WO2015095498A1

WO2015095498A1 - Lignin-enriched biomass pyrolysis

Info

Publication number: WO2015095498A1
Application number: PCT/US2014/071115
Authority: WO
Inventors: Rachid Taha; Daniel B. Garbark; Mark J. Perry; Megan Sesslar Moore
Original assignee: Battelle Memorial Institute
Priority date: 2013-12-18
Filing date: 2014-12-18
Publication date: 2015-06-25

Abstract

Pyrolysis of lignin-enriched biomass feeds may improve aspects of pyrolytic generation of bio-oil products thereof compared to pyrolysis of biomass alone.

Description

LIGNIN-ENRICHED BIOMASS PYROLYSIS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from U.S. Provisional Patent Application No. 61/917,932, filed on December 18, 2013, which is incorporated by reference herein in its entirety.

BACKGROUND

[0002] The extraction of bio-oil from biomass for use as a biofuel is of interest in the search for reliable, renewable sources of energy and chemical precursors based on biomass.

Biomass such as lignocellulosic substances (e.g., wood), may be subjected to pyrolysis to create a hot pyrolysis vapor, from which liquid products, including bio-oil, may be extracted.

For example, fast pyrolysis is a thermo-chemical conversion process that may transform biomass into bio-oil by rapid heating of the biomass at temperatures between, e.g., about

400-550°C under anaerobic conditions. By-products may include a carbon-rich char and gases, including, e.g., carbon monoxide (CO) and carbon dioxide (CO₂). The composition and yield of these products may depend upon factors such as the input biomass feedstock, biomass pretreatment, reactor temperatures, reaction rates, catalyst, and the like. Without additional processing, such bio-oil may have limited use in various applications, e.g., boilers, furnaces, engines, and turbines due to its relatively low heating value (~17 MJ/kg), high oxygen content (-45 wt% oxygen), corrosiveness due to acid content, and the like. It is desirable to improve the bio-oil quality and yield. Various methods have been implemented to improve bio-oil, for example: in-line esterification of pyrolysis vapor with ethanol to improve bio-oil quality, which may decrease acetic acid concentration by as much as 42%, and may improve the bio-oil pH, viscosity, and cold flow properties; upgrading using 1- octene and 1-butanol over sulfuric acid resin catalysts, which may lead to partial deoxygenation, a slight increase in energy density and decrease in acidity; and reforming of bio-oil to produce a hydrocarbon product using high temperatures, pressures, and hydrogen concentration. Esterification and catalytic upgrading may require large amounts of expensive resources (e.g., ethanol, 1-butanol, and 1-octene) and are at an early stage, potentially needing significant investment before production scale implementation. Reforming may require high pressures, along with large quantities of catalyst and hydrogen.

[0003] The present disclosure appreciates that improving pyrolysis of biomass to bio-oil products of desirable quality and/or energy content may be a challenging endeavor.

SUMMARY

[0004] In one embodiment, a method of producing a bio-oil is provided. The method may include providing lignin. The method may also include providing lignocellulosic biomass. The method may further include pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil.

[0005] In another embodiment, a bio-oil is provided. The bio-oil may be produced by a process. The process may include providing lignin. The process may also include providing lignocellulosic biomass. The process may further include pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil.

[0006] In one embodiment, a pyrolytic bio-oil is provided. The pyrolytic bio-oil may be derived from pyrolysis of a lignin-enriched feedstock.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The accompanying figures, which are incorporated in and constitute a part of the specification, illustrate example methods and apparatuses, and are used merely to illustrate example embodiments.

[0008] FIG. 1 depicts a flow diagram of an example method 100; [0009] FIG. 2 is a block diagram of an example pyrolysis reactor 200 that may be employed to carry out example method 100;

[0010] FIG. 3 is a graph 300 showing various thermo-gravimetric parameters as a function of time for the pyrolysis of EXAMPLE IB;

[0011] FIG. 4 displays Table 1, reporting the material balance of various feedstocks and products of EXAMPLES 2A, 2B, 2C, and 2D; and

[0012] FIG. 5 displays Table 2, reporting an analysis of various organic phase products as measured by ³¹P NMR for EXAMPLES 2B, 2C, and 2D.

DETAILED DESCRIPTION

[0013] FIG. 1 depicts a flow diagram of an example method 100. Method 100 may include operation 102, "PROVIDE LIGNIN." Method 100 may also include operation 104, "PROVIDE LIGNOCELLULOSIC BIOMASS." Method 100 may further include operation 106, "PYROLYZE LIGNIN AND LIGNOCELLULOSIC BIOMASS TO PRODUCE BIO- OIL."

[0014] In various embodiments, a bio-oil is provided. The bio-oil may be produced by a process. The process may include any aspects of the method provided herein, e.g., method 100. For example, the process may include providing lignin as in operation 102. The process may also include providing lignocellulosic biomass, as in operation 104. The process may further include pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil as in operation 106.

[0015] FIG. 2 is a block diagram of an example pyrolysis reactor system 200 that may be employed to carry out the pyrolysis methods and processes described herein. Pyrolysis reactor system 200 may include furnace 202, e.g., a tubular furnace. Furnace 202 may be, for example, a tubular two-inch diameter by 28 inch long stainless steel reactor surrounded by a heater (not shown), e.g., a ceramic insulated heating mantle, heating tape, or the like. Alternatively, furnace 202 may be an auger pyrolysis furnace (not shown). Furnace 202 may be provided with an inert atmosphere by an inert gas feed 204, which may provide, for example, a nitrogen atmosphere at a desired pressure, e.g., 15 pounds per square inch gauge (psig). The lignin and the lignocellulosic biomass may be provided by feedstock feeder 206. The lignin and the lignocellulosic biomass may be pyrolyzed in furnace 202. Pyrolysis products, including the bio-oil, may be produced in furnace 202 and may exit furnace 202 to a condensing system 208 that may include, e.g., one or more condensers 208A, 208B, and/or 208C. The one or more condensers 208A, 208B, and/or 208C may be the same or different and may operate at the same or different temperature. For example, condensers 208A, 208B, and/or 208C may include a glass type condenser, a stainless steel tube in tube condenser, a coil-type condenser submerged in a cooling fluid, and the like. Condensers such as 208A, 208B, and/or 208C may operate at the same or different temperatures, for example, 208A at 10 °C, 208B at 3 °C, and 208C at 3 °C, and the like. The pyrolysis products, including the bio-oil, may be swept out of furnace 202 to one or more condensers 208A, 208B, and/or 208C by one or more of a flow provided by inert gas feed 204 and a flow provided by production of the gaseous pyrolysis products in furnace 202.

[0016] In various embodiments, the method or process may also include contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock. The pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

[0017] In some embodiments, the method or process may also include contacting the lignin and the lignocellulosic biomass by incipient wetness impregnation of the lignocellulosic biomass with the lignin to form a lignin-enriched feedstock. The pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include pyrolyzing the lignin-enriched feedstock to produce the bio-oil. For example, the method or process may include contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock by contacting the lignin in particulate form to a fluid to form a lignin slurry. The method or process may also include contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock by contacting the lignin slurry to the lignocellulosic biomass effective to impregnate a portion of the lignin in particulate form into the lignocellulosic biomass to form the lignin-enriched feedstock. The pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

[0018] In several embodiments, the fluid may include one or more of water or an organic solvent. Organic solvents may include, for example, alcohols such as methanol, ethanol, propanol, butanol, and the like; acetone, methyl ethyl ketone, and the like; dimethyl sulfoxide; dimethyl formamide; alkylene glycols and alkylene glycol ethers such as ethylene glycol, propylene glycol, diglyme; and the like. Such organic solvents may be used alone, in combination, or mixed with water.

[0019] In various embodiments, the slurry may include a lignin: fluid weight ratio of about 5:95, 10:90, 15:85, 16.7:83.3, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50 (1 : 1), 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 83.3: 16.7, 85: 15, 90: 10, or 95:5. For example, the slurry may include the lignin:fluid weight ratio at about 16.7:83.3 or about 1 :5. The slurry may include the lignin: fluid weight ratio between about any two of the preceding ratios, for example, between about 5:95 and about 1 : 1.

[0020] In some embodiments, the method or process may include removing the fluid from the lignin-enriched feedstock. For example, the fluid may be removed from the lignin- enriched feedstock by one or more of: heating, reduced pressure, spray-drying, filtering, settling, or centrifuging. The fluid may be removed by heating. The fluid may be removed by reduced pressure. The fluid may be removed by spray-drying. The fluid may be removed by filtering. The fluid may be removed by settling, e.g., under the influence of gravity or vibration. The fluid may be removed by centrifuging.

[0021] In several embodiments, contacting the lignin slurry to the lignocellulosic biomass may include one or more of: drop-wise application of the lignin slurry to the lignocellulosic biomass, mechanical agitation of the lignin slurry and the lignocellulosic biomass, sonication of the lignin slurry and the lignocellulosic biomass, or pressure cycling of the lignin slurry and the lignocellulosic biomass. For example, contacting the lignin slurry to the lignocellulosic biomass may include drop-wise application of the lignin slurry to the lignocellulosic biomass. Contacting the lignin slurry to the lignocellulosic biomass may include mechanical agitation of the lignin slurry and the lignocellulosic biomass. Contacting the lignin slurry to the lignocellulosic biomass may include sonication of the lignin slurry and the lignocellulosic biomass. Contacting the lignin slurry to the lignocellulosic biomass may include pressure cycling of the lignin slurry and the lignocellulosic biomass.

[0022] In several embodiments, the lignin particulates may be characterized by an average particulate diameter. The lignocellulosic biomass may include pores characterized by an average pore diameter. Pores in biomass may have a range of diameters. For example, a variety of softwoods and hardwoods may include pores in a range between about 1 nanometer (nm) and about 500 micrometers (μιη). At least a plurality of pores in the lignocellulosic biomass may be characterized by an average pore diameter that is greater than the average particulate diameter. The plurality of pores may be a subset of all pores in the lignocellulosic biomass. In some examples, the average diameter of all pores in the lignocellulosic biomass need not be larger than the average particulate diameter so long as the average diameter of the plurality of pores is larger than the average particulate diameter. The average diameter of the plurality of pores may be greater than the average particulate diameter effective to provide the impregnation of the portion of the lignin particulates into the plurality of pores of the lignocellulosic biomass. The average diameter of the lignin particulates may be, for example, about 1 nm, 2 nm, 10 nm, 50 nm, 75 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1 μιη, 2 μηι, 3 μιη, 4 μηι, 5 μιη, 10 μιη, 15 μιη, 20 μιη, 25 μιη, 30 μιη, 35 μιη, 40 μιη, 45 μιη, 50 μιη, 55 μιη, 60 μιη, 65 μιη, 70 μιη, 75 μιη, 80 μιη, 85 μιη, 90 μιη, 95 μιη, 100 μιη, 125 μιη, 150 μιη, 175 μιη, 200 μιη, or 250 μm, or a range between any two of the preceding values. For example, the average particulate diameter may be between about 2 nm and about or less than about 60 μιη, between about 1 nm and about or less than about 80 nm, between about 80 nm and about or less than about 500 nm, between about 500 nm and about or less than about 2 μηι, between about 2 μηι and about or less than about 4 μηι, between about 2 μηι and about or less than about 60 μιη, and the like.

[0023] In various embodiments, the average pore diameter of the plurality of pores may be, for example, about 1 nm, 2 nm, 10 nm, 50 nm, 75 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1 μηι, 2 μηι, 3 μιη, 4 μιη, 5 μιη, 10 μιη, 15 μιη, 20 μιη, 25 μιη, 30 μιη, 35 μιη, 40 μιη, 45 μιη, 50 μιη, 55 μιη, 60 μιη, 65 μιη, 70 μιη, 75 μιη, 80 μιη, 85 μιη, 90 μιη, 95 μιη, 100 μιη, 125 μιη, 150 μιη, 175 μιη, 200 μιη, or 250 μιη, or a range between any two of the preceding values. For example, the average pore diameter of the plurality of pores may be between about 2 nm and about 60 μιη, between about 1 nm and about 80 nm, between about 80 nm and about 500 nm, between about 500 nm and about 2 μηι, between about 2 μηι and about 60 μιη, and the like. . Any of the preceding values or range of values may be selected for the average particulate diameter and the average pore diameter of the plurality of pores so long as the average pore diameter of the plurality of pores is larger than the average particulate diameter. For example, the average pore diameter of the plurality of pores may be 60 μιη and the average particulate diameter may be less than about 60 μιη; the average pore diameter of the plurality of pores may be between about 2 μηι and about 60 μιη and the average particulate diameter may be between about 500 nm and less than about 2 μηι; and the like.

[0024] In various embodiments, the method or process may also include drying the lignocellulosic biomass. The lignocellulosic biomass may be dried prior to contacting the lignin slurry to the lignocellulosic biomass. The lignocellulosic biomass may include a plurality of pores. The drying the lignocellulosic biomass may be effective to cause a reduction in a moisture content in the plurality of pores. Alternatively or in addition, the drying the lignocellulosic biomass may be effective to cause an increase in an average pore diameter of the plurality of pores. The drying may include reducing a moisture content of the lignocellulosic biomass to a percentage by weight of less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0.05%, or to a range between about any two of the preceding values. For example, the drying may include reducing a moisture content of the lignocellulosic biomass to a percentage by weight of between about 3% and about 0.05%, for example, about 2%. The drying may include heating the lignocellulosic biomass to a temperature in °C of about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, or 150, or between about any two of the preceding values, for example, between about 50 °C and about 150 °C. For example, the drying may include heating the lignocellulosic biomass to about 50 °C. The drying may include heating the lignocellulosic biomass for a period of time effective to reach the desired moisture content. For example, the drying may include heating the lignocellulosic biomass overnight, e.g, about 12 hours, at about 60 °C.

[0025] In some embodiments, the method or process may include contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock such that a lignin: lignocellulosic biomass dry weight ratio in the lignin-enriched feedstock is about 5:95, 10:90, 15:85, 16.7:83.3, 18:82, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50 (1 : 1), 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 82: 18, 83.3 : 16.7, 85: 15, 90: 10, or 95:5, or between about any two of the preceding ratios. For example, the lignin:lignocellulosic biomass dry weight ratio in the lignin-enriched feedstock may be between about 5:95 and about 95:5, e.g., about 18:82.

[0026] In several embodiments, the method or process may also include contacting the lignin and the lignocellulosic biomass to form the lignin-enriched feedstock. The pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include pyrolyzing the lignin-enriched feedstock to produce the bio-oil at a temperature in °C of about 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values. For example, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include pyrolyzing the lignin-enriched feedstock at between about 450 °C and about 650 °C, for example, at about 500 °C. In some embodiments, the pyrolyzing may include heating the lignocellulosic biomass and the lignin at different temperatures. For example, the pyrolyzing may include heating the lignocellulosic biomass at a temperature in °C of about 130, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values, for example, between about 130 °C and about 500 °C. Further, for example, the pyrolyzing may include heating the lignin at a temperature in °C of about 130, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values, for example, between about 130 °C and about 650 °C.

[0027] In various embodiments, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may include heating the lignin and the lignocellulosic biomass at a heating rate in °C per minute of at least about or greater than 10, 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, or 1000, or between about any two of the preceding values, for example, between about 10 °C per minute and about 500 °C per minute, e.g., greater than about 10 °C per minute or greater than about 500 °C per minute.

[0028] In some embodiments, the method or process may include contacting the lignin and the lignocellulosic biomass to form the lignin-enriched feedstock. The lignin-enriched feedstock may include the lignocellulosic biomass in a fraction effective to reduce formation of fine char compared to pyrolysis of the lignin in the absence of the lignocellulosic biomass. For example, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil may produce fine char in a weight percent yield of less than about 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, or 5%.

[0029] In several embodiments, the lignin may be derived from any source of lignin such as lignocellulosic biomass or byproducts or derivatives thereof. The lignin may be specifically isolated from biomass, or may be derived as a byproduct of another process conducted on biomass. For example, the lignin may be derived from liquor, e.g., black liquor produced by a wood pulping process. The liquor may be acidified, or the lignin may be derived from an acidified liquor. In another example, the lignin may be a byproduct of ethanol production, e.g., lignin as a byproduct of cellulosic ethanol production. In a further example, the lignin may be a byproduct of separating nondigestible components, including lignin, from digestible materials in biomass. The lignin may be acidified. The lignin may be in the form of a solid particulate powder. The lignin may be in the form of slurry of a solid particulate lignin powder dispersed in a fluid comprising one or more of water or an organic solvent.

[0030] In various embodiments, the method or process may also include conducting the pyrolyzing under anaerobic conditions. For example, the pyrolyzing may be conducted under a nitrogen atmosphere. The method or process may also include collecting the bio-oil by condensing a vapor phase of the bio-oil produced by the pyrolyzing.

[0031] In some embodiments, the lignin may be characterized compared to the lignocellulosic biomass by one or more of: a lower oxygen concentration, a higher energy value, or a higher content of aromatic rings. For example, the lignin may be characterized compared to the lignocellulosic biomass by a lower oxygen concentration. The lignin may be characterized compared to the lignocellulosic biomass by a higher energy value. The lignin may be characterized compared to the lignocellulosic biomass by a higher content of aromatic rings.

[0032] In some embodiments, the bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by one or more of: a lower oxygen content, a lower acidity, a higher energy value, a higher yield, or a lower water content. For example, the bio-oil may be characterized compared to a low- quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower oxygen content. The bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower acidity. The bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a higher energy value. The bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a higher yield. The bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower water content.

[0033] In several embodiments, the bio-oil may be produced in a liquid product yield of greater than about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, or in a range between any two of the preceding values, for example, between about 30% and about 90%. The bio-oil may be produced with a hydroxyl value in milligrams of potassium hydroxide (KOH) per gram of less than about 300, 290, 285, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 1 10, 100, 90, 80, 70, 60, 50, 40, 30, or 20, e.g., less than about 285 mg KOH/g, or between about any two of the preceding values, for example, between about 285 and about 20 mg KOH/g. The bio-oil may be produced with an acid value in mg KOH/g of less than about 44, 40, 35, 30, 25, 20, 15, 10, or 5, e.g., less than about 44 mg KOH/g, or between about any two of the preceding values, for example, between about 44 and about 5 mg KOH/g.

[0034] In various embodiments, the bio-oil may be produced with a phenolic value in mol % OH of greater than about 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85, e.g., greater than about 40 mol % phenolic OH, or between about any two of the preceding values, for example, between about 40 and about 85 mol % phenolic OH.

[0035] In some embodiments, the bio-oil may be produced with a heating value in mega Joules per kilogram (MJ/kg) of greater than about 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 55, or between about any two of the preceding values, for example, between about 17 and about 34 MJ/kg.

[0036] In various embodiments, a pyrolytic bio-oil is provided. The pyrolytic bio-oil may be derived from pyrolysis of a lignin-enriched feedstock.

[0037] In some embodiments of the pyrolytic bio-oil, the lignin-enriched feedstock may include lignin and lignocellulosic biomass. The lignin-enriched feedstock may include lignin particulates. The lignin particulates may be characterized by an average particulate diameter. The lignocellulosic biomass may include a plurality of pores characterized by an average pore diameter. The average pore diameter may be greater than the average particulate diameter. The lignin particulates may be characterized by an average particulate diameter of between about 2 μηι and about 4 μηι.

[0038] In several embodiments of the pyrolytic bio-oil, the lignin-enriched feedstock may include or be characterized by a lignin: lignocellulosic biomass dry weight ratio of about 5:95, 10:90, 15:85, 16.7:83.3, 18:82, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50 (1 : 1), 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 82: 18, 83.3 : 16.7, 85: 15, 90: 10, or 95:5, or between about any two of the preceding ratios. For example, the lignin:lignocellulosic biomass dry weight ratio in the lignin-enriched feedstock may be between about 5:95 and about 95:5, e.g., about 18:82. between about 5:95 and about 95:5.

[0039] In various embodiments, the pyrolytic bio-oil may be derived from pyrolysis of the lignin-enriched feedstock at a temperature in °C of about 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values. For example, the pyrolytic bio-oil may be derived from pyrolyzing the lignin-enriched feedstock at between about 450 °C and about 650 °C, for example, at about 500 °C. In some embodiments, the pyrolyzing may include heating lignocellulosic biomass and lignin in the lignin-enriched feedstock at different temperatures. For example, the pyrolyzing may include heating the lignocellulosic biomass at a temperature in °C of about 130, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values, for example, between about 130 °C and about 500 °C. Further, for example, the pyrolyzing may include heating the lignin at a temperature in °C of about 130, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, or 650, or between about any two of the preceding values, for example, between about 130 °C and about 650 °C. [0040] In some embodiments, the pyrolytic bio-oil may be derived from pyrolysis of the lignin-enriched feedstock at a heating rate in °C per minute of at least about or greater than 10, 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 700, 800, 900, or 1000, or between about any two of the preceding values, for example, between about 10 °C per minute and about 500 °C per minute, e.g., greater than about 10 °C per minute or greater than about 500 °C per minute.

[0041] In several embodiments of the pyrolytic bio-oil, the lignin may be derived from any source of lignin such as lignocellulosic biomass or byproducts or derivatives thereof. The lignin may be specifically isolated from biomass, or may be derived as a byproduct of another process conducted on biomass. For example, the lignin may be derived from liquor, e.g., black liquor produced by a wood pulping process. The liquor may be acidified, or the lignin may be derived from an acidified liquor. In another example, the lignin may be a byproduct of ethanol production, e.g., lignin as a byproduct of cellulosic ethanol production. In a further example, the lignin may be a byproduct of separating nondigestible components, including lignin, from digestible materials in biomass. The lignin may be acidified. The lignin may be in the form of a solid particulate powder. The lignin may be in the form of slurry of a solid particulate lignin powder dispersed in a fluid comprising one or more of water or an organic solvent.

[0042] In various embodiments of the pyrolytic bio-oil, the lignin in the lignin-enriched feedstock may be characterized compared to lignocellulosic biomass in the lignin-enriched feedstock by one or more of: a lower oxygen concentration, a higher energy value, or a higher content of aromatic rings. For example, the lignin may be characterized compared to the lignocellulosic biomass by a lower oxygen concentration. The lignin may be characterized compared to the lignocellulosic biomass by a higher energy value. The lignin may be characterized compared to the lignocellulosic biomass by a higher content of aromatic rings.

[0043] In some embodiments, the pyrolytic bio-oil may be derived from pyrolysis of the lignin-enriched feedstock under anaerobic conditions, for example, under a nitrogen atmosphere.

[0044] In several embodiments, the pyrolytic bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from a lignocellulosic biomass in the absence of a lignin by one or more of: a lower oxygen content, a lower acidity, a higher energy value, a higher yield, or a lower water content. For example, the pyrolytic bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower oxygen content. The pyrolytic bio-oil may be characterized compared to a low- quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower acidity. The pyrolytic bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a higher energy value. The pyrolytic bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a higher yield. The pyrolytic bio-oil may be characterized compared to a low-quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by a lower water content.

[0045] In several embodiments, the pyrolytic bio-oil may be characterized by a liquid product yield of greater than about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, or in a range between any two of the preceding values, for example, between about 30% and about 90%. The pyrolytic bio-oil may be characterized by a hydroxyl value in milligrams of potassium hydroxide (KOH) per gram of less than about 300, 290, 285, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, or 20, e.g., less than about 285 mg KOH/g, or between about any two of the preceding values, for example, between about 285 and about 20 mg KOH/g. The pyro lytic bio-oil may be characterized by an acid value in mg KOH/g of less than about 44, 40, 35, 30, 25, 20, 15, 10, or 5, e.g., less than about 44 mg KOH/g, or between about any two of the preceding values, for example, between about 44 and about 5 mg KOH/g.

[0046] In various embodiments, pyrolytic bio-oil may be characterized by a phenolic value in mol % OH of greater than about 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85, e.g., greater than about 40 mol % phenolic OH, or between about any two of the preceding values, for example, between about 40 and about 85 mol % phenolic OH.

[0047] In some embodiments, the pyrolytic bio-oil may be characterized by a heating value in mega Joules per kilogram (MJ/kg) of greater than about 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50,51, 52, 53, 54, 55, or between about any two of the preceding values, for example, between about 17 and about 34 MJ/kg.

EXAMPLES

[0048] PROPHETIC EXAMPLE 1A: Preparation of lignin-enriched feedstock by incipient wetness impregnation of biomass with lignin. Powdered, particulate lignin may be obtained having an average diameter of 2 microns. About 2.2 g of the powdered lignin may be mixed with acetone to form a slurry, while the powdered lignin may be added to the acetone in a solid:liquid weight ratio of about 1 :5. Lignocellulosic biomass may be obtained as about 10 grams of white pine particles. The lignocellulosic biomass as white pine particles may be dried at 100 °C to attain a moisture content of less than about 3%. After drying, the lignocellulosic biomass as white pine particles may be characterized by an average pore size of about 50 microns, greater than the average particle size of the lignin of about 2 microns. The lignin slurry may be contacted to the dried lignocellulosic biomass in drop-wise fashion. Capillary forces may drive the lignin particles in the lignin slurry into the pores in the lignocellulosic biomass to form the lignin enriched feedstock comprising the liquid from the slurry. The liquid from the slurry may be removed from the lignin enriched feedstock by filtration and drying. Compared to pyrolysis of the lignocellulosic biomass as white pine particles alone, pyrolysis of the lignin enriched feedstock may produce better bio-oil quality and yield, for example, lower oxygen content and acidity, higher energy value and yield, and lower amount of water, e.g., as described in EXAMPLES 2A, 2B, 2C and 2D.

[0049] EXAMPLE IB: TGA Analysis of Lignin and White Pine. Thermo Gravimetric Analysis (TGA) of lignin and pine was conducted to determine comparative weight loss profiles as a function of temperature. This test was run under a nitrogen atmosphere. FIG. 3 is a graph 300 showing various thermogravimetric results as a function of time for the pyrolysis of the lignin and the white pine. The weight loss of the white pine biomass 302 and the weight loss of the lignin 304 are shown against the rate of weight loss of the white pine biomass 306 and the rate of weight loss of the lignin 308. The thermogravimetric heating profile was run at a rate of 10 °C/minute from 30 °C to 700 °C over 67 minutes, at which point the sample was heated at a steady temperature of 700 °C for an additional 30 minutes for a total run time of 97 minutes. The graph shows that the white pine lignocellulosic biomass decomposes between 130 °C and 500 °C. Also, the graph shows that lignin starts decomposing below 130 °C and is still decomposing above 650 °C. The graph is consistent with the rate of bio-oil decomposition being higher than the rate of decomposition of the white pine lignocellulosic biomass (e.g., to form char and non- condensable gases). The graph data supports pyrolysis of the blended biomass/lignin feedstock at temperatures above 450 °C. For example, in the following EXAMPLES 2A, 2B, 2C and 2D, a pyrolysis temperature of 500 °C was selected because higher temperatures may lead to reduced lifetime of the reactor and may favor product gas formation.

[0050] EXAMPLE 2A: Pyrolysis Of White Pine. Ten grams of white pine were placed in a ceramic boat (e.g., feedstock feeder 206 in FIG. 2) which was then placed inside a tube furnace (e.g., tubular furnace 202). The tube furnace was flushed with nitrogen (e.g., via inert gas feed 204) to remove air and heated at about 10 °C/min to about 500 °C under a constant flow of nitrogen, e.g., about 0.22 Liters per minute (Lpm). The liquid product was captured by a condensing system including (i) a glass bottle type condenser cooled at about 10 °C, and (ii) a glass bottle type condenser at about 3 °C. Liquid pyrolytic bio-oil was collected in the condensing system. The condenser system did not appear to collect all condensable material. Char products were produced in the ceramic boat. The maximum biomass heating rate was 10 °C/min.

[0051] EXAMPLE 2B: Pyrolysis Of White Pine. Ten grams of white pine were placed in a ceramic boat (e.g., feedstock feeder 206 in FIG. 2) which was then placed inside a tube furnace (e.g., tubular furnace 202). The tube furnace was flushed with nitrogen (e.g., via inert gas feed 204) to remove air and heated at about 10 °C/min to about 500 °C under a constant flow of nitrogen, e.g., about 0.22 Liters per minute (Lpm). The liquid product was captured by a condensing system including (i) a glass bottle type condenser cooled at about 10 °C, and (ii) a vertically mounted, ¼ inch diameter by 28 inch long stainless steel tube-in- tube condenser at about 3 °C. . Liquid pyrolytic bio-oil was collected in the condensing system. . The tube-in-tube condenser did not collect any material. A minor amount of liquid was not trapped by the condensers and affected flow meter calibration. Some bio-oil condensed in a polyethylene tube connecting the two condensers. Char products were produced in the ceramic boat. The maximum biomass heating rate was 10 °C/min. [0052] EXAMPLE 2C: Pyrolysis Of Lignin. Ten grams of dry lignin were placed in the ceramic boat which was then placed inside the tube furnace. The tube furnace was flushed with nitrogen to remove air and heated at about 10 °C/min to about 500 °C under a constant flow of nitrogen, e.g., about 0.22 Lpm. The liquid product was captured by a condensing system including (i) a glass bottle type condenser cooled at about 10 °C, (ii) a ¼ inch diameter polyethylene coiled tube cooled at about 3 °C, and (iii) a glass bottle type condenser cooled at about 3 °C. The condensers were effective at trapping most condensable material. . The lignin appeared to melt and overflow the sample boat before foaming into a light carbon solid residue. The light carbon solid residue prompted disassembly and cleaning of the furnace.

[0053] Based on this finding, pyrolysis of lignin in an auger reactor may be challenging since it may produce fine char powder. The fine char powder may accumulate in the auger, which may limit mobility and may plug or jam the auger. The fine char may also travel with the bio-oil vapor and may cause obstruction downstream of the reactor (e.g., in outflow pipes,the condensing system, or the like) which may lead to undesirable system shut down and maintenance.

[0054] EXAMPLE 2D: Pyrolysis Of Lignin-Enriched White Pine Sawdust. About 20 grams of dry biomass as white pine sawdust were impregnated with 25 grams of an acetone solution containing 4.5 grams of dry lignin, prepared analogously to EXAMPLE IB. The resulting impregnated lignin-enriched biomass was dried in a box furnace at 60 °C overnight, about 12 hours. The resulting dry lignin-enriched biomass feedstock was characterized as having 18% lignin and 82% white pine. The lignin-enriched biomass feedstock was placed in the tube furnace, flushed with nitrogen to remove air, then heated at a rate of about 10 °C/min to about 500 °C. The liquid product was captured by a condensing system including (i) a glass bottle type condenser cooled at about 10 °C, (ii) a ¼ inch diameter polyethylene coiled tube cooled at about 3 °C, and (iii) a glass bottle type condenser cooled at about 3 °C. . The condensers were effective at trapping most condensable material. Char formed as individual particles similar to EXAMPLES 2A and 2B with plain white pine, in contrast to the potentially problematic fine char formed in EXAMPLE 2C. An outlet nitrogen gas meter was found to collect some soot. The pine sawdust may act as a diluent preventing accumulation of lignin powder and consequent fine char formation in the reactor.

[0055] FIG. 4 displays Table 1, reporting the material balance of various feedstocks and products of EXAMPLES 2A, 2B, 2C, and 2D. Table 1 and manual monitoring of EXAMPLES 2A, 2B, 2C, and 2D provide the following observations. The liquid pyrolytic bio-oil product has two phases: organic (20-40%) and aqueous (60-80%). The low liquid product yield may be due to the slow biomass heating rates of 10 °C/min (slow pyrolysis), which promotes char formation. The low heating rate of 10 ° C/min was merely a limitation of the particular test-scale reactor used.

[0056] FIG. 5 displays Table 2, reporting an analysis of various organic phase products as measured by ³¹P NMR for EXAMPLES 2A, 2B, 2C, and 2D . Based on ³¹P NMR (nuclear magnetic resonance) analysis, pyrolysis of pine impregnated with 18% lignin (EXAMPLE 2D) has lower acidity and higher phenolic compounds compared to pure pine (EXAMPLE 2B).

[0057] PROPHETIC EXAMPLE 3A: Pilot scale lignin enriched biomass pyrolysis.

About 60 pounds of dry biomass as white pine sawdust may be impregnated with 33 pounds of an acetone solution containing about 6 pounds of dry lignin. The dry lignin may have an average particle diameter of between about 2 μιη and about 4 μιη. The average particle diameter of between about 2 μιη and about 4 μιη may reduce plugging of a pilot pyrolysis reactor compared to larger diameter lignin particles. The dry lignin may first be prepared to remove non-lignin impurities, such as cellulose, hemicellulose, inorganic materials, and the like.

[0058] The resulting impregnated lignin-enriched biomass may be dried in a box furnace at 60 °C overnight, about 12 hours. The resulting dry lignin-enriched biomass feedstock may be characterized as having 10% lignin and 90% white pine. The lignin-enriched biomass feedstock may be placed in the pilot pyrolysis reactor equipped with an auger, and flushed with nitrogen to remove air. The pyrolysis zone may be heated to about 500 °C. The dry lignin-enriched biomass feedstock may be transported through the pyrolysis zone via the auger. A liquid pyrolytic bio-oil product may be captured by a condensing system at about 3 °C. The liquid pyrolytic bio-oil product may have, compared to the products of one or more of EXAMPLES 2A and 2B, one or more of a lower acid value and a higher phenolic content. Char may be formed as individual particles similar to EXAMPLE 2A and 2B with plain white pine, in contrast to the potentially problematic fine char formed in EXAMPLE 2C. The pine sawdust may act as a diluent preventing accumulation of lignin powder and consequent fine char formation in the reactor.

[0059] PROPHETIC EXAMPLE 3B: Pilot scale lignin enriched biomass pyrolysis.

About 30 pounds of dry biomass as white pine sawdust may be impregnated with 33 pounds of an acetone solution containing about 6 pounds of dry lignin. The dry lignin may have an average particle diameter of between about 2 μιη and about 4 μιη. The dry lignin may first be prepared as in EXAMPLE 3A. The resulting impregnated lignin-enriched biomass may be dried in a box furnace at 60 °C overnight, about 12 hours. The resulting dry lignin-enriched biomass feedstock may be characterized as having 20% lignin and 80% white pine. The lignin-enriched biomass feedstock may be placed in the pilot pyrolysis reactor equipped with an auger, and flushed with nitrogen to remove air. The pyrolysis zone may be heated to about 520 °C. The dry lignin-enriched biomass feedstock may be transported through the pyrolysis zone via the auger. A liquid pyrolytic bio-oil product may be captured by a condensing system at about 3 °C. The liquid pyrolytic bio-oil product may have, compared to the products of one or more of EXAMPLES 2A, 2B, and 3A, one or more of a lower acid value and a higher phenolic content. Char may be formed as individual particles similar to EXAMPLE 2A and 2B with plain white pine, in contrast to the potentially problematic fine char formed in EXAMPLE 2C. The pine sawdust may act as a diluent preventing accumulation of lignin powder and consequent fine char formation in the reactor.

[0060] PROPHETIC EXAMPLE 3C: Pilot scale lignin enriched biomass pyrolysis.

About 11 pounds of dry biomass as white pine sawdust may be impregnated with 33 pounds of an acetone solution containing about 6 pounds of dry lignin. The dry lignin may have an average particle diameter of between about 2 μιη and about 4 μιη. The dry lignin may first be prepared as in EXAMPLE 3A. The resulting impregnated lignin-enriched biomass may be dried in a box furnace at 60 °C overnight, about 12 hours. The resulting dry lignin-enriched biomass feedstock may be characterized as having 35% lignin and 65% white pine. The lignin-enriched biomass feedstock may be placed in the pilot pyrolysis reactor equipped with an auger, and flushed with nitrogen to remove air. The pyrolysis zone may be heated to about 540 °C. The dry lignin-enriched biomass feedstock may be transported through the pyrolysis zone via the auger. A liquid pyrolytic bio-oil product may be captured by a condensing system at about 3 °C. The liquid pyrolytic bio-oil product may have, compared to the products of one or more of EXAMPLES 2A, 2B, 3A, and 3B, one or more of a lower acid value and a higher phenolic content. Char may be formed as individual particles similar to EXAMPLE 2A and 2B with plain white pine, in contrast to the potentially problematic fine char formed in EXAMPLE 2C. The pine sawdust may act as a diluent preventing accumulation of lignin powder and consequent fine char formation in the reactor. [0061] PROPHETIC EXAMPLE 3D: Pilot scale lignin enriched biomass pyrolysis.

About 6 pounds of dry biomass as white pine sawdust may be impregnated with 33 pounds of an acetone solution containing about 6 pounds of dry lignin. The dry lignin may have an average particle diameter of between about 2 μιη and about 4 μιη. The dry lignin may first be prepared as in EXAMPLE 3A. The resulting impregnated lignin-enriched biomass may be dried in a box furnace at 60 °C overnight, about 12 hours. The resulting dry lignin-enriched biomass feedstock may be characterized as having 50% lignin and 50% white pine. The lignin-enriched biomass feedstock may be placed in the pilot pyrolysis reactor equipped with an auger, and flushed with nitrogen to remove air. The pyrolysis zone may be heated to about 550 °C. The dry lignin-enriched biomass feedstock may be transported through the pyrolysis zone via the auger. A liquid pyrolytic bio-oil product may be captured by a condensing system at about 3 °C. The liquid pyrolytic bio-oil product may have, compared to the products of one or more of EXAMPLES 2A, 2B, 3A, 3B, and 3C, one or more of a lower acid value and a higher phenolic content. Char may be formed as individual particles similar to EXAMPLE 2A and 2B with plain white pine, in contrast to the potentially problematic fine char formed in EXAMPLE 2C. The pine sawdust may act as a diluent preventing accumulation of lignin powder and consequent fine char formation in the reactor.

[0062] To the extent that the term "includes" or "including" is used in the specification or the claims, it is intended to be inclusive in a manner similar to the term "comprising" as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term "or" is employed (e.g., A or B) it is intended to mean "A or B or both." When the applicants intend to indicate "only A or B but not both" then the term "only A or B but not both" will be employed. Thus, use of the term "or" herein is the inclusive, and not the exclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995). Also, to the extent that the terms "in" or "into" are used in the specification or the claims, it is intended to additionally mean "on" or "onto." To the extent that the term "selectively" is used in the specification or the claims, it is intended to refer to a condition of a component wherein a user of the apparatus may activate or deactivate the feature or function of the component as is necessary or desired in use of the apparatus. To the extent that the terms "coupled" or "operatively connected" are used in the specification or the claims, it is intended to mean that the identified components are connected in a way to perform a designated function. To the extent that the term "substantially" is used in the specification or the claims, it is intended to mean that the identified components have the relation or qualities indicated with degree of error as would be acceptable in the subject industry.

[0063] As used in the specification and the claims, the singular forms "a," "an," and "the" include the plural unless the singular is expressly specified. For example, reference to "a compound" may include a mixture of two or more compounds, as well as a single compound.

[0064] As used herein, the term "about" in conjunction with a number is intended to include ± 10% of the number. In other words, "about 10" may mean from 9 to 1 1.

[0065] As used herein, the terms "optional" and "optionally" mean that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.

[0066] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, and the like. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, and the like. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," include the number recited and refer to ranges which can be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. For example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art.

[0067] As stated above, while the present application has been illustrated by the description of embodiments thereof, and while the embodiments have been described in considerable detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art, having the benefit of the present application. Therefore, the application, in its broader aspects, is not limited to the specific details, illustrative examples shown, or any apparatus referred to. Departures may be made from such details, examples, and apparatuses without departing from the spirit or scope of the general inventive concept.

[0068] As used herein, "substituted" refers to an organic group as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein may be replaced by a bond to non-hydrogen or non-carbon atoms. Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom may be replaced by one or more bonds, including double or triple bonds, to a heteroatom. A substituted group may be substituted with one or more substituents, unless otherwise specified. In some embodiments, a substituted group may be substituted with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent groups include: halogens (e.g., F, CI, Br, and I); hydroxyls; alkoxy, alkenoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes; hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides; sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides; hydrazines; hydrazides; hydrazones; azides; amides; ureas; amidines; guanidines; enamines; imides; isocyanates; isothiocyanates; cyanates; thiocyanates; imines; nitro groups; or nitriles. A "per"-substituted compound or group is a compound or group having all or substantially all substitutable positions substituted with the indicated substituent. For example, 1,6-diiodo perfluoro hexane indicates a compound of formula C₆F12I2, where all the substitutable hydrogens have been replaced with fluorine atoms.

[0069] Substituted ring groups such as substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups also include rings and ring systems in which a bond to a hydrogen atom may be replaced with a bond to a carbon atom. Substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined below.

[0070] Alkyl groups include straight chain and branched chain alkyl groups having from 1 to 12 carbon atoms, and typically from 1 to 10 carbons or, in some examples, from 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of straight chain alkyl groups include groups such as methyl, ethyl, w-propyl, w-butyl, w-pentyl, w-hexyl, w-heptyl, and w-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, tert- butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. Representative substituted alkyl groups may be substituted one or more times with substituents such as those listed above and include, without limitation, haloalkyl (e.g., trifluoromethyl), hydroxyalkyl, thioalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkoxyalkyl, or carboxyalkyl.

[0071] Cycloalkyl groups include mono-, bi- or tricyclic alkyl groups having from 3 to 12 carbon atoms in the ring(s), or, in some embodiments, 3 to 10, 3 to 8, or 3 to 4, 5, or 6 carbon atoms. Exemplary monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments, the number of ring carbon atoms ranges from 3 to 5, 3 to 6, or 3 to 7. Bi- and tricyclic ring systems include both bridged cycloalkyl groups and fused rings, such as, but not limited to, bicyclo[2.1.1]hexane, adamantyl, or decalinyl. Substituted cycloalkyl groups may be substituted one or more times with non-hydrogen and non-carbon groups as defined above. However, substituted cycloalkyl groups also include rings that may be substituted with straight or branched chain alkyl groups as defined above. Representative substituted cycloalkyl groups may be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups, which may be substituted with substituents such as those listed above.

[0072] Aryl groups may be cyclic aromatic hydrocarbons that do not contain heteroatoms. Aryl groups herein include monocyclic, bicyclic and tricyclic ring systems. Aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups. In some embodiments, aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups. In some embodiments, the aryl groups may be phenyl or naphthyl. Although the phrase "aryl groups" may include groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl or tetrahydronaphthyl), "aryl groups" does not include aryl groups that have other groups, such as alkyl or halo groups, bonded to one of the ring members. Rather, groups such as tolyl may be referred to as substituted aryl groups. Representative substituted aryl groups may be mono-substituted or substituted more than once. For example, monosubstituted aryl groups include, but are not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or naphthyl, which may be substituted with substituents such as those above.

[0073] Aralkyl groups may be alkyl groups as defined above in which a hydrogen or carbon bond of an alkyl group may be replaced with a bond to an aryl group as defined above. In some embodiments, aralkyl groups contain 7 to 16 carbon atoms, 7 to 14 carbon atoms, or 7 to 10 carbon atoms. Substituted aralkyl groups may be substituted at the alkyl, the aryl or both the alkyl and aryl portions of the group. Representative aralkyl groups include but are not limited to benzyl and phenethyl groups and fused (cycloalkylaryl)alkyl groups such as 4-indanylethyl. Substituted aralkyls may be substituted one or more times with substituents as listed above.

[0074] Groups described herein having two or more points of attachment (e.g., divalent, trivalent, or polyvalent) within the compound of the technology may be designated by use of the suffix, "ene." For example, divalent alkyl groups may be alkylene groups, divalent aryl groups may be arylene groups, divalent heteroaryl groups may be heteroarylene groups, and so forth. In particular, certain polymers may be described by use of the suffix "ene" in conjunction with a term describing the polymer repeat unit.

[0075] Alkoxy groups may be hydroxyl groups (-OH) in which the bond to the hydrogen atom may be replaced by a bond to a carbon atom of a substituted or unsubstituted alkyl group as defined above. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, or hexoxy. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentoxy, or isohexoxy. Examples of cycloalkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, or cyclohexyloxy. Representative substituted alkoxy groups may be substituted one or more times with substituents such as those listed above.

[0076] The term "amine" (or "amino"), as used herein, refers to R5R₆ groups, wherein R5 and R6 may be independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein. In some embodiments, the amine may be alkylamino, dialkylamino, arylamino, or alkylarylamino. In other embodiments, the amine may be H2, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, isopropylamino, phenylamino, or benzylamino. The term "alkylamino" may be defined as R7R₈, wherein at least one of R7 and Rs may be alkyl and the other may be alkyl or hydrogen. The term "arylamino" may be defined as NR₉R1₀, wherein at least one of R₉ and Rio may be aryl and the other may be aryl or hydrogen.

[0077] The term "halogen" or "halo," as used herein, refers to bromine, chlorine, fluorine, or iodine. In some embodiments, the halogen may be fluorine. In other embodiments, the halogen may be chlorine or bromine.

[0078] The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

1. A method of producing a bio-oil, comprising:

providing lignin;

providing lignocellulosic biomass; and

pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil.

2. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

3. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass by incipient wetness impregnation of the lignocellulosic biomass with the lignin to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

4. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock by:

contacting the lignin in particulate form to a fluid to form a lignin slurry; and contacting the lignin slurry to the lignocellulosic biomass effective to impregnate a portion of the lignin in particulate form into the lignocellulosic biomass to form the lignin- enriched feedstock,

wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio- oil includes pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

5. The method of claim 5, wherein the fluid comprises one or more of water or an organic solvent.

6. The method of claim 5, wherein the slurry comprises a lignin:fluid weight ratio of between about 5:95 and about 1 : 1.

7. The method of claim 5, further comprising removing the fluid from the lignin- enriched feedstock by one or more of: heating, reduced pressure, spray-drying, filtering, settling, or centrifuging.

8. The method of claim 5, wherein contacting the lignin slurry to the lignocellulosic biomass comprises one or more of: drop-wise application of the lignin slurry to the lignocellulosic biomass, mechanical agitation of the lignin slurry and the lignocellulosic biomass, sonication of the lignin slurry and the lignocellulosic biomass, or pressure cycling of the lignin slurry and the lignocellulosic biomass.

9. The method of claim 5, the lignin particulates being characterized by an average particulate diameter and the lignocellulosic biomass comprising a plurality of pores characterized by an average pore diameter greater than the average particulate diameter effective to provide the impregnation of the portion of the lignin particulates into the plurality of pores of the lignocellulosic biomass.

10. The method of claim 5, the lignin particulates being characterized by an average particulate diameter of between about 2 μιη and about 4 μιη.

11. The method of claim 5, further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass.

12. The method of claim 5, further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the lignocellulosic biomass comprising a plurality of pores, the drying effective to cause one or more of: a reduction in a moisture content in the plurality of pores or an increase in average pore diameter of the plurality of pores.

13. The method of claim 5, further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the drying comprising reducing a moisture content of the lignocellulosic biomass to a percentage by weight of less than about 10%.

14. The method of claim 5, further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the drying comprising heating the lignocellulosic biomass to a temperature of between about 50 °C and about 150 ^°C.

15. The method of claim 5, further comprising removing the fluid of the lignin slurry from the lignin-enriched feedstock by one or more of: heating, reduced pressure, spray-drying, filtering, settling, or centrifuging.

16. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock such that a lignin:lignocellulosic biomass dry weight ratio in the lignin-enriched feedstock is between about 5:95 and about 95:5.

17. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock at a temperature of between about 450 °C and about 650 °C to produce the bio-oil.

18. The method of claim I, the pyrolyzing comprising heating the lignocellulosic biomass between about 130 °C and about 500 °C

19. The method of claim I, the pyrolyzing comprising heating the lignin between about 130 °C and about 650 °C.

20. The method of claim 1, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil comprising heating the lignin and the lignocellulosic biomass at a heating rate greater than about 10 °C per minute.

21. The method of claim 1, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil comprising heating the lignin and the lignocellulosic biomass at a heating rate greater than about 500 °C per minute.

22. The method of claim 1, further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock comprising the lignocellulosic biomass in a fraction effective to reduce formation of fine char compared to pyrolysis of the lignin in the absence of the lignocellulosic biomass.

23. The method of claim 1, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil producing fine char in a weight percent yield of less than about 55%.

24. The method of claim 1, the lignin being derived from liquor produced by a wood pulping process.

25. The method of claim 1, the lignin being in the form of a solid particulate powder.

26. The method of claim 1, the lignin being in the form of slurry of a solid particulate lignin powder dispersed in a fluid comprising one or more of water or an organic solvent.

27. The method of claim 1, further comprising conducting the pyrolyzing under anaerobic conditions.

28. The method of claim 1, further comprising conducting the pyrolyzing under a nitrogen atmosphere.

29. The method of claim 1, further comprising collecting the bio-oil by condensing a vapor phase of the bio-oil produced by the pyrolyzing.

30. The method of claim 1, the lignin being characterized compared to the lignocellulosic biomass by one or more of: a lower oxygen concentration, a higher energy value, or a higher content of aromatic rings.

31. The method of claim 1 , the bio-oil being characterized compared to a low- quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by one or more of: a lower oxygen content, a lower acidity, a higher energy value, a higher yield, or a lower water content.

32. The method of claim 1, the bio-oil being produced in a liquid product yield of greater than about 30%.

33. The method of claim 1, the bio-oil being produced with a hydroxyl value of less than about 285 milligrams KOH per gram.

34. The method of claim 1, the bio-oil being produced with an acid value of less than about 44 milligrams KOH per gram.

35. The method of claim 1, the bio-oil being produced with a phenolic value of greater than about 40 mol %OH.

36. The method of claim 1, the bio-oil being produced with a heating value of greater than about 17 MJ/kg.

37. The method of claim 1, the bio-oil being produced with a heating value of greater than about 20 MJ/kg.

38. A bio-oil, produced by a process comprising:

providing lignin;

providing lignocellulosic biomass; and

pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil.

39. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

40. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass by incipient wetness impregnation of the lignocellulosic biomass with the lignin to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock to produce the bio-oil.

41. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock by:

42. The bio-oil of claim 41, wherein the fluid comprises one or more of water or an organic solvent.

43. The bio-oil of claim 41, wherein the slurry comprises a lignin:fluid weight ratio of between about 5:95 and about 1 : 1.

44. The bio-oil of claim 41, the process further comprising removing the fluid from the lignin-enriched feedstock by one or more of: heating, reduced pressure, spray- drying, filtering, settling, or centrifuging.

45. The bio-oil of claim 40, wherein contacting the lignin slurry to the lignocellulosic biomass comprises one or more of: drop-wise application of the lignin slurry to the lignocellulosic biomass, mechanical agitation of the lignin slurry and the lignocellulosic biomass, sonication of the lignin slurry and the lignocellulosic biomass, or pressure cycling of the lignin slurry and the lignocellulosic biomass.

46. The bio-oil of claim 41, the lignin particulates being characterized by an average particulate diameter and the lignocellulosic biomass comprising a plurality of pores characterized by an average pore diameter greater than the average particulate diameter effective to provide the impregnation of the portion of the lignin particulates into the plurality of pores of the lignocellulosic biomass.

47. The bio-oil of claim 41, the lignin particulates being characterized by an average particulate diameter of between about 2 μιη and about 4 μιη.

48. The bio-oil of claim 41, the process further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass.

49. The bio-oil of claim 41, the process further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the lignocellulosic biomass comprising a plurality of pores, the drying effective to cause one or more of: a reduction in a moisture content in the plurality of pores or an increase an average pore diameter of the plurality of pores.

50. The bio-oil of claim 41, the process further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the drying comprising reducing a moisture content of the lignocellulosic biomass to a percentage by weight of less than about 10%.

51. The bio-oil of claim 41, the process further comprising drying the lignocellulosic biomass prior to contacting the lignin slurry to the lignocellulosic biomass, the drying comprising heating the lignocellulosic biomass to a temperature of between about 50 °C and about 150 °C.

52. The bio-oil of claim 41, the process further comprising removing the fluid of the lignin slurry from the lignin-enriched feedstock by one or more of: heating, reduced pressure, spray-drying, filtering, settling, or centrifuging.

53. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock such that a lignin: lignocellulosic biomass dry weight ratio in the lignin-enriched feedstock is between about 5:95 and about 95:5.

54. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock, wherein the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil includes pyrolyzing the lignin-enriched feedstock at a temperature of between about 450 °C and about 650 °C to produce the bio-oil.

55. The bio-oil of claim 38, the pyrolyzing comprising heating the lignocellulosic biomass between about 130 °C and about 500 °C

56. The bio-oil of claim 38, the pyrolyzing comprising heating the lignin between about 130 °C and about 650 °C.

57. The bio-oil of claim 38, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil comprising heating the lignin and the lignocellulosic biomass at a heating rate greater than about 10 °C per minute.

58. The bio-oil of claim 38, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil comprising heating the lignin and the lignocellulosic biomass at a heating rate greater than about 500 °C per minute.

59. The bio-oil of claim 38, the process further comprising contacting the lignin and the lignocellulosic biomass to form a lignin-enriched feedstock comprising the lignocellulosic biomass in a fraction effective to reduce formation of fine char compared to pyro lysis of the lignin in the absence of the lignocellulosic biomass.

60. The bio-oil of claim 38, the pyrolyzing the lignin and the lignocellulosic biomass to produce the bio-oil producing fine char in a weight percent yield of less than about 55%.

61. The bio-oil of claim 38, the lignin being derived from liquor produced by a wood pulping process.

62. The bio-oil of claim 8, the lignin being in the form of a solid particulate powder.

63. The bio-oil of claim 38, the lignin being in the form of slurry of a solid particulate lignin powder dispersed in a fluid comprising one or more of water or an organic solvent.

64. The bio-oil of claim 38, the process further comprising conducting the pyrolyzing under anaerobic conditions.

65. The bio-oil of claim 38, the process further comprising conducting the pyrolyzing under a nitrogen atmosphere.

66. The bio-oil of claim 38, the process further comprising collecting the bio-oil by condensing a vapor phase of the bio-oil produced by the pyrolyzing.

67. The bio-oil of claim 38, the lignin being characterized compared to the lignocellulosic biomass by one or more of: a lower oxygen concentration, a higher energy value, or a higher content of aromatic rings.

68. The bio-oil of claim 38, the bio-oil being characterized compared to a low- quality bio-oil pyrolyzed from the lignocellulosic biomass in the absence of the lignin by one or more of: a lower oxygen content, a lower acidity, a higher energy value, a higher yield, or a lower water content.

69. The bio-oil of claim 38, the bio-oil being produced in a liquid product yield of greater than about 30%.

70. The bio-oil of claim 38, the bio-oil being characterized by a hydroxyl value of less than about 285 milligrams KOH per gram.

71. The bio-oil of claim 38, the bio-oil being characterized by an acid value of less than about 44 milligrams KOH per gram.

72. The bio-oil of claim 37, the bio-oil being characterized by a phenolic value of greater than about 40 mol %OH.

73. The bio-oil of claim 38, the bio-oil being characterized by a heating value of greater than about 17 MJ/kg.

74. The bio-oil of claim 38, the bio-oil being characterized by a heating value of greater than about 20 MJ/kg.

75. A pyro lytic bio-oil, derived from pyrolysis of a lignin-enriched feedstock.

76. The pyrolytic bio-oil of claim 75, the lignin-enriched feedstock comprising lignin and lignocellulosic biomass

77. The pyrolytic bio-oil of claim 75, the lignin-enriched feedstock comprising lignin particulates characterized by an average particulate diameter and the lignocellulosic biomass comprising a plurality of pores characterized by an average pore diameter greater than the average particulate diameter.

78. The pyrolytic bio-oil of claim 75, the lignin-enriched feedstock comprising lignin particulates characterized by an average particulate diameter of between about 2 μηι and about 4 μηι.

79. The pyrolytic bio-oil of claim 75, the lignin-enriched feedstock comprising a lignin: lignocellulosic biomass dry weight ratio between about 5:95 and about 95:5.

80. The pyrolytic bio-oil of claim 75, derived from pyrolysis of the lignin- enriched feedstock at a temperature of between about 450 °C and about 650 °C.

81. The pyrolytic bio-oil of claim 75, derived from pyrolysis of the lignin- enriched feedstock at a heating rate greater than about 10 °C per minute.

82. The pyrolytic bio-oil of claim 75, derived from pyrolysis of the lignin- enriched feedstock at a heating rate greater than about 500 °C per minute.

83. The pyrolytic bio-oil of claim 76, the lignin being derived from liquor produced by a wood pulping process or the lignin being derived from a cellulosic ethanol process.

84. The pyrolytic bio-oil of claim 76, the lignin being in the form of a solid particulate powder.

85. The pyrolytic bio-oil of claim 76, the lignin being in the form of slurry of a solid particulate lignin powder dispersed in a fluid comprising one or more of water or an organic solvent.

86. The pyrolytic bio-oil of claim 76, the lignin being characterized compared to the lignocellulosic biomass by one or more of: a lower oxygen concentration, a higher energy value, or a higher content of aromatic rings.

87. The pyrolytic bio-oil of claim 75, derived from pyrolysis of the lignin- enriched feedstock under anaerobic conditions.

88. The pyrolytic bio-oil of claim 75, derived from pyrolysis of the lignin- enriched feedstock under a nitrogen atmosphere.

89. The pyrolytic bio-oil of claim 75, characterized compared to a low-quality bio- oil pyrolyzed from a lignocellulosic biomass in the absence of a lignin by one or more of: a lower oxygen content, a lower acidity, a higher energy value, a higher yield, or a lower water content.

90. The pyrolytic bio-oil of claim 75, characterized by a liquid product yield of greater than about 30%.

91. The pyrolytic bio-oil of claim 75, characterized by a hydroxyl value of less than about 285 milligrams KOH per gram.

92. The pyrolytic bio-oil of claim 75, characterized by an acid value of less than about 44 milligrams KOH per gram.

93. The pyrolytic bio-oil of claim 75, characterized by a phenolic value of greater than about 40 mol %OH.

94. The pyrolytic bio-oil of claim 75, characterized by a heating value of greater than about 17 MJ/kg.

95. The pyrolytic bio-oil of claim 75, characterized by a heating value of greater than about 20 MJ/kg.