Reduction of Acid Condensation Catalyst Coke Yield by Selective Vaporization of the Hydrodeoxygenation Heavies Stream

This application claims the benefit of priority to U.S. Provisional Application No. 63/662,829, filed Jun. 21, 2024, the entire contents of which is incorporated by reference herein.

Significant amount of attention has been placed on developing new technologies for more efficient energy production. Bioreforming processes can produce aromatic hydrocarbons and other useful compounds from biomass feedstocks, including 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) or other compounds into hydrocarbons.

APR and HDO methods and techniques are described in U.S. Pat. Nos. 6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all to Cortright et al., entitled “Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons”); U.S. Pat. No. 6,953,873 (to Cortright et al., entitled “Low-Temperature Hydrocarbon Production from Oxygenated Hydrocarbons”); and U.S. Pat. Nos. 7,767,867; 7,989,664; and 8,198,486 (all to Cortright, entitled “Methods and Systems for Generating Polyols”), all of which are incorporated herein by reference. Various other APR and HDO methods and techniques are also described in U.S. Pat. Nos. 8,053,615; 8,017,818; 7,977,517; 8,362,307; 8,367,882; and 8,455,705 (all to Cortright and Blommel, entitled “Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons”); U.S. Pat. No. 8,231,857 (to Cortright, and entitled “Catalysts and Methods for Reforming Oxygenated Compounds”); U.S. Pat. No. 8,350,108 (to Cortright et al., entitled “Synthesis of Liquid Fuels from Biomass”); and International Patent Application No. PCT/US2008/056330 (to Cortright and Blommel, entitled “Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons” and published as WO2008109877A1), all of which are incorporated herein by reference.

It is well established that coking leads to the deactivation of acid condensation catalysts. This phenomenon is a ubiquitous problem in the modern petrochemical and energy transformation industries. The acid condensation catalyst gradually accumulates deposits of coke as the reaction proceeds. The activity of the catalyst gradually declines due to the buildup of coke. Coke formation is believed to result from the deposition of coke precursors including high molecular weight materials and condensed ring aromatic molecules on the catalyst, these polymerizing to form coke. Eventually, economics dictates the necessity of reactivating the catalyst. Consequently, in all processes of this type, the catalyst must necessarily be periodically regenerated. Regeneration often requires time-consuming, costly steps that may remove the catalytic system from operation.

Accordingly, there is a need for methods and systems for reducing coke yield to prolong the activity of catalysts.

Some aspects of the present disclosure provide a method of producing a Ccompound, including the steps of: (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation (HDO) catalyst to produce an HDO product stream; (ii) vaporizing the HDO product stream in a vaporizer to produce a gaseous HDO product stream comprising COhydrocarbons; and (iii) reacting the gaseous HDO product stream in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the Ccompound.

The HDO product stream can be introduced to a packed bed in an upper section of the vaporizer.

At least a first portion of the AC product stream can be recycled to the vaporizer and contacted with the HDO product stream, such that the gaseous HDO product stream is produced from vaporizing the HDO heavy stream and the recycled AC product stream. In some embodiments, at least a second portion of the AC product stream is recycled to the gaseous HDO product stream.

The AC product stream recycled to the vaporizer can be a gas. The temperature of the gaseous AC product stream entering the vaporizer has an inlet temperature of at least 160° C. The AC product stream recycled to the vaporizer can enter the vaporizer at a location below the packed bed to which the HDO heavy stream is introduced.

Step (ii) can further comprise introducing a superheated high-pressure steam to the vaporizer. For example, the superheated high-pressure steam can enter the vaporizer at a location below the AC product stream recycled to the vaporizer.

The HDO product stream can be preheated before entering the vaporizer.

The ratio of the feed rate of the AC product stream recycled to the vaporizer to the feed rate of the HDO product stream can be about 0.5:1 to about 10:1.

The vaporizer can be operated at a temperature of at about 150° C. to about 300° C.

Some aspects of the present disclosure provide a system for producing a Ccompound, the system including (i) an hydrodeoxygenation (HDO) reactor, in which an aqueous feed stream comprising an oxygenated hydrocarbon reacts with hydrogen in the presence of an HDO catalyst to produce an HDO product stream; (ii) a vaporizer, in which the HDO product stream is vaporized to produce a gaseous HDO product stream comprising COhydrocarbons; and (iii) an acid condensation (AC) reactor, in which the gaseous HDO product stream reacts in the presence of an AC catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the Ccompound.

The present disclosure relates to processes and systems for acid condensation (AC) reactions, including as can be implemented downstream of HDO reactions. The methods and systems for reducing coke yield to prolong the activity of AC catalysts.

In one aspect, disclosed herein are methods of producing a Ccompound, including (i) reacting an aqueous feed stream including an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation (HDO) catalyst to produce an HDO product stream; (ii) vaporizing the HDO product stream in a vaporizer to produce a gaseous HDO product stream including COhydrocarbons; and (iii) reacting the gaseous HDO product stream in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the Ccompound.

In another aspect, disclosed herein are systems for producing a Ccompound, the system including: (i) an hydrodeoxygenation (HDO) reactor, in which an aqueous feed stream including an oxygenated hydrocarbon reacts with hydrogen in the presence of an HDO catalyst to produce an HDO product stream; (ii) a vaporizer, in which the HDO product stream is vaporized to produce a gaseous HDO product stream including COhydrocarbons; and (iii) an acid condensation (AC) reactor, in which the gaseous HDO product stream reacts in the presence of an AC catalyst at a condensation temperature and condensation pressure to produce an AC product stream including the Ccompound.

Generally, the technology disclosed herein can be used to improve AC processing for a wide range of feed streams. As an example context,illustrates a system for treatment of HDO products in advance of AC processing, with the relevant HDO reactions being implemented for a feed stream from an upstream hydrogenation reactor system (not shown). A wide variety of systems can be implemented to provide a feed stream to an AC reactor system (e.g., as variously disclosed in U.S. Pat. Nos. 6,699,457; 6,964,757; 6,964,758; 7,618,612; 6,953,873; 7,767,867; 7,989,664; 6,953,873; 7,767,867; 7,989,664; 8,198,486; 8,053,615; 8,017,818; 7,977,517; 8,362,307; 8,367,882; 8,455,705 8,231,857; and 8,350,108; in International Patent Publication WO2008109877A1; or as otherwise known in the art). In some cases, the aqueous feed stream is derived from biomass.

The products of HDO reaction can be fractionated into an HDO light stream and an HDO heavy stream. As used herein, the term “HDO light stream” or “HDO lights” can refer to products deriving from the vapor stream leaving the bottom of a HDO reactor. In practice, a certain portion of vapor products can flash off from the HDO reactor liquid product when the pressure is letdown in a HDO product flash drum, which can be referred to as HDO product flash drum overheads. As used herein, the term “HDO heavy stream” or “HDO heavies” can refer to a remaining liquid phase when the HDO reactor liquid product is let down in pressure from about 125 bara to 20 bara in an adiabatic flash that is carried out in the HDO product flash drum (with a resulting temperature of 230-290° C.). The HDO heavies can include Cproducts as main components, including C-Cdiols as well as heavy Ccomponents such as 1,4-sorbitan and 2,5-bis(hydroxymethyl)tetrahydrofuran. The term “HDO product stream” can typically refer to the HDO heavy stream as defined herein or an HDO reaction-derived stream fed in to the vaporizer, which comprises at least a portion of the HDO heavy stream. The HDO light stream may be directly fed to downstream AC reaction. The present method can be used to isolate gaseous HDO products from the HDO heavy stream. The isolated gaseous HDO products can then be combined with the HDO light stream and fed to the AC reaction.

For example, referring to, the present method can include: (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation (HDO) catalyst to produce an HDO light stream including a first pool of COhydrocarbons and an HDO heavy stream (); (ii) vaporizing at least a portion of the HDO heavy stream in a vaporizer to produce a gaseous HDO product stream () including a second pool of COhydrocarbons; and (iii) feeding the HDO light stream and the gaseous HDO product stream to an acid condensation (AC) reactor, thereby reacting the first and second pools of COhydrocarbons in the presence of an acid condensation catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the Ccompound.

As used herein, the term “vaporize” or “vaporization” refers to converting a material to the gas phase or to a vapor (e.g., a mist). Any suitable vaporizer can be used to vaporize the HDO product stream. In some cases, the vaporizer is a selective vaporize. For example, the vaporizer can be a pressure vessel with a bed of packing or multiple beds of packing. The vaporizer may include a bed of packing. In some cases, the bed of packing may be random. In some cases, the bed of packing may be structured. In some cases, the vaporizer has an upper section, a middle section, and a lower section. In some cases, the bed of packing is located in a middle section, an upper section, or a lower section. In some cases, the HDO product stream is introduced to a packed bed in an upper section of the vaporizer. In some cases, the HDO heavy stream is introduced in an upper section of the vaporizer, above a bed of packing. In some cases, the HDO product stream may be introduced to the vaporizer via a liquid distributor. For example, the liquid distributor can be a spray nozzle where the stream is liquid only. In some cases, the HDO product stream is preheated before entering the vaporizer by a preheater (see, structure B). In some cases, the HDO heavy stream is preheated () before entering the vaporizer. For example, the stream is heated upstream of the selective vaporizer in a heat exchanger using hot oil. A portion of the stream can be vaporized in the heat exchanger itself such that the feed to the selective vaporizer is a vapor/liquid stream. In such cases, the inlet device can be a 2-phase inlet device (e.g., from a distillation column internals vendor such as Sulzer or Koch-Glitsch). In some cases, the HDO product stream (e.g., the HDO heavy stream) is introduced to the vaporizer at a feed rate. The feed rate of the HDO product stream can vary depending on the capacity of the plant. For lab scale tests, the feed rate can be about 100 g/hr to about 200 g/hr, about 50 g/hr to about 500 g/hr, about 75 g/hr to about 250 g/hr, or about 90 g/hr to about 210 g/hr. On a production scale, the HDO heavy stream feed rate may, in some embodiments, vary from 25 to 60 metric tons per hour. In another aspect, the vaporizer is operated at a temperature of at about 150° C. to about 300° C., such as about 200° C. to about 300° C., about 250° C. to about 300° C., about 250° C. to about 280° C., or about 250° C. to about 275° C. The operating temperature can vary based on the temperature of the AC product stream. In some embodiments, the AC product stream has a temperature of about 300° C. and the vaporizer is operated at a temperature of 280° C. at the start of run (SOR) and 265° C. at the end of run (EOR).

In another aspect, and still referring to, at least a first portion of the AC product stream () (e.g., preheated AC recycle gas) can be recycled to the vaporizer and contacted with the HDO heavy stream, such that the gaseous HDO product stream is produced from vaporizing the HDO heavy stream and the recycled AC product stream. Optionally, at least a second portion of the AC product stream is recycled to the gaseous HDO product stream. In some cases, the AC product stream is recycled to the gaseous HDO product stream via a Selective Vaporizer bypass line (). In some cases, the AC product stream recycled to the vaporizer enters the vaporizer at a location below the packed bed to which the HDO heavy stream is introduced (e.g., the AC product stream is introduced in a middle section of the vaporizer). In some cases, the AC product stream recycled to the vaporizer is a gas. In another aspect, the temperature of the AC product stream entering the vaporizer has an inlet temperature. In some cases, the inlet temperature is at least 100° C., at least 110° C., at least 120° C., at least 130° C., at least 140° C., at least 160° C., at least 170° C., at least 180° C., at least 190° C., at least 200° C., or at least 250° C. In some embodiments, the inlet temperature is about 300° C.

In another aspect, the step of vaporizing at least a portion of the HDO heavy stream in a vaporizer to produce a gaseous HDO product stream () including a second pool of COhydrocarbons may further include introducing a superheated high-pressure steam () to the vaporizer. As shown in, the superheated high-pressure steam enters the vaporizer at a location below the AC product stream (e.g., in a lower section of the vaporizer) recycled to the vaporizer. The AC product stream recycled to the vaporizer is introduced to the vaporizer at a feed rate. The feed rate of the AC product stream can vary depending on the capacity of the plant. For lab scale tests, the feed rate can be about 100 g/hr to about 1000 g/hr, about 1 g/hr to about 2000 g/hr, about 50 g/hr to about 100 g/hr, about 75 g/hr to about 1200 g/hr, or about 90 g/hr to about 1100 g/hr. On a production scale, the feed rate of the AC product stream recycled to the vaporizer heavy stream may, in some embodiments, vary from 200 to 260 metric tons per hour.

In another aspect, the feed rate of the AC product stream to the vaporizer and the feed rate of the HDO heavy stream to the vaporizer may be in a ratio. In some cases, the feed rate of the AC product stream and the feed rate of the HDO heavy stream is about 0.2:1 to about 100:1, about 0.5:1 to about 100:1, about 0.5:1 to about 50:1, about 0.5:1 to about 10:1; about 1:1 to about 50:1, about 2:1 to about 50:1, about 4:1 to about 20:1; about 4:1 to about 15:1, or about 4:1 to about 10:1. For example, the feed rate of the AC product stream and the feed rate of the HDO heavy stream can be about 4:8:1 at the start of run (SOR) to about 7.4:1 at the end of run (EOR).

Referring to, disclosed herein is a method including (i) reacting an aqueous feed stream including an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation (HDO) catalyst to produce an HDO product stream (); (ii) vaporizing the HDO product stream in a vaporizer to produce a gaseous HDO product stream including COhydrocarbons (); and (iii) reacting the gaseous HDO product stream in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the Ccompound (). In some cases, step (ii,) further includes introducing a superheated high-pressure steam to the vaporizer (). In some cases, at least a first portion of the AC product stream is recycled to the vaporizer and contacted with the HDO product stream (), such that the gaseous HDO product stream is produced from vaporizing the HDO heavy stream and the recycled AC product stream. Optionally, wherein at least a second portion of the AC product stream is recycled to the gaseous HDO product stream ().

The methods and systems disclosed herein may be carried out or operated batchwise or continuously.

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, Tl, and combinations thereof. In some embodiments, the HDO catalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W or Mo. In some embodiments, the HDO catalyst includes Fe or Re and at least one transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In some embodiments, the HDO catalyst includes Fe, Re and at least Cu or one Group VIIIB transition metal. In some embodiments, the metal of the HDO catalyst comprises Pd, W, Mo, Ni, Pt, Ru, or a combination thereof. In some embodiments, the HDO catalyst comprises a promoter. As an example, the promoter of the deoxygenation catalyst can comprise Sn, W, or a combination thereof. The support may include a nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacids, kieselguhr, hydroxyapatite, or a mixture thereof. In some embodiments, the support comprises zirconia.

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

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

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

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

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

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

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

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

The methods disclosed herein may reduce the coke yield on fouled acid condensation catalyst. The technology disclosed herein can be used to reduce coke yield on AC catalyst fouled during processing of a wide range of feed streams. As an example context, AC processing of hydrodeoxygenation (HDO) products, with the relevant HDO reactions being implemented for a feed stream from an upstream hydrogenation reactor system (not shown), are considered. A wide variety of systems can be implemented to provide a feed stream to an AC reactor system (e.g., as variously disclosed in U.S. Pat. Nos. 6,699,457; 6,964,757; 6,964,758; 7,618,612; 6,953,873; 7,767,867; 7,989,664; 6,953,873; 7,767,867; 7,989,664; 8,198,486; 8,053,615; 8,017,818; 7,977,517; 8,362,307; 8,367,882; 8,455,705 8,231,857; and 8,350,108; in International Patent Publication WO2008109877A1; or as otherwise known in the art). In some cases, the feed stream is derived from biomass. In some cases, the biomass feedstock includes cellulose, hemicellulose, and lignin. For instance, cellulose and hemicellulose.

In some examples, reacting the HDO product stream (or another product stream) in the presence of a condensation catalyst (i.e., in the AC reactor, D) can produce a Ccompound. The Ccompound can include a member selected from the group consisting of Calcohol, Cketone, Calkane, Calkene, Ccycloalkane, Ccycloalkene, aryl, fused aryl, and a mixture thereof. In one exemplary embodiment, the Calkane comprises a branched or straight chain Calkane, or a branched or straight chain C, C, Calkane, or a mixture thereof. In another exemplary embodiment, the Calkene comprises a branched or straight chain Calkene, or a branched or straight chain C, C, Calkene, or a mixture thereof. In another exemplary embodiment, the Ccycloalkane comprises a mono-substituted or multi-substituted Ccycloalkane, and at least one substituted group is a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, straight chain Calkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the Ccycloalkene comprises a mono-substituted or multi-substituted Ccycloalkene, and at least one substituted group is a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, straight chain Calkylene, 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 Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, 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 Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof, or a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the Calcohol comprises a compound according to the formula R—OH, wherein Ris a branched Calkyl, straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a substituted Ccycloalkane, an unsubstituted Ccycloalkane, a substituted Ccycloalkene, an unsubstituted Ccycloalkene, an aryl, a phenyl, or a combination thereof.

In another exemplary embodiment of method of making the Ccompound, the Cketone comprises a compound according to the formula

wherein Rand Rare independently a branched Calkyl, a straight chain Calkyl, a branched Calkylene, a straight chain Calkylene, a substituted Ccycloalkane, an unsubstituted Ccycloalkane, a substituted Ccycloalkene, an unsubstituted Ccycloalkene, an aryl, a phenyl, or a combination thereof. Examples of desirable Cketones include, without limitation, butanone, pentanone, hexanone, heptanone, octanone, nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone, pentadecanone, hexadecanone, heptyldecanone, octyldecanone, nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone, tetraeicosanone, or isomers thereof.

The condensation catalyst is generally a catalyst capable of forming longer chain compounds by linking two molecules (e.g., oxygen containing species or other functionalized compounds, including olefins) 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 (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48), 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, Fe, 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.

The condensation catalyst may include one or more zeolite structures comprising cage-like structures of silica-alumina. Zeolites are crystalline microporous materials with well-defined pore structures. Zeolites contain active sites, usually acid sites, which can be generated in the zeolite framework. The strength and concentration of the active sites can be tailored for particular applications. Examples of suitable zeolites for condensing secondary alcohols and alkanes may comprise aluminosilicates, optionally modified with cations, such as Ga, In, Zn, Mo, and mixtures of such cations, as described, for example, in U.S. Pat. No. 3,702,886, which is incorporated herein by reference. As recognized in the art, the structure of the particular zeolite or zeolites may be altered to provide different amounts of various hydrocarbon species in the product mixture. Depending on the structure of the zeolite catalyst, the product mixture may contain various amounts of aromatic and cyclic hydrocarbons.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5, and the conventional preparation thereof, is described in U.S. Pat. No. 3,702,886; Re. 29,948 (highly siliceous ZSM-5); U.S. Pat. Nos. 4,100,262 and 4,139,600, all incorporated herein by reference. Zeolite ZSM-11, and the conventional preparation thereof, is described in U.S. Pat. No. 3,709,979, which is also incorporated herein by reference. Zeolite ZSM-12, and the conventional preparation thereof, is described in U.S. Pat. No. 3,832,449, incorporated herein by reference. Zeolite ZSM-23, and the conventional preparation thereof, is described in U.S. Pat. No. 4,076,842, incorporated herein by reference. Zeolite ZSM-35, and the conventional preparation thereof, is described in U.S. Pat. No. 4,016,245, incorporated herein by reference. Another preparation of ZSM-35 is described in U.S. Pat. No. 4,107,195, the disclosure of which is incorporated herein by reference. ZSM-48, and the conventional preparation thereof, is taught by U.S. Pat. No. 4,375,573, incorporated herein by reference. Other examples of zeolite catalysts are described in U.S. Pat. Nos. 5,019,663 and 7,022,888, also incorporated herein by reference. An exemplary condensation catalyst is a ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Re, Ni, Sn, or combinations thereof.

As described in U.S. Pat. No. 7,022,888, which is incorporated herein by reference, the condensation catalyst may be a bifunctional pentasil zeolite catalyst including at least one metallic element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolite may have strong acidic sites, and may be used with reactant streams containing an oxygenated hydrocarbon at a temperature of below 580° C. The bifunctional pentasil zeolite may have ZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of a large number of 5-membered oxygen-rings (i.e., pentasil rings). In one embodiment the zeolite will have a ZSM-5 type structure.

Alternatively, solid acid catalysts such as alumina modified with phosphates, chloride, silica, and other acidic oxides may be used. Also, sulfated zirconia, phosphated zirconia, titania zirconia, or tungstated zirconia may provide the necessary acidity. Re and Pt/Re catalysts are also useful for promoting condensation of oxygenates to Chydrocarbons and/or Cmono-oxygenates. The Re is sufficiently acidic to promote acid-catalyzed condensation. In certain embodiments, acidity may also be added to activated carbon by the addition of either sulfates or phosphates.

The specific Ccompounds produced will depend on various factors, including, without limitation, the type of oxygenated compounds in the reactant stream, condensation temperature, condensation pressure, the reactivity of the catalyst, and the flow rate of the reactant stream as it affects the space velocity, GHSV, LHSV, and WHSV. In certain embodiments, the reactant stream is contacted with the condensation catalyst at a WHSV that is appropriate to produce the desired hydrocarbon products. In one embodiment the WHSV is at least 0.1 grams of volatile (CO) oxygenates in the reactant stream per gram catalyst per hour. In another embodiment the WHSV is between 0.1 to 10.0 g/g hr, including a WHSV of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g/g hr, and increments between.

In certain embodiments the condensation reaction is carried out at a temperature and pressure at which the thermodynamics of the proposed reaction are favorable. For volatile COoxygenates the reaction may be carried out at a temperature where the vapor pressure of the volatile oxygenates is at least 0.1 atm (and preferably a good deal higher). The condensation temperature will vary depending upon the specific composition of the oxygenated compounds. The condensation temperature will generally be greater than 80° C., or 100° C., or 125° C., or 150° C., or 175° C., or 200° C., or 225° C., or 250° C., and less than 500° C., or 450° C., or 425° C., or 375° C., or 325° C., or 275° C. For example, the condensation temperature may be between 80° C. to 500° C., or between 125° C. to 450° C., or between 250° C. to 425° C. The condensation pressure will generally be greater than 0 psig, or 10 psig, or 100 psig, or 200 psig, and less than 2000 psig, or 1800 psig or, or 1600 psig, or 1500 psig, or 1400 psig, or 1300 psig, or 1200 psig, or 1100 psig, or 1000 psig, or 900 psig, or 700 psig. For example, the condensation pressure may be greater than 0.1 atm, or between 0 and 1500 psig, or between 0 and 1200 psig.

Calkanes and Calkenes produced from acid condensation can have from 4 to 30 carbon atoms (Calkanes and Calkenes) and may be branched or straight chained alkanes or alkenes. The Calkanes and Calkenes may also include fractions of C, C, Calkanes and alkenes, respectively, with the Cfraction directed to gasoline, the Cfraction directed to jet fuels, and the Cfraction directed to diesel fuel and other industrial applications, such as chemicals. Examples of various Calkanes and Calkenes include, without limitation, butane, butene, pentane, pentene, 2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane, octene, 2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene, pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomers thereof.