residue for their lowest conversion point, indicating that there may be condensation or other reactions occurring at low temperature that lead to higher residue.

FIG. 13 shows pictures of the feed and products from the HDO catalyst testing. The color in the feed would generally be correlated to the higher residue.

Example 2: Upgrading Conditions

To determine the optimal set of conditions to run the PV bottoms reactor, a single 1″ reactor was used for the testing. Two different lots of PV bottoms were used as feedstock. Various temperatures, pressures, and flow rates were tested to determine the optimal conditions to run the upgrading reactor. The loading diagram used for this test is shown in FIG. 14. Two batches of PV bottoms were used as feedstock (AP9204-5 and AP9204-3) for these tests, the compositions of which are shown in FIG. 15. AP9204-5 was produced with HDO-2 tablets (with relatively lower overall conversion) and AP9204-3 was produced with standard HDO-1 catalyst (with relatively higher overall conversion).

For this set of experiments, an upgrading reactor was run independently, using PV bottoms material which had been produced and composited from the Eagle unit. The upgrading reactor was never coupled to AC for these tests, performance was based on HDO product profiles alone, primarily H/C_eff of the products (based on product analysis, not H₂ consumption). A total of 11 data points were generated during the experiment. Four conditions were investigated: temperature, WHSV, pressure, and feed H/Cerf. FIGS. 16-20 show the impacts of each parameter individually. In each of FIGS. 16-20, the colors represent data points where all other conditions were held constant except for the parameter of interest, which is the x-axis. The parameters held constant for each color series are shown in FIGS. 16-19. The colors are not consistent from one chart to the next. The catalyst used for this set of experiments is a tablet containing 1% Pd, 1% Mo, 0.25% Sn on ZrO₂ and is double impregnated.

Temperature

The impact of reactor temperature (inlet) on product H/C_eff is shown in FIG. 16. The temperature of the upgrading reactor had a significant impact on the extent of conversion. On average, an increase of 10° C. resulted in ˜0.1 additional H/C_eff of the products, which would be a significant change. Compared to the impact of pressure, which adding 1100 psi from 660 psig to 1760 psig (nearly tripling) only increased conversion by ˜0.08 H/Ceff, a similar amount as adding ˜8° C. higher inlet temperature. The impact of feedstock H/C_eff was that it correlated to product H/C_eff (a more highly converted feedstock led to more highly converted product), especially at the lower temperatures. The impact of feedstock H/C_eff was significantly less at higher temperatures.

Weight Hourly Space Velocity (WHSV)

The results are shown in FIG. 17. For this experiment, WHSV was defined as the ratio of non-water components in the PV bottoms stream being fed to the upgrading reactor per mass of upgrading catalyst per hour. As an example, with this definition, a PV bottoms rate of 125 g/hr with 20 wt % water (80 wt % non-water components, or 100 g/hr of non-water components) fed across 100 g of catalyst would result in an upgrading WHSV of 1. As was the case for temperature, the upgrading catalyst WHSV was also an important parameter. On average, a reduction of 0.1 WHSV resulted in ˜0.07 H/C_eff. Compared to temperature, a 10° C. increase in inlet temperature would be equivalent to decreasing the WHSV by ˜0.26. The impact from feedstock H/C_eff was similar to that of temperature, in that a less converted feedstock led to less converted product, although the difference was more apparent at lower conversion conditions and much less apparent at higher conversion conditions.

Pressure

The results are shown in FIG. 18. The pressure of the upgrading reactor did not have a strong impact on conversion. On average, the H/C_eff of the products increased by ˜0.1 H/C_eff per 1000 psi additional pressure. Compared to temperature, an increase of 10° C. resulted in a similar improvement in H/C_eff as increasing pressure by 800 psi. Considering the commercial scale equipment design and costs, it is much more likely that a lower pressure higher temperature reactor would be more favorable than another high-pressure reactor. This minimal impact from pressure possibly suggests that this reaction isn't constrained by the incorporation of gas phase H₂ in the same way that the primary HDO reactor is (which does have a stronger impact of pressure on the performance of the reactor).

Feedstock H/C_eff

The results of this comparison are shown in FIG. 19. When running at conditions which otherwise produced a lower extent of conversion (lower temperature, higher WHSV), the starting H/C_eff did have an impact on the final H/C_eff achieved. A lower starting H/C_eff led to a lower final H/C_eff at these conditions. When running at higher conversion conditions (higher temperature, lower WHSV), the impact from the starting H/C_eff was minimal. A practical implication of these results is that less conversion may be needed in the primary HDO reactor.

Water Content in the Feed to the Upgrading Reactor

The impact of water content in the feed to the upgrading reactor was also studied. A sample of PV bottoms was diluted with water to various degrees, from ˜ 17 wt % water (native water concentration in the PV bottoms) to ˜65 wt % water. The mixtures were subsequently fed to an HDO catalyst (HDO-2), which was prepared on crushed support and loaded in a ½″ reactor. With additional water added, the feed rate was increased so that the flow of carbon remained constant. The results of the test are shown in FIG. 20. There was essentially no loss of performance with increasing water content up to ˜30 wt %. Beyond that, there was a ˜25% loss of conversion with higher water content in the feed. These results indicate that the performance of the upgrading process is not highly sensitive to the concentration of water.

Further studies may be conducted according to the conditions listed in Table 2. In particular, the primary HDO reactor can be run at a higher WHSV (less conversion) and the same amount of catalyst taken from the base case loading (without upgrading) can be used as the PV bottoms upgrading catalyst, resulting in a scenario where the total amount of HDO catalyst was the same as in the base case. A PFD of the flow scheme is shown in FIG. 1B.

TABLE 2
Conditions for Integrated PV Bottoms Upgrading

	Baseline	Primary	Upgrading

	WHSV	0.6	0.7	0.75
	(g NW/hr/g cat)
	PV BOT C Yield	0.2	0.24
	Catalyst Mass	1	0.86	0.14
	(relative to baseline)
	Pressure (psig)	1800	1800	650

In order for the PV bottoms upgrading to work more effectively, the balance of conversion needs to be shifted so that most of the conversion still happens in the primary reactor. The feed for the upgrading reactor should be sufficiently converted first so that the upgrading reactor (and catalyst) can be optimized to convert the components which were not easily converted in the primary reactor. In addition, the temperature of the upgrading reactor should be controlled to avoid runaway reactions.

For reasons of completeness, various aspects of the invention are set out in the following numbered clauses:

• • Clause 1. A method for producing an oxygenate product, the method comprising:
  • (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream;
  • (ii) fractionating the intermediate stream into a first oxygenate stream comprising a first pool of C₁₊O_1-3 hydrocarbons and a heavy residual stream;
  • (iii) 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 C₁₊O_1-3 hydrocarbons, wherein the upgrading catalyst catalyzes hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream; and
  • (iv) combining at least a portion of the first oxygenate stream and at least a portion of the second oxygenate stream to form an upgraded oxygenate stream.
  • Clause 2. The method of clause 1, wherein the intermediate stream has a H/C_eff of 1.6 or less.
  • Clause 3. The method of any one of clauses 1-2, wherein the heavy residual stream has a water content of less than 25% by weight.
  • Clause 4. The method of any one of clauses 1-3, wherein the heavy residual stream has a boiling point that is higher than a boiling point of the first oxygenate stream.
  • Clause 5. The method of any one of clauses 1-4, wherein the heavy residual stream has a H/C_eff of 1.3 or less.
  • Clause 6. The method of any one of clauses 1-5, wherein step (i) is carried out in a first reactor and step (iii) is carried out in a second reactor, and wherein the first and second reactors are different.
  • Clause 7. The method of any one of clauses 1-5, wherein step (i) and step (iii) are carried out in a single reactor.
  • Clause 8. The method of any one of clauses 1-7, wherein the hydrodeoxygenation catalyst is a first hydrodeoxygenation catalyst and the upgrading catalyst is a second hydrodeoxygenation catalyst.
  • Clause 9. The method of clause 8, wherein the first hydrodeoxygenation catalyst and the second hydrodeoxygenation catalyst are identical.
  • Clause 10. The method of any one of clauses 1-7, wherein the upgrading catalyst catalyzes hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream.
  • Clause 11. The method of any one of clauses 1-10, wherein the upgrading catalyst comprises a heterogeneous catalyst comprising palladium, molybdenum, and tin.
  • Clause 12. The method of clause 11, wherein the upgrading catalyst further comprises tungsten.
  • Clause 13. The method of clause 11, wherein the upgrading catalyst comprises from 0.05 wt % to 5.0 wt % palladium.
  • Clause 14. The method of clause 11, wherein the upgrading catalyst comprises from 0.05 wt % to 10.0 wt % molybdenum.
  • Clause 15. The method of clause 11, wherein the upgrading catalyst comprises from 0.0125 wt % to 5.0 wt % tin.
  • Clause 16. The method of clause 12, wherein the upgrading catalyst comprises from 0.1 wt % to 20 wt % tungsten.
  • Clause 17. The method of any one of clauses 11-16, wherein the upgrading catalyst comprises a support.
  • Clause 18. The method of clause 17, wherein the support is selected from the group consisting of nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, zeolites, tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, iron aluminate, phosphated alumina, theta alumina, niobia, niobia phosphate, oxides of the foregoing, and mixtures thereof.
  • Clause 19. The method of clause 17, wherein the support further comprises a modifier selected from the group consist of tungsten, titania, sulfate, phosphate, or silica.
  • Clause 20. The method of clause 6, wherein the second reactor has a reaction pressure from 70 psig to 2000 psig.
  • Clause 21. The method of clause 6, wherein the second reactor has a reaction temperature from 100° C. to 300° C.
  • Clause 22. The method of any one of clauses 1-21, wherein the heavy residual stream is contacted with the upgrading catalyst at a weight hour space velocity of at least 0.01 grams of the oxygenated hydrocarbon per gram of upgrading catalyst per hour.
  • Clause 23. The method of any one of clauses 1-22, wherein the upgrading catalyst is in operation for at least 20 days without a regeneration of the catalyst.
  • Clause 24. A method for producing a C₄₊ compound, the method comprising:
  • producing the upgraded oxygenate stream according to the method of any one of clauses 1-23; and
  • reacting the upgraded oxygenate stream in the presence of a condensation catalyst to produce the C₄₊ compound.