Recovery of C4+ hydrocarbons from acid condensation product

Abstract

A method for producing a C4+ compound, including the steps of: (i) reacting a feed stream including C1+O1-3 hydrocarbons in the presence of an acid condensation (AC) catalyst at a condensation tempera

Description

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 662,803, filed June 21, 2024, the entire contents of which is incorporated by reference herein. BACKGROUND

[0002] 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.

[0003] 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. Patent No. 8,231,857 (to Cortright, and entitled “Catalysts and Methods for Reforming Oxygenated Compounds”); U.S. Patent 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.

[0004] Accordingly, there is a need for methods for efficiently recovering hydrocarbons produced during bioreforming processes. SUMMARY OF THE INVENTION

[0005] Some aspects of the present disclosure provide a method of producing a C4+ compound, including the steps of: (i) reacting a feed stream including C1+O1-3 hydrocarbons in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the C4+ compound; (ii) fractionating AC product stream into an AC liquid product stream comprising organic products and a vapor stream; (iii) compressing the vapor stream to form a compressed vapor stream; (iv) cooling a first portion of the compressed vapor stream to produce a first recovered liquid product stream and a first purge vapor stream; (v) recycling a second portion of the compressed vapor stream to the reaction of step (i); (vi) combining the AC liquid product stream and the first recovered liquid product stream to form a combined liquid product stream.

[0006] Step (ii) can be carried out in phase separator.

[0007] Step (iii) can be carried out by a gas compressor.

[0008] Step (iv) can comprise: (iv-a) cooling the first portion of the compressed vapor stream by a compressor suction cooler to produce a cooled vapor stream; and (iv-b) fractionating the cooled vapor stream in a separator into the first recovered liquid product stream and the first purge vapor stream. Step (iv) can further comprise (iv-c) fractionating the first purge vapor stream to produce a second recovered liquid product stream and a second purge vapor stream, optionally wherein the fractionating step comprises compressing and cooling the first vapor stream.

[0009] Step (vi) can comprise combining the AC liquid product stream, the first recovered liquid product stream, and the second recovered liquid product stream to form the combined liquid product stream.

[0010] The present method can further comprise (vii) isolating a liquid C4+ compound product stream from the combined liquid product stream. BRIEF DESCRIPTION OF DRAWINGS

[0011] FIG. 1 shows a schematic illustration of a method in accordance with some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present disclosure relates to processes and systems for recovery of C4+ products from acid condensation (AC) products.

[0013] In one aspect, referring to FIG. 1, disclosed herein are methods of producing a C4+ compound, including the steps of: (i) reacting a feed stream including C1+O1-3 hydrocarbons in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the C4+ compound (1); (ii) fractionating AC product stream into an AC liquid product stream (2) comprising organic products and a vapor stream (4); (iii) compressing the vapor stream to form a compressed vapor stream (5); (iv) cooling a first portion of the compressed vapor stream (6) to produce a first recovered liquid product stream (8) and a first purge vapor stream (9); (v) recycling a second portion of the compressed vapor stream to the reaction of step (i); (vi) combining the AC liquid product stream and the first recovered liquid product stream to form a combined liquid product stream. In some cases, the methods disclosed herein may further include isolating a liquid C4+ compound product stream (16) from the combined liquid product stream (15).

[0014] Generally, the technology disclosed herein can be used to improve AC processing for a wide range of feed streams. 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. Patents 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. In some cases, the feed stream may include C1+O1-3 hydrocarbons.

[0015] In one aspect, the methods disclosed herein include fractionating AC product stream into an AC liquid product stream, including organic products, and a vapor stream. Following the AC reaction, the crude AC product can be fed to an AC product separator, which acts as a decanter to separate the water in the crude AC product from the organic components, which can then be fed to a column for fractionation into the AC liquid and vapor streams (e.g., a Lights Column). Referring to FIG. 1, the AC product separator (component A) may perform the fractionation to produce stream AC Organic product (2) and vapor stream (4). An aqueous product stream (3) can also be produced, which can be sent for organics recovery. Fractionation may be accomplished by any suitable separation methods and systems known in the art. In some cases, fractionation is carried out by a phase separator. For example, the separator can be a 3-phase separator, which produces an aqueous liquid, an organic liquid, and a vapor phase.

[0016] In another aspect, the methods disclosed herein include compressing the vapor stream to form a compressed vapor stream. Referring to FIG. 1, vapor stream (4) by be compressed by an AC recycle compressor (B). Compression of the vapor stream (stream 4 of FIG. 1) may be accomplished by a gas compressor. For example, the AC recycle compressor can be a centrifugal compressor, a reciprocating compressor (piston or diaphragm), or a screw compressor depending on the production scale. In some embodiments, A reciprocating diaphragm compressor is used for the present method for relatively small-scale production.

[0017] In another aspect, the methods disclosed herein include cooling a first portion of the compressed vapor stream to produce a first recovered liquid product stream and a first purge vapor stream. This step may include cooling the first portion of the compressed vapor stream. In some cases, cooling the first portion of the compressed vapor stream may be carried out by a compressor suction cooler. For example, an air cooler, a cooling water exchanger, or a combination there of can be used to. In some embodiments, a combination of air cooler and cooling water exchanger is used to minimize cooling water usage. For example, in FIG 1, an AC purge gas compressor suction cooler (C) may be used to produce a cooled vapor stream (7). This step may further include fractionating the cooled vapor stream (7) in a vapor / liquid separator (FIG. 1, component D, “AC purge gas compressor knock out drum”) into the first recovered liquid product stream (8) and the first purge vapor stream (9). The separated vapor stream can then be sent to a compressor (FIG. 1, component E, “AC purge gas compressor”). In some cases, the method may further include fractionating the first purge vapor stream (9) to produce a second recovered liquid product stream (13) and a second purge vapor stream (14). As demonstrated herein, the fractionation process of the first purge vapor stream (9) can include compressing and cooling, as well as phase separation (FIG. 1, component H “AC purge gas knockout pot”), such that the second recovered liquid product stream (13) and the second purge vapor stream (14) can be produced (FIG. 1).

[0018] In another aspect, still referring to FIG. 1, the methods disclosed herein include combining the AC liquid product stream (2) (e.g., AC organic product) and the first recovered liquid product stream (8) (e.g., recovered liquids from the AC purge gas compressor suction drum) to form a combined liquid product stream (15) (e.g., lights column feed). This step may include combining the AC liquid product stream (2), the first recovered liquid product stream (8), and the second recovered liquid product stream (13) (e.g., recovered liquids from AC purge gas knock out pot) to form the combined liquid product stream (15).

[0019] In some cases, the methods disclosed herein may further include step (vii) isolating a liquid C4+ compound product stream (16) from the combined liquid product stream (15). In some cases, a yield of Ce+ compounds in the liquid C4+ compound product stream (16) of step (vii) is at least 0.1 wt%, at least 0.25 wt%, at least 0.5 wt%, at least 0.8 wt%, at least 0.9 wt %, at least 1.0 wt%, at least 1.3 wt% higher than a yield of Ce+ compounds in the AC liquid product stream (2) of step (ii).

[0020] AC Catalyst and AC Reactions

[0021] The methods and systems disclosed herein may be used for recovery of C4+ hydrocarbons produced from catalytic processes. 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. Patents 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.

[0022] 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 C4+ compound. The C4+ compound can include a member selected from the group consisting of C4+ alcohol, C4+ ketone, C4+ alkane, C4+ alkene, C5+ cycloalkane, C5+ cycloalkene, aryl, fused aryl, and a mixture thereof. In one exemplary embodiment, the C4+ alkane comprises a branched or straight chain C4-30 alkane, or a branched or straight chain C4-9, C7-14, C12-24 alkane, or a mixture thereof. In another exemplary embodiment, the C4+ alkene comprises a branched or straight chain C4-30 alkene, or a branched or straight chain C4-9, C7-14, C12-24 alkene, or a mixture thereof. In another exemplary embodiment, the C5+ cycloalkane comprises a mono-substituted or multi-substituted C5+ cycloalkane, and at least one substituted group is a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain Ci+ alkylene, a phenyl, or a combination thereof, or a branched C3-12 alkyl, a straight chain C1-12 alkyl, a branched C3-12 alkylene, a straight chain C1-12 alkylene, a phenyl, or a combination thereof, or a branched C3-4 alkyl, a straight chain Cm alkyl, a branched C3-4 alkylene, straight chain Cm alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the C5+ cycloalkene comprises a mono-substituted or multi-substituted C5+ cycloalkene, and at least one substituted group is a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl, or a combination thereof, or a branched C3-12 alkyl, a straight chain C1-12 alkyl, a branched C3-12 alkylene, a straight chain C2-12 alkylene, a phenyl, or a combination thereof, or a branched C3-4 alkyl, a straight chain Cm alkyl, a branched C3-4 alkylene, straight chain C2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the aryl comprises an unsubstituted aryl, or a mono-substituted or multi-substituted aryl, and at least one substituted group is a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl, or a combination thereof, or a branched C3-12 alkyl, a straight chain C1-12 alkyl, a branched C3-12 alkylene, a straight chain C2-12 alkylene, a phenyl, or a combination thereof, or a branched C3-4 alkyl, a straight chain Cm alkyl, a branched C3-4 alkylene, a straight chain C2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the fused aryl comprises an unsubstituted fused aryl, or a mono-substituted or multi-substituted fused aryl, and at least one substituted group is a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl, or a combination thereof, or a branched C3-4 alkyl, a straight chain Cm alkyl, a branched C3-4 alkylene, a straight chain C2-4 alkylene, a phenyl, or a combination thereof. In another exemplary embodiment, the C4+ alcohol comprises a compound according to the formula R'-OH, wherein R1 is a branched C4+ alkyl, straight chain C4+ alkyl, a branched C4+ alkylene, a straight chain C4+ alkylene, a substituted C5+ cycloalkane, an unsubstituted C5+ cycloalkane, a substituted C5+ cycloalkene, an unsubstituted C5+ cycloalkene, an aryl, a phenyl, or a combination thereof.

[0023] In another exemplary embodiment of method of making the C4+ compound, the C4+ ketone comprises a compound according to the formula R\ R4 wherein R3 and R4 are independently a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a substituted C5+ cycloalkane, an unsubstituted C5+ cycloalkane, a substituted C5+ cycloalkene, an unsubstituted C5+ cycloalkene, an aryl, a phenyl, or a combination thereof. Examples of desirable C4+ ketones 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.

[0024] 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.

[0025] 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.

[0026] The condensation catalyst may include one or more zeolite structures comprising cagelike 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.

[0027] 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. No. 5,019,663 and U.S. Pat. No. 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.

[0028] 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.

[0029] 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 C5+ hydrocarbons and / or C5+ monooxygenates. 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.

[0030] The specific C4+ compounds 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 (C2+O1-3) 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.

[0031] In certain embodiments the condensation reaction is carried out at a condensation temperature and a condensation pressure at which the thermodynamics of the proposed reaction are favorable. For volatile C2+O1-3 oxygenates 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.

[0032] C4+ alkanes and C4+ alkenes produced from acid condensation can have from 4 to 30 carbon atoms (C4+ alkanes and C4+ alkenes) and may be branched or straight chained alkanes or alkenes. The C4+ alkanes and C4+ alkenes may also include fractions of C4-9, C7-14, C12-24 alkanes and alkenes, respectively, with the C4-9 fraction directed to gasoline, the C7-16 fraction directed to jet fuels, and the Cn-24 fraction directed to diesel fuel and other industrial applications, such as chemicals. Examples of various C4+ alkanes and C4+ alkenes 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.

[0033] C5+ cycloalkanes and C5+ cycloalkenes produced from acid condensation can have from 5 to 30 carbon atoms and may be unsubstituted, mono-substituted or multi-substituted. In the case of mono-substituted and multi-substituted compounds, the substituted group may include a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl or a combination thereof. By way of example, at least one of the substituted groups include a branched C3-12 alkyl, a straight chain C1-12 alkyl, a branched C3-12 alkylene, a straight chain C1-12 alkylene, a straight chain C2-12 alkylene, a phenyl or a combination thereof. By way of further example, at least one of the substituted groups include a branched C3-4 alkyl, a straight chain C1-4 alkyl, a branched C1-4 alkylene, straight chain C1-4 alkylene, straight chain C2-4 alkylene, a phenyl or a combination thereof. Examples of desirable C5+ cycloalkanes and C5+ cycloalkenes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene, ethylcyclohexane, ethyl-cyclohexene, propyl-cyclohexane, butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane, pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, and isomers thereof.

[0034] Aryls will generally consist of an aromatic hydrocarbon in either an unsubstituted (phenyl), mono-substituted or multi-substituted form. In the case of mono-substituted and multisubstituted compounds, the substituted group may include a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl or a combination thereof. By way of example, at least one of the substituted groups include a branched C3+ alkyl, a straight chain C1-12 alkyl, a branched C3-12 alkylene, a straight chain C2-12 alkylene, a phenyl or a combination thereof. By way of further example, at least one of the substituted groups include a branched C3-4 alkyl, a straight chain Cm alkyl, a branched C3-4 alkylene, straight chain C2-4 alkylene, a phenyl or a combination thereof. Examples of various aryls include, without limitation, benzene, toluene, xylene (dimethylbenzene), ethyl benzene, para xylene, meta xylene, ortho xylene, C9+ aromatics, butyl benzene, pentyl benzene, hexyl benzene, heptyl benzene, octyl benzene, nonyl benzene, decyl benzene, undecyl benzene, and isomers thereof.

[0035] Fused aryls will generally consist of bicyclic and polycyclic aromatic hydrocarbons, in either an unsubstituted, mono-substituted, or multi-substituted form. In the case of monosubstituted and multi-substituted compounds, the substituted group may include a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl or a combination thereof. By way of example, at least one of the substituted groups include a branched C3-4 alkyl, a straight chain C1-4 alkyl, a branched C3-4 alkylene, straight chain C2-4 alkylene, a phenyl or a combination thereof. Examples of various fused aryls include, without limitation, naphthalene, anthracene, and isomers thereof.

[0036] Polycyclic compounds will generally consist of bicyclic and polycyclic hydrocarbons, in either an unsubstituted, mono-substituted, or multi-substituted form. Although polycyclic compounds generally include fused aryls, as used herein the polycyclic compounds generally have at least one saturated or partially saturated ring. In the case of mono-substituted and multisubstituted compounds, the substituted group may include a branched C3+ alkyl, a straight chain Ci+ alkyl, a branched C3+ alkylene, a straight chain C2+ alkylene, a phenyl or a combination thereof. By way of example, at least one of the substituted groups include a branched C3-4 alkyl, a straight chain C1-4 alkyl, a branched C3-4 alkylene, straight chain C2-4 alkylene, a phenyl or a combination thereof. Examples of various fused aryls include, without limitation, tetrahydronaphthalene and decahydronaphthalene, and isomers thereof.

[0037] The C4+ alcohols may also be cyclic, branched or straight chained, and have from 4 to 30 carbon atoms. In general, the C4+ alcohols may be a compound according to the formula R1-OH, wherein R1 is a member selected from a branched C4+ alkyl, straight chain C4+ alkyl, a branched C4+ alkylene, a straight chain C4+ alkylene, a substituted C5+ cycloalkane, an unsubstituted C5+ cycloalkane, a substituted C5+ cycloalkene, an unsubstituted C5+ cycloalkene, an aryl, a phenyl or combinations thereof. Examples of desirable C4+ alcohols include, without limitation, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol, nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol, tetraeicosanol, or isomers thereof.

[0038] In some embodiments, a condensation product stream comprising C4+ compounds can be fractionated into various product streams, such as gasoline, jet fuel (kerosene), diesel fuel, and aromatics. For example, the condensation product stream may be passed through a three-phase separator to separate the condensation product stream into an acid condensation gas stream, an organic stream, and an aqueous stream. The organic stream and aqueous stream can be separated by density difference, while the acid condensation gas stream comprising uncondensed gases can be recycled to the acid condensation reactor to generate additional C4+ compounds. In some embodiments, a gas transport device, such as a blower or compressor, can be configured in the acid condensation gas stream to control the recycle pressure. In some embodiments, an optional purge stream may also be used to control the pressure of the recycle loop in the acid condensation gas stream. In some embodiments, the aqueous stream is discarded from the process, or further processed in downstream process units.

[0039] In some embodiments, the organics stream is fractionated in a distillation column to separate the organic stream into a light product stream and a heavy product stream. In some embodiments, the distillation unit is configured to remove co-boiling contaminants for benzene, toluene, or a combination thereof.

[0040] In some embodiments, the distillation column is configured to generate a heavy stream that is free or substantially free of co-boiling non-aromatic contaminants for benzene. The distillation column may remove co-boiling nonaromatic contaminants for benzene by fractionating the organic stream into a Ce- stream comprising benzene, co-boiling non-aromatic contaminants for benzene, and lighter products through the light product stream. The distillation column may further fractionate the organic stream into a heavy product stream comprising C7+ compounds.

[0041] In some embodiments, the distillation column is configured to generate a heavy stream that is free or substantially free of co-boiling nonaromatic contaminants for toluene. The distillation column may remove co-boiling nonaromatic contaminants for toluene by fractionating the organic stream into a C7- or Cs- stream comprising toluene, co-boiling nonaromatic contaminants for toluene, and lighter products through the light product stream. The distillation column may further fractionate the organic stream into a heavy product stream comprising Cs or C9+ compounds.

[0042] In some embodiments, the heavy product stream is fractionated in a distillation column to separate the heavy product stream comprising C7+ compounds, Cs compounds, or C9+ compounds into the mixed aromatic feed stream and a heavy product stream. In some embodiments, the distillation column is configured to fractionate the heavy product stream 140 into a mixed aromatic feed stream 16 comprising C7+ compounds and a heavy product feed stream comprising C11+ compounds. In some embodiments, the mixed aromatic feed stream comprises C7+ compounds, or Cs compounds, or C9+ compounds, or C7-10 compounds, or Cs-io compounds, or C9-10 compounds.

[0043] In some embodiments, the heavy stream may be further separated for use as kerosene (e.g., Cn-14 as jet fuel use), diesel fuel use (e.g., C12-24), and lubricants or fuel oils (e.g., C25+). Alternatively, the heavy stream may be cracked to produce addition fractions for use in gasoline, kerosene, aromatics, and / or diesel fractions.

[0044] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms. As used herein, the terms “include” and “including” have the same meaning as the terms “comprise” and “comprising.” The terms “comprise” and “comprising” should be interpreted as being “open” transitional terms that permit the inclusion of additional components further to those components recited in the claims. The terms “consist” and “consisting of’ should be interpreted as being “closed” transitional terms that do not permit the inclusion of additional components other than the components recited in the claims. The term “consisting essentially of’ should be interpreted to be partially closed and allowing the inclusion only of additional components that do not fundamentally alter the nature of the claimed subject matter. As used herein, the singular forms "a", "an", and "the" include plural embodiments unless the context clearly dictates otherwise. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” may refer to plus or minus 10% of the indicated number. For example, "about 10%" may indicate a range of 9% to 11 %, and "about 1" may mean from 0.9-1.1.

[0045] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0046] The present invention has been described in terms of one or more preferred embodiments, and it should be appreciated that many equivalents, alternatives, variations, and modifications, aside from those expressly stated, are possible and within the scope of the invention. Examples

[0047] The purge gas from the AC Recycle loop contains a significant concentration of C4+ hydrocarbons which it would be beneficial to include in the liquid BioFormate product. Referring to FIG. 1, the AC recycle loop includes vapor from the AC product separator (4), a AC recycle compressor (B), and an AC recycle stream (5). The C4+ hydrocarbons potentially recaptured with the methods and systems disclosed herein amount to a yield increase of about 2%. The purge gas is taken from the Discharge of the AC Recycle Compressor to allow the AC Purge Gas Compressor to be single stage reciprocating machine. The purge gases are first cooled, with some initial hydrocarbon liquids condensed out and sent to the feed of the Lights Column. The resulting dry gas is then compressed to about 40 bar and cooled again with more hydrocarbon liquids condensing out. These liquids are also sent to the feed of the Lights Column. The uncondensed gases in the cooled AC Purge Gas Compressor discharge are sent to the Hydrogen plant as supplemental feedstock, which reduces the natural gas consumption of the hydrogen plant.

[0048] Example 1: Process description

[0049] Referring to FIG. 1, cooled AC reactor effluent (1) passes to the AC Product Separator (A) where it is separated into the AC organic product (2), AC aqueous effluent (3) and a vapor phase (4). The AC organic product (2) is pumped to the Lights Column (J) by the Lights Column Feed Pump (I) for lights removal and stabilization. The AC aqueous effluent (3) is sent to the Organics Recovery Column (not shown) where as much of the organic content as possible is recovered with the remaining wastewater stream sent to Outside Battery Limits (OSBL) Wastewater Treatment.

[0050] The majority of the vapor (4) leaving the AC Product Separator is recycled back to the AC Reactors via the AC Recycle Compressor (B) as stream 5. A small purge (6) is taken to control the pressure in the AC loop and prevent the build-up of lights. This purge gas is cooled in the AC Purge Gas Compressor Suction Cooler (C) and condensed liquids are removed in the AC Purge Gas Compressor KO Drum (D). These condensed liquids (8) contain product range material and so are sent to the Lights Column (J).

[0051] The remaining vapor (9) is then further compressed to about 42 bara in the AC Purge Gas Compressor (E). Taking the purge gas from the AC Recycle Compressor (B) discharge at about 21 bara rather than the suction allows the AC Purge Gas Compressor to be a single stage machine. The compressed purge gas (10, AC purge gas compressor discharge) is then cooled, firstly by air to about 54°C in the AC Purge Gas Cooler (F). This stream (11, purge gas from AC purge gas cooler) is then to 40°C by cooling water in the AC Purge Gas Trim Cooler (G) to produce a purge gas from AC purge gas trim cooler stream (12). This cooled stream is then sent to the AC Purge Gas Knockout Pot (H) where condensed liquids (13) are recovered and sent to the Lights Column. The vapor (14, AC vapor purge to hydrogen plant) leaving the AC Purge Gas Knockout Pot (H) is then sent to the OSBL Hydrogen Plant where it can be used as supplemental process feed, thereby reducing the Hydrogen Plant’s natural gas requirement.

[0052] The majority of the Ce+ components present in the recovered liquid streams (8 &13) is incorporated into the BioFormate product (16) leaving the Lights Column (J).

[0053] In addition, some of the C4- components that are recovered into the Lights Column feed (15) leave in the light hydrocarbon recycle stream (not shown) and recycled back to the AC reactors where they pass over the AC catalyst again and a portion of them are converted into product range material.

[0054] The methods and systems may further include a Lights column condenser (K), Lights column reflux drum (L), Lights column reflux pump (M), Light hydrocarbon recycle pump (N), and a lights column reboiler (O), as shown in FIG. 1.

[0055] Example 2: Consequences of operation without Example 1

[0056] Referring to FIG. 1, a system and method lacking the components and steps of Example 1 would result in the exclusion of Equipment items C to H. The AC loop purge gas would most likely be taken from the suction of the AC Recycle Compressor (B). The purge gas would not be at sufficient pressure for inclusion in the Hydrogen Plant process feed and so it would likely be used as fuel gas either in the Hydrogen Plant or elsewhere in the BioForming facility. Alternatively, it could be compressed and incorporated into the Hydrogen Plant process feed either by a dedicated compressor or the Hydrogen Plant natural gas feed compressor (if one is required, depending on natural gas supply pressure).

[0057] Any product range material present in this purge gas would be lost and the overall yield of sugars to liquid products would be negatively impacted.

[0058] Example 3: Impact of Example 1 on Overall Liquid Products Yield

[0059] Feed to the Lights Column consists of the AC organic product (2) from the AC Product Separator (A) and the recovered liquids from the AC Purge Gas Compressor KO Drum (D) and AC Purge Gas Knockout Pot (H) (e.g., streams 8 &13). Looking at the component mass flows in the Lights Column bottoms (16) compared to those in the AC organic product (2) shows that additional material has been incorporated into the Lights Column bottoms product due to this invention. This is summarized in the Tables 1-2 below, which shows that essentially all of the Ce+ components present in the AC loop vapor purge have been incorporated into the Lights Column bottoms.

[0060] Table 1: Component mass flows of streams depicted in FIG. 1. AC Loop Vapour Purge Recovered Liquids from AC Purge Gas Compressor KO Drum Recovered Liquids from AC Purge Gas Knock Out Pot AC Vapour Purge to Hydrogen Plant Stream according to FIG. 1 6 8 13 14 Start of Run (SOR) Ce+ Alkanes / Alkenes kg / h 204 201 2.8 0.2 Ce+ Aromatics kg / h 285 282 2.7 0.2 End of Run (EOR) Ce+ Alkanes / Alkenes kg / h 575 493 67 15 Ce+ Aromatics kg / h 166 155 10 2

[0061] Table 2: Component mass flows of streams depicted in FIG. 1. AC Organic Product Lights Column Bottoms Difference due to AC Purge Gas System Stream according to FIG. 1 2 16 - Start of Run (SOR) Ce+ Alkanes / Alkenes kg / h 5684 5887 203 Ce+ Aromatics kg / h 43678 43963 284 End of Run (EOR) Ce+ Alkanes / Alkenes kg / h 13144 13671 526 Ce+ Aromatics kg / h 30718 30882 164

[0062] The Lights Column bottoms flow is 55141kg / h at Start of Run (SOR) and 51704 kg / h at End of Run (EOR) with the methods and systems described in Example 1. The yield increase is 0.89% at SOR on a mass basis, whilst at EOR the yield increase is 1.35%. Yield increase can be determined as increase in Ce+ content divided by (Lights Column bottoms flow - increase in Ce+ content). For EOR, this is: 691 / (51704-691).

Claims

What is claimed is:

1. A method of producing a C4+ compound, the method comprising:(i) reacting a feed stream comprising C1+O1-3 hydrocarbons in the presence of an acid condensation (AC) catalyst at a condensation temperature and condensation pressure to produce an AC product stream comprising the C4+ compound;(ii) fractionating AC product stream into an AC liquid product stream comprising organic products and a vapor stream;(iii) compressing the vapor stream to form a compressed vapor stream;(iv) cooling a first portion of the compressed vapor stream to produce a first recovered liquid product stream and a first purge vapor stream;(v) recycling a second portion of the compressed vapor stream to the reaction of step (i);(vi) combining the AC liquid product stream and the first recovered liquid product stream to form a combined liquid product stream.

2. The method of claim 1, wherein step (ii) is carried out in phase separator.

3. The method of any one of claims 1-2, wherein step (iii) is carried out by a gas compressor.

4. The method of any one of claims 1-3, wherein step (iv) comprises:(iv-a) cooling the first portion of the compressed vapor stream by a compressor suction cooler to produce a cooled vapor stream; and(iv-b) fractionating the cooled vapor stream in a separator into the first recovered liquid product stream and the first purge vapor stream.

5. The method of claim 4, further comprising(iv-c) fractionating the first purge vapor stream to produce a second recovered liquid product stream and a second purge vapor stream, optionally wherein the fractionating step comprises compressing and cooling the first vapor stream.

6. The method of claim 5, wherein step (vi) comprises combining the AC liquid product stream, the first recovered liquid product stream, and the second recovered liquid product stream to form the combined liquid product stream.

7. The method of any one of claims 1 -6, further comprising(vii) isolating a liquid C4+ compound product stream from the combined liquid product stream.

8. The method of claim 7, wherein a yield of Ce+ compounds in the liquid C4+ compound product stream of step (vii) is at least 0.5 wt% higher than a yield of Ce+ compounds in the AC liquid product stream of step (ii).

9. The method of any one of claims 1-8, wherein the acid condensation catalyst comprises carbides, nitrides, zirconia, alumina, silica, aluminosilicates, phosphates, zeolites, titanium oxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides, magnesium oxides, cerium oxides, barium oxides, calcium oxides, hydroxides, heteropolyacids, inorganic acids, and combinations thereof.

10. The method of claim 9, wherein the acid condensation catalyst further comprises a modifierselected from the group consisting of Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and a combination thereof.

11. The method of any one of claims 1-10, wherein the feed stream is derived from biomass.

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