Upgrading of hdo heavy products

Abstract

The present disclosure provides a method for producing oxygenates from an aqueous feed stream, which involves hydrodeoxygenation (HDO) and catalytic upgrading of heavy components of the HDO product. The oxygenate stream from the HDO product and the upgraded heavy components can be combined to form an upgraded oxygenate stream, which can then be converted to useful compounds by acid condensation (AC). Advantageously, the inventive method can reduce coking on the AC catalyst while maintaining a high overall yield of useful compounds.

Description

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Application No. 63 / 568,918, filed March 22, 2024, the contents of which are incorporated herein by reference in their entirety.

[0002] background Bioreforming processes can produce aromatic hydrocarbons and other useful compounds from biomass feedstocks such as cellulose, hemicellulose, and lignin. For example, cellulose and hemicellulose can be used as feedstocks in a variety of bioreforming processes, including aqueous reforming (APR) and hydrodeoxygenation (HDO)-catalytic reforming, which, when combined with hydrogenation, can convert cellulose and hemicellulose into a range of products, including hydrogen, liquid fuels, aromatic compounds, kerosene, diesel fuel, lubricants, and fuel oils, among others. Furthermore, catalytic acid condensation (AC) can be used to convert oxygenates (e.g., those produced by HDO) into hydrocarbons.

[0003] HDO products represent a range of conversion products, from highly converted alkanes to completely unconverted feedstocks (e.g., sugars from biomass). The least desirable products from HDO (e.g., heavy components) may not constitute a large portion of the total product, but they typically have the highest impact on subsequent acid condensation due to their significant selectivity in coke formation. It has been shown that the least desirable HDO products can be selectively purged from AC by distillation because they have the lowest volatility. This method can significantly reduce coke yield in AC, but at the cost of a significantly reduced product yield.

[0004] Therefore, there remains a need for methods and reactor systems that can improve the quality of these undesirable HDO products and achieve lower coking in AC without yield loss. Invention Overview This document describes a method for producing oxygen-containing compound products. This method may include: (i) Reacting an aqueous feed stream containing oxygen-containing hydrocarbons with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream; (ii) Fractionating the intermediate stream into a fraction containing the first C 1+ O 1-3 The first oxygenated compound stream and the heavy residual stream from the hydrocarbon pool; (iii) Reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a second C 1+ O 1-3 The second oxygen-containing compound stream in the hydrocarbon pool, wherein a upgrading catalyst catalyzes the hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof of the heavy residue stream; and (iv) Combining at least a portion of the first oxygenated compound stream and at least a portion of the second oxygenated compound stream to form an improved oxygenated compound stream.

[0006] In another aspect, this disclosure provides a method for producing C 4+ A method for producing compounds. This method may include producing an upgraded oxygen-containing compound stream according to an oxygen-containing compound production method as described herein; and reacting the upgraded oxygen-containing compound stream in the presence of a condensation catalyst to produce C. 4+ Compounds. Brief description of the attached diagram Figure 1A An exemplary system for improving the quality of HDO heavy products is shown. Figure 1B A process flow diagram (PFD) of one embodiment of an integrated HDO heavy product upgrading reactor is shown.

[0008] Figure 2 This paper illustrates alternative implementation methods for the upgrading of HDO heavy materials.

[0009] Figure 3 The figure illustrates the relationship between the purged HDO tower bottoms material and the coking in the AC.

[0010] Figure 4 Some benefits of the present invention’s system for improving the quality of HDO heavy products are shown.

[0011] Figure 5 A diagram showing reactor loading for testing the upgrading catalyst is presented.

[0012] Figure 6 The decomposition of the PV tower substrate composite material (AP9204-1) used as the raw material for testing is shown.

[0013] Figure 7 The composite H / C ratio of the product from PV column bottoms upgrading is shown for two standard HDO catalyst formulations. eff (The numbers on the chart refer to WC#, which is basically the number of days on stream).

[0014] Figure 8 The composite H / C ratio of the product from PV column bottoms upgrading is shown for two semi-commercial catalyst formulations. eff (The numbers on the chart refer to WC#, which is basically the number of days the system is running).

[0015] Figure 9 The composite H / C ratio of the product from PV column bottoms uplift is shown for two other virent catalyst formulations. eff(The numbers on the chart refer to WC#, which is basically the number of days the system is running).

[0016] Figure 10 The composite H / C of the product from the PV column bottoms upgrade is shown in the stability test of the HDO catalyst. eff (The numbers on the chart refer to WC#, which is basically the number of days the system is running).

[0017] Figure 11 The composite H / C of the product from the PV column bottoms upgrade is shown in the stability test of the HDO catalyst. eff Changes over time.

[0018] Figure 12 The results show the change in residues from the product tested with the upgrading catalyst as a function of temperature.

[0019] Figure 13 Images of feed and product from an HDO catalyst upgrading test are shown.

[0020] Figure 14 A diagram showing reactor loading for testing upgrading conditions is presented.

[0021] Figure 15 The decomposition of the PV tower bottom composite material, used as feedstock for testing upgrading conditions, is shown.

[0022] Figure 16 The H / C ratio of the products from the upgrading reactor is shown. eff With changes in reactor inlet temperature.

[0023] Figure 17 The H / C ratio of the products from the upgrading reactor is shown. eff The WHSV of the upgrading reactor varies.

[0024] Figure 18 The H / C ratio of the products from the upgrading reactor is shown. eff With changes in the pressure of the upgrading reactor.

[0025] Figure 19 The H / C ratio of the products from the upgrading reactor is shown. eff With raw material H / C eff Changes in (PV tower substrate).

[0026] Figure 20 The H / C ratio of the products from the upgrading reactor is shown. eff The change depends on the water content of the raw materials.

[0027] Detailed Explanation This disclosure relates to processes and systems for upgrading HDO products, particularly heavy components that cause coking on catalysts used in downstream AC reactions. In one aspect, this disclosure provides a method for producing oxygen-containing compound products, the method comprising: (i) Reacting an aqueous feed stream containing oxygen-containing hydrocarbons with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream; (ii) Fractionating the intermediate stream into a fraction containing the first C 1+ O 1-3 The first oxygenated compound stream and the heavy residual stream from the hydrocarbon pool; (iii) Reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a second C 1+ O 1-3 The second oxygen-containing compound stream in the hydrocarbon pool, wherein a upgrading catalyst catalyzes the hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof of the heavy residue stream; and (iv) Combining at least a portion of the first oxygenated compound stream and at least a portion of the second oxygenated compound stream to form an improved oxygenated compound stream.

[0028] The method of this invention can be carried out in an HDO heavy product upgrading reactor system. An exemplary system for upgrading HDO heavy products is described in... Figure 1A As shown in the figure. The system includes components for: (1) fractionating HDO products (distillation / flash distillation) in a manner that concentrates heavier products (e.g., by composition or boiling point) and (2) upgrading the heavier products with H2 and a suitable catalyst that promotes chemical reactions such as hydrogenation, hydrodeoxygenation, and cracking, such that the selectivity for coke formation is reduced when supplied to an acid condensation (AC) reactor without causing a significant loss of product yield. Reference Figure 1AA feed stream containing products from the hydrogenation reaction (HYD) is introduced into the 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 oxygenated compound stream) and a heavy residue stream 4. The heavy residue stream 4, along with H2, is supplied to an upgrading reactor 5. The upgraded product 6 (i.e., the second oxygenated compound stream) produced in the upgrading reactor 5 can then be combined with the first oxygenated compound stream 3 to form an upgraded oxygenated compound stream 7 (i.e., the HDO product stream). The heaviest product from the HDO reactor 1, such as the tank composition or product taken from the bottom of the product vaporizer (PV) column, can be fed through a separate reactor. This additional reactor will likely be much smaller than the primary HDO reactor 1. Typically, the product vaporizer can be a separator (e.g., a single-stage flash unit) operating at a given temperature and pressure, which provides separation of the first oxygenated compound stream and the heavy residue stream, either alone or additionally. Then, the HDO product stream 7 is directed back into the AC reactor.

[0029] Another exemplary system for improving the quality of HDO heavy products Figure 1B As shown in the image. Figure 1B A process flow diagram (PFD) of the integrated HDO heavy product upgrading reactor is shown. After intermediate stream 2 is generated in HDO reactor 1, intermediate stream 2 is separated into light stream 3 (i.e., the first oxygen-containing compound stream) and heavy residue stream 4. Heavy residue stream 4 is supplied to HDO upgrading reactor 5. Then, the upgraded product 6 (i.e., the second oxygen-containing compound stream) generated in upgrading reactor 5 is directed to AC reactor.

[0030] Option embodiments of the present invention system for improving the quality of HDO heavy products are as follows: Figure 2 As shown in the diagram. In this configuration, the recirculated stream to the upgrading reactor 5 undergoes an upgrading reaction, which is installed in the same reactor vessel 10 as the primary HDO reactor 1. This concept avoids most of the challenges surrounding thermal integration and reduces overall cost.

[0031] Feed flow The method of the present invention comprises reacting an aqueous feed stream containing oxygenated hydrocarbons with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream. The feed stream used in the method of the present invention can be derived from any source, but is preferably derived from biomass. Biomass typically comprises three main components: cellulose, a primary sugar source for bioconversion processes, comprising high molecular weight polymers formed from tightly linked glucose monomers; hemicellulose, a secondary sugar source, comprising shorter polymers formed from multiple sugars; and lignin, comprising phenylpropionic acid moieties polymerized in a complex three-dimensional structure. For lignocellulose biomass, the total composition will vary based on plant variety or type and is generally 40%–50% cellulose, 20%–25% hemicellulose, and 25%–35% lignin by weight percentage. This composition can be deconstructed using any one or more methods, including, individually or in combination, the following: (1) thermochemical treatment using inorganic acids, strong bases, water, gaseous catalysts, oxidative catalysts, and / or organic solvents under autohydrolysis conditions; (2) enzymatic hydrolysis; and most recently, (3) catalytic deconstruction of biomass. Regardless of the process used, the resulting product may contain desired oxygenated hydrocarbons (e.g., lignocellulose derivatives, lignin derivatives, cellulose derivatives, and hemicellulose derivatives) suitable for use in the methods of this invention.

[0032] Feed streams can be pure materials, purified mixtures, or raw materials, such as sugars and starches derived from corn, sugarcane, beet sugar, rice, wheat, algae, or energy crops. Some suitable feed streams are also commercially available and can be obtained as byproducts from other processes, such as glycerol produced from biodiesel fuels. 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 stages of sugar hydrogenation.

[0033] In addition to oxygenated hydrocarbons, the feed stream may also include lignin, one or more extracts, one or more ash components, or one or more organic products (e.g., lignin derivatives). Extracts will typically include terpenes, stilbenes, flavonoids, phenols, aliphatic compounds, lignans, alkanes, protein 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-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, vanillin, 4-propyl syringol, vitamin E, steroids, long-chain hydrocarbons, long-chain fatty acids, stilbenes, etc.

[0034] Generally, the feed stream comprises any oxygen-containing hydrocarbon having three or more carbon atoms and an oxygen-to-carbon ratio between about 0.5:1 and about 1:1.2. In one aspect, the oxygen-containing hydrocarbon has 3 to 12 carbon atoms or 3 to 6 carbon atoms. In another aspect, the oxygen-containing hydrocarbon has more than 12 carbon atoms. Preferred, non-limiting examples of oxygen-containing hydrocarbons include monosaccharides, disaccharides, trisaccharides, polysaccharides, oligosaccharides, sugars, sugar alcohols, sugar degradation products, alditols, hemicellulose, cellulose derivatives, lignocellulose derivatives, lignin derivatives, hemicellulose derivatives, starch, organic acids, polyols, and the like. Preferably, the oxygen-containing hydrocarbon includes polysaccharides, oligosaccharides, trisaccharides, disaccharides, monosaccharides, sugars, sugar alcohols, sugar degradation products, and other polyhydric alcohols. More preferably, the oxygenated hydrocarbon is a trisaccharide, disaccharide, sugar such as glucose, fructose, sucrose, maltose, lactose, mannose, or xylose, or a sugar alcohol such as arabinitol, erythritol, glycerol, isomaltitol, lactitol, maltitol, mannitol, sorbitol, xylitol, arabinitol, or a glycol. The oxygenated hydrocarbon may also include alcohols derived by hydrogenation of the aforementioned substances.

[0035] 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, and hydrofluoric acid; bioreforming solvents; and water. The solvent may be from an external source, recycled, or generated in situ, such as an in-situ generated oxygenated compound.

[0036] To generate the intermediate stream, oxygen-containing hydrocarbons are combined with water to provide an aqueous feed stream with a concentration that effectively induces the formation of the desired reaction products. The water-to-carbon ratio, on a molar basis, can 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 in between. The feed stream can also be characterized as a solution of oxygen-containing hydrocarbons having at least 1.0 weight percentage (wt%) of the total stream. For example, the solution may include one or more oxygen-containing hydrocarbons, wherein the total concentration of oxygen-containing hydrocarbons in the solution is at least 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or greater by weight, including any percentage in between, and depending on the oxygen-containing hydrocarbons used. In one embodiment, at least some of the oxygen-containing hydrocarbons have four or more carbon atoms. In such an embodiment, the feed stream comprises, by weight, at least about 1%, 5%, 10%, 20%, 30%, 40%, 50%, or 60%, 70%, 80%, or 90% 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 the foregoing ranges are also included.

[0037] Oxygenated hydrocarbons can be any water-soluble oxygenated hydrocarbon (C) having one or more carbon atoms and at least one oxygen atom. 1+ O 1+ Hydrocarbons. In one embodiment, "oxygenated hydrocarbons" may include carbohydrates (e.g., monosaccharides, disaccharides, oligosaccharides, polysaccharides, and starch), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols and other polyhydroxy alcohols (e.g., diols, triols, polyols) and / or sugar degradation products (e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, furfural, etc.). In one embodiment, oxygenated hydrocarbons include polysaccharides, disaccharides, monosaccharides, cellulose derivatives, lignin derivatives, hemicellulose, sugars, sugar alcohols, or mixtures thereof. In another embodiment, oxygenated hydrocarbons include C 1-12 O 1-11 Hydrocarbons or C 1-6 O 1-6 Hydrocarbons. In yet another embodiment, C 1-12 O 1-11 Hydrocarbons include sugar alcohols, sugars, monosaccharides, disaccharides, aldoses, cellulose derivatives, lignocellulose derivatives, glucose, fructose, sucrose, maltose, lactose, mannose, xylose, arabinitol, erythritol, glycerol, isomaltitol, lactitol, maltitol, mannitol, sorbitol, xylitol, or mixtures thereof. In another embodiment, the oxygen-containing hydrocarbons also include recycled C24.1+ O 1+ hydrocarbon.

[0038] HDO catalyst and HDO reaction The term "hydrodeoxygenation catalyst" (HDO catalyst) refers to a catalyst that catalyzes the removal of oxygen from oxygen-containing compounds in the presence of hydrogen. Suitable HDO catalysts and processes include, for example, those described in whole or in part by reference in WO 2014 / 152370 and WO / 2023 / 064565, which are incorporated herein by reference.

[0039] In some embodiments, the HDO catalyst comprises a heterogeneous catalyst having one or more materials capable of catalyzing the reaction between hydrogen and a feed solution to remove one or more oxygen atoms from the feed solution to produce one or more oxygen-containing compounds. In some embodiments, the HDO catalyst comprises one or more metals adhered to a support, and may include, but is not limited to, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys thereof, 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, Tl, and combinations thereof. In some embodiments, the HDO catalyst comprises Pt, Ru, Cu, Re, Co, Fe, Ni, W, or Mo. In some embodiments, the HDO catalyst comprises Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In some embodiments, the HDO catalyst comprises 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 combinations thereof. In some embodiments, the HDO catalyst includes a promoter. As an example, the promoter of the deoxygenation catalyst may include Sn, W, or combinations thereof. The support may include nitrides, carbon, silica, alumina, zirconium oxide, titanium dioxide, vanadium oxide, cerium dioxide, zinc oxide, chromium oxide, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, or mixtures thereof. In some embodiments, the support comprises zirconium oxide.

[0040] Aqueous feed streams react with hydrogen in the presence of an HDO catalyst at specific temperatures, pressures, and gravity hourly space velocities (WHSVs) to effectively produce the desired oxygen-containing products. The specific oxygen-containing compounds produced will depend on a number of factors, including the feed solution, reaction temperature, reaction pressure, water concentration, hydrogen concentration, catalyst reactivity, and feed solution flow rate, as the feed solution flow rate affects the hourly space velocity (mass / volume of reactants per unit time per unit catalyst), gas hourly space velocity (GHSV), and gravity hourly space velocity (WHSV). For example, increasing the flow rate over time, and thus reducing the feed stream's exposure to the HDO catalyst, will limit the extent of the possible reaction, resulting in higher yields of di- and tri-oxygen-containing compounds, while decreasing yields of ketones, alcohols, and cyclic ethers.

[0041] Generally, the reaction may include a temperature gradient to allow partial deoxygenation of oxygenated hydrocarbons at temperatures below the caramelization point of the feedstock from which the aqueous feed stream originates. Including a temperature gradient helps prevent the oxygenated hydrocarbons in the feed stream from condensing on the catalyst (e.g., caramelizing) and generating a significant pressure drop on the reactor, which could lead to reactor inoperability. 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 and 290°C. In another embodiment, no temperature gradient is used.

[0042] Operating pressures up to approximately 2000 psig can be used to help maintain the carbon backbone, minimize the amount of light organic acids and ketones formed, and increase product selectivity for alcohols. By increasing the operating pressure, the thermodynamics of the reaction favors the conversion of alcohols to ketones and organic acids, thereby altering product selectivity, maintaining the carbon backbone, and increasing product yield. Light organic acids are particularly undesirable products due to their high corrosiveness. Producing fewer light organic acids provides greater flexibility in the construction materials of the reactor system, as corrosion is not a concern.

[0043] The reaction temperature and pressure are preferably selected such that at least a portion of the feedstock, from which the aqueous feed stream is generated, is retained in the liquid phase at the reactor inlet. However, it is recognized that temperature and pressure conditions can also be selected to more favorably produce the desired product in the gas phase. Generally, the reaction should be carried out under process conditions in which the thermodynamics of the proposed reaction is favorable. For example, the minimum pressure required to retain a portion of the feedstock in the liquid phase may vary with the reaction temperature. If desired, higher pressures will generally be required to retain the feedstock in the liquid phase as the temperature increases. Pressures higher than those required to retain the feedstock in the liquid phase (i.e., the gas phase) are also suitable operating conditions.

[0044] In condensed-phase liquid reactions, the pressure within the reactor must be sufficient to retain 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 psig and 1950 psig, or between about 1000 psig and 1900 psig, or between about 1050 psig and 1800 psig.

[0045] For gas-phase reactions, the reaction should be carried out at a temperature in which the vapor pressure of the oxygen-containing 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 on the specific oxygen-containing hydrocarbon compound used, but for gas-phase reactions it 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. In one embodiment, the reaction temperature is between about 120°C and about 500°C, or between about 250°C and about 400°C.

[0046] Generally, the HDO reaction should be carried out under conditions in which the residence time of the aqueous feed stream on the catalyst is suitable for producing the desired product. For example, the WHSV of the reaction can be at least 0.01 g oxygenated hydrocarbons / g catalyst / hour (g / gh). In some embodiments, the WHSV of the HDO reaction is from 0.01 g / gh to about 40.0 g / gh, such as from about 0.05 g / gh to about 40.0 g / gh, from about 1.0 g / gh to about 40.0 g / gh, from about 5.0 g / gh to about 40.0 g / gh, or from about 1.0 g / gh to about 20.0 g / gh. The WHSV can be, for example, about 0.05 g / gh, 0.1 g / gh, 0.25 g / gh, 0.5 g / gh, 0.75 g / gh, 1.0 g / gh, 1.0 g / gh, 1.1 g / gh, 1.2 g / gh, 1.3 g / gh, 1.4 g / gh, 1.5 g / gh, 1.6 g / gh, 1.7 g / gh, 1.8 g / gh, 1.9 g / gh, 2.0 g / gh, 2.1 g / gh, 2.2 g / gh, 2.3 g / gh, 2.4 g / gh, 2.5 g / gh, 2.6 g / gh, 2.7 g / gh, 2.8 g / gh, 2.9 g / gh, 3.0 g / gh, 3.1g / gh, 3.2 g / gh, 3.3 g / gh, 3.4 g / gh, 3.5 g / gh, 3.6 g / gh, 3.7 10 g / gh, 11 g / gh, 12 g / gh, 13 g / gh, 14 g / gh, 15 g / gh, 20 g / gh, 25 g / gh, 30 g / gh, 35 g / gh or 40 g / gh.

[0047] In some implementations, the amount of hydrogen supplied 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%, based on the total molar number of oxygen-containing hydrocarbons in the feedstock. 0%, 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% The range is -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%, inclusive of all intervals therein. Hydrogen can be external hydrogen or recycled hydrogen. The term "external H2" refers to hydrogen added to the reactor system from an external source, not derived from the feed solution. The term "recycled H2" refers to unconsumed hydrogen that is collected and then recycled back into the reactor system for further use.

[0048] Oxygen-containing compound products The method of the present invention further includes fractionating the intermediate stream into a first oxygen-containing compound stream and a heavy residual stream. The chemical composition of the oxygen-containing compound product stream can be determined by H:C eff Ratio (H / C) eff Characterization. As used herein, the term "H:C" refers to... eff The "ratio" is based on the amount of carbon, oxygen, and hydrogen in the feed and is calculated as follows: 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. H:C effThe ratio applies to both individual components and mixtures of components, but is invalid for components containing atoms other than carbon, hydrogen, and oxygen. For mixtures, C, H, and O are summed over all components except water and molecular hydrogen. In some embodiments, H:C eff The ratio can be controlled or adjusted by changing the hydrodeoxygenation catalyst and operating conditions (e.g., temperature, pressure, WHSV, feed source selection and concentration).

[0049] In some implementations, the intermediate stream has an H / C ratio of 1.6 or less. eff For example, the H / C ratio of intermediate streams. eff It 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 ratio of the intermediate flow. eff The concentration 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 contains H:C 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. eff .

[0050] The intermediate stream can be fractionated into a first oxygen-containing compound stream and a heavy residue stream using known techniques, including but not limited to distillation or phase separation. In some embodiments, fractionation is carried out by distillation.

[0051] The first oxygen-containing compound stream includes the first C 1+ O 1-3 Hydrocarbon pool, the C 1+ O 1-3 Hydrocarbons are compounds having one or more carbon atoms and between one and three oxygen atoms, such as alcohols, ketones, aldehydes, furans, hydroxycarboxylic acids, carboxylic acids, diols, triols, and mixtures thereof. In some embodiments, C 1+ O 1-3 Hydrocarbons have 1 to 7 carbon atoms, such as 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 3 to 6 carbon atoms.

[0052] Exemplary alcohols in deoxygenation product stream 18 may include, but are not limited to, primary C. 1+ Alcohols, secondary C 1+ alcohols, linear C 1+ alcohols, branched C 1+ alcohols or cyclic C 1+ Alcohols, such as methanol, ethanol, n-propanol, isopropanol, butyl alcohol, isobutanol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 2-methyl-cyclopentanol, heptanol, octanol, nonanol, decanol, undecylol, dodecanol and their isomers.

[0053] Exemplary ketones may include, but are not limited to, hydroxy ketones, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybut-2-one, pentanone, cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone, decanone, undecaneone, dodecaneone, methylglyoxal, butanedione, pentanone, diketohexane, and their isomers.

[0054] Exemplary aldehydes may include, but are not limited to, hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde, pentanaldehyde, hexanal, heptaldehyde, octanaldehyde, nonanaldehyde, decanaldehyde, undecaldehyde, dodecanaldehyde, and their isomers.

[0055] Exemplary carboxylic acids may include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, their isomers and derivatives, including hydroxylated derivatives such as 2-hydroxybutyric acid and lactic acid.

[0056] Exemplary diols may include, but are not limited to, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and their isomers.

[0057] Exemplary triols may include, but are not limited to, glycerol, 1,1,1-tris(hydroxymethyl)-ethane (tris(hydroxymethyl)ethane), trimethylolpropane, hexanetriol, and their isomers. Exemplary furans and furfural include, but are not limited to, furan, tetrahydrofuran, dihydrofuran, 2-furanethanol, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methylfuran, 2-ethyl-tetrahydrofuran, 2-ethylfuran, hydroxymethylfurfural, 3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethylfuran, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furonic acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfural alcohol, 1-(2-furanyl)ethanol, hydroxymethyltetrahydrofurfural, and their isomers.

[0058] The first oxygen-containing compound stream can have an H:C ratio between 0.5 and 2.0. eff Ratio. For example, the H / C ratio of the first oxygen-containing compound stream. eff It 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.

[0059] Heavy residual streams may include water, unreacted components of the feed stream, and / or products of hydrodeoxygenation reactions. For example, a heavy residual stream may be a mixture of water and at least one component selected from sugar alcohols, polyoxygenated compounds, glycols, hydroxycyclic ethers, and dioxygenated compounds. Heavy residual streams may include C 8+ Compounds, such as C8 compounds, C9 compounds, C 10 Compound, C 11 Compound or C 12+ Compounds. Heavy residual streams may include aromatic compounds, non-aromatic compounds, or both.

[0060] On average, the heavy residual stream may contain higher molecular weight compounds (e.g., compounds with a greater number of carbon and / or oxygen atoms) than the first oxygen-containing compound stream. As a result, the heavy residual stream can separate from the first oxygen-containing compound stream due to differences in their physical properties, such as boiling point, density, or viscosity. In some embodiments, the heavy residual stream has a higher boiling point than the first oxygen-containing compound stream. This difference in boiling point can be used to fractionate intermediate streams from the first oxygen-containing compound stream and the heavy residual stream.

[0061] Heavy residual streams have H / C eff The H / C ratio can be lower than that of the first oxygen-containing compound stream. eff In some implementations, the heavy residual stream has an H / C ratio of 1.3 or less. eff For example, the H / C ratio of heavy residual streams. eff It can be from 0.5 to 1.2, from 0.8 to 1.1, or from 0.8 to 1.0.

[0062] 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.

[0063] Upgrading catalyst and upgrading reaction The method of the present invention further includes reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a product containing a second C 1+ O 1-3 The second oxygen-containing compound stream in the hydrocarbon pool. The upgrading catalyst can catalyze the upgrading reaction of the heavy residue stream, which includes hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof. As a result of the upgrading reaction, compounds in the heavy residue stream can be converted into other products that cause less coking, for use in the subsequent AC reaction.

[0064] In some embodiments, the upgrading catalyst may be a hydrodeoxygenation catalyst as described above. In some embodiments, the hydrodeoxygenation catalyst used to generate the intermediate stream is a first hydrodeoxygenation catalyst, and the upgrading catalyst is a second hydrodeoxygenation catalyst. The first and second hydrodeoxygenation catalysts may be the same or different. In some embodiments, the first and second hydrodeoxygenation catalysts are the same.

[0065] In some embodiments, the upgrading catalyst is heterogeneous and comprises palladium, molybdenum, and tin. In some embodiments, the upgrading catalyst may also comprise tungsten. The upgrading catalyst may also comprise another Group VIII transition metal (i.e., Pt, Ni, Co, Rh, Ir, Ru, Fe, Os, etc.) as a substitute or complement to palladium, and / or be disposed on an acidic support.

[0066] In some embodiments, the loading of palladium or other Group VIII transition metals ranges from 0.05 wt% to 5.0 wt% based on the total weight of the upgrading catalyst. The palladium content 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 palladium from greater than 0.05 wt% to less than 5.0 wt% based on the total weight of the catalyst.

[0067] In some embodiments, the molybdenum loading ranges from 0.05 wt% to 10 wt% based on the total weight of the upgrading catalyst. The molybdenum content 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 molybdenum from greater than 0.05 wt% to less than 10.0 wt% based on the total weight of the catalyst.

[0068] In some embodiments, the tin loading ranges from 0.0125 wt% to 5 wt% based on the total weight of the upgrading catalyst. The tin content 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 tin from greater than 0.0125 wt% to less than 5.0 wt% based on the total weight of the catalyst.

[0069] In some embodiments, the tungsten loading ranges from 0.1 wt% to 20 wt% based on the total weight of the upgrading catalyst. The tungsten content 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 tungsten from greater than 0.1 wt% to less than 20 wt% based on the total weight of the catalyst.

[0070] The atomic ratio of palladium to molybdenum can range 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 tin to molybdenum can range from 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 range from 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 optional Group VIII transition metal is used, the atomic ratio can be the same as that of palladium described above. In some embodiments, the catalyst is adhered to a tungsten-modified support, and the catalyst material composition is from 0.30 wt% to 18 wt% of the support. In some embodiments, the catalyst is adhered to a tungsten-modified acidic support, and the catalyst material composition is from 0.30 wt% to 18 wt% of the support.

[0071] The upgrading catalyst may include a support suitable for suspending the catalyst in the reaction stream. The support should provide a stable platform for the catalyst and reaction conditions. The support can take any form that is stable under the selected reaction conditions to function at the desired level, and is particularly stable in aqueous feed stream solutions, i.e., the support is hydrothermally stable. Such supports include, but are not limited to, nitrides, carbon, silica, alumina, zirconium oxide, titanium dioxide, vanadium oxide, cerium dioxide, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, zinc oxide, chromium oxide, zeolites, tungstate-treated zirconium oxide, titanium dioxide-zirconia, sulfated zirconium oxide, phosphorylated zirconium oxide, acidic alumina, silica-alumina, sulfated alumina, ferric aluminate, phosphorylated alumina, θ-alumina, niobium oxide, niobium phosphate, oxides of the foregoing, and mixtures thereof. Nanoporous supports, such as zeolites, carbon nanotubes, or carbofullerenes, may also be used.

[0072] In some embodiments, the support comprises zirconium oxide. Zirconia can be produced, for example, by precipitation of zirconium hydroxide from a zirconium salt, by sol-gel treatment, or any other method. Zirconia is preferably present in a crystalline form achieved by calcining the precursor material at temperatures exceeding 400°C, and can comprise both tetragonal and monoclinic phases. Modifying agents can be added to improve the structural or catalytic properties of zirconium oxide. Such modifiers include, but are not limited to, sulfates, tungstates, phosphates, titanium dioxide, silica, and oxides of Group IIIB metals (especially Ce, La, or Y).

[0073] In some embodiments, the upgrading catalyst support further includes a modifier. For example, the support can be modified by treating it with a modifier selected from the group consisting of tungsten, titanium dioxide, sulfate, phosphate, or silica. In some embodiments, the upgrading catalyst includes Pd, Mo, Sn, and / or W on tungsten-modified monoclinic zirconia. In some embodiments, the upgrading catalyst includes Pd, Mo, Sn, and / or W on tungsten-modified tetragonal zirconia.

[0074] In some embodiments, the upgrading catalyst catalyzes the hydrogenation, hydrocracking, or a combination thereof of the heavy residue stream. In some embodiments, in addition to the HDO reaction of the heavy residue stream, the upgrading catalyst catalyzes the hydrogenation or hydrocracking reaction.

[0075] In some embodiments, the upgrading catalyst is a hydrogenation catalyst. The hydrogenation catalyst may include a support and Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, Re, Cu, their alloys, or combinations thereof. In some embodiments, the hydrogenation catalyst further includes Ag, Au, Cr, Zn, Mn, Sn, Bi, Mo, W, B, P, their alloys, or combinations thereof. In some embodiments, the support comprises any one selected from nitrides, carbon, silica, alumina, zirconium oxide, titanium dioxide, vanadium oxide, cerium dioxide, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, zinc oxide, chromium oxide, and mixtures thereof. In some embodiments, the support is carbon treated with hydrogen peroxide. In some embodiments, the support is modified by treating the support with a modifier, said modifier being a silane, alkali metal compound, alkaline earth metal compound, or lanthanide. In some embodiments, the support comprises carbon nanotubes, carbofullerenes, and zeolites.

[0076] In some embodiments, the upgrading catalyst is a hydrocracking catalyst. The hydrocracking catalyst is a bifunctional catalyst capable of rearranging and disrupting hydrocarbon chains and adding hydrogen to aromatic compounds and olefins to produce cycloalkanes and alkanes. The hydrocracking catalyst combines acid and hydrogenation functions. The acid function can be provided by a support with a large surface area and surface acidity, such as alumina halides, zeolites, amorphous silica-alumina, clay, or mixtures thereof. The hydrogenation function can be provided 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 catalyst for catalytic hydrocracking can consist of a weakly acidic support.

[0077] In some embodiments, an aqueous feed stream undergoes an HDO reaction with hydrogen in a first reactor to produce an intermediate stream, and a upgrading reaction of a heavy residue stream occurs in a second reactor. In some embodiments, the first and second reactors are different, allowing independent control of conditions in each reactor. 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 may be the same, and the HDO reaction and the upgrading reaction may be carried out in a single reactor containing such a catalyst. The first and second reactors may be housed in a single reactor vessel. For example, the HDO reaction and the upgrading reaction may be carried out in a first reactor and a second reactor housed in a single reactor vessel, respectively. In some embodiments, the hydrodeoxygenation catalyst and the upgrading catalyst are selected independently of whether the first and second reactors are in the same reactor vessel or in different reactor vessels. For example, when the first and second reactors are in the same reactor vessel, the catalysts may be the same or different. Alternatively, when the first and second reactors are in different reactor vessels, the catalysts may be the same or different.

[0078] In some embodiments, the reaction pressure of the second reactor is from 70 psig to 2000 psig, including but not limited to 100 psig to 1800 psig, 100 psig to 1500 psig, 100 psig to 1200 psig, 100 psig to 1000 psig, 100 psig to 800 psig, or 100 psig 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.

[0079] In some embodiments, the reaction temperature in the second reactor is from 100°C to 300°C, including but not limited to 120°C to 300°C, 150°C to 300°C, 200°C to 300°C, and 200°C to 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.

[0080] In some embodiments, the heavy residual stream is reacted with the upgrading catalyst at a rate of at least 0.01 g oxygen-containing hydrocarbons / g upgrading catalyst (e.g., heterogeneous catalyst) / hour (g / g). h -1 or h -1 Contact. In some implementations, the WHSV is from 0.01h. -1 Up to 40.0 h -1 including but not limited to 0.01 h -1 0.025 h -1 0.05 h -1 0.075 h -1 0.1 h -1 0.25 h -1 0.5 h -1 0.75 h -1 1.0 h -1 1.0 h -1 1.1 h -1 1.2 h -1 1.3 h -1 1.4 h -1 1.5 h -1 1.6 h -1 1.7h -1 1.8 h -1 1.9 h -1 2.0 h -1 2.1 h -1 2.2 h -1 2.3 h -1 2.4 h -1 2.5 h -1 2.6 h -1 2.7 h -1 2.8 h -1 2.9 h -1 3.0 h -1 3.1 h -1 3.2 h -1 3.3 h -1 3.4 h -1 3.5 h -13.6 h -1 3.7 h -1 3.8h -1 3.9 h -1 4.0 h -1 4.1 h -1 4.2 h -1 4.3 h -1 4.4 h -1 4.5 h -1 4.6 h -1 4.7 h -1 4.8 h -1 4.9 h -1 5.0 h -1 6 h -1 7 h -1 8 h -1 9 h -1 10 h -1 11 h -1 12 h -1 13 h -1 14 h -1 15 h -1 20h -1 25 h -1 30 h -1 35 h -1 and 40 h -1 .

[0081] In some embodiments, the upgrading catalyst operates without catalyst regeneration for at least 20 days, 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 catalyst can operate without catalyst regeneration for durations ranging from 20 to 300 days, from 30 to 270 days, from 30 to 240 days, from 30 to 210 days, from 30 to 180 days, from 30 to 150 days, from 30 to 120 days, from 30 to 90 days, or from 30 to 60 days.

[0082] At least a portion of the first oxygen-containing compound stream and at least a portion of the second oxygen-containing compound stream may be combined to form an upgraded oxygen-containing compound stream. In some embodiments, all first oxygen-containing compound streams and all second oxygen-containing compound streams are combined to form an upgraded oxygen-containing compound stream.

[0083] In another aspect, this disclosure provides a method for producing C 4+ A method for producing an upgraded oxygen-containing compound stream according to a method as described herein, and reacting the upgraded oxygen-containing compound stream in the presence of a condensation catalyst to produce C. 4+ Compounds.

[0084] C 4+ Compounds include members selected from the group consisting of: C 4+ alcohols, C 4+ Ketones, C 4+ Alkanes, C 4+ Olefins, C 5+ Cycloalkane, C 5+ Cyclic olefins, aryl groups, fused aryl groups, and mixtures thereof. In one exemplary embodiment, C 4+ Alkanes include branched or straight-chain C46 ... 4-30 Alkanes, or branched or straight-chain C 4-9 Alkanes, C 7-14 Alkanes, C 12-24 Alkanes, or mixtures thereof. In another exemplary embodiment, C 4+ Olefins include branched or straight-chain C466. 4-30 Alkenes, or branched or straight-chain C 4-9 Olefins, C 7-14 Olefins, C 12-24 Olefins, or mixtures thereof. In another exemplary embodiment, C 5+ Cycloalkanes include mono-substituted or poly-substituted C46 ... 5+ Cycloalkanes, wherein at least one substituted group is a branched C. 3+ Alkyl, straight-chain C 1+ Alkyl, branched C 3+ Alkylene, straight-chain C 1+ alkylene, phenyl or combinations thereof, or branched C 3-12 Alkyl, straight-chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight-chain C 1-12 alkylene, phenyl or combinations thereof, or branched C 3-4 Alkyl, straight-chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight-chain C 1-4 Alkylene, phenyl, or combinations thereof. In another exemplary embodiment, C 5+ Cyclic alkenes include mono- or poly-substituted C-14 atoms. 5+ Cyclic olefins, wherein at least one substituted group is a branched C. 3+ Alkyl, straight-chain C 1+ Alkyl, branched C 3+Alkylene, straight-chain C 2+ alkylene, phenyl or combinations thereof, or branched C 3-12 Alkyl, straight-chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight-chain C 2-12 alkylene, phenyl or combinations thereof, or branched C 3-4 Alkyl, straight-chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight-chain C 2-4 Alkylene, phenyl, or combinations thereof. In another exemplary embodiment, the aryl group comprises an unsubstituted aryl group, or a monosubstituted or polysubstituted aryl group, and at least one substituted group is a branched C-chain group. 3+ Alkyl, straight-chain C 1+ Alkyl, branched C 3+ Alkylene, straight-chain C 2+ alkylene, phenyl or combinations thereof, or branched C 3-12 Alkyl, straight-chain C 1-12 Alkyl, branched C 3-12 Alkylene, straight-chain C 2-12 alkylene, phenyl or combinations thereof, or branched C 3-4 Alkyl, straight-chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight-chain C 2-4 Alkylene, phenyl, or combinations thereof. In another exemplary embodiment, the fused aryl group comprises an unsubstituted fused aryl group, or a monosubstituted or polysubstituted fused aryl group, and at least one substituted group is a branched C. 3+ Alkyl, straight-chain C 1+ Alkyl, branched C 3+ Alkylene, straight-chain C 2+ alkylene, phenyl or combinations thereof, or branched C 3-4 Alkyl, straight-chain C 1-4 Alkyl, branched C 3-4 Alkylene, straight-chain C 2-4 Alkylene, phenyl, or combinations thereof. In another exemplary embodiment, C 4+ Alcohols include those according to formula R 1 Compounds with -OH groups, where R 1 It is a branch C 4+ Alkyl, straight-chain C 4+ Alkyl, branched C 4+ Alkylene, straight-chain C 4+ Alkylene, substituted C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloolefins, unsubstituted C 5+Cycloolefins, aryl groups, phenyl groups, or combinations thereof. In the preparation of C... 4+ In another exemplary embodiment of the compound method, C 4+ Ketones include those according to formula The compound in which R 3 and R 4 Independently, it is branch C 3+ Alkyl, straight-chain C 1+ Alkyl, branched C 3+ Alkylene, straight-chain C 2+ Alkylene, substituted C 5+ Cycloalkanes, unsubstituted C 5+ Cycloalkanes, substituted C 5+ Cycloolefins, unsubstituted C 5+ Cycloolefins, aryl groups, phenyl groups, or combinations thereof.

[0085] Condensation catalysts are generally catalysts capable of forming longer-chain compounds by linking two molecules (e.g., oxygen-containing substances) via new carbon-carbon bonds and converting the resulting compound into hydrocarbons, alcohols, or ketones. In some embodiments, the condensation catalyst is an acid condensation catalyst. Condensation catalysts can include, but are not limited to, carbides, nitrides, zirconium oxide, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxide, zinc oxide, vanadium oxide, lanthanum oxide, yttrium oxide, scandium oxide, magnesium oxide, cerium oxide, barium oxide, calcium oxide, hydroxides, heteropoly acids, inorganic acids, acid-modified resins, base-modified resins, and combinations thereof. Condensation catalysts can include, alone or in combination with, modifiers such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. Condensation catalysts may also include metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, their alloys and combinations thereof, to provide metallic functionality.

[0086] Condensation catalysts can be self-supporting (i.e., the catalyst does not require another material as a support) or may require a separate support suitable for suspending the catalyst in the reaction stream. A particularly advantageous support is silica, especially silica with a high surface area (greater than 100 m² / g) obtained through sol-gel synthesis, precipitation, or fumigation. In other embodiments, particularly when the condensation catalyst is a powder, the catalyst system may include a binder to help shape the catalyst into a desired catalyst shape. Suitable molding processes include extrusion, granulation, oil dropleting, or other known processes. Zinc oxide, alumina, and a peptizing agent can also be mixed together and extruded to produce a shaped material. After drying, the material is calcined at a temperature suitable for forming the catalytically active phase, which typically requires temperatures exceeding 450°C.

[0087] Unrestricted by any theory, the relationship between the purged HDO tower substrate material and coking in the AC can be established. Figure 3 The figure is shown in the middle. The baseline situation, where all products from the HDO are supplied to the AC, is represented by the upper right corner of the graph. The data points shown represent the case where the bottom stream from the separator is not fed to the AC (purged AC) and only the volatile overhead fraction is fed to the AC. The y-axis represents, as a baseline, how much carbon is still fed forward to the AC (blue points show only ~20% supplied to the AC / 80% purged, and orange points show ~75% of the carbon fed forward / purge ~25%). The x-axis then shows how much the coking rate (similar to specific productivity) is reduced due to the effect of not feeding the bottom stream to the AC. If the purged bottom material is perfectly homogeneous, the data points will descend along a 45° isohyet line (i.e., removing half the carbon results in a halved coking rate). The fact that these points lie above this line shows that the purged bottom material results in a disproportionate reduction in coking on the AC. For example, orange dots indicate that the coke contributed by the bottom material to the AC catalyst is approximately 3-4 times greater than that contributed by lighter products. Therefore, these data suggest that the less volatile HDO products contribute more significantly to AC coking.

[0088] As a non-limiting illustration, certain important advantages of the system of the present invention for upgrading heavy HDO products (such as those from PV tower bottoms) are as follows: Figure 4 The following is shown. The basic situation of a single reactor for HDO is shown in the left column. The total H / C ratio of all HDO products is also shown. eff The total H / C is represented by the blue circle. eff In many historical runs, it was ~1.5. The total H / C effThis includes two subsets of HDO products: PV bottoms (orange) and all volatile / top HDO products (green). The size of the circles indicates the relative amount of carbon in each group. The H / C ratio of the HDO top products is also shown. eff H / C of PV tower bottom eff There are significant differences between them in their selectivity for coking in the AC reactor. Increasing the conversion level of the PV bottoms stream is desirable to avoid excessive coking in the AC that this stream would cause. In the middle column, the PV bottoms conversion is increased by simply increasing the conversion level in a single primary HDO reactor. This increase in conversion will also lead to an increase in overhead products, which is undesirable because they will no longer form much coke on the AC catalyst, and the H / C ratio of this stream... eff The higher the concentration of alkane, the lighter the alkanes produced in the AC process, resulting in lower yields of AC liquid products (e.g., aromatic products). Upgrading the PV column bottoms (right column) achieves two objectives. In this case, the PV column bottoms are upgraded in a separate reactor while the HDO column overhead remains unchanged, achieving the optimal result of the highest AC liquid product yield and the lowest AC coking.

[0089] Unless otherwise explicitly stated in the context, the term "a" may be understood to mean "at least one / a". As used herein, the term "or" may be understood to mean "and / or". The terms "comprising" and "including" may be understood to cover the listed components or steps, whether presented individually or together with one or more additional components or steps. The terms "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 allow for variations in standards (e.g., 10%), as understood by one of ordinary skill in the art. Within the scope provided herein, endpoints are included.

[0090] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. All definitions as defined herein and as used herein should be understood as control dictionary definitions, definitions in incorporated documents by reference, and / or the ordinary meaning of the defined terms.

[0091] The invention has been described according to one or more preferred embodiments, and it should be understood that many equivalents, substitutions, variations and modifications are possible and within the scope of the invention, in addition to those expressly stated.

[0092] Example Example 1: Testing of upgrading catalyst Reactors and conditions for catalyst testing A single 1 / 2” reactor was used to test each catalyst. There was no liquid circulation, and H2 was supplied in a single pass. The reactor was loaded by volume, and therefore the mass of each catalyst loaded varied, and the supply rate was adjusted to maintain a constant WHSV (~1 g non-aqueous component / h / g catalyst) for each catalyst. The reactor loading diagram is shown in […]. Figure 5 As shown in the figure, a batch of composite PV tower bottom product was used as feedstock AP9204-1, and the decomposition of this feedstock was carried out in... Figure 6 As shown in the figure. Typically, each catalyst is operated at several temperatures to evaluate performance. All catalysts were tested at 1800 psig and a high H2 co-supply rate (~4 mol H2 / mol C).

[0093] Test Results Three temperatures were tested to determine the total H / C of the product after upgrading. eff The two catalysts tested (HDO-1 and HDO-2) were standard HDO formulations. HDO-1 had a 2% Pd loading, and HDO-2 had a 1% Pd loading. Figure 7 The test results are shown. The composite feed (PV tower bottoms) has an H / C ratio of ~1.14. eff Furthermore, the products of both the HDO-1 and HDO-2 catalysts exhibited higher H / C ratios. eff The reaction typically exhibits a linear trend with temperature. Since there is no significant performance difference between the two catalysts, this indicates that these reactions are not limited by the metal content of the catalyst. Considering that for these products, the H / C ratio is ~1.4 to 1.8... eff The range will be desirable, as excessively high conversion rates may result in yield losses, and these results indicate that the conversion step will require a relatively mild temperature range of 250°C–270°C.

[0094] After testing the standard HDO catalyst, the performance of two semi-commercial catalysts was tested. These results were presented in... Figure 8As shown in the figure. KF-200 is a catalyst prepared by Albemarle (now Ketjen) with pgm functionality and a proprietary support. KL6560 is a Ni-based hydrotreating catalyst. KF-200 appears to fall on a similar slope to the HDO-1 and HDO-2 catalysts, although its activity may be slightly higher at the same temperature. The KL6560 catalyst exhibits unusual behavior, with a product H / C ratio regardless of temperature. eff Both are relatively stable. KL6560 may have deactivated more than other catalysts, and the effects of deactivation were unexpectedly offset by each gravimetric check (WC) at higher temperatures.

[0095] To test the theory that additional acid functionality on the catalyst would be beneficial, two alternative catalysts were tested. One was the DHOG catalyst, a tungsten-tungsten-supported zirconia catalyst with Pd / Ag, where tungsten provides the acidity. The other catalyst, W-HDO, is a standard HDO catalyst, but similarly fabricated with a tungsten-tungsten-supported zirconia. Results for both catalysts were obtained in... Figure 9 As shown in the figure. Both catalysts typically produce higher conversions at lower temperatures than the standard HDO catalyst. The DHOG catalyst is more typical in its operation, with its activity shifting towards lower temperatures. The DHOG catalyst showed almost no conversion at the initial temperature of 225 °C, indicating the potential lower limit of the reactor's service, at least for this particular catalyst. The W-supported HDO catalyst (W-HDO) was more challenging to operate. With each increase in temperature, the reaction rate increased significantly, leading to overconversion to highly alkane products. After collecting this high conversion data point, the temperature was cooled until significant exothermicity was lost, and then very slowly reheated back to the higher inlet temperature, where no significant exothermicity or overconversion was encountered in the subsequent time. This pattern was repeated several times during the tests. These catalysts demonstrate that the addition of tungsten for acidity results in a significant improvement in catalyst activity. The composition of the catalysts used in these tests is summarized in Table 1.

[0096] Table 1. Composition of the tested catalysts. Stability test The stability of the standard HDO catalyst was also tested. For this test, a 2% Pd HDO-1 formulation was used, but this time it was loaded onto the extrudate instead of onto a crushed support as all previously tested catalysts. The catalyst was run at a consistent temperature for several days. Results were... Figure 10 and Figure 11 As shown in the figure, there was a significant loss of activity during the first three days of testing, followed by relatively stable performance over the next three days.

[0097] Residue testing Another aspect measured in these tests is residue. Residue testing qualitatively assesses the amount of fouling that may occur in the AC evaporator when HDO products are evaporated for use in an acid condensation (AC) reactor. This test involves boiling a sample of HDO products on a hot plate and measuring the amount of residue remaining as the starting liquid changes. For all catalysts tested, the results of this test are in… Figure 12 As shown in the figure, the feed residue is indicated on the graph as ~0.2 wt%. All catalysts cause a reduction in product residue after reaching a moderate amount of conversion, typically reaching virtually zero at higher conversions. The three catalysts with some added acidity (KF-200, DHOG, and W-HDO) all showed an increase in residue at their lowest conversion points, indicating the possible presence of condensation or other reactions occurring at low temperatures that lead to higher residues.

[0098] Figure 13 Images of feed and product from HDO catalyst testing are shown. Color in the feed will generally be associated with higher residue levels.

[0099] Example 2: Quality Improvement Conditions To determine the optimal set of conditions for operating the PV bottoms reactor, a single 1” reactor was used for testing. Two different batches of PV bottoms were used as feedstock. Various temperatures, pressures, and flow rates were tested to determine the optimal conditions for operating the upgrade reactor. The loading diagram used for this test is shown in [link to diagram]. Figure 14 As shown in the figure. Two batches of PV tower bottoms were used as feedstock for these tests (AP9204-5 and AP9204-3), and their composition is shown in the figure. Figure 15 As shown in the figure, AP9204-5 was produced using HDO-2 tablets (with a relatively low total conversion), while AP9204-3 was produced using a standard HDO-1 catalyst (with a relatively high total conversion).

[0100] For this set of experiments, the upgrading reactor was operated independently using PV tower substrate material already produced and composited by the Eagle unit. For these tests, the upgrading reactor was never connected to the AC unit, and performance was based solely on the HDO product profile, primarily the H / C ratio of the products. eff (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 / C. eff . Figures 16-20 The effect of each parameter is shown separately. Figures 16-20In each of these series, the color represents a data point where all conditions remain constant except for the parameter of interest (which is the x-axis). For each color series, the parameter that remains constant is... Figures 16-19 As shown in the figure. The colors are inconsistent from one chart to the next. The catalyst used in this set of experiments was a sheet containing 1% Pd, 1% Mo, and 0.25% Sn on ZrO2, and was double-impregnated.

[0101] temperature Reactor temperature (inlet) affects the product H / C ratio eff The impact in Figure 16 As shown in the figure, the temperature of the upgrading reactor has a significant impact on the degree of conversion. On average, an increase of 10°C results in a ~0.1% increase in the H / C ratio of the product. eff This would be a significant change. Compared to the effect of pressure, an increase of 1100 psi (nearly three times) from 660 psig to 1760 psig only increases the conversion by ~0.08 H / C. eff This is a similar amount to increasing the inlet temperature by ~8°C. Raw material H / C eff The effect lies in its interaction with the product H / C eff Related (a more highly converted feedstock leads to a more highly converted product), especially at lower temperatures. Feedstock H / C eff The effect is significantly lower at higher temperatures.

[0102] Heavy Time Airspeed (WHSV) The result is Figure 17 As shown in the figure. For this experiment, WHSV was defined as the ratio of non-aqueous components in the PV bottom stream of the upgrading reactor per hour per mass of upgrading catalyst. As an example, using this definition, a PV bottom stream rate of 125 g / h would result in an upgrading WHSV of 1 when 20 wt% water (80 wt% non-aqueous components, or 100 g / h non-aqueous components) is supplied with 100 g of catalyst. As with the case of temperature, upgrading catalyst WHSV is also an important parameter. On average, a decrease of 0.1 WHSV results in ~0.07 H / C. eff Compared to temperature, a 10°C increase in inlet temperature will be equivalent to a decrease in WHSV of ~0.26. (From raw material H / C) eff The effect is similar to that of temperature, as less conversion of the feedstock leads to less conversion of the product, although this difference is more pronounced under lower conversion conditions and less pronounced under higher conversion conditions.

[0103] pressure The result is Figure 18As shown in the figure, the pressure in the upgrading reactor has no strong effect on the conversion rate. On average, for every 1000 psi of additional pressure, the H / C ratio of the product increases. eff Increase by ~0.1 H / C eff Compared to temperature, a 10°C increase results in an H / C ratio similar to an 800 psi increase in pressure. eff Improvements are needed. Considering commercial-scale equipment design and costs, a lower-pressure, higher-temperature reactor is likely to be far more advantageous than another high-pressure reactor. This minimal impact from pressure may indicate that the reaction is not limited by the incorporation of gaseous H2 in the same manner as the primary HDO reactor (which does have a stronger pressure effect on reactor performance).

[0104] Raw material H / C eff The result of the comparison is Figure 19 As shown in the diagram. When operating under conditions that otherwise produce a lower degree of conversion (lower temperature, higher WHSV), the initial H / C... eff Indeed for the final H / C implementation eff It has an impact. Under these conditions, a lower initial H / C eff This leads to a lower final H / C eff When operating under higher conversion conditions (higher temperature, lower WHSV), the initial H / C... eff The impact is minimal. The practical implications of these results are that lower conversion rates may be necessary in primary HDO reactors.

[0105] Water content in the feed to the upgrading reactor The effect of water content in the feed to the upgrading reactor was also investigated. Samples of the PV tower bottoms were diluted with water to varying degrees, from ~17 wt% water (the natural water concentration in the PV tower bottoms) to ~65 wt% water. The mixture was then fed into an HDO catalyst (HDO-2), which was prepared on a crushed support and loaded in a 1 / 2” reactor. With the addition of additional water, the feed rate was increased to maintain a constant carbon flow. The test results were presented in… Figure 20 As shown in the figure, there is essentially no performance loss as the water content increases up to ~30 wt%. However, there is a ~25% conversion loss with increasing water content in the feed. These results indicate that the performance of the upgrading process is not highly sensitive to water concentration.

[0106] Further studies can be conducted based on the conditions listed in Table 2. Specifically, the primary HDO reactor can be operated at a higher WHSV (lower conversion), and the same amount of catalyst taken from the baseline loading (without upgrading) can be used as the PV tower bottom upgrading catalyst, resulting in the same total HDO catalyst load as the baseline. The PFD in the flow diagram is... Figure 1B As shown in the image.

[0107] Table 2. Conditions for integrated PV tower bottoms upgrading To make PV tower bottoms upgrading work more effectively, the conversion equilibrium needs to be altered so that most of the conversion still occurs in the primary reactor. The feed to the upgrading reactor should be fully converted first, allowing for optimization of the upgrading reactor (and catalyst) to convert components that are difficult to convert in the primary reactor. Furthermore, the temperature of the upgrading reactor should be controlled to prevent runaway reactions.

[0108] For the sake of completeness, several aspects of the present invention are set forth in the following numbered items: Project 1. A method for producing an oxygen-containing compound product, the method comprising: (i) Reacting an aqueous feed stream containing oxygen-containing hydrocarbons with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream; (ii) Fractionating the intermediate stream into a fraction containing the first C 1+ O 1-3 The first oxygenated compound stream and the heavy residual stream from the hydrocarbon pool; (iii) Reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a second C 1+ O 1-3 The second oxygen-containing compound stream in the hydrocarbon pool, wherein a upgrading catalyst catalyzes the hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof of the heavy residue stream; and (iv) Combining at least a portion of the first oxygenated compound stream and at least a portion of the second oxygenated compound stream to form an improved oxygenated compound stream.

[0109] Project 2. The method according to Project 1, wherein the intermediate stream has an H / C ratio of 1.6 or less. eff .

[0110] Project 3. The method according to any one of Projects 1-2, wherein the heavy residual stream has a water content of less than 25% by weight.

[0111] Project 4. The method according to any one of Projects 1-3, wherein the heavy residual stream has a boiling point higher than that of the first oxygen-containing compound stream.

[0112] Project 5. The method according to any one of Projects 1-4, wherein the heavy residual stream has an H / C ratio of 1.3 or less. eff .

[0113] Item 6. The method according to any one of Items 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 reactor and the second reactor are different.

[0114] Item 7. The method according to any one of Items 1-5, wherein steps (i) and (iii) are carried out in a single reactor.

[0115] Project 8. The method according to any one of Projects 1-7, wherein the hydrodeoxygenation catalyst is a first hydrodeoxygenation catalyst and the upgrading catalyst is a second hydrodeoxygenation catalyst.

[0116] Project 9. The method according to Project 8, wherein the first hydrodeoxygenation catalyst and the second hydrodeoxygenation catalyst are the same.

[0117] Project 10. The method according to any one of Projects 1-7, wherein the upgrading catalyst catalyzes the hydrogenation, hydrocracking, or a combination thereof of heavy residual streams.

[0118] Item 11. The method according to any one of items 1-10, wherein the upgrading catalyst comprises a heterogeneous catalyst comprising palladium, molybdenum and tin.

[0119] Project 12. The method according to Project 11, wherein the upgrading catalyst further comprises tungsten.

[0120] Item 13. The method according to Item 11, wherein the upgrading catalyst comprises from 0.05 wt% to 5.0 wt% palladium.

[0121] Item 14. The method according to Item 11, wherein the upgrading catalyst comprises molybdenum from 0.05 wt% to 10.0 wt%.

[0122] Item 15. The method according to Item 11, wherein the upgrading catalyst comprises tin from 0.0125 wt% to 5.0 wt%.

[0123] Item 16. The method according to Item 12, wherein the upgrading catalyst comprises tungsten from 0.1 wt% to 20 wt%.

[0124] Item 17. The method according to any one of items 11-16, wherein the upgrading catalyst comprises a support.

[0125] Item 18. The method according to Item 17, wherein the carrier is selected from the group consisting of: nitrides, carbon, silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, vanadium oxide, cerium dioxide, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, zinc oxide, chromium oxide, zeolite, tungstate-treated zirconium oxide, titanium dioxide zirconium oxide, sulfated zirconium oxide, phosphorylated zirconium oxide, acidic aluminum oxide, silicon dioxide-alumina, sulfated aluminum oxide, ferric aluminate, phosphorylated aluminum oxide, θ-alumina, niobium oxide, niobium phosphate, oxides of the foregoing and mixtures thereof.

[0126] Item 19. The method according to Item 17, wherein the carrier further comprises a modifier selected from the group consisting of tungsten, titanium dioxide, sulfate, phosphate or silica.

[0127] Item 20. The method according to Item 6, wherein the second reactor has a reaction pressure ranging from 70 psig to 2000 psig.

[0128] Item 21. The method according to Item 6, wherein the second reactor has a reaction temperature from 100°C to 300°C.

[0129] Project 22. The method according to any one of Projects 1-21, wherein the heavy residual stream is contacted with the upgrading catalyst at a weight hourly space velocity of at least 0.01 g oxygenated hydrocarbon / g upgrading catalyst / hour.

[0130] Project 23. The method according to any one of Projects 1-22, wherein the upgrading catalyst operates continuously for at least 20 days without catalyst regeneration.

[0131] Project 24. A method for producing C 4+ A method for compounding, the method comprising: Producing an upgraded oxygenated compound stream according to any one of items 1-23; and In the presence of a condensation catalyst, the upgraded oxygen-containing compound stream is reacted to produce C. 4+ Compounds.

Claims

1. A method for producing an oxygen-containing compound product, the method comprising: (i) Reacting an aqueous feed stream containing oxygen-containing hydrocarbons with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream; (ii) Fractionating the intermediate stream into a fraction containing a first C 1+ O 1-3 The first oxygenated compound stream and the heavy residual stream from the hydrocarbon pool; (iii) Reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a product containing a second C 1+ O 1-3 A second oxygenated compound stream in a hydrocarbon pool, wherein the upgrading catalyst catalyzes the hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof of the heavy residual stream; as well as (iv) Combining at least a portion of the first oxygenated compound stream and at least a portion of the second oxygenated compound stream to form an improved oxygenated compound stream.

2. The method of claim 1, wherein the intermediate stream has an H / C ratio of 1.6 or less. eff .

3. The method according to any one of claims 1-2, wherein the heavy residual stream has a water content of less than 25% by weight.

4. The method according to any one of claims 1-3, wherein the heavy residual stream has a boiling point higher than that of the first oxygen-containing compound stream.

5. The method according to any one of claims 1-4, wherein the heavy residual stream has an H / C ratio of 1.3 or less. eff .

6. The method according to any one of claims 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 reactor and the second reactor are different.

7. The method according to any one of claims 1-5, wherein steps (i) and (iii) are carried out in a single reactor.

8. The method according to any one of claims 1-7, wherein the hydrodeoxygenation catalyst is a first hydrodeoxygenation catalyst, and the upgrading catalyst is a second hydrodeoxygenation catalyst.

9. The method according to claim 8, wherein the first hydrodeoxygenation catalyst and the second hydrodeoxygenation catalyst are the same.

10. The method according to any one of claims 1-7, wherein the upgrading catalyst catalyzes the hydrogenation, hydrocracking, or a combination thereof of the heavy residual stream.

11. The method according to any one of claims 1-10, wherein the upgrading catalyst comprises a heterogeneous catalyst, and the heterogeneous catalyst comprises palladium, molybdenum and tin.

12. The method of claim 11, wherein the upgrading catalyst further comprises tungsten.

13. The method of claim 11, wherein the upgrading catalyst comprises from 0.05 wt% to 5.0 wt% palladium.

14. The method of claim 11, wherein the upgrading catalyst comprises from 0.05 wt% to 10.0 wt% molybdenum.

15. The method of claim 11, wherein the upgrading catalyst comprises from 0.0125 wt% to 5.0 wt% tin.

16. The method of claim 12, wherein the upgrading catalyst comprises from 0.1 wt% to 20 wt% tungsten.

17. The method according to any one of claims 11-16, wherein the upgrading catalyst comprises a support.

18. The method of claim 17, wherein the carrier is selected from the group consisting of: nitrides, carbon, silicon dioxide, aluminum oxide, zirconium oxide, titanium dioxide, vanadium oxide, cerium dioxide, boron nitride, heteropolyacids, diatomaceous earth, hydroxyapatite, zinc oxide, chromium oxide, zeolite, tungstate-treated zirconium oxide, titanium dioxide zirconium oxide, sulfated zirconium oxide, phosphorylated zirconium oxide, acidic aluminum oxide, silicon dioxide-alumina, sulfated aluminum oxide, ferric aluminate, phosphorylated aluminum oxide, θ-alumina, niobium oxide, niobium phosphate, oxides of the foregoing and mixtures thereof.

19. The method of claim 17, wherein the carrier further comprises a modifier selected from the group consisting of tungsten, titanium dioxide, sulfate, phosphate or silicon dioxide.

20. The method of claim 6, wherein the second reactor has a reaction pressure from 70 psig to 2000 psig.

21. The method of claim 6, wherein the second reactor has a reaction temperature from 100°C to 300°C.

22. The method according to any one of claims 1-21, wherein the heavy residual stream is contacted with the upgrading catalyst at a weight hourly space velocity of at least 0.01 g of oxygenated hydrocarbon / g of upgrading catalyst / hour.

23. The method according to any one of claims 1-22, wherein the upgrading catalyst operates for at least 20 days without the regeneration of the catalyst.

24. A method for producing C 4+ A method for compounding, the method comprising: The method according to any one of claims 1-23 produces the improved oxygenated compound stream; as well as The upgraded oxygen-containing compound stream is reacted in the presence of a condensation catalyst to produce the C. 4+ Compounds.

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