WO2014031776A2 - System for making renewable fuels including gasoline, diesel, and jet fuel - Google Patents

Abstract

Multiple catalytic processing stations coupled with a system which produces volatile gas streams from biomass decomposition at discrete increasing temperatures or constant temperature. These catalytic processing stations can be programmed to maximize conversion of biomass to jet fuel components. The system may also include a processing station for subjecting biomass within the stations to at least one programmable starting temperature (T_start) and for incrementing an individual processing station temperature by programmable increments (ΔΤ) to produce a volatile and a non- volatile component. Further, methods for converting biomass and char to renewable jet fuel, diesel, and kerosene are disclosed.

Description

SYSTEM FOR MAKING RENEWABLE FUELS INCLUDING GASOLINE, DIESEL, AND JET FUEL

Related Applications

[0001] This application claims priority to, and is a continuation in part of,

PCT Application No. PCT/US2012/068616, filed December 7, 2012, which claims priority to U.S. Application No. 13/361,840, filed January 30, 2012, now U.S. Pat. No. 8,431,757, and U.S. Application No. 13/361,828, filed January 30, 2012, now U.S. Pat. No. 8,383,049, which are incorporated herein by reference in their entirety. This application further claims priority to U.S. Provisional Application No. 61/691,713, filed August 21, 2012, which is incorporated herein by reference in its entirety.

Technical Field

[0002] The present disclosure relates generally to systems for making renewable fuels, and more particularly to the thermal chemical conversion of biomass to renewable fuels and other useful chemical compounds, including gasoline, diesel and jet fuel, via a series of catalysts using an optionally programmable system.

Description of the Related Art

[0003] As the world continues to run through its precious resources of fossil fuels, it is going to be forced to turn to other sources of energy. Present global objectives include getting energy cheaply and quickly. Through the ages, mankind has turned to biomass to furnish energy in terms of heat by burning wood and other biomass. This is inherently a very inefficient process. Combustion may be made more efficient by introducing programmability. It is similar to introducing computers to a building that needs to be heated. In order to heat the building only when the person is present, one places a sensor in the building so that the heater turns on when the sensor detects a person. This is an example of a programmable system. Similarly, a programmable system may be introduced for chemical bond breakage resulting in efficient conversion of biomass to higher value added products, wherein only the minimum number of bonds are broken and, consequently, the minimum amount of energy is spent breaking these bonds.

[0004] Bond breaking and making are essential aspects of conversion of biomass to industrially useful products such as gasoline and diesel. Various forms of laboratory and small scale commercial biomass pyrolyzers have been developed to generate useful chemical products from the controlled pyrolysis of biomaterials ranging from wood chips to sewage sludge. Although some pyrolyzers are focused simply on producing syngas, there is considerable effort in the development of milder pyrolyzing conditions, which typically results in a condensed liquid commonly called bio-oil or pyrolysis oil. A

programmable system that operates with mild pyrolysis conditions would be an example of efficient bond breaking and making. Many forms of pyrolyzers have been developed at the laboratory level to produce these intermediate compounds, which are collectively referred to as bio-oil or pyrolysis oil. Configurations include simple tube furnaces where the biomass is roasted in ceramic boats, ablative pyrolyzers where wood is rubbed against a hot surface, various forms of fluidized bed pyrolyzers where biomass is mixed with hot sand, and various simpler configurations that are based on earlier coking oven designs.

[0005] The fundamental problem with the resultant pyrolysis oil is that it is made up of hundreds to thousands of compounds, which are the result of subjecting the raw biomass to a wide range of temperature, time, and pressure profiles in bulk. When this process is complicated by the thousands of major bio-compounds in the original bio- feedstock, the result is a nearly intractable array of resultant compounds all mixed together. Pyrolysis oils from such processes are typically not thermodynamically stable. They contain active oxygenated free radicals that are catalyzed by organic acids and bases such that these oils typically evolve over a period of a few days from light colored liquids to dark mixtures with tar and resinous substances entrained in the mix. Also, attempts to re-gasify pyrolysis oil typically result in additional chemical reactions, which produce additional biochar and a shift to lower molecular weight components in the resulting gas stream. Although fairly high yields of pyrolysis oil can be achieved in laboratory scale experiments, larger industrial scale demonstration projects typically produce much lower yield. This is presumably due to the wider range of temperatures, hold times, and localized pressures within the much larger heated three dimensional volumes of such scale -up architectures.

[0006] Previous efforts to introduce a programmable adaptability to catalytic systems include Gehrer's design of building several parallel reactors, in analogy to a microprocessor bus, to study catalytic gas reactions. (Journal of Physics E: Scientific

Instruments 18 (1985) 836). U.S. Patent 6,548,026 by Dales et al. and U.S. Patent 6,994,827 by Safir et. al. disclose programmable parallel reactors capable of controlling vessel stirring rate, temperature and pressure. Additionally, U.S. Patent Application 2010/0223839 to Garcia-Perez et al. discloses heating biomass to a first temperature aimed to enhance the subsequent anhydro sugar content developed in the oil portion of the biomass pyrolysis product. The aim is to enhance the fermentation capability of the oil portion for subsequent ethanol production. This is an example of a somewhat programmable system for biomass conversion.

Brief Summary of Embodiments of the Invention

[0007] Embodiments of the present application provide a system and method for the conversion of biomass to renewable fuels, renewable fuel meaning any combustible fuel that is derived from biomass. Renewable fuels can find use for transportation, heating or other purposes, and can be used in the preparation, blending or formation of such fuels as gasoline, diesel, jet fuel, kerosene or other useful fuel blends (such as a blend of benzene, toluene and xylene (BTX)).

[0008] Some embodiments of the invention involve a system and method for creating an optionally programmable process wherein chemical compounds derived from biomass decomposition are routed to distinct catalyst processes to produce products containing renewable fuels and other value added products.

[0009] Further embodiments of this invention are directed toward an efficient system for the conversion of biomass pyrolysis products into useful chemicals and renewable fuels.

[0010] Additional embodiments are directed toward a process for extracting the maximum amount of energy from biomass for the conversion to gasoline or diesel that is correlated to the temperature of devolatilization of the biomass.

[0011] Yet another embodiment of this invention involves a process for extracting the maximum amount of energy from biomass for the conversion to gasoline or diesel that is correlated to load balancing of a catalyst output at certain temperatures.

[0012] In a still further embodiment, the invention is directed toward a system for the conversion of biomass to diesel or jet fuel, comprising: a device containing a number of processing stations (N) and a series of catalysts; each processing station capable of subjecting biomass within the station to at least one starting temperature (T_start) to produce a volatile and a non- volatile component; at least one catalyst reactor for receiving volatile components generated in each processing station; and wherein, the at least one catalyst reactor contains a catalyst selected from the group consisting of: dehydration catalysts, olefin oligomerization catalysts and hydrotreating catalysts.

[0013] In another embodiment the system comprises additional catalyst reactors.

[0014] In a further embodiment the additional catalyst reactors are used in series.

[0015] In a further embodiment the additional catalyst reactors are used in parallel.

[0016] In a further embodiment the system comprises a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ).

[0017] In a another embodiment the non- volatile component is a carbonaceous material.

[0018] In an embodiment the system further comprises a gasifier for converting the carbonaceous material to syngas.

[0019] In an embodiment the system further comprises a conduit from the gasifier to a catalyst reactor for the introduction of syngas.

[0020] In an embodiment the system further comprises the number of processing stations (N) ranging from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C. Further, the temperature increment (ΔΤ) ranges from 0°C to 200°C.

[0021] In another embodiment, the system further comprises a reservoir for housing a a co-feed, and a conduit for introduction of the co-feed to the volatile components or to at least one of the processing stations, wherein the co-feed is selected from the group consisting of alcohols, aldehydes, ketones, ethers, carboxylic acids, and hydrocarbons. [0022] In another embodiment, the system comprises a conduit from the gasifier to a catalyst reactor containing a syngas conversion catylast wherein the co-feed is generated via the syngas conversion catalyst.

[0023] In another embodiment, the biomass is selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

[0024] In a further embodiment, the biomass is a mixture of two or more types of biomass selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

[0025] In a still further embodiment, T_start is selected according to the type of biomass with the highest concentration in the mixture of two or more types of biomass. In another embodiment, at least two processing stations are set at the same T_start. In another embodiment, all of the processing stations are set at the same T_start. In another embodiment, the Tstart is a substantially constant temperature. In another embodiment, the non-volatile component is thermally conductive. In another embodiment, the non-volatile component at the Nth processing station comprises char.

[0026] In a further embodiment, the Nth processing station comprises an input capable of receiving an external source of water, carbon dioxide or methane, or internally provided recycled water or combustible gases arising from the catalyst treatment.

[0027] In yet another embodiment, the dehydration catalyst comprises any acid catalyst or combination of acid catalysts. In a further embodiment, the olefin

oligomerization catalyst is a dehydration catalyst.

[0028] In another embodiment, the system further comprises conduits to direct water, carbon dioxide, and methanol generated in the system to the gasifier for use in the conversion of the non- volatile components to syngas.

[0029] In another embodiment, the non-volatile component from a station comprises feedstock for the next station.

[0030] In another embodiment, the diesel or jet fuel produced comprises one or more kerosene components. In another embodiment, wherein the diesel or jet fuel produced comprises one or more jet fuel components. In another embodiment, the diesel or jet fuel produced comprises one or more diesel fuel components. [0031] In another embodiment, the internally generated water, carbon dioxide, methanol are used as reactants in the conversion of the carbonaceous material to syngas.

[0032] In a further embodiment, the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a fluidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier and a vacuum moving bed reactors.

[0033] In an embodiment the invention includes a system for converting char to a renewable fuel, comprising: a device containing a plurality of processing stations (N) and a series of catalysts; each processing station capable of subjecting char within the station to at least one starting temperature (T_start) to produce syngas; at least one catalyst reactor for receiving syngas generated in each processing station; and wherein, the at least one catalyst reactor contains a catalyst selected from the group consisting of: syngas conversion catalysts, methanol synthesis catalyst, DME synthesis catalysts, dehydration catalysts, olefin oligomerization catalysts and hydrotreating catalysts. In another embodiment, the system comprises additional catalyst reactors. Those additional catalyst reactors can be used in series or parallel.

[0034] In another embodiment, the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a fluidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier and a vacuum moving bed reactors.

[0035] Yet another embodiment involves a method for converting biomass to diesel or jet fuel, comprising: dispensing biomass into a plurality of processing stations (N); subjecting biomass within the station to at least one starting temperature (T_start) to produce a volatile and a non-volatile component; directing the volatile component to at least one catalyst reactor designed to perform one or more of the processes selected from the group consisting of dehydration, olefin oligomerization and hydrotreating; collecting the diesel or jet fuel produced in the at least one catalyst reactor.

[0036] A further embodiment comprising a method for converting char to diesel or jet fuel, comprising: dispensing char into a plurality of processing stations (N); subjecting char within the station to at least one starting temperature (T_start) to produce syngas; directing the syngas to at least one catalyst reactor designed to perform one or more of the processes selected from the group consisting of syngas conversion catalysts, methanol synthesis catalyst, DME synthesis catalysts, dehydration, olefin oligomerization and hydrotreating; collecting the diesel or jet fuel produced in the at least one catalyst reactor.

[0037] In another embodiment, the method further comprises additional catalyst reactors. In another embodiment, the additional catalyst reactors are used in series. In another embodiment, the additional catalyst reactors are used in parallel.

[0038] In a further embodiment of the method, the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a fluidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier and a vacuum moving bed reactors.

[0039] In another embodiment , the method uses a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ). In a further embodiment, the number of processing stations (N) ranges from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C. In another embodiment, the temperature increment (ΔΤ) ranges from 0°C to 200°C.

[0040] Other features and aspects of the invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the features in accordance with embodiments of the invention. The summary is not intended to limit the scope of the invention, which is defined solely by the claims attached hereto. Brief Description of the Drawings

[0041] The present invention, in accordance with one or more various embodiments, is described in detail with reference to the following figures. The drawings are provided for purposes of illustration only and merely depict typical or example embodiments of the invention. These drawings are provided to facilitate the reader's understanding of the invention and shall not be considered limiting of the breadth, scope, or applicability of the invention. It should be noted that for clarity and ease of illustration these drawings are not necessarily made to scale.

[0042] FIG. 1 is a drawing illustrating N processing stations on a race track, wherein each processing station is operating at a particular temperature.

[0043] FIG. 2 is a detailed flow diagram of the optionally programmable catalyst chain used to generate renewable fuels, in accordance with one or more embodiments of the invention.

[0044] FIG. 3 is a flow diagram illustrating an optionally programmable catalyst chain with three stations configured to process incoming biomass of different compositions, in one or more embodiments of the invention.

[0045] FIG. 4 is a flow diagram of optionally programmable catalyst chains as applied to the production of renewable jet fuel, kerosene, and diesel fuel in addition to gasoline according to one or more embodiments.

[0046] FIG. 5 is a flow diagram of programmable catalyst chains as applied to the production of renewable jet fuel, kerosene, and diesel fuel in addition to gasoline according to one or more embodiments.

[0047] FIG. 6 is a flowchart depicting an algorithm that depends on incrementing the processing station temperature until a desired maximum temperature is reached, in accordance with the principles of the invention.

[0048] FIG. 7 is a flowchart depicting an algorithm that depends on balancing output from various catalyst chains, in accordance with the principles of the invention. [0049] FIG. 8 A is a plot of fuel output versus temperature for sunflower seeds using a dehydration catalyst, aromatization catalyst and gas-upgrading catalyst; FIG. 8B shows a comparative output of the A cut (after dehydration catalyst) versus U.S. Diesel #2 and Biodiesel B99; and FIGS. 8C and 8D show gas chromatograms (GC) data for renewable fuels obtained after the aromatization catalyst and gas-upgrading catalyst.

[0050] FIG. 9 is a GC plot of volatile gases collected after the aromatization catalyst using red fir as input biomass.

[0051] The figures are not intended to be exhaustive or to limit the invention to the precise form disclosed. It should be understood that the invention can be practiced with modification and alteration, and that the invention be limited only by the claims and the equivalents theredof.

Detailed Description of the Embodiments of the Invention

[0052] In one embodiment of the present invention, a system for routing biomass decomposition products through a system comprised of processing stations and a series of catalysts is described. In one embodiment, it realizes an optionally programmable system for maximizing output from a pyrolysis system. There are three basic approaches in this optionally programmable system: a) routing based on knowledge of the initial composition of the biomass, b) routing based on knowledge of the temperature of biomass devolatilization, and c) routing based on load balancing. The full nature of these approaches will now be described by reference to the figures.

[0053] Methods of introducing biomass into a processing station include introduction via conveyor belts, hoppers, and/or pulverizers. The processing stations can provide one or both of pulverization and/or pyrolysis of a biomass. The processing stations described herein may include these components enveloped in one system, where, for example, the pulverization and pyrolysis components are intimately connected. Biomass may be introduced in raw form or dry form, or may be dried within the pyrolysis chamber when the pyrolysis starts.

[0054] As used herein, the term 'biomass' includes any material derived or readily obtained from plant sources. Such material can include without limitation: (i) plant products such as bark, leaves, tree branches, tree stumps, hardwood chips, softwood chips, grape pumice, sugarcane bagasse, switchgrass; and (ii) pellet or chopped material such as grass, wood and hay pellets, crop products such as corn, wheat and kenaf. This term may also include seeds such as vegetable seeds, fruit seeds, and legume seeds.

[0055] The term 'biomass' can also include: (i) waste products including animal manure such as poultry derived waste; (ii) commercial or recycled material including plastic, paper, paper pulp, cardboard, sawdust, timber residue, wood shavings and cloth; (iii) municipal waste including sewage waste; (iv) agricultural waste such as coconut shells, pecan shells, almond shells, coffee grounds; and (v) agricultural feed products such as rice straw, wheat straw, rice hulls, corn stover, corn straw, and corn cobs. Biomass is typically comprised of a wide array of compounds classified within the categories of cellulose, hemicelluloses, lignin, starches, and lipids. Biomass can also be comprised of plant residue, seed residue and seed cake, the left over material after oil extraction from the seeds.

[0056] Referring to FIG. 1, a series of N processing stations 50 are arranged around a rectangular track 52 sequentially. A processing station 50 may comprise any of a number of well-known pyrolysis reactors, including fixed bed reactors, fluidized bed reactors, circulating bed reactors, bubbling fluid bed reactors, vacuum moving bed reactors, entrained flow reactors, cyclonic or vortex reactors, rotating cone reactors, auger reactors, ablative reactors, microwave or plasma assisted pyrolysis reactors, and vacuum moving bed reactors. It may also comprise a chamber in a biomass fractionating system as described in co-owned U.S. Patent Publication No. 2010/0180805, now U.S. Patent 8,216,430, the content of which is incorporated herein by reference in its entirety.

[0057] At any one time, each processing station 50 is operated at a certain temperature (marked next to each processing station in FIG. 1 as Ti ... T_N). Thus, the first processing station is Station 1 that is operated at Ti and the Nth station is operated at temperature T_N-. Each processing station 50 can operated at any temperature that is equal to or higher than the previous processing station. The starting processing station temperature is typically determined by the initial composition of the biomass. The device accommodates a total of N processing stations, where N is operator adjustable from 2 to 1000, preferably between 2 and 100, and most preferably between 2 and 50. A station temperature can be incremented by a variable increment ΔΤ, which can be in the range of 0°C to 200°C. In one embodiment, all processing stations 50 operate at the same temperature. In another embodiment, each subsequent processing station temperature is incrementally higher by ΔΤ from the previous processing station. In still another embodiment, a group of adjacent processing stations are operated at the same temperature T, followed by another group of adjacent processing stations which are operated at temperature T + χ*ΔΤ, followed still by another group of processing stations operating at temperature T + y*AT, where x and y are any numbers greater or equal to 1. In still further embodiments, the temperature increments may be attained via the application of temperature ramps in the presence of a concomitant application of pressure shocks to the biomass. This technique has been described in detail in co-pending U.S. Patent Application 13/019,236, now U.S. Patent 8,293,958 and U.S. Patent Application 13/103,905, now U.S. Patent 8,367,881, the contents of which are incorporated herein by references in their entireties..

[0058] The processing stations 50 produce volatile and non- volatile components when heated. Because the material can be heated within a relatively narrow temperature range and selected time, the non-volatile component (in the form of partially formed char) has additional volatile components embedded therein, which are extractable and processed in subsequent processing stations as a result of, for example, extended time under the selected temperature or exposure to a higher temperature. In some embodiments, a single biomass sample is stepped from processing station to processing station, each processing station at the same temperature. The additional time under the selected temperature results in extraction of additional volatile components at each station. In some embodiments, a single biomass sample is stepped from processing station to processing station, each processing station at a temperature greater than the previous station. The additional time under the selected temperature results in extraction of additional volatile components at each station. In other embodiments, each station contains a different biomass sample. The time and temperature of pyrolysis is optimized for the particular biomass being pryolized.

[0059] Thus, the processing stations can be operated in a number of different ways to obtain volatile components having different compositions. The output of these processing stations is connected to an array of catalysts as described below.

[0060] Biomass is typically comprised of a wide array of compounds classified within the categories of cellulose, hemicelluloses, lignin, starches, and lipids. These compounds go through multiple steps of decomposition when subject to the pyrolysis process. For example, hemicelluloses comprise C5 sugars such as fructose and xylose, which yield furfural and hydroxymethylfurfurals upon thermolysis. The latter compounds can be further converted to fuel intermediates furan and tetrahydrofuran. The relatively narrow temperature windows experienced within a processing station 50 allows for the collection of these useful intermediates.

[0061] FIG. 2 depicts an embodiment of the invention having eight processing stations 50 and a series of catalyst channels comprising a dehydration catalyst 60, an aromatization catalyst 61 and a gas-upgrading catalyst 62. The output from each catalytic array when cooled is comprised of volatile gases (at the cooling temperature), renewable fuel and water. The volatile gases then pass through subsequent catalytic columns. Depending on the temperature of the processing station 50 and the biomass composition, the volatile components from any given processing station can be channeled through one or more catalysts 60, 61, 62 using selector switches 55, 56, 57. In some embodiments, the volatile components from multiple processing stations can be combined and the combined volatile components can be channeled through one or more catalysts 60, 61, 62 using selector switches 55, 56, 57. Line 21 shows that an optional co-solvent may be added as an additional input to the aromatization catalyst 61, which can help improve the yield of the liquid fuel component. The co-solvent may be generated in situ from a typical syngas converter 64. Carbon monoxide and hydrogen for the syngas converter (used to generate the co-solvent) may be obtained via well-known reactions, e.g., with the left-over carbonaceous solid from pyro lysis of the biomass in a processing station 50 or other known method. The co-solvent may comprise oxygenates such as aldehydes, alcohols, ketones, ethers, and carboxylates, as well as hydrocarbons. In other embodiments, the co-solvent may be obtained from

commercially available sources.

[0062] If the volatile components from the processing station 50 are selected to go through a dehydration catalyst 60, then the output is passed through a room temperature separator 32, which separates the output into water, renewable fuel 33, and volatile gases 34. The volatile gases are then routed through the aromatization catalyst 61 to produce a product that upon cooling with cold separator 35, e.g., at a temperature that is less than the room temperature, gives water, renewable fuel 36 and volatile gases 37, which may include combustible gases 41, e.g., C1-C5 containing compounds. These combustible gases can then be released via a variable release valve 58. The variable release valve can control the routing of the volatile gases 37 to either a gas-upgrading catalyst chamber, or a combustible gas treatment plant, or both. Upon cooling via cold separator 38, the product from the gas- upgrading catalyst 62 produces water, renewable fuel 39 and volatile gases 40, which may include combustible gas mixture 42. This combustible gas mixture can be either treated in a combustible gas treatment plant or recycled via a recirculation pump 59 to the aromatization catalyst chamber. In another embodiment, the combustible gas mixture 42 may be recycled to one or more of the following: (a) at least one or more of the processing stations 50, (b) the dehydration catalyst 60, (c) the aromatization catalyst 61, and the (d) gas-upgrading catalyst 62.

[0063] FIG. 3 shows an embodiment 300 of the using knowledge of the initial composition of the biomass for converting various types of biomass feedstocks with three processing stations 50 and an array of catalytic columns for optimal product yield. The biomass feedstocks in various stations can come from a single biomass input which are processed using the three stations, or from multiple independent biomass inputs. While the number of processing stations can vary, the same catalytic columns are used to convert the volatile gases to renewable fuels. The order in which the catalytic columns are selected can vary.

[0064] In one or more embodiments, the first station includes a lipid rich biomass (A). While the figure indicates that only one station is used, it is understood that multiple stations at the same or different temperatures may be employed to generate the volatile components. Station 1 when fed with a lipid rich biomass (A) produces a product comprising a volatile gas and a carbonaceous solid. Station 1 preferably operates at less than 300°C. The volatile components are passed through a dehydration catalyst 60 to produce a first product. This first product is cooled using a room temperature trap and is comprised of water, a first renewable fuel (which is typically a liquid under collection conditions) and a second volatile component. The first renewable fuel is then recovered. The dehydration catalyst operates at less than 2 bar pressure, preferably in the temperature range of 400- 700°C, most preferably in the range of 400°C to 500°C, and serves to recover water from the volatile gas.

[0065] The dehydration catalyst 60 can be any acid catalyst. Suitable acid catalysts for the present application are heterogeneous (or solid) acid catalysts. The at least one solid acid catalyst may be supported on at least one catalyst support (herein referred to as a supported acid catalyst). Solid acid catalysts include, but are not limited to, (1)

heterogeneous heteropolyacids (HP As) and their salts, (2) natural clay minerals, such as those containing alumina or silica (including zeolites), (3) cation exchange resins, (4) metal oxides, (5) mixed metal oxides, (6) inorganic acids or metal salts derived from these acids such as metal sulfides, metal sulfates, metal sulfonates, metal nitrates, metal phosphates, metal phosphonates, metal molybdates, metal tungstates, metal borates, and (7) combinations of groups 1 to 6.

[0066] Suitable HPAs include compounds of the general Formula X_a M_bO_c ^q", where X is a heteroatom such as phosphorus, silicon, boron, aluminum, germanium, titanium, zirconium, cerium, cobalt or chromium, M is at least one transition metal such as tungsten, molybdenum, niobium, vanadium, or tantalum, and q, a, b, and c are individually selected whole numbers or fractions thereof. Methods for preparing HP As are well known in the art. Natural clay minerals are well known in the art and include, without limitation, kaolinite, bentonite, attapulgite, montmorillonite and zeolites. Suitable cation exchange resins are styrene-divinylbenzene copolymer-based strong cation exchange resins such as Amberlyst® (Rohm & Haas; Philadelphia, PA), Dowex® (for example, Dowex® Monosphere M-31) (Dow; Midland, MI), CG resins from Resintech, Inc. (West Berlin, NJ), and Lewatit resins such as MonoPlusTM S 100 H from Sybron Chemicals Inc. (Birmingham, NJ). When present, the metal components of groups 4 to 6 may be selected from elements from Groups I, Ila, Ilia, Vila, Villa, lb and lib of the Periodic Table of the Elements, as well as aluminum, chromium, tin, titanium and zirconium. Fluorinated sulfonic acid polymers can also be used as solid acid catalysts for the processes disclosed herein.

[0067] The second volatile component is then routed to an aromatization catalyst 61 to produce a second product, which enriches the product in aromatic compounds. This second product in turn is cooled using a cold trap at 0-20°C, more preferably at 0-5°C. The output from the cold trap is comprised of water, a second renewable fuel and a third volatile component. The second renewable fuel is then recovered. The aromatization catalyst

61 is operated at less than 2 bar pressure, preferably in the temperature range of 300°C to 500°C, most preferably in the range of 325°C to 400°C. The aromatization catalyst 61 can be comprised of MFI type zeolites and metal modified MFI type zeolites, where the metal is selected from the group consisting of: Group VIB metals, Group VIIB metals, Group VIII metals, Group IB metals, Group IIB metals, Ga, In, and all combinations thereof.

[0068] The third volatile component is then routed to a gas-upgrading catalyst

62 to produce a third product. This third product in turn is cooled using a cold trap at 0-20°C, more preferably at 0-5°C. The output from the cold trap is comprised of water, a third renewable fuel and a fourth volatile component. The third renewable fuel is then recovered. The gas-upgrading catalyst 62 is operated at less than 2 bar pressure and preferably in the temperature range of 400°C to 700°C, most preferably in the range of 500°C to 600°C. The gas-upgrading catalyst 62 can be comprised of metal modified MFI type zeolites, where the metal is selected from the group consisting of: Ga, Zn, In, Mo, W, Cr, Pt, Pd, Rh, Ru, Au, Ir, and combinations thereof. The fourth volatile component can be recirculated to at least one of the following: a) one or more processing stations 50, b) the dehydration catalyst 60, c) the aromatization catalyst 61, d) the gas-upgrading catalyst 62, and e) a combustible gas treatment plant.

[0069] Referring still to FIG. 3, Station 2 can comprise a hemicellulose rich biomass (B) derived from another biomass feedstock or a carbonaceous solid from a previous station 50 that contains volatile components that did not volatilize in the prior station. While the figure indicates that only one station is used, it is understood that multiple stations at the same or different temperatures may be employed to generate the volatile components.

Station 2 preferably operates at greater than 300°C and less than 500°C. The temperature in Station 2 can be optionally programmably incremented (ΔΤ) by the operator. The temperature increment can preferably be in the range of 10-200°C. Station 2 produces a product which is comprised of a volatile component and a carbonaceous solid that is different than the carbonaceous solid produced in the previous station, by virtue of the different starting biomass and/or the different starting temperature. The volatile component produced in Station 2 is then routed through the aromatization catalyst 61 to produce a fourth product. This fourth product is then cooled using a cold trap at 0-20°C, most preferably at 0-5°C. The fourth renewable fuel is then recovered. The output from the cold trap is comprised of water, a fourth renewable fuel and a fifth volatile component. The aromatization catalyst 61 is operated at less than 2 bar pressure and preferably in the temperature range of 300°C to 500°C, most preferably in the range of 325°C to 400°C.

[0070] The fifth volatile component is then routed to the gas-upgrading catalyst 62 to produce a fifth product. This fifth product in turn is cooled using a cold trap at 0^_,20°C, most preferably at 0-5°C. The output from the cold trap is comprised of water, a fifth renewable fuel and a sixth volatile component. The fifth renewable fuel is then recovered. The gas-upgrading catalyst 62 is operated at less than 2 bar pressure and preferably in the temperature range of 400°C to 700°C, most preferably in the range of 500°C to 600°C. The sixth volatile component can be recirculated to at least one of the following: a) one or more processing stations 50, b) the dehydration catalyst 60, c) the aromatization catalyst 61, d) the gas-upgrading catalyst 62, and e) a combustible gas treatment plant.

[0071] Still referring to FIG. 3, Station 3 operates at greater than 500°C processing either an independent lignin-rich biomass feedstock or the leftover carbonaceous solid from the previous station. While the figure indicates that only one station is used, it is understood that multiple stations at the same or different temperatures may be employed to generate the volatile components. Station 3 produces a product which contains volatile gases and a different carbonaceous solid, by virtue of the different starting biomass and/or the different starting temperature. These volatile components are passed through a dehydration catalyst 60 to produce a sixth product. This sixth product is cooled using a room temperature trap and is comprised of water, a sixth renewable fuel and a seventh volatile component. The sixth renewable fuel is then recovered. The dehydration catalyst 60 operates at less than 2 bar pressure and preferably in the temperature range of 400-700°C, most preferably in the range of 400°C to 500°C. The dehydration catalyst 60 can be the same as described above.

[0072] The seventh volatile component is then routed to the previously described aromatization catalyst 61 to produce a seventh product. This seventh product in turn is cooled using a cold trap at 0-20°C, most preferably at 0-5°C. The output from the cold trap is comprised of water, a seventh renewable fuel and an eighth volatile component. The seventh renewable fuel is then recovered. The aromatization catalyst 61 is operated at less than 2 bar pressure and preferably in the temperature range of 300°C to 500°C, most preferably in the range of 325°C to 400°C.

[0073] The eighth volatile component is then routed to the previously described gas-upgrading catalyst 62 to produce an eighth product. This eighth product in turn is cooled using a cold trap at 0-20°C, most preferably at 0-5°C. The output from the cold trap is comprised of water, an eighth renewable fuel and a ninth volatile component. The eighth renewable fuel is then recovered. The gas-upgrading catalyst 62 is operated at less than 2 bar pressure and preferably in the temperature range of 400°C to 700°C, most preferably in the range of 500°C to 600°C. The ninth volatile component can be recirculated to at least one of the following: a) one or more processing stations 50, b) the dehydration catalyst 60, c) the aromatization catalyst 61, d) the gas-upgrading catalyst 62, and e) a combustible gas treatment plant.

[0074] While the process has been described generally for the production of renewable fuels, it may be desirable to produce specific fuels, such as jet fuel, diesel, gasoline and kerosene or components that can be readily blended to prepare jet fuel, diesel, gasoline and kerosene. Jet and diesel fuel are a mixture of a large number of different hydrocarbons of varying carbon number (carbon atoms per molecule). Kerosene-type jet fuel has a carbon number distribution between about 8 and 16, while wide-cut or naphtha-type jet fuel has a carbon number distribution of between about 5 and 15. Jet fuel typically has a higher aliphatic hydrocarbon and lower aromatic hydrocarbon content than gasoline. Diesel gas is heavier than jet fuel, with a higher number of slightly larger hydrocarbon chains, though both are primarily paraffin oils (kerosene).

[0075] FIG. 4 is directed toward an embodiment for the production of renewable jet fuel, diesel, gasoline and kerosene components. In the embodiment, the series of catalyst reactors are chosen to contain an oxygenate synthesis catalyst, a dehydration catalyst, an olefin production catalyst and an olefin oligomerization catalyst. A system 400 comprised of N stations is shown in FIG. 4. Biomass of unspecified composition is subjected first to temperature T_starti in processing station 1. T _starti is selected by the operator. It is chosen based upon the biomass composition, or to achieve optimum production of volatile components. T _starti can typically range from 200°C to 500°C, and preferably in some cases from 300°C to 550°C. The temperature may be attained via the application of heat in the presence of a concomitant application of pressure shocks to the biomass. The magnitude of the pressure shocks can vary in some embodiments preferentially from 0.2 MPa to 10 GPa, and most preferentially from 0.5 MPa to 5 GPa. The heating and/or pressure of biomass in Station 1 produces a first volatile gas and a non-volatile carbonaceous solid, labeled as Solid 1 in FIG. 4. The volatile gas is subjected to dehydration catalyst column 161 to produce a first product which upon cooling produces a second volatile component, a first renewable fuel, and water. The second volatile component, comprised primarily of C₂-C5 olefins, is then subjected to an oligomerization catalyst 162 to produce a second product which upon cooling to 0-20°C, and preferably in some cases to 0-5°C, outputs a third volatile product, and a second renewable fuel which comprising a mixture of gasoline and diesel fractions. The renewable diesel fuel obtained from this process according to one or more embodiments is characterized by Subjecting the diesel component of this second renewable fuel to a hydrotreating catalyst 163 in the presence of hydrogen yields, upon cooling, a fourth volatile component, renewable kerosene or renewable jet fuel, and water. The renewable jet fuel obtained from this process according to one or more embodiments is characterized by

[0076] The Solid 1 recovered from the process at the first processing station in

FIG. 4 is next subjected in Processing Station 2 to a second mild stepwise pyro lysis of the biomass. The temperature can be the same as that in processing station 1 or it can be temperature T _starti + ΔΤι, where ΔΤι is a temperature increment selected by the operator, and is typically in the range of 10-200°C, preferably in some cases in the range of 10-100°C, and most preferably in some cases in the range of 10-50°C. The temperature increment is chosen to attain a mild stepwise pyrolysis of the biomass to volatile components and conversion of said components to renewable jet fuel. The temperature increments may be attained via the application of temperature ramps in the presence of a concomitant application of pressure shocks to the biomass. T In some embodiments, the temperature ramps can vary

preferentially from about 0.001°C/sec to about 1000°C/sec, and most preferentially from about O.OlC/sec to lOOC/sec. The magnitude of the pressure shocks can vary in some embodiments preferentially from 0.2 MPa to 10 GPa, and most preferentially from 0.5 MPa to 5 GPa. The volatile components arising from the treatment at Processing Station 2 are subjected to the same series of catalysts as outlined above for volatile components arising from Processing Station 1. FIG. 4 illustrates the stepwise conversion of biomass to jet fuel for Processing Stations 1 through N-1 , at which point a carbonaceous solid N-1 remains.

[0077] As illustrated in FIG. 5, the Nth processing station, subjects the carbonaceous Solid N-1 to a temperature T_starti + ΔΤ_Ν that is sufficiently high to generate very little volatile components and mostly residual char. This char may be subsequently transferred to an external gas converter unit which can comprise any conventional gasifier. The processing temperature and the gasification temperature are typically greater than 700°C. In some cases, the gas converter unit reacts the carbonaceous Solid N-1 with one of: external sources of water, carbon dioxide, methane, or combustible gases. In other cases, the gas converter unit reacts the carbonaceous Solid N-1 with one of: internally generated carbon dioxide, water/methanol mixture, or combustible gases. The product from the gas converter is synthesis gas (syngas), which is compressed and fed into a catalytic column containing an oxygenate synthesis catalyst 160 (such as dimethyl ether or methanol) to yield a (2N-l)th product. This product is passed through a water-based separator to yield a renewable fuel comprising a water/methanol fraction, unreacted syngas along with carbon dioxide, and a volatile component (4N-4) primarily comprising dimethyl ether with an equilibrium amount of methanol. The water/methanol fraction and the unreacted syngas with carbon dioxide may be vented, rerouted back to the gasifier, or used for other purposes, such as running a genset.

[0078] Oxygenate synthesis catalysts are able to catalyze the synthesis of oxygenates such as aldehydes, alcohols, ketones, ethers, and carboxylates. Such catalysts are well known and may comprise co-precipitated oxides of Cu and Zn. These oxides may be co-precipitated with various oxides known to those skilled in the art to drive the equilibrium to the formation of dimethyl ether. The oxides include oxides of aluminum, chromium, manganese, zirconium and boron. Typical ratios of Cu to Zn may vary from 5 : 1 to 1 :5. In the case of aluminum oxide, Al to Cu ratio may vary from 0.05 to 2 and Al to Zn ratio may vary from 0.1 to 1. Typical catalyst operating temperatures are 200°C to 300°C, and typical ultimate compressor pressures range from 40 bar to 80 bar, although pressures as low as 10 bar may yield conversion rates close to equilibrium for certain catalyst formulations.

[0079] Referring to FIG. 5, the volatile fraction 4N-4 comprised of oxygenates can be fed to dehydration catalyst 161, which yields a 2Nth product. Upon cooling in a cold trap at 0-20°C (In some cases, preferably in the range of 0-5°C), this produces a 2Nth renewable fuel and a volatile component comprised of C2-C5 olefins (4N-3). The dehydration catalyst 161 can comprise any of well-known acid catalysts such as SAPO-34, ZSM-5-type catalysts such as ZSM-5, A1P0₄ modified ZSM-5, ZSM-11, and MCM-22. These catalysts are used in methanol/DME to olefins (MTO) processes. Typical operating temperatures are 300°C-600°C, and typical operating pressures are 0.1-10 bar. The olefins produced may comprise a mixture of C₂, C₃, C₄ and C₅ olefins, including ethylene, propene, butene, pentene and structural and stereoisomers of these olefins.

[0080] These olefins can be oligomerized in oligomerization catalyst 162 to produce a (2N+l)th product which upon cooling in a cold trap yields a (2N+l)th renewable fuel components comprised primarily of C6-C20 olefins, in the gasoline and diesel ranges, and volatile component (4N-2). Oligomerization catalyst 162 can comprise an acid catalyst similar to the MTO stage as described earlier, but operating conditions are different, with pressures ranging from 10-60 bar, and temperatures in the range of 200°C to 350°C . The volatile component (4N-2) can be routed back to the gasifier. [0081] The diesel component of the (2N+l)th liquid renewable fuel from the oligomerization treatment can be routed to a reactor containing hydrotreating catalyst 163 that, along with hydrogen, yields a product which upon cooling to 0-20°C (in some cases, cooling to 0-5°C is preferred), yields renewable jet fuel, diesel fuel, kerosene components, and a volatile component (4N+1). The volatile component (4N+1) can be recycled back to the gasifier. Hydrotreating or hydroprocessing catalysts include CoMo, NiMO, high pore volume Ni, and high pore volume Mo. The resulting renewable fuel can comprise a mixture of liquid fuels typically categorized as kerosene, diesel fuel, jet fuel, or aviation gasoline.

[0082] The above embodiments 3 involve an approach that exploits knowing the initial composition of the biomass input, and then adjusting the routing of the

decomposition products based on this initial composition. Accordingly, given a hemicellulose rich feedstock, it may be beneficial to set all of the processing stations 50 to a temperature greater than 300°C. Similarly, given a lignin-rich feedstock, it may be beneficial to operate all the processing stations 50 at temperatures greater than 500°C. Such an operation is expected to utilize all the stations in the most efficient manner for maximizing fuel output.

[0083] Another approach entails the use of an algorithm that raises an individual processing station temperature by ΔΤ until a desired end temperature is reached. This approach is illustrated in FIG. 6, which shows a temperature algorithm flowchart 600 for a single processing station. For three cuts derived from lipids, hemicellulose and lignins, one would select T_Low around 300°C, and T_HIG_H around 500°C.

[0084] Referring to FIG. 6, T=T_start at operation 405. Operation 410 involves raising the biomass temperature by ΔΤ. Next, operation 415 involves determining whether T< T_LOW for the lipids. If so, the next steps entail routing the biomass through the lipid catalyst chain (operation 420), collecting the product (operation 425), and proceeding to raise the biomass temperature by ΔΤ (operation 410). If operation 415 is false, operation 440 involves determining whether T_LOW<T<T_HIG_H for the hemicellulose. If so, the next steps include routing the biomass through the hemicellulose catalyst chain (operation 445), collecting the product (operation 450), and proceeding to raise the biomass temperature by ΔΤ (operation 410). If operation 440 is false, operation 470 involves determining whether T>T_RIG_H for the lignins. If so, the next steps entail routing the biomass through the lignin catalyst chain (operation 475), collecting the product (operation 480), and proceeding to raise the biomass temperature by ΔΤ (operation 410). The algorithm ends if operation 470 is false. [0085] Yet another approach involves load balancing the output from each catalytic chain in order to maximize product yield. This approach is illustrated in FIG. 7, which depicts a load balancing algorithm flowchart 700 for one processing station. According to this approach, knowledge of composition is not required. Rather, the optimal catalytic route is determined by comparing product output yield from each route. Subsequently, the temperature is incremented until a final desired temperature is achieved.

[0086] Referring to FIG. 7, T=T_start at operation 505. Operation 510 involves opening all routes. Next, operation 515 comprises raising the biomass temperature by ΔΤ. At this point, this approach splits into three routes, specifically catalyst chain A (operation 520), catalyst chain B (operation 525), and catalyst chain C (operation 530). Product is collected for each catalyst chain in subsequent operations 540, 545, 550. Operation 560 entails determining the optimal catalytic route is calculated by comparing product output yield from each route and determining the catalyst chain having the highest product yield. Then, operation 565 comprises closing all routes except the one with the highest yield. Operation 570 involves determining whether the product output is below a threshold level. If so, the algorithm proceeds to open all routes (operation 510). If not, the algorithm proceeds to raise the biomass temperature by ΔΤ (operation 515).

ILLUSTRATIVE EXAMPLE 1

[0087] Referring now to FIG. 8 A, this illustrative example is the equivalent to six processing stations 50 operating at six different temperatures wherein the input biomass is fed at 325°C and the final carbonaceous solid is removed at 575°C. 150g of biomass consisting of commercial sunflower seeds, which is a lipid rich biomass, along with dimethyl ether as co-solvent were devolatilized starting at a temperature of 325°C and ending at 575°C with a temperature increment of 50°C for every hour . 13 lg of methanol was passed through a silica alumina catalyst to generate the required co-solvent. The output was passed through three different catalyst columns in series including a dehydration catalyst 60, an

aromatization catalyst 61, and a gas-upgrading catalyst 62 as illustrated in FIG. 3 for cut A. More particularly, this experiment employed a silica alumina dehydration catalyst, a Zn and Cr modified ZSM-5 aromatization catalyst, and a Ga modified ZSM-5 gas-upgrading catalyst. FIG. 8 A is a chart showing the fuel collected at each temperature for each catalyst at half-hour intervals. A grand total of 46.5 ml of renewable fuel is produced by the three catalysts by the end of the run, including: (i) a total of 26.5 ml of renewable fuel collected from the aromatization catalyst 61, (ii) a total of 18 ml of renewable fuel collected from the dehydration catalyst 60, and (iii) a total of 2 ml of renewable fuel collected from the gas- upgrading catalyst 62.

[0088] FIG. 8B is a chart showing the gas chromatogram profile of the renewable fuel collected from the dehydration catalyst 60 along with comparative charts of regular US Diesel #2 fuel and Bio Diesel B99 obtained from a commercial source. The renewable fuel produced from the dehydration catalyst according to the present disclosure is significantly different when compared to the Biodiesel B99 and more resembles the profile of the regular US Diesel #2. Gas chromatograms shown in FIGS. 8C and 8D represent renewable fuel composition from the aromatization catalyst 61 and the gas-upgrading catalyst 62, respectively. Significant amount of aromatic hydrocarbons are present in both renewable fuels.

ILLUSTRATIVE EXAMPLE 2

[0089] This illustrative example is the equivalent to six processing stations operating at six different temperatures wherein the input biomass is again fed at 325°C and the final carbonaceous solid is removed at 525°C. 76g of biomass consisting of commercial corn cobs along with lOOg of methanol were devolatilized starting at a temperature of 325°C and ending at 525°C with a temperature increment of 50°C for every hour. This example assumes that corn cobs contain significant amounts of hemicellulose (C5 sugars), which may decompose in the presence of a dehydration catalyst 60, leading to more breakage of chemical bonds than necessary. Therefore, the output was passed through two different catalyst columns in series, one consisting of an aromatization catalyst 61, followed by a gas- upgrading catalyst 62 as illustrated in FIG. 3 for cut B. In this example, ZSM-5 was employed as the aromatization catalyst, and Ga modified ZSM-5 was employed as the gas- upgrading catalyst. A total of 29 ml of renewable fuel was collected by the end of the run from the aromatization catalyst, while a total of 5.5 ml of renewable fuel was collected from the gas-upgrading catalyst, Further analysis of the two renewable fuels collected indicated significant presence of aromatic compounds similar in composition as shown in Illustrative Example 1. ILLUSTRATIVE EXAMPLE 3

[0090] This illustrative example is equivalent to six processing stations operating at six different temperatures wherein the input biomass is again fed at 325°C and the final carbonaceous solid is removed at 575°C. lOOg of biomass consisting of red fir wood along with 131g of methanol were devolatilized starting at a temperature of 325°C and ending at 575°C with a temperature increment of 50°C for every hour. This example assumes that red fir contains significant amounts of lignins which are needed to be decomposed for efficient biomass conversion. The output was passed through two different catalyst columns in series, beginning with the dehydration catalyst 60, and followed by an aromatization catalyst 61. This experiment utilized silica alumina as the dehydration catalyst, and Zn and Cr modified ZSM-5 as the aromatization catalyst. A total of 30.5 ml of renewable fuel was collected by the end of the run from the aromatization catalyst 61, whereas a total of 1 ml of renewable fuel was collected from the dehydration catalyst 60. While the fuel from the silica alumina catalyst was diesel-like, the fuel from the aromatization catalyst had significant amounts of aromatic hydrocarbons. The volatile gases after the aromatization catalyst 61 had significant amounts of C1-C5 non-condensable hydrocarbons, as shown in FIG. 9.

ILLUSTRATIVE EXAMPLE 4

[0091] This illustrative example is equivalent to six processing stations operating at six different temperatures (alternatively the temperature could be held constant in each processing stations) wherein the input biomass is again fed at 325°C and the final carbonaceous solid is removed at 575°C. Biomass along with methanol are devolatilized starting at a temperature of 325°C and ending at 575°C with a temperature increment of 50°C for every hour. The output is passed through three different catalyst columns in series, beginning with the dehydration catalyst, followed by an oligomerization catalyst, and finally a hydrotreating catalyst. Renewable jet fuel is collected by the end of the run from the hydrotreating catalyst. The jet fuel from the hydrotreating catalyst is rich in aliphatic hydrocarbons and is suitable for blending with other components to make renewable jet fuel.

[0092] Although the invention is described above in terms of various exemplary embodiments and implementations, it should be understood that the various features, aspects and functionality described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment with which they are described, but instead can be applied, alone or in various combinations, to one or more of the other embodiments of the invention, whether or not such embodiments are described and whether or not such features are presented as being a part of a described embodiment. Thus, each and every embodiment described above can be combined with any one or more than one of the other embodiments. Therefore, the breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments.

[0093] Terms and phrases used in this document, and variations thereof, unless otherwise expressly stated, should be construed as open ended as opposed to limiting. As examples of the foregoing: the term "including" should be read as meaning "including, without limitation" or the like; the term "example" is used to provide exemplary instances of the item in discussion, not an exhaustive or limiting list thereof; the terms "a" or "an" should be read as meaning "at least one," "one or more" or the like; and adjectives such as

"conventional," "traditional," "normal," "standard," "known" and terms of similar meaning should not be construed as limiting the item described to a given time period or to an item available as of a given time, but instead should be read to encompass conventional, traditional, normal, or standard technologies that may be available or known now or at any time in the future. Likewise, where this document refers to technologies that would be apparent or known to one of ordinary skill in the art, such technologies encompass those apparent or known to the skilled artisan now or at any time in the future.

[0094] The presence of broadening words and phrases such as "one or more,"

"at least," "but not limited to" or other like phrases in some instances shall not be read to mean that the narrower case is intended or required in instances where such broadening phrases may be absent. Additionally, the various embodiments set forth herein are described in terms of exemplary block diagrams, flow charts and other illustrations. As will become apparent to one of ordinary skill in the art after reading this document, the illustrated embodiments and their various alternatives can be implemented without confinement to the illustrated examples. These illustrations and their accompanying description should not be construed as mandating a particular architecture or configuration.

Claims

Claims

1. A system for the conversion of biomass to diesel or jet fuel, comprising: a device containing a number of processing stations (N) and a series of catalysts; each processing station capable of subjecting biomass within the station to at least one starting temperature (T_start) to produce a volatile and a non-volatile component; at least one catalyst reactor for receiving volatile components generated in each processing station; and wherein, the at least one catalyst reactor contains a catalyst selected from the group consisting of: dehydration catalysts, olefin oligomerization catalysts and hydrotreating catalysts.

2. The system of claim 1, further comprising additional catalyst reactors.

3. The system of claim 2, wherein the additional catalyst reactors are used in series.

4. The system of claim 2, wherein the additional catalyst reactors are used in parallel.

5. The system of claim 1, further comprising a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ).

6. The system of claim 1, wherein the non- volatile component is a carbonaceous material.

7. The system of claim 1 , further comprising a gasifier for converting the carbonaceous material to syngas.

8. The system of claim 7, further comprising a conduit from the gasifier to a catalyst reactor for the introduction of syngas.

9. The system of claim 1, wherein N ranges from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C.

10. The system of claim 5, wherein the temperature increment (ΔΤ) ranges from 0°C to 200°C.

11. The system of claim 1 , further comprising a reservoir for housing a a co-feed, and a conduit for introduction of the co-feed to the volatile components or to at least one of the processing stations, wherein the co-feed is selected from the group consisting of alcohols, aldehydes, ketones, ethers, carboxylic acids, and hydrocarbons.

12. The system of claim 11, further comprising a conduit from the gasifier to a catalyst reactor containing a syngas conversion catylast wherein the co-feed is generated via the syngas conversion catalyst.

13. The system of claim 1, wherein biomass is selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

14. The system of claim 13, wherein the biomass is a mixture of two or more types of biomass selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

15. The system of claim 13, wherein T_start is selected according to the type of biomass with the highest concentration in the mixture of two or more types of biomass.

16. The system of claim 1, wherein at least two processing stations are set at the same T_st_art-

17. The system of claim 1, wherein all of the processing stations are set at the same T_st_art.

18. The system of claim 1, wherein the T_start is a substantially constant

temperature.

19. The system of claim 1, wherein the non- volatile component is thermally conductive.

20. The system of claim 1 , wherein the non- volatile component at the Nth processing station comprises char.

21. The system of claim 1 , wherein the Nth processing station comprise an input capable of receiving an external source of water, carbon dioxide or methane, or internally provided recycled water or combustible gases arising from the catalyst treatment.

22. The system of claim 1, wherein the dehydration catalyst comprises any acid catalyst or combination of acid catalysts.

23. The system of claim 1, wherein the olefin oligomerization catalyst is a dehydration catalyst.

24. The system of claim 1, further comprising conduits to direct water, carbon dioxide, and methanol generated in the system to the gasifier for use in the conversion of the non-volatile components to syngas.

25. The system of claim 24, wherein the non- volatile component from a station comprises feedstock for the next station.

26. The system of claim 1, wherein the diesel or jet fuel produced comprises one or more kerosene components.

27. The system of claim 1, wherein the diesel or jet fuel produced comprises one or more jet fuel components.

28. The system of claim 1, wherein the diesel or jet fuel produced comprises one or more diesel fuel components.

29. The system of claim 6, wherein internally generated water, carbon dioxide, methanol are used as reactants in the conversion of the carbonaceous material to syngas.

30. The system of claim 1, wherein the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a f uidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier, and a vacuum moving bed reactors.

31. A system for converting char to a renewable fuel, comprising: a device containing a plurality of processing stations (N) and a series of catalysts; each processing station capable of subjecting char within the station to at least one starting temperature (T_start) to produce syngas; at least one catalyst reactor for receiving syngas generated in each processing station; and wherein, the at least one catalyst reactor contains a catalyst selected from the group consisting of: syngas conversion catalysts, methanol synthesis catalyst, DME synthesis catalysts, dehydration catalysts, olefin oligomerization catalysts and hydrotreating catalysts.

32. The system of claim 31 , further comprising additional catalyst reactors.

33. The system of claim 32, wherein the additional catalyst reactors are used in series.

34. The system of claim 32, wherein the additional catalyst reactors are used in parallel.

35. The system of claim 31 , wherein the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a fluidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier, and a vacuum moving bed reactors.

36. The system of claim 31 , further comprising a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ).

37. The system of claim 31 , wherein N ranges from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C.

38. The system of claim 36, wherein the temperature increment (ΔΤ) ranges from 0°C to 200°C.

39. The system of claim 31 , further comprising a reservoir for housing a co-feed, and a conduit for introduction of the co-feed to the volatile components or to at least one of the processing stations, wherein the co-feed is selected from the group consisting of alcohols, aldehydes, ketones, ethers, carboxylic acids, and hydrocarbons.

40. The system of claim 31 , wherein the Nth processing station comprises an input capable of receiving an external source of water, carbon dioxide or methane, or internally provided recycled water or combustible gases arising from the catalyst treatment.

41. The system of claim 31 , wherein the dehydration catalyst comprises any acid catalyst or combination of acid catalysts.

42. The system of claim 31 , wherein the olefin oligomerization catalyst is a dehydration catalyst.

43. The system of claim 31 , wherein the renewable fuel comprises one or more kerosene components, or one or more jet fuel components.

44. A method for converting biomass to diesel or jet fuel, comprising: dispensing biomass into a plurality of processing stations (N); subjecting biomass within the station to at least one starting temperature (T_start) to produce a volatile and a non- volatile component; directing the volatile component to at least one catalyst reactor designed to perform one or more of the processes selected from the group consisting of dehydration, olefin oligomerization and hydrotreating; collecting the diesel or jet fuel produced in the at least one catalyst reactor.

45. The method of claim 44, further comprising additional catalyst reactors.

46. The method of claim 45, wherein the additional catalyst reactors are used in series.

47. The method of claim 45, wherein the additional catalyst reactors are used in parallel.

48. The method of claim 44, further comprising using a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ).

49. The method of claim 44, wherein the non-volatile component is a

carbonaceous material.

50. The method of claim 44, further comprising converting the carbonaceous material to syngas.

51. The method of claim 44, wherein N ranges from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C.

52. The method of claim 44, wherein the temperature increment (ΔΤ) ranges from 0°C to 200°C.

53. The method of claim 1 , further comprising introducing co-feed to the volatile components or to at least one of the processing stations, wherein the co-feed is selected from the group consisting of alcohols, aldehydes, ketones, ethers, carboxylic acids, and hydrocarbons.

54. The method of claim 53, further comprising a catalyst reactor containing a syngas conversion catylast wherein the co-feed is generated via the syngas conversion catalyst.

55. The method of claim 44, wherein biomass is selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

56. The method of claim 55, wherein the biomass is a mixture of two or more types of biomass selected from the group consisting of lipids, hemicellulose, cellulose and lignins.

57. The method of claim 56, wherein T_start is selected according to the type of biomass with the highest concentration in the mixture of two or more types of biomass.

58. The method of claim 44, wherein at least two processing stations are set at the same T_st_art-

59. The method of claim 44, wherein all of the processing stations are set at the same T_st_art.

60. The method of claim 44, wherein the T_start is a substantially constant temperature.

61. The method of claim 44, wherein the non- volatile component is thermally conductive.

62. The method of claim 44, wherein the non-volatile component at the Nth processing station comprises char.

63. The method of claim 44, wherein the Nth processing station comprise an input capable of receiving an external source of water, carbon dioxide or methane, or internally provided recycled water or combustible gases arising from the catalyst treatment.

64. The method of claim 44, wherein the dehydration catalyst comprises any acid catalyst or combination of acid catalysts.

65. The method of claim 44, wherein the olefin oligomerization catalyst is a dehydration catalyst.

66. The method of claim 44, wherein water, carbon dioxide, and methanol generated in the system are used in the conversion of the non-volatile components to syngas.

67. The method of claim 44, wherein the non-volatile component from a station comprises feedstock for the next station.

68. The method of claim 44, wherein the diesel or jet fuel produced comprises one or more kerosene components.

69. The method of claim 44, wherein the diesel or jet fuel produced comprises one or more jet fuel components.

70. The method of claim 44, wherein the diesel or jet fuel produced comprises one or more diesel fuel components.

71. The method of claim 49, wherein internally generated water, carbon dioxide, methanol are used as reactants in the conversion of the carbonaceous material to syngas.

72. The method of claim 44, wherein the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a fluidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier, and a vacuum moving bed reactors.

73. A method for converting char to diesel or jet fuel, comprising: dispensing char into a plurality of processing stations (N); subjecting char within the station to at least one starting temperature (T_start) to produce syngas; directing the syngas to at least one catalyst reactor designed to perform one or more of the processes selected from the group consisting of syngas conversion catalysts, methanol synthesis catalyst, DME synthesis catalysts, dehydration, olefin oligomerization and hydrotreating; collecting the diesel or jet fuel produced in the at least one catalyst reactor.

74. The method of claim 73, further comprising additional catalyst reactors.

75. The method of claim 74, wherein the additional catalyst reactors are used in series.

76. The method of claim 74, wherein the additional catalyst reactors are used in parallel.

77. The method of claim 73, wherein the processing station is selected from the group consisting of a pyrolysis reactor, a fixed bed reactor, a f uidized bed reactor, a circulating bed reactor, a bubbling fluid bed reactor, a vacuum moving bed reactor, an entrained flow reactor, a cyclonic reactor, a vortex reactor, a rotating cone reactor, an auger reactor, an ablative reactor, a microwave assisted pyrolysis reactor, a plasma assisted pyrolysis reactor, a chamber in a biomass fractionating system, gasifier, and a vacuum moving bed reactors.

78. The method of claim 73, further comprising using a temperature controller for incrementing an individual processing station temperature by increments (ΔΤ).

79. The method of claim 73, wherein N ranges from 2 to 1000, and wherein T_start ranges from 100°C to 1000°C.

80. The method of claim 78, wherein the temperature increment (ΔΤ) ranges from 0°C to 200°C.

81. The method of claim 73, further comprising introducing co-feed to the volatile components or to at least one of the processing stations, wherein the co-feed is selected from the group consisting of alcohols, aldehydes, ketones, ethers, carboxylic acids, and

hydrocarbons..

82. The method of claim 73, wherein the Nth processing station receives an external source of water, carbon dioxide or methane, or internally provided recycled water or combustible gases arising from the catalyst treatment.

83. The method of claim 73, wherein the dehydration catalyst comprises any acid catalyst or combination of acid catalysts.

84. The method of claim 73, wherein the olefin oligomerization catalyst is a dehydration catalyst.

85. The method of claim 73, wherein the renewable fuel comprises one or more kerosene components, or one or more jet fuel components.