BIOMASS PRETREATMENT WITH A CATALYST BY HIGH VELOCITY AGITATION AND SEPARATION

FIELD OF THE INVENTION

[0001] The invention relates to pretreating biomass for conversion into fuels and specialty chemicals. The invention relates more particularly to controlled size reduction and catalyst contact of solid biomass as pretreatment for catalytic processing.

BACKGROUND OF THE INVENTION

[0002] Biomass, in particular biomass of plant origin, is recognized as an abundant potential source of fuels and specialty chemicals. See, for example, "Energy production from biomass," by P. McKendry - Bioresource Technology 83 (2002) p 37-46 and "Coordinated development of leading biomass pretreatment technologies" by Wyman et al, Bioresource Technology 96 (2005) 1959-1966. Refined biomass feedstock, such as vegetable oils, starches, and sugars, can be substantially converted to liquid fuels including biodiesel (e.g., methyl or ethyl esters of fatty acids) and ethanol. However, using refined biomass feedstock for fuels and specialty chemicals can divert food sources from animal and human consumption, raising financial and ethical issues.

[0003] Alternatively, inedible biomass can be used to produce liquid fuels and specialty chemicals. In many cases, inedible biomass does not at present have an economic use and is therefore considered waste. Examples of inedible biomass include agricultural waste, such as bagasse, straw, corn stover, corn husks, and the like. Other examples include forestry waste, such as wood chips and saw dust from logging operations, or waste from paper and/or paper mills. Inedible biomass generally includes three main components: lignin, amorphous hemi-cellulose, and crystalline cellulose. These components reduce the chemical and physical accessibility of the biomass, which can reduce the susceptibility to chemical and/or enzymatic conversion.

BRIEF SUMMARY OF THE INVENTION

[0004] In various embodiments the invention includes methods, apparatuses, and compositions for converting cellulosic (e.g., including lingo- and hemi- cellulosic) material in biomass (e.g., including inedible and inedible portions) into fuels and/or specialty chemicals under conditions that can mitigate equipment cost, energy cost, and/or degradation or undesirable reaction of conversion product. For example, the invention includes pretreatment of biomass with a catalyst, which can improve the accessibility, impregnation, and/or dissolution of the biomass and catalyst, and thus can improve conversion of the biomass into fuels and/or specialty chemicals. Pretreatment can have a synergistic effect, reducing the temperature necessary for catalytic conversion of the biomass and/or increasing the conversion efficiency of the biomass. The invention can enhance the contact and thus catalytic effect by contacting a biomass with a catalyst at a high velocity (and low temperature, e.g., T < 300, 275, 250, 225, 200, 175, 150, 125, or 100 °C) before conversion (at a higher temperature). The invention can result in a controlled particle size reduction of biomass and contacting with a catalyst. For example, the invention can couple high velocity contacting of a catalyst and a solid biomass with a cyclonic separation, whereby the fines are routed to the higher temperature reaction zone and the coarser fraction is wholly or partly recycled for further particle size reduction. [0005] In one aspect, the invention features a method for preparing solid biomass particles for catalytic conversion. The method includes contacting solid biomass particles and a catalyst by conveyance at a high velocity sufficient to produce a biomass-catalyst mixture having reduced solid biomass particle sizes. The invention also includes separating the biomass-catalyst mixture in a cyclone separator into a fine fraction capable of being transported to a catalytic conversion reaction zone and a coarse fraction capable of being recycled for further contacting and separating. The biomass-catalyst mixture can include at least a portion of the catalyst interacting with at least a portion of the solid biomass particles.

[0006] In another aspect, the invention features a method for preparing solid biomass particles for catalytic conversion. The method includes agitating solid biomass particles, to reduce a size characterizing at least a portion of the particles. The method also includes separating a biomass-catalyst mixture into a fine fraction and a coarse fraction. The biomass-catalyst mixture includes the particles and a catalyst. The fine fraction includes particles of about a predetermined size. The

coarse fraction includes particles of greater than about the predetermined size. The biomass-catalyst mixture can include at least a portion of the catalyst interacting with at least a portion of the solid biomass particles.

[0007] In still another aspect, the invention features an apparatus for preparing solid biomass particles for catalytic conversion. The apparatus includes an agitator for reducing a size characterizing at least a portion of solid biomass particles. The apparatus also includes a separator for dividing a biomass-catalyst mixture into a fine fraction and a coarse fraction. The biomass-catalyst mixture includes the particles and a catalyst. The fine fraction includes particles of about a predetermined size. The coarse fraction includes particles of greater than about the predetermined size. The biomass-catalyst mixture can include at least a portion of the catalyst interacting with at least a portion of the solid biomass particles.

[0008] In yet another aspect, the invention features a composition including a biomass-catalyst mixture. The mixture includes a plurality of solid biomass particles and a catalyst. The plurality of solid biomass particles are substantially characterized by sizes below about 500 microns. The biomass-catalyst mixture can include at least a portion of the catalyst interacting with at least a portion of the solid biomass particles.

[0009] In other examples, any of the aspects above, or any method, apparatus, or composition of matter described herein, can includes one or more of the features described in the paragraphs below.

[0010] In various embodiments, the fine fraction is suitable as feedstock to a refinery or chemical production facility unit such as fluid catalytic cracking unit, fluid and delayed coking unit, fluid catalytic cracking pretreater unit, resid HT unit, deasphalting unit, lube oil HT unit, ethylene polymerization unit, or propylene polymerization unit.

[0011] In some embodiments, the catalyst includes a solid particulate catalyst and the biomass-catalyst mixture includes at least a portion of the catalyst mechano- chemically interacting with at least a portion of the solid biomass particles. [0012] In certain embodiments, the catalyst includes a catalyst capable of being at least partly dissolved or suspended in a liquid and the biomass-catalyst mixture includes at least a portion of the catalyst impregnating at least a portion of the solid biomass particles.

[0013] In various embodiments, the method includes kneading the solid biomass particles and the catalyst, to make at least a portion of the solid biomass particles accessible to at least a portion of the catalyst. An apparatus can include a kneader for kneading the solid biomass particles and the catalyst, to make at least a portion of the solid biomass particles accessible to at least a portion of the catalyst.

[0014] In some embodiments, the method includes processing plant matter at a location in close proximity to an agricultural site (e.g., used to produce such plant matter), to produce the solid biomass particles. An apparatus can include a disintegrator for processing plant matter at a location in close proximity to a cultivation site or an agricultural site used to produce such plant matter, to produce the solid biomass particles. A disintegrator can include a mill, fragmenter, fractionator, granulator, pulverizer, chipper, chopper, grinder, shredder, mincer, or a crusher. Such a cultivation or agricultural site may be a satellite site within the context of a broader biomass refinery or fuel production system. [0015] In certain embodiments, agitating includes causing the solid biomass particles to move at a velocity of greater than about 1 m/s. Agitating can include causing the solid biomass particles to move at a velocity of greater than about 10 m/s. Agitating can include causing at least a portion of the solid biomass particles to move at a velocity of greater than about 100 m/s. An agitator can be adapted to cause the solid biomass particles to move at a velocity of greater than about 1 m/s, greater than about 10 m/s, and/or greater than about 100 m/s. An agitator can include a cyclone capable of causing at least a portion of the solid biomass particles to move at a velocity of greater than about 100 m/s.

[0016] In some embodiments, agitating is facilitated by fluid conveyance, including, without limitation, by gas flow or pneumatic conveyance. Agitating can be conducted in a riser or downer. An agitator can include a conveyor, a riser, or downer. Agitating can be facilitated by a gas. Exemplary gases useful in the invention include, without limitation, air, steam, flue gas, carbon dioxide, carbon monoxide, hydrogen, hydrocarbons, methane, activated reactive methane, and any combination of two or more of the foregoing. Agitating can facilitate formation of a mechano-chemical interaction between at least a portion of the catalyst and at least a portion of the solid biomass particles.

[0017] In various embodiments, up to about 10%, 20%, 30% or 50% of a petroleum feedstock to a conventional refinery or chemical production facility is replaced with a conversion product of the fine fraction. Up to about 50%, 60%, 70%, 80%, 90% or 100% of a biomass feedstock to a biomass refinery or chemical production facility can be replaced with a conversion product of the fine fraction. [0018] In certain embodiments, separating is facilitated by a cyclonic action.

Separating can be conducted in a cyclone separator. A cyclone separator can include a single cyclone or a plurality of cyclones arranged in parallel, series, as a third stage separator, or as a fourth stage separator.

[0019] In various embodiments, methods include delivering the fine fraction to a thermal reactor. Methods can include liquefying at least a portion of the fine fraction in a thermal reactor, to produce a liquid product. Methods can also include blending a refinery feedstock and at least a portion of the liquid product, to produce a blended feedstock and reacting the blended feedstock in a conventional refinery unit. Methods can include recycling the coarse fraction for further agitation. Methods can include subjecting the coarse fraction to additional agitating and separating steps. Apparatuses can include a recycler adapted for subjecting the coarse fraction to additional agitating and separating steps.

[0020] In some embodiments, methods include contacting the solid biomass particles and the catalyst to produce the biomass-catalyst mixture after agitating. Methods can include contacting the solid biomass particles and the catalyst to produce the biomass-catalyst mixture before agitating. Agitating the solid biomass particles can include agitating the biomass-catalyst mixture.

[0021] In certain embodiments, methods include liquefying at least a portion of the fine fraction. Apparatuses can include a thermal reactor for liquefying at least a portion of the fine fraction. Methods can include pyrolyzing at least a portion of the fine fraction. Methods can include catalytically cracking at least a portion of the fine fraction.

[0022] In various embodiments, the biomass-catalyst mixture can include an inorganic particulate material.

[0023] In some embodiments, methods include removing at least a portion of ash precursors from the biomass in at least one of the agitating and a kneading step. [0024] In certain embodiments, at least one of the agitator and a kneader are adapted to remove at least a portion of ash precursors from the biomass. At least one

of the agitator and a kneader can be adapted to swell the biomass and/or condition the biomass with inorganic or organics acid or bases.

[0025] In various embodiments, at least a certain percentage of the plurality of solid biomass particles are characterized by a size less than a predetermined maximum size. A predetermined maximum size can be about 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, or 10 microns. In some embodiments, at least a fraction of the plurality of solid biomass particles is characterized by sizes below a predetermined maximum size. A fraction of the plurality of solid biomass particles that are characterized by sizes below a predetermined maximum size can be about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100%. For example, the composition can include least about 50% of the plurality of solid biomass particles characterized by sizes below about 300 microns. For example, the composition can include least about 50% of the plurality of solid biomass particles characterized by sizes below about 125 microns. [0026] Other aspects and advantages of the invention will become apparent from the following drawings and description, all of which illustrate principles of the invention, by way of example only.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The advantages of the invention described above, together with further advantages, may be better understood by referring to the following description taken in conjunction with the accompanying drawings. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention.

[0028] FIG. 1 shows a flow diagram of an embodiment of a method for preparing solid biomass particles for catalytic conversion.

[0029] FIG. 2 shows an embodiment of an apparatus for high velocity pretreatment of biomass with a solid catalyst.

[0030] FIG. 3 shows an embodiment of an apparatus for high velocity pretreatment of biomass with a dissolved and/or suspended catalyst.

[0031] FIG. 4 shows an embodiment of an apparatus for high velocity pretreatment of a biomass catalyst composite.

[0032] FIG. 5 shows an embodiment of an apparatus for high velocity pretreatment of biomass and plant matter processing.

DETAILED DESCRIPTION OF THE INVENTION

[0033] The invention provides methods, apparatuses, and compositions for converting cellulosic material in biomass into fuels and/or specialty chemicals under conditions that can mitigate equipment cost, energy cost, and/or degradation or undesirable reaction of conversion product. In one aspect, the method and apparatuses of the invention are useful for improving the processing characteristics of biomass feedstock. According to one embodiment, the invention includes pretreatment of biomass with a catalyst, which can improve the accessibility, impregnation, and/or dissolution of the biomass and catalyst, and thus can improve conversion of the biomass into fuels and/or specialty chemicals. In another embodiment, the invention includes contacting a biomass with a catalyst at a high velocity (and low temperature, e.g., T < 300, 275, 250, 225, 200, 175, 150, 125, or 100 ⁰ C) before conversion (e.g., at a higher temperature), which can result in enhanced contact and thus catalytic effect. In another embodiment, the invention includes coupling high velocity contacting of a catalyst and a solid biomass with a cyclonic separation, whereby the fines are routed to the higher temperature reaction zone and the coarser fraction is wholly or partly recycled for further particle size reduction. Accordingly, methods of the invention provide a controlled particle size reduction of biomass and improved contact with a catalyst. [0034] Pretreatment can have a synergistic effect, reducing the temperature necessary for catalytic conversion of the biomass and/or increasing the conversion efficiency of the biomass and/or facilitating processing of biomass. For example, pretreatment (e.g., biomass particle size reduction, swelling, demineralization, catalyst addition, and or formation of a mechanic-chemical interaction between the biomass and catalyst, described below) can facilitate catalytic conversion under less severe conditions (e.g., lower temperatures and/or shorter time) and with a more efficiency (e.g., higher conversion of the biomass and better quality products from the conversion) than can be achieved in conventional refinery units. In various embodiments, lower temperature can be between about 550 and about 150 ⁰ C. For example, the temperature can be below about 550, 525, 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, or 150 ⁰ C. In some embodiments, the synergistic effect can include increasing the yield of organic compounds usable as a fuel, feedstock, and/or specialty chemical, and/or reducing the yield of undesirable

products such as coke, char, tar and/or unconverted biomass in conventional refinery units. In certain embodiments, the synergistic effect can include converting different biomass components (e.g., cellulose, hemicellulose and/or lignin) under milder conditions (e.g., lower temperature than conventional catalytic cracking) in conventional refinery units. The synergistic effect can also include making the products of catalytic conversion more uniform, or increasing the selectivity or proportion of the production of desired products (e.g., increasing the proportion of a fraction usable as a fuel, feedstock, or specialty chemical). These results can be accomplished utilizing equipment already present in conventional refinery units. [0035] An overview of an embodiment of the invention is shown in FIG. 1, which depicts a flow diagram of a pretreatment method 100 for preparing solid biomass particles 105 for catalytic conversion including a step 110 of agitating solid biomass particles, to reduce a size characterizing at least a portion of the particles and a step 115 of separating a biomass-catalyst mixture into a fine fraction and a coarse fraction. The agitating step can include, e.g., grinding, crushing, and pulverizing steps. Preferably, the biomass-catalyst mixture includes the particles and a catalyst. The fine fraction includes particles of about a predetermined size. The coarse fraction includes particles of greater than about the predetermined size. The method 100 can also include a further processing step 120 (e.g., physical or chemical conversion).

Solid Biomass Particles

[0036] In various embodiments, biomass includes materials of photosynthetic

(e.g., plant) origin having cellulose, hemicellulose, and/or lignin. Biomass includes materials produced by photosynthetic conversion of carbon dioxide and water using solar energy. In general, biomass including cellulose, hemicellulose, and/or lignin originates from land plants. Some aquatic plants include little or no lignin. However, the invention is applicable to any biomass including any amount of cellulose, hemicellulose, and/or lignin. Biomass sources include, but are not limited to, cereal grains (e.g., including corn), grasses, sugar cane, trees, and the like. Biomass sources also include by-products of agricultural or forestry activities, such as straw, chopped straw, cotton linters, corn husks, corn stalks, corn cobs, wood chips, saw dust, bagasse, sugar beet pulp, tree bark, grasses, and the like. Biomass sources also include aquatic sources such as algae and seaweed.

[0037] Biomass sources can be used without requiring chemical preprocessing (e.g., chemically altering the biomass). In various embodiments, biomass sources include (chemically) unrefined material of photosynthetic origin. Biomass sources can be subjected to a drying and/or a particle size reduction step. Such a drying and/or a particle size reduction step does not necessarily significantly change the relative composition of the biomass in terms of cellulose, hemicellulose, ash, and/or lignin and therefore such a step is not necessarily considered refining. [0038] In various embodiments, biomass feedstock can include particles that are solid and in a finely divided form (e.g., saw dust and ground straw). Biomass feedstock can include solid materials as well as materials that might be classified as liquids, but that have a very high viscosity. Biomass particles can be prepared from biomass sources and larger particles by techniques such as milling, grinding, pulverization, and the like. For example, biomass from sources such as straw and wood can be converted to particles in a size range of about 5 mm to about 5 cm using techniques such as milling or grinding.

Agitation of Biomass Particles

[0039] In various embodiments, the method includes agitating solid biomass particles, to reduce a size characterizing at least a portion of the particles. In some embodiments, agitating is facilitated by fluid conveyance, including, without limitation, by gas flow or pneumatic conveyance. Agitating can be conducted in a vertical vessel, such as a riser or downer. An agitator can include a conveyor, a riser, or downer. Agitating can be facilitated by a gas (e.g., gas can convey the particles such that they are abraded or ground by other particles, catalyst, and/or inorganic particulate material). The gas can be one or more of air, steam, flue gas, carbon dioxide, carbon monoxide, hydrogen, hydrocarbons, and methane. The gas can be a gas having a reduced level of oxygen (compared to air) or can be substantially oxygen-free. In another embodiment, an agitator can be a kneader or mixer (e.g., for mechanical, as opposed to pneumatic, agitation).

[0040] In certain embodiments, agitating includes causing the solid biomass particles to be conveyed at a velocity of greater than about 1 m/s. For example, the velocity can be measured relative to a vessel in which the particles are conveyed. Agitating can include causing the solid biomass particles to move at a velocity of greater than about 10 m/s. Agitating can include causing at least a portion of the solid

biomass particles to move at a velocity of greater than about 100 m/s. An agitator can be adapted to cause the solid biomass particles to move at a velocity of greater than about 1 m/s, greater than about 10 m/s, and/or greater than about 100 m/s. Other velocities include velocities of greater than about 5, 25, 50, 75, 125, 150, 175, 200, 225, 250, 300, 350, 400, 450, 500, 550, 600, 650, and 700 m/s. [0041] For example, the velocity is selected from the group consisting of: between about 10 and about 20 m/s; between about 20 and about 30 m/s; between about 30 and about 40 m/s; between about 40 and about 50 m/s; between about 50 and about 60 m/s; between about 60 and about 70 m/s; between about 70 and about 80 m/s; between about 80 and about 90 m/s; and between about 90 and about 100 m/s. The velocity can be about 10 m/s, about 20 m/s, about 30 m/s, about 40 m/s, about 50 m/s, about 60 m/s, about 70 m/s, about 80 m/s, about 90 m/s, or about 100 m/s. The velocity can be greater than about 10 m/s, about 20 m/s, about 30 m/s, about 40 m/s, about 50 m/s, about 60 m/s, about 70 m/s, about 80 m/s, about 90 m/s, or about 100 m/s. A velocity can be a sonic or near-sonic velocity.

[0042] In various embodiments, agitating solid biomass particles, to reduce a size characterizing at least a portion of the particles, is facilitated by agitating solid biomass particles together with a material that is harder than the biomass. For example, the material can be a catalyst or another inorganic particulate material. The amount of size reduction, and thus the size of the resulting solid biomass particles can be modulated by the duration of agitation and the velocity of agitation. Other factors such as the relative hardness of the catalyst of another inorganic particulate material, the dryness (e.g., brittleness), and the method/vessel(s) in which agitation occurs also modulate the amount of size reduction.

[0043] In embodiments using an abrading or grinding material that is a catalyst, the catalyst can become embedded in the biomass particles and/or the biomass particles can become embedded in the catalyst, which can facilitate catalytic conversion of the biomass. In such embodiments, agitating can facilitate formation of a mechano-chemical interaction between at least a portion of the catalyst and at least a portion of the solid biomass particles, which can facilitate catalytic conversion of the biomass.

[0044] Agitation can be carried out at an elevated temperature, for any one or more of drying, toasting, roasting, and torrefying the biomass. An elevated temperature can be a temperature sufficient to dry the biomass, for example, between

about 50 and about 150 or 300 °C. Higher temperatures (e.g., about 300 °C) can be used, for example, where an agitating gas is oxygen-poor or substantially oxygen-free. Agitation can also be carried out at ambient temperature with dried biomass. Drying can increase the hardness of the biomass particles, making the particles more susceptible to size reduction.

[0045] Agitation can be carried out by various different methods and in various different vessels. For example, in order of increasing abrasion, the agitation can be carried out in a fluid bed, a bubbling or ebullient bed, a spouting bed, or a conveyor. In one embodiment, agitation is carried out by fluid conveyance, including without limitation by gas flow or pneumatic conveyance. In one embodiment, agitation is carried out in a riser or a downer.

[0046] Agitating solid biomass particles, to reduce a size characterizing at least a portion of the particles, can result in a dispersion of particle sizes. For example, proper agitation the solid biomass particles as described above can result in individual particles sizes ranging from microns, to tens of microns, to tenths of centimeters, to centimeters or greater. In various embodiments, at least a fraction of the biomass particles are reduced to a size below about 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, or 5 microns. In one embodiment, at least a fraction of the biomass particles are reduced to a size below about 500, 300, 125, 15, or 10 microns. In some embodiments, at least a fraction of the plurality of solid biomass particles is characterized by sizes below a predetermined maximum size. A fraction of the plurality of solid biomass particles that are characterized by sizes below a predetermined maximum size can be about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100%.

[0047] In various embodiments, the plurality of solid biomass particles are substantially characterized by an average size between about 50 and about 70 microns and individual sizes between about 5 and about 250 microns. In other embodiments, the plurality of solid biomass particles are substantially characterized by an average size between about 10 and about 20 microns and individual sizes between about 5 and about 50 microns. In other embodiments, the plurality of solid biomass particles are substantially characterized by an average size between about 100 and about 150 microns and individual sizes between about 5 and about 500 microns.

[0048] Solid biomass particles do not necessarily assume a spherical or spheroid shape. For example, solid biomass particles can be needle shaped and/or assume another cylinder-like or elongated shape. Accordingly, size does not necessarily correspond to a single diameter (although it could correspond to an average diameter or diameter in a singe, for example largest or smallest, dimension). In various embodiments, size can correspond to the mesh size or a screen size used in separation and/or sizing the solid biomass particles.

[0049] International Publication No. WO 2007/128798 Al by O'Connor, the disclosure of which is incorporated herein by reference in its entirety, discloses agitating solid biomass particles and catalysts. In particular, paragraphs [0027] to [0072] of WO 2007/128798 Al are incorporated herein by reference. [0050] International Publication No. WO 2008/009643 A2 by O'Connor, the disclosure of which is incorporated herein by reference in its entirety, discloses agitating solid biomass particles and catalysts. In particular, paragraphs [0009] to [0051] of WO 2007/128798 Al are incorporated herein by reference.

Separation of Biomass Particles

[0051] In various embodiments, methods include separating a biomass- catalyst mixture into a fine fraction and a coarse fraction. The biomass-catalyst mixture includes the particles and a catalyst. The fine fraction includes particles of about a predetermined size. The coarse fraction includes particles of greater than about the predetermined size. Separating the mixture into a fine fraction and a coarse fraction can have several effects. For example, a fine fraction can be selected to include particles of about a predetermined size, below about a predetermined size, and/or within a predetermined size range. In some embodiments, the fine fraction can be selected to consist essentially of particles of about a predetermined size, below about a predetermined size, and/or within a predetermined size range. Furthermore, a coarse fraction can be recycled for further size reduction and/or to produce more of a fine fraction.

[0052] A predetermined size can be selected based upon one or more requirements of a subsequent reaction. For example, a predetermined size can be selected to facilitate substantial catalytic conversion of the fine fraction in a subsequent reaction. A predetermined size can be selected to facilitate contact, impregnation, and/or interaction of the catalyst and the biomass. In some

embodiments, a predetermined size can be about below about 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, or 5 microns. In one embodiment, at least a fraction of the biomass particles are reduced to a size below about 500, 300, 125, 15, or 10 microns. [0053] Separating can be facilitated by a cyclonic action, and the separation step 120 of FIG. 1 can include one or more cyclones. A separator can include a single cyclone. Alternatively, a separator can include a plurality of cyclones arranged, for example, in parallel, series, as a third stage separator, or as a fourth stage separator. U.S. Patent No. 6,971,594 to Polifka, the disclosure of which is incorporated herein by reference in its entirety, discloses cyclonic action and cyclone separators that can be adapted and employed with the invention. In particular, FIG.2, the text corresponding to FIG. 2, and the text corresponding to column 4, line 55 to column 11, line 55 of U.S. Patent No. 6,971,594 is incorporated herein by reference. [0054] Separating can be achieved by other known methods. For example, separating can be achieved by screening, settling, clarification, and the like.

Pre-treating Biomass

[0055] In various embodiments, biomass feedstock can be chemically and/or physically pre-treated. Examples of pretreatment steps in which recycled aqueous phase can be used include demineralization, heat treatment, and steam explosion. [0056] Demineralization can include removing at least a fraction of a naturally occurring mineral from biomass (e.g., prior to a pyrolysis or catalytic cracking reaction). Demineralization can improve control over the reaction of the biomass. Many of the minerals naturally present in the biomass material can be catalytically active (e.g., potassium, iron). Although these materials can catalyze reactions, they can also increase coke yield, which is generally undesirable. Even when catalytic activity is desired, it can be preferable to first demineralize the biomass material so as to control the composition of their catalyst system.

[0057] One method of demineralization includes contacting biomass with an aqueous solvent and allowing the biomass material to swell. After swelling, at least part of the aqueous solvent can then be removed from the biomass by mechanical action (e.g., kneading, pressing). Swelling and dewatering steps can be repeated to control the amount of minerals that are removed from the biomass. In addition to

removing minerals from the biomass, the swelling and dewatering steps can make the biomass material more susceptible to a subsequent reaction. [0058] Although essentially any aqueous solvent can be used for demineralization, the aqueous phase of a liquid pyrolysis product can be particularly effective. The effectiveness is believed to be due to the presence of organic acids (e.g., carboxylic acid, acetic acid) in the aqueous phase. Without wishing to be bound by any theory, the acidity of the aqueous phase can facilitate the mobilization of minerals in the biomass. For example, the chelating effects of carboxylic acids can contribute to the solubilization and removal of mineral cations. [0059] Solvent explosion can include contacted the biomass with a pressurized solvent at a temperature above its natural boiling point (e.g., at atmospheric pressure). The pressurized solvent is in a liquid phase and swells the biomass. Then, the solvent is de-pressurized, causing rapid evaporation (i.e., boiling) of the solvent. This rapid evaporation can be referred to as solvent explosion. The solvent explosion can physically rupture the biomass material, thereby making it more accessible in a subsequent reaction.

[0060] Examples of solvents that can be used in solvent explosion include ammonia, carbon dioxide, water, and the like. If water is used as the solvent, the process can be referred to as steam explosion. It will be understood that the term steam explosion can be considered a misnomer, and that the term water explosion can be more accurate. Nevertheless, the term steam explosion will be used herein because it is an accepted term of art. The aqueous phase of the liquid pyrolysis product can be used in a steam explosion.

[0061] When steam explosion is combined with demineralization, the steam explosion can be carried out before or after the demineralization. For example, it can be advantageous to conduct the demineralization after the steam explosion because the steam explosion pretreatment can make the minerals more accessible, thereby making the demineralization more effective.

[0062] Heat treatment can include heating the biomass to a temperature of about 100-300 °C in an oxygen-poor or oxygen-free atmosphere. The term oxygen- poor can refer to an atmosphere containing less oxygen than ambient air. The heat treatment can carried out in the presence of sufficient solvent (e.g., water) to swell the biomass material. The heat treatment can be carried out in a closed vessel to mitigate evaporation of the solvent. In some examples, the vapor (e.g., steam) formed under

these conditions can displace oxygen present in the vessel and produce an oxygen- poor atmosphere. In one example, the aqueous phase of a liquid pyrolysis product can be the solvent in such a heat treatment.

[0063] Heat treatment can be carried out at a temperature low enough to mitigate carbon loss due to the formation of gaseous conversion products (e.g., CO, CO ₂ ). A heat treatment can use, for example, a temperature of about 100-200 ⁰ C. For example, a temperature can be about 100-140 °C. A heat treatment can have a duration, for example, of about 2 min to 2 hours. For example, a duration can be about 20-60 min. In various examples, pressure can be released at the end of a heat treatment by opening the heat treatment vessel, which can allows the heat treatment to be combined with a steam explosion pretreatment step. [0064] Even where the heat treatment essentially does not produce any gaseous conversion products, it can still result in a modification of the biomass. For example, the heat treatment can make the biomass more brittle and more hydrophobic. Both effects can be desirable from the perspective of a subsequent reaction. For example, increased brittleness can facilitate girding the biomass to a small particle size, to increase reactivity in a pyrolysis reaction, and increased hydrophobicity can facilitate drying the biomass.

[0065] A heat pretreatment step can be combined with one or more additions pretreatment steps (e.g., demineralization, steam explosion). Because of the increased hydrophobicity of heat treated biomass, it can be preferable to conduct any demineralization and/or steam explosion steps prior to the heat treatment; with the exception that steam explosion can be combined with heat treatment as described above.

Catalysts and Inorganic Particulate Materials

[0066] A catalyst can be any material that facilitates the conversion of organic components of the biomass into fuels, specialty chemicals, or precursors thereof. In various embodiments, the catalyst includes a solid particulate catalyst and the biomass-catalyst mixture includes at least a portion of the catalyst mechano- chemically interacting with at least a portion of the solid biomass particles. In some embodiments, the catalyst includes a catalyst capable of being at least partly dissolved or suspended in a liquid and the biomass-catalyst mixture includes at least a portion of the catalyst impregnating at least a portion of the solid biomass particles.

[0067] In various embodiments, a catalyst is a particulate inorganic oxide.

The particulate inorganic oxide can be a refractory oxide, clay, hydrotalcite, crystalline aluminosilicate, layered hydroxyl salt, or a mixture thereof. Suitable refractory inorganic oxides include alumina, silica, silica-alumina, titania, zirconia, and the like. In one embodiment, the refractory inorganic oxides have a high specific surface (e.g., a specific surface area as determined by the Brunauer Emmett Teller ("BET") method of at least 5 or 50 m ² /g). Suitable clay materials include cationic and anionic clays, for example, smectite, bentonite, sepiolite, atapulgite, hydrotalcite, and the like. Suitable metal hydroxides and metal oxides include bauxite, gibbsite and their transition forms. Other suitable (and inexpensive) catalysts include lime, brine, and/or bauxite dissolved in a base (e.g., NaOH), or a natural clay dissolved in an acid or a base, or fine powder cement (e.g., from a kiln). Suitable hydrotalcites include hydrotalcite, mixed metal oxides and hydroxides having a hydrotalcite-like structure, and metal hydroxyl salts.

[0068] In some embodiments, a catalyst can be a catalytic metal. The catalytic metal can be used alone or together with another catalyst, refractory oxide, and/or bonder. A catalytic metal can be used in a metallic, oxide, hydroxide, hydroxyl oxide, or salt form, or as a metallo-organic compound, or as a material including a rare earth metal (e.g., bastnesite). In certain embodiments, the catalytic metal is a transition metal. The catalytic metal can be a non-noble transition metal. For example, the catalytic metal can be iron, zinc, copper, nickel, and manganese. In one embodiment, the catalytic metal is iron.

[0069] A catalytic metal can be contacted with the biomass by various methods. In one embodiment, the catalyst is added in its metallic form, in the form of small particles. Alternatively, the catalyst can be added in the form of an oxide, hydroxide, or a salt. In another embodiment, a water-soluble salt of the metal is mixed with the biomass and the inert particulate inorganic material in the form of an aqueous slurry. The biomass and the aqueous solution of the metal salt can be mixed before adding the inert particulate inorganic material to facilitate the metal impregnating the biomass. The biomass can also be mixed with the inert particulate inorganic material prior to adding the aqueous solution of the metal salt. In still another embodiment, an aqueous solution of a metal salt is mixed with the inert inorganic material, the material is dried prior to mixing it with the particulate

biomass, and the inert inorganic material is thus converted to a heterogeneous catalyst.

[0070] The biomass-catalyst mixture can include an inorganic particulate material. An inorganic particulate material can be inert or catalytic. An inorganic material can be present in a crystalline or quasi- crystalline form. Exemplary inert materials include inorganic salts such as the salts of alkali and alkaline earth metals. Although these materials do not necessarily contribute to a subsequent chemical conversion of the polymeric material, it is believed that the formation of discrete particles of these materials within the biomass can work as a wedge to mechanically breaking up or opening the structure of the biomass, which can increase the biomass surface accessible to microorganisms and/or catalysts. In one embodiment, the breaking up or opening is facilitated by crystalline or quasi-crystalline particles. [0071] Inorganic particulate material can have catalytic properties. For example, a catalytic inorganic particulate material can be a metal oxide or hydroxide such as an alumina, silica, silica aluminas clay, zeolite, ionic clay, cationic layered material, layered double hydroxide, smectite, saponite, sepiolite, metal hydroxyl salt, and the like. Carbonates and hydroxides of alkali metals, and the oxides, hydroxides and carbonates of alkali earth metals can also have catalytic properties. Inorganic particulate material can include mixtures of inorganic materials. Inorganic particulate material can include a spent (resid) fluid catalytic cracking catalyst containing (thermally treated) layered material. Employing spent catalyst can involve reusing waste material. The spent catalyst can be ground of pulverized into smaller particles to increasing dispersibility. Inorganic particulate material can also include sandblasting grit. Employing sandblasting grit can involve reusing waste material, which can include particles of iron, and lesser quantities of other suitable metals such as nickel, zinc, chromium, manganese, and the like (e.g., grit from steel sandblasting). [0072] Contacting the catalyst, and optionally the inorganic particulate material, with the biomass, can be achieved by various methods. One method includes heating and fluidizing a mixture of the particulate biomass material and the inert inorganic material, and adding the catalyst to the mixture as fine solid particles. Another method includes dispersing the catalytic material in a solvent (e.g., water), and adding the solvent to the mixture of particulate biomass material and the inert inorganic material.

[0073] European Patent Application No. EP 1 852 466 Al by O'Connor, the disclosure of which is incorporated herein by reference in its entirety, discloses catalysts and contacting catalysts and biomass. In particular, paragraphs [0011] to [0043] of EP 1 852 466 Al are incorporated herein by reference. [0074] International Publication No. WO 2007/128799 Al by O'Connor, the disclosure of which is incorporated herein by reference in its entirety, discloses catalysts and contacting catalysts and biomass. In particular, paragraphs [0015] to [0054] of WO 2007/128799 Al are incorporated herein by reference.

Removing Metals and/or Minerals

[0075] In various embodiments, a pretreatment can reduce an ash content of biomass, or a hazardous disposal characteristic of an ash that may be subsequently produced. Removal of minerals (e.g., ash precursors) from the biomass can reduce the ash content. Removal of metals (e.g., ash precursors), particularly heavy metals, can also reduce ash content and prevent metal contamination of waste products, thereby facilitating disposal of waste by providing an uncontaminated waste product and reducing the cost of disposing of the waste product. [0076] A pretreatment for reducing ash content can include swelling the biomass with a solvent and then removing solvent from the swollen biomass material by applying mechanical action to the biomass material. Ash precursors, such as dissolved minerals and/or metals, will thus be removed with the solvent. The solvent can be aqueous. The solvent can include an acid or base (e.g., inorganic acid or base). The mechanical action can occur in an agitator and/or a kneader. The mechanical action can be exerted by equipment such as a high shear mixer, kneader, colloid mill, planetary mixer, mix-miller, or ball mill. The pretreatment can reduce ash content to less than about 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt%, based on dry weight of the biomass material. The pretreatment can reduce metal (e.g., Fe) content to less than about 3,000, 2,500, 2,000, 1,500, 1,000, or 500 mg/kg, based on dry weight of the biomass.

Examples

[0077] FIGS. 2-5 show exemplary apparatuses for pretreating biomass with catalyst. The invention also includes methods corresponding to the operation of the apparatuses of FIGS. 2-5.

[0078] FIG. 2 shows an apparatus 200 for high velocity pretreatment of biomass with a solid catalyst. The apparatus 200 includes an agitator 210, a solid biomass source 220, a solid catalyst source 230, a separator 240 for separating a fine fraction and a coarse fraction, a recycler 250 for recycling the coarse fraction, a system 260 for providing the fine fraction for further processing, and a system 270 for collecting a gas fraction. Devices such as apparatus 200 can produce a biomass- catalyst mixture where the catalyst coats and/or mechano-chemically interacts with the biomass particles and where the biomass particles are substantially characterized by less than about a predetermined size. The solid catalyst can facilitate size reduction (e.g., grinding) of the solid biomass.

[0079] The agitator 210 agitates solid biomass particles, to reduce a size characterizing at least a portion of the particles. The agitator 210 can facilitate formation of a mechano-chemical interaction between at least a portion of the solid catalyst and at least a portion of the solid biomass particles. The agitator 210 can facilitate the solid catalyst coating at least a portion of the solid biomass particles. The agitator 210 can provide the solid particles having a reduced size to the separator 240. In various embodiments, the agitator 210 is a gas flow or pneumatic conveyor. The agitator 210 can be a riser or downer. In various embodiments, the agitator 210 can be a line between about 5 and about 50 m long. In one embodiment, the agitator 210 includes a loop, to increase the resonance time of the solid biomass particles, which can increase the degree of size reduction.

[0080] The agitator 210 can also use a gas dispersion (e.g., aeration) to facilitate mixing, agitation, and the formation of mechano-chemcial interactions. The gas can include one or more of air, steam, flue gas, carbon dioxide, carbon monoxide, hydrogen, hydrocarbons, methane, activated reactive methane. In one embodiment, the agitator 210 also dries (e.g., dehydrates) the solid biomass particles. For example, the gas can be a heated gas that can reduce the water content of the solid biomass particles. The agitator 210 can be adapted to cause the solid biomass particles to move at a velocity of greater than about 1 m/s, greater than about 10 m/s, and/or greater than about 100 m/s. The agitator 210 can include an instrument for controlling the velocity of the solid biomass particles, such as mass flow measurement devices. If the agitator is, for example, a mixing auger or screw pump, a measurement output can be used to control the motor speed, such as from a flow or velocity measurement. In embodiments where temperature control is a critical factor,

the drive motor energy input can be controlled based on a desired temperature set point.

[0081] In some embodiments, methods include contacting the solid biomass particles and the catalyst to produce the biomass-catalyst mixture after agitating. Methods can include contacting the solid biomass particles and the catalyst to produce the biomass-catalyst mixture before agitating, or between agitation steps. Thus, agitating the solid biomass particles can include agitating the biomass-catalyst mixture.

[0082] The solid biomass source 220 and the solid catalyst source 230 provide solid biomass and solid catalyst to the agitator 210. Although FIG. 2 shows the biomass source 220 providing biomass to the agitator 210 before the catalyst source 230, the apparatus 200 can be modified to include embodiments where a catalyst source provides catalyst to an agitator before the biomass source is introduced. An apparatus can include a single source that provides pre-mixed biomass and catalyst. An apparatus can also include multiple biomass and/or catalyst sources (e.g., where multiple biomasses and/or catalysts are used). An apparatus can also include a source of inorganic particulate material. Sources can include one or more sprayers, nozzles, pipes, passages, channels, conduits, conveyors, ducts, hoses, lines, tubes, vents, and the like adapted for providing the biomass, catalyst, and/or inorganic particulate material. Sources can also include one or more hoppers, tanks, tubs, silos, bags, canisters, kettles, and the like adapted for storing the biomass, catalyst, and/or inorganic particulate material.

[0083] The separator 240 separates the biomass-catalyst mixture into a fine fraction including particles of about a predetermined size and a coarse fraction including particles of greater than about the predetermined size. In various embodiments, the separator 240 includes a cyclone. The separator 240 can include a single cyclone. Alternatively, the separator 240 can includes a plurality of cyclones arranged in parallel, series, as a third stage separator, or as a fourth stage separator. The separator 240 can include an instrument for controlling the predetermined size. In various embodiments, the particles have a velocity of at least about 10, 15, 20, 25, or 30 m/s. In some embodiments, the particles can have a velocity up to about a near- sonic or sonic velocity.

[0084] The recycler 250 is adapted for subjecting the coarse fraction to additional agitating and separating steps. The recycler 250 receives the coarse

fraction from the separator 240 and can direct it to the agitator 210, for further size reduction. Inerts (e.g., nonreactants and debris) can be removed at this stage. The recycler 250 can include a pipe, passage, channel, conduit, conveyor, duct, hose, line, tube, vent, and the like adapted for providing the coarse fraction from the separator 240 to the agitator 210. After further size reduction, the particles can be provided to the separator 240, for further separation. The agitator 210, separator 240, and recycler 250 function as a system to produce a fine fraction having particles of about a predetermined size. For example, the agitator 210, separator 240, and recycler 250 can iteratively reduce the size of the particles, separate the fine fraction and the coarse fraction, and recycle the coarse fraction for further size reduction. The apparatus 200 can operate be operated in a batch mode, or continuously, where new biomass and catalyst are introduced and agitated together with the recycled coarse fraction. [0085] The system 260 for providing the fine fraction for further processing can include, for example, a pipe, passage, channel, conduit, conveyor, duct, hose, line, tube, vent, clarifϊer, settler, fine to prevent the carry over of coarse materials, or merely a static cyclone, and the like, adapted for providing the fine fraction from the separator 240 to a subsequent reaction or storage vessel. In various embodiments, the system 260 can provide the fine fraction to a reactor for liquefying, pyrolyzing, and/or cracking at least a portion of the fine fraction. In some embodiments, the system 260 can provide the fine fraction as feedstock to a refinery or chemical production facility unit such as fluid catalytic cracking unit, fluid and delayed coking unit, fluid catalytic cracking pretreater unit, resid HT unit, thermal reactor, deasphalting unit, lube oil HT unit, ethylene polymerization unit, or propylene polymerization unit. [0086] In some embodiments, the fine fraction (e.g., the fine fraction itself or a reacted or further processed fine fraction) replaces a portion of a petroleum feedstock to a conventional refinery or chemical production facility. A conversion product of the fine fraction can replace up to about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100% of the petroleum feedstock. In certain embodiments, a conversion product of the fine fraction, without a petroleum feedstock, is the feedstock to a refinery (e.g., conventional or biomass) or chemical production facility. [0087] In various embodiments, the separator 240 can function as a gas-solid separator. In such embodiments, the apparatus 200 can include a system 270 for collecting a gas fraction. The system 270 can collect a gas fraction from the separator

240, and provide the gas fraction as feedstock to a refinery or chemical production facility, or employ the gas fraction for another industrial purpose. [0088] While FIG. 2 shows a generalized depiction of an apparatus 200, it should be understood that various elements of such apparatus 200 can be shown in different configurations. For example, as depicted in FIG. 2A, the separator 240A can be a cyclone that primarily separates larger particulate matter (e.g., biomass) for recycle and further processing via a bottoms stream 250A. Large inert and non- reactive materials can also be removed from the bottoms, for example, by using a coarse strainer (not shown). In embodiments where the particle sizes of the solid recycled materials and the non-reactants are too similar, separation techniques based on density differences can be used. Of course, any fine particulate non-reactants can exit with the cyclone overheads, as discussed below.

[0089] The feed streams to the cyclone 220A, 230A are preferably mixed and ground into intimate contact with each other using the agitator function 210A. To promote effective cyclone operation, solvent or carrier gas can be added to the feed stream (not shown), for example, at a point between the agitator 210A discharge and the cyclone 240A. In some embodiments the carrier medium can be reactive, facilitating the processing of the biomass.

[0090] The fines and any gas (or solvent) can exit the cyclone overheads and be subsequently separated 275A, for example, into an overhead gas or vapor stream 270A and a fine particulates stream 260A. Depending upon the particle sizes and densities involved, and the overall fluid velocity and conditions of the overhead stream, this secondary separation can occur in a knockout drum, a secondary cyclone designed for this purpose, or using other known separation technologies. [0091] FIG. 3 shows an apparatus 300 for high velocity pretreatment of biomass with a dissolved and/or suspended catalyst. The apparatus 300 includes an agitator 310, a solid biomass source 320, a dissolved and/or suspended catalyst source 330, a separator 340 for separating a fine fraction and a coarse fraction, a recycler 350 for recycling the coarse fraction, a system 360 for providing the fine fraction for further processing, and a system 370 for collecting a gas fraction. Devices such as apparatus 300 can produce a biomass-catalyst mixture where the catalyst coats, sticks to, and/or impregnates the biomass particles and where the biomass particles are substantially characterized by less than about a predetermined size.

[0092] In various embodiments, the agitator 310, biomass source 320, catalyst source 330, separator 340, recycler 350, and systems 360 and 370 are substantially the same as the agitator 210, biomass source 220, catalyst source 230, separator 240, recycler 250, and systems 260 and 270 described in connection with FIG. 2, except where differences or deviations are required or reasonable due to distinctions between a dissolved and/or suspended catalyst and a solid catalyst. [0093] The agitator 310 agitates solid biomass particles, to reduce a size characterizing at least a portion of the particles. The agitator 310 can facilitate the dissolved and/or suspended catalyst coating, sticking to, and/or impregnating the biomass particles and where the biomass particles. Where the dissolved and/or suspended catalyst is used alone, the solid biomass can facilitate its own size reduction (e.g., grind itself). In some embodiments, a solid catalyst and/or inorganic particulate material can be added to facilitate size reduction. [0094] The solid biomass source 320 and the dissolved and/or suspended catalyst source 230 provide solid biomass and solid catalyst to the agitator 310. In various embodiments, the solid biomass source 320 introduces the biomass into the agitator 310 and the dissolved and/or suspended catalyst source 230 then introduces the catalyst (e.g., sprays a colloidal catalyst in a solvent such as water). However, other arrangements are also possible (e.g., where the catalyst is introduced prior to the biomass or where the catalyst and biomass are introduced concurrently). [0095] FIG. 4 shows an apparatus 400 for high velocity pretreatment of a biomass catalyst composite, which combines a cyclone and a kneader. The apparatus 400 includes an agitator 410, a kneader 420, a biomass-catalyst source 430, a separator 440 for separating a fine fraction and a coarse fraction, a recycler 450 for recycling the coarse fraction, a system 460 for providing the fine fraction for further processing, and a system 470 for collecting a gas fraction. Apparatuses like apparatus 400 can produce a biomass-catalyst mixture where the biomass is sensitized to the catalyst.

[0096] In various embodiments, the agitator 410, biomass-catalyst source 330, separator 340, recycler 350, and systems 360 and 370 are substantially the same as the agitator 210, biomass source 220 and/or 320, catalyst source 230 and/or 330, separator 240, recycler 250, and systems 260 and 270 described in connection with FIGS. 2 and 3, except where differences or deviations are required or reasonable due to the properties of the sensitized biomass-catalyst mixture.

[0097] The kneader 420 kneads the solid biomass particles and the catalyst, to make at least a portion of the solid biomass particles accessible to at least a portion of the catalyst. The kneader 420 can also be an extruder, miller, or grinder. For example, the kneader 420 can be a screw extruder, or a ball miller or grinder. The kneader 420 can operate at greater than ambient temperature. For example, the kneader 420 can be heated and/or heated gas (e.g., steam) can be provided to heat the biomass and catalyst.

[0098] In various embodiments, the kneader 420 employs a solvent. The solvent can be water, an alcohol (e.g., ethanol or glycerol), a bio-oil or another product from the conversion of the biomass, a liquid acid, an aqueous acid or base, liquid CO ₂ , and the like. In one embodiment, the solvent is water (e.g., added water and/or water inherent in the biomass), which can be selected for its availability, low cost, and/or ease of handling. In another embodiment, the solvent is a liquid produced during the subsequent conversion of the biomass, which can be selected for its availability. A solvent can be selected to improve penetration of a catalyst into biomass. A solvent can also improve penetration of a catalyst into biomass because a dry biomass can be more difficult to penetrate. A solvent can also be selected to remove ash precursors. Solvents can be removed (e.g., by drying) prior to subsequent processing and/or conversion. A kneader can remove at least a portion of a solvent absorbed in a biomass (e.g., by mechanical action and draining). Embodiments employing a kneader and a solvent can reduce the ash and/or mineral and/or metal content of the biomass.

[0099] FIG. 4 shows one arrangement of an apparatus including a kneader

(e.g., kneading -> agitating -> separating). However, various embodiments include alternative arrangements of apparatuses including a kneader. In another embodiment, the operations can be resequenced, e.g., such that kneading follows agitating (e.g., agitating -> kneading -> separating).

[00100] In still another embodiment, an apparatus includes a kneader and a separator. The kneader can function as an agitator, to reduce a size characterizing at least a portion of the particles, sensitize the particles, and provide the particles directly to a separator (e.g., kneading -> separating; the apparatus does not also include an agitator such as a gas flow conveyor or pneumatic conveyor).

[00101] In yet another embodiment, a kneader can knead a fraction from a separator (e.g., agitating -> separating -» kneading). For example, the kneader can knead a fine fraction. The fine fraction can then be subjected to further processing (e.g., catalytic conversion). For example, the kneader can knead a coarse fraction. The coarse fraction can then be subjected to further size reduction (e.g., in an agitator and/or in the kneader itself). Kneading a fraction from a separator can be re-kneading or kneading for a first time. In one example, a coarse fraction kneaded prior to separation can be recycled for further kneading. In another example, a fine fraction can be kneaded for a first time after separation (e.g., to employ the increased surface area to volume ratio of smaller particles to increase the effectiveness of sensitization, or to add a different catalyst).

[00102] In various embodiments, the biomass can be kneaded with one or more solid catalyst and/or inorganic particulate material. In some embodiments, the biomass can be kneaded with a dissolved and/or suspended catalyst. The dissolved and/or suspended catalyst can be used together with one or more solid catalyst and/or inorganic particulate material. Kneading can be continued and/or repeated to produce a biomass-catalyst mixture having the desired properties (e.g., particle size and/or degree of sensitization).

[00103] International Publication No. WO 2007/128800 Al by O'Connor, the disclosure of which is incorporated herein by reference in its entirety, discloses catalysts and sensitizing biomass, as well as sensitizing by kneading. In particular, paragraphs [0025] to [0074] with respect to catalysts and sensitizing biomass, as well paragraphs [0076] to [0086] with respect to sensitizing by kneading, of WO 2007/128800 Al are incorporated herein by reference.

[00104] FIG. 5 shows an apparatus 500 for high velocity pretreatment of biomass and plant matter processing. The apparatus 500 includes an agitator 510, a solid biomass source 520, a solid catalyst source 530, a separator 540 for separating a fine fraction and a coarse fraction, a recycler 550 for recycling the coarse fraction, a system 560 for providing the fine fraction for further processing, a system 570 for collecting a gas fraction, and a disintegrator 580. Apparatuses like apparatus 500 can process plant matter at a location in close proximity to an agricultural site (e.g., used to produce such plant matter), to produce the solid biomass particles.

[00105] The disintegrator 580 processes plant matter at a location in close proximity to an agricultural site used to produce such plant matter, to produce the solid biomass particles. In operation, a disintegrator can be used to modify the consistency of, e.g., biomass feedstock, and/or to reduce its average particle size. The disintegrator can include at least one of a mill, fragmenter, fractionator, granulator, pulverizer, chipper, chopper, grinder, shredder, mincer, and a crusher. Apparatuses including a disintegrator can process plant matter at a location in close proximity to an agricultural site used to produce such plant matter, to produce the solid biomass particles. U.S. Patent No. 6,485,774 to Bransby, the disclosure of which is incorporated herein by reference in its entirety, discloses a method of preparing and handling chopped plant materials. In particular, the text corresponding to column 1, line 45 to column 4, line 65 of U.S. Patent No. 6,485,774 is incorporated herein by reference.

[00106] In various embodiments, methods and apparatuses for pretreating biomass with catalyst can produce compositions of a biomass-catalyst mixture including a plurality of solid biomass particles and a catalyst, where the plurality of solid biomass particles are substantially characterized by sizes below about a predetermined size. The predetermined size can be about 500, 300, 125, 15, or 10 microns. At least a about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% of the solid biomass particles can be below about the predetermined size. [00107] In some embodiments, the catalyst include a solid particulate catalyst and the biomass-catalyst mixture include at least a portion of the catalyst mechano- chemically interacting with at least a portion of the solid biomass particles. In certain embodiments, the catalyst inclμdes a catalyst capable of being at least partly dissolved or suspended in a liquid and the biomass-catalyst mixture includes at least a portion of the catalyst impregnating at least a portion of the solid biomass particles. The composition can also include an inorganic particulate material. [00108] In certain embodiments, any of the apparatuses or methods can include a system or step for receiving pressurized gas from a cyclone and providing the pressurized gas to a regenerator. Accordingly, pressurized gas can be used both to convey material through the cyclone and recycled to the regenerator, which can provide an economic savings by reducing the amount of energy expended on pressurizing gas.

[00109] The compositions can be used as feedstock in a subsequent catalytic conversion process. On one embodiment, the subsequent conversion process is catalytic cracking. Subsequent conversion process can also include hydrothermal conversion, enzymatic conversion, pyrolytic conversion, mild thermal conversion, fermentation, conventional refining, hydroprocessing, hydrocracking, hydrotreating, ethanol production, gasification, and the like. The compositions can be converted to liquid and/or gaseous fuels, intermediates (e.g., petrochemicals or plastics), or to specialty chemicals.

[00110] While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as defined by the appended claims.