ORGANIC SOLVENT

FIELD

This disclosure relates, at least in part, to compositions comprising lignocellulosic biomass and organic solvent. The disclosure further relates to uses, apparatus, methods, and the like.

BACKGROUND

For environmental, economic, and resource security reasons, there is a desire to obtain energy and material products from bio-renewable resources and particularly from "waste" and/or non-food biomass feedstocks. The various chemical components within typical biomass can be employed in a number of ways. For example, the cellulose and hemicellulose in plant matter may fermented into fuel grade alcohol, synthetic biodiesel, fuel grade butanol, xylitol, succinic acid, and other useful materials. The lignin component from biomass, and other types of extractives, have potential as a useful source of chemicals for certain industrial applications. Extracting these valuable resources from biomass could increase the

commercial viability of the various biorefining pulping processes. However, to date most biomass fractionation techniques employed by industry have been optimized for the production of high-quality fibre rather than the production of lignins and their derivatives. Thus, large-scale commercial application of the extractives, particularly those isolated in traditional pulping processes employed in the manufacture of pulp for paper production, has been limited due to, for example, the inconsistency of their chemical and functional properties. These inconsistencies may, for example, be due to changes in feedstock supplies and the particular extraction, generation, and/or recovery conditions. These issues are exacerbated by the complexity of the molecular structures of the extractives, such as lignin derivatives, produced by the various extraction methods and the difficulty in performing reliable routine analyses of the structural conformity and integrity of recovered extractives. Despite this lignin derivatives obtained via organosolv extraction, such as the Alcell® process (Alcell is a registered trademark of Lignol Innovations Ltd., Burnaby, BC, CA), have been used in rubber products, adhesives, resins, plastics, asphalt, cement, casting resins, agricultural products, oil-field products and as feedstocks for the production of fine chemicals. Various processes are known for the biorefining of lignocellulosic feedstocks. These include, for example, ammonia pretreatment, dilute acid pretreatment, dilute ammonia pretreatment, concentrated acid hydrolysis, steam explosion, lime treatment, and the like. These treatment processes often produce a carbohydrate-rich stream which is frequently fermented into a biofuel such as biodiesel. These processes usually produce further chemicals such as lignin derivatives at the like. Additionally, these processes can leave a solid or semisolid lignaceaus residue which may comprise lignins, recalcitrant cellulose, and other substances. This material is typically considered 'waste' and may be burnt for its fuel value.

SUMMARY

The present disclosure relates, at least in part, to compositions comprising

lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises 35% or greater of lignin material. The present disclosure relates, at least in part, to

compositions comprising lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises 50% or less of carbohydrate. The present lignocellulosic biomass may comprise 35% or greater of lignin material and 50% or less of carbohydrate.

The present disclosure relates, at least in part, to compositions comprising

lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises 5% or greater recalcitrant cellulose.

In certain embodiments the present compositions may have a viscosity of 5000 cps or less.

The present disclosure relates, at least in part, to methods of processing lignaceaus residue. The present disclosure in part provides a process for extracting lignin and/or other derivatives from the lignaceaus residue of a cellulosic bioethanol plant. For example, an embodiment of the present disclosure provides for organosolv extraction of lignin derivatives from the lignaceaus residue of a steam explosion-type process. As previously stated the lignaceaus residue has usually been considered of use for its fuel value only. It has been found that this residue may be treated via an organosolv process to produce useful products such as, for example, reactive carbohydrates (which may, for example, be used in the production of ethanol), lignin derivatives, and/or other extractives.

The compositions, methods, processes or systems of present disclosure may improve the economic viability of a biorefinery processes. For example, the compositions, methods, processes or systems of present disclosure may provide additional carbohydrate residue for conversion into biofuel and/or additional extractives. The present compositions comprising lignocellulosic biomass and an organic solvent may be in a 'pumpable' form which is easier to process in a continuous manner.

The present disclosure in part provides compounds extracted from lignaceaus residue.

The present disclosure in part provides uses of compounds that may be extracted from lignaceaus residue.

As used herein, the term "biorefining" refers to the production of carbohydrate and/or other bio-based products (e.g. lignin derivatives) from biomass. The carbohydrate is frequently fermented into biofuel such as ethanol. Examples of biorefining processes include, but are not limited to, ammonia pretreatment, dilute acid pretreatment, dilute ammonia pretreatment, concentrated acid hydrolysis, steam explosion, lime treatment, and the like.

As used herein, the term "lignaceaus residue" refers to the solid or semi-solid material that remains after a lignocellulosic feedstock has been treated in a biorefining process. Such residue generally comprises lignin and/or recalcitrant cellulose. Other materials such as protein and ash may also be present.

The term "recalcitrant cellulose" refers to the relatively unreactive cellulose fraction remaining after a biomass has undergone biorefining. As used herein, "recalcitrant" means cellulose which is hydrolysed to glucose at a rate of less than 10% per day when incubated at 40°C in the presence of 20 mg cellulase protein per g cellulose substrate.

As used herein, the term "organosolv" refers to a biomass extraction processes wherein the biomass is subject to an extraction step using an organic solvent at an elevated temperature.

As used herein, the term "lignocellulosic biomass" refers to biologically-derived material which when in its natural state comprises cellulose and lignin. The biomass will usually be derived from plants.

As used herein, the term "native lignin" refers to lignin in its natural state, in plant biomass.

As used herein, the terms "lignin derivatives" and "derivatives of native lignin" refer to lignin material including to polymeric and oligomeric compounds extracted from lignocellulosic biomass. Usually, such material will be a mixture of lignin-derived chemical compounds that are generated during the extraction process.

Unless otherwise indicated or implied through their context all percentages herein should be considered percentage by weight. This summary does not necessarily describe all features of the invention. Other aspects, features and advantages of the invention will be apparent to those of ordinary skill in the art upon review of the following description of specific embodiments of the invention.

DETAILED DESCRIPTION

The present disclosure relates, at least in part, to compositions comprising

lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises 25% or greater of lignin material. For example, about 26% or greater, about 28% or greater, about 30% or greater, about 32% or greater, about 34% or greater, about 35% or greater, about 36% or greater, about 38% or greater, about 40% or greater, about 42% or greater, about 44% or greater, about 46% or greater, about 48% or greater, about 50% or greater, of lignin material. The present disclosure relates, at least in part, to compositions comprising lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises 50% or less of carbohydrate. For example, about 48% or less, about 46% or less, about 44% or less, about 42% or less, about 40% or less, about 38% or less, about 36% or less, about 34% or less, about 32% or less, about 30% or less, of carbohydrate, The present

lignocellulosic biomass may comprise 35% or greater of lignin material and 50% or less of carbohydrate. The present disclosure relates, at least in part, to compositions comprising lignocellulosic biomass and an organic solvent wherein the lignocellulosic biomass comprises about 5% or greater, about 10% or greater, about 15% or greater, about 20% or greater, recalcitrant cellulose.

It is known in the art to add organic solvent to lignocellulosic biomass (see, for example, US Patent 4,100,016; US Patent 4,764,596; US Patent 5,681,427; US Patent 7,465,791 ; US Patent Application 2009/01 18477; US Patent Application 2009/0062516; US Patent Application 2009/00669550; or US Patent 7,649,086). The lignocellulosic biomass in the present compositions comprises a higher lignin content, a lower carbohydrate content, or both, when compared to the lignocellulosic biomass used in these prior art processes. While not wishing to be bound by theory, it is believed that useful products may be extracted from compositions comprising lignocellulosic biomass according to the present disclosure and organic solvent. For example, organic solvent may be added to the lignaceaus residue of a biorefmery, which is typically considered waste, and when subjected to an organosolv treatment, lignin-derived aromatic products may be recovered. Additionally, it is believed that the recalcitrant cellulose contained in the lignaceaus residue may be made more susceptible to further processing.

The present compositions may have a viscosity of 5000 cps or less. Such as, for example, 4500 cps or less, 4000 cps or less, 3500 cps or less, 3000 cps or less, 2500 cps or less, 2000 cps or less, 1500 cps or less, 1000 cps or less, 800 cps or less, 600 cps or less, 400 cps or less, 200 cps or less (viscosity measurements made using viscometer Viscolite 700 (Hydramotion Ltd., Malton, York Y017 6YA England).

The weight ratio of solvent liquor to biomass in the present compositions may be any suitable ratio such as, for example, from about 20:1 to about 2:1, 10:1 to about 3:1, about 9:1 to about 4: 1, about 8:1 to about 5:1.

The present compositions may have any suitable pH such as, for example, from about 1.5 or greater, 1.6 or greater, 1.7 or greater. The present composition may have any suitable pH such as, for example, from about 2.5 or lower, 2.4 or lower, 2.3 or lower. For example, the composition may have a pH of from about 1.5 to about 2.5. For example, the pH may be from about 1.6 to about 2.3.

From about 1.5% or greater, 1.7% or greater, 1.9% or greater, 2% or greater, by weight, of acid (based on dry weight of biomass) may be added to the present compositions. From about 3% or lower, 2.7% or lower, 2.5% or lower, by weight, of acid (based on dry weight wood) may be added to the present compositions.

The organic solvent herein may be a mixture comprising, for example, about 40% or more, 42% or more, 44% or more, 46% or more, 48% or more, 50% or more, organic solvent such as ethanol. The solvent herein may comprise about 80% or less, about 75% or less, about 70% or less, 68% or less, 66%) or less, 64% or less, 62% or less, 60% or less, 58% or less, 56% or less, organic solvent such as ethanol. For example, the solvent may comprise about 45% to about 60%, about 50% to about 55% organic solvent such as ethanol. The remainder of the solvent may be any suitable substance such as, for example, water.

The present organic solvent may be selected from any suitable solvent. For example, aromatic alcohols such as phenol, catechol, and combinations thereof; short chain primary and secondary alcohols, such as methanol, ethanol, propanol, and combinations thereof. The organic solvent may be ethanol.

Any suitable lignocellulosic biomass may be utilized herein including hardwoods, softwoods, annual fibres, energy crops, municipal waste, and combinations thereof.

Hardwood feedstocks include Acacia; Afzelia; Synsepalum duloificum; Albizia; Alder (e.g. Alnus glutinosa, Alnus rubra); Applewood; Arbutus; Ash (e.g. F. nigra, F. quadrangulata, F. excelsior, F. pennsylvanica lanceolata, F. latifolia, F. profunda, F.

americana); Aspen (e.g. P. grandidentata, P. tremula, P. tremuloides); Australian Red Cedar (Toona ciliata); Ayna (Distemonanthus benthamianus); Balsa (Ochroma pyramidale);

Basswood (e.g. T. americana, T. heterophylla); Beech (e.g. F. sylvatica, F. grandifolia); Birch; (e.g. Betula populifolia, B. nigra, B. papyrifera, B. lenta, B. alleghaniensis/B. lutea, B. pendula, B. pubescens); Blackbean; Blackwood; Bocote; Boxelder; Boxwood; Brazilwood; Bubinga; Buckeye (e.g. Aesculus hippocastanum, Aesculus glabra, Aesculus flava/Aesculus octandra); Butternut; Catalpa; Cherry (e.g. Prunus serotina, Prunus pennsylvanica, Prunus avium); Crabwood; Chestnut; Coachwood; Cocobolo; Corkwood; Cottonwood (e.g. Populus balsamifera, Populus deltoides, Populus sargentii, Populus heterophylla); Cucumbertree; Dogwood (e.g. Cornus florida, Cornus nuttallii); Ebony (e.g. Diospyros kurzii, Diospyros melanida, Diospyros crassiflord); Elm (e.g. Ulmus americana, Ulmus procera, Ulmus thomasii, Ulmus rubra, Ulmus glabra); Eucalyptus; Greenheart; Grenadilla; Gum (e.g. Nyssa sylvatica, Eucalyptus globulus, Liquidambar styraciflua, Nyssa aquatica); Hickory (e.g. Carya alba, Carya glabra, Carya ovata, Carya laciniosa); Hornbeam; Hophornbeam; Ipe; Iroko; Ironwood (e.g. Bangkirai, Carpinus caroliniana, Casuarina equisetifolia,

Choricbangarpia subargentea, Copaifera spp., Eusideroxylon zwageri, Guajacum officinale, Guajacum sanctum, Hopea odorata, Ipe, Krugiodendron ferreum, Lyonothamnus lyonii (L. floribundus), Mesua ferrea, Olea spp., Olneya tesota, Ostrya virginiana, Parrotia persica, Tabebuia serratifolia); Jacaranda; Jotoba; Lacewood; Laurel; Limba; Lignum vitae; Locust (e.g. Robinia pseudacacia, Gleditsia triacanthos); Mahogany; Maple (e.g. Acer saccharum, Acer nigrum, Acer negundo, Acer rubrum, Acer saccharinum, Acer pseudoplatanus);

Meranti; Mpingo; Oak (e.g. Quercus macrocarpa, Quercus alba, Quercus stellata, Quercus bicolor, Quercus virginiana, Quercus michauxii, Quercus prinus, Quercus muhlenbergii, Quercus chrysolepis, Quercus lyrata, Quercus robur, Quercus petraea, Quercus rubra, Quercus velutina, Quercus laurifolia, Quercus falcata, Quercus nigra, Quercus phellos, Quercus texana); Obeche; Okoume; Oregon Myrtle; California Bay Laurel; Pear; Poplar (e.g. P. balsamifera, P. nigra, Hybrid Poplar {Populus x canadensis)); Ramin; Red cedar;

Rosewood; Sal; Sandalwood; Sassafras; Satinwood; Silky Oak; Silver Wattle; Snakewood; Sourwood; Spanish cedar; American sycamore; Teak; Walnut (e.g. Juglans nigra, Juglans regia); Willow (e.g. Salix nigra, Salix alba); Yellow poplar (Liriodendron tulipifera);

Bamboo; Palmwood; and combinations/ hybrids thereof.

For example, hardwood feedstocks for the present invention may be selected from Acacia, Aspen, Beech, Eucalyptus, Maple, Birch, Gum, Oak, Poplar, and - - combinations/hybrids thereof. The hardwood feedstocks for the present invention may be selected from Populus spp. (e.g. Populus tremuloides), Eucalyptus spp. (e.g. Eucalyptus globulus), Acacia spp. (e.g. Acacia dealbata), and combinations/hybrids thereof.

Compositions of the present disclosure comprising hardwood biomass may comprise about 26% or greater, about 28% or greater, about 30% or greater, about 32% or greater, about 34% or greater, about 35% or greater, about 36% or greater, lignin material.

Compositions of the present disclosure comprising hardwood biomass may comprise about 50% or less, about 45% or less, about 40% or less, about 38% or less, about 36% or less, about 34% or less, carbohydrate.

Softwood feedstocks include Araucaria (e.g. A. cunninghamii, A. angustifolia, A. araucana); softwood Cedar (e.g. Juniperus virginiana, Thuja plicata. Thuja occidentalis, Chamaecyparis thyoides Callitropsis nootkatensis); Cypress (e.g. Chamaecyparis, Cupressus Taxodium, Cupressus arizonica, Taxodium distichum, Chamaecyparis obtusa,

Chamaecyparis lawsoniana, Cupressus semperviren); Rocky Mountain Douglas fir;

European Yew; Fir (e.g. Abies balsamea, Abies alba, Abies procera, Abies amabilis);

Hemlock (e.g. Tsuga canadensis, Tsuga mertensiana, Tsuga heterophylla); Kauri; Kaya; Larch (e.g. Larix decidua, Larix kaempferi, Larix laricina, Larix occidentalis); Pine (e.g. Pinus nigra, Pinus bandana, Pinus contorta, Pinus radiata, Pinus ponderosa, Pinus resinosa, Pinus sylvestris, Pinus strobus, Pinus monticola, Pinus lambertiana, Pinus taeda, Pinus palustris, Pinus rigida, Pinus echinata); Redwood; Rimu; Spruce (e.g. Picea abies, Picea mariana, Picea rubens, Picea sitchensis, Picea glauca); Sugi; and

combinations/hybrids thereof.

For example, softwood feedstocks which may be used herein include cedar; fir; pine; spruce; and combinations/hybrids thereof. The softwood feedstocks for the present invention may be selected from loblolly pine (Pinus taeda), radiata pine, jack pine, spruce (e.g., white, interior, black), Douglas fir, Pinus silvestris, Picea abies, and combinations/hybrids thereof. The softwood feedstocks for the present invention may be selected from pine (e.g. Pinus radiata, Pinus taeda); spruce; and combinations/hybrids thereof.

Compositions of the present disclosure comprising softwood biomass may comprise about 35% or greater, about 36% or greater, about 38% or greater, about 40% or greater, about 42% or greater, about 44% or greater, about 46% or greater, lignin material.

Compositions of the present disclosure comprising softwood biomass may comprise about 65% or less, about 60% or less, about 55% or less, about 50% or less, about 48% or less, about 46% or less, carbohydrate. - -

Annual fibre feedstocks include biomass derived from annual plants, plants which complete their growth in one growing season and therefore must be planted yearly. Examples of annual fibres include: flax, cereal straw (wheat, barley, oats), sugarcane bagasse, rice straw, corn stover, corn cobs, hemp, fruit pulp, alfalfa grass, esparto grass, switchgrass, palm fibre/residue, miscanthus, giant reed, and combinations/hybrids thereof. Industrial residues like corn cobs, fruit peals, seeds, etc. may also be considered annual fibres since they are commonly derived from annual fibre biomass such as edible crops and fruits. For example, the annual fibre feedstock may be selected from wheat straw, corn stover, corn cobs, sugar cane bagasse, and combinations/hybrids thereof.

Compositions of the present disclosure comprising annual fibre biomass may comprise about 30% or greater, about 32% or greater, about 34% or greater, about 35% or greater, about 36% or greater, about 38% or greater, about 40% or greater, lignin material.

Compositions of the present disclosure comprising annual fibre biomass may comprise about 50% or less, about 25% or less, about 24% or less, about 22% or less, about 20% or less, about 18% or less, carbohydrate.

The present disclosure provides in part methods, processes, and systems for the treatment of the lignaceaus residue of a biorefinery process. The present methods, processes, and systems comprise the organosolv treatment of the lignaceaus residue of a biorefinery. For example, the present method, process or system may comprise the organosolv treatment of the lignaceaus residue of a acid hydrolysis-type biorefinery. For example, the present method, process or system may comprise the organosolv treatment of the lignaceaus residue of a biorefinery using a dilute acid pretreatment-type. For example, the present method, process or system may comprise the organosolv treatment of the lignaceaus residue of dilute ammonia pretreatment-type biorefinery. For example, the present method, process or system may comprise the organosolv treatment of the lignaceaus residue of steam explosion-type biorefinery.

In an embodiment the present process comprises:

a. Obtaining a lignocellulosic material;

b. Performing a steam-explosion treatment process on the lignocellulosic

material to obtain at least a carbohydrate-rich stream and a lignaceaus residue; c. Optionally, further processing the carbohydrate-rich stream to generate sugars and/or fermentation products;

d. Separating at least a part of the lignaceaus residue; e. Mixing at least a portion of the separated lignaceaus residue with an organic solvent to form an extraction mixture;

f. Subjecting the mixture to an elevated temperature and pressure and,

optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

In an embodiment the present process comprises:

a. Obtaining a lignocellulosic material;

b. Performing an concentrated acid-hydrolysis treatment process on the

lignocellulosic material to obtain a carbohydrate-rich stream and a lignaceaus residue;

c. Optionally, further processing the carbohydrate stream to generate sugars and/or fermentation products;

d. Separating at least a part of the solid lignaceaus residue;

e. Mixing at least a portion of the lignaceaus residue with an organic solvent to form an extraction mixture;

f. Subjecting the mixture to an elevated temperature and pressure and,

optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

In an embodiment the present process comprises:

a. Obtaining a lignocellulosic material;

b. Performing a dilute acid treatment process on the lignocellulosic material to obtain a carbohydrate-rich stream and a lignaceaus residue;

c. Optionally, further processing the carbohydrate stream to generate sugars and/or fermentation products;

d. Separating at least a part of the solid lignaceaus residue;

e. Mixing at least a portion of the lignaceaus residue with an organic solvent to form an extraction mixture;

f. Subjecting the mixture to an elevated temperature and pressure and,

optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

In an embodiment the present process comprises: - - a. Obtaining a lignocellulosic material;

b. Performing a ammonia treatment process on the lignocellulosic material to obtain a carbohydrate stream and a lignaceaus residue;

c. Optionally, further processing the carbohydrate-rich stream to generate sugars and/or fermentation products;

d. Separating at least a part of the solid lignaceaus residue;

e. Mixing at least a portion of the lignaceaus residue with an organic solvent to form an extraction mixture;

f. Subjecting the mixture to an elevated temperature and pressure and,

optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

In an embodiment the present process comprises:

a. Obtaining a lignocellulosic material;

b. Performing a dilute ammonia treatment process on the lignocellulosic material to obtain a carbohydrate stream and a lignaceaus residue;

c. Optionally, further processing the carbohydrate-rich stream to generate sugars and/or fermentation products;

d. Separating at least a part of the solid lignaceaus residue;

e. Mixing at least a portion of the lignaceaus residue with an organic solvent to form an extraction mixture;

f. Subjecting the mixture to an elevated temperature and pressure and,

optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

In an embodiment the present process comprises:

a. Obtaining a lignocellulosic material;

b. Performing a lime treatment process on the lignocellulosic material to obtain a carbohydrate stream and a lignaceaus residue;

c. Optionally, further processing the carbohydrate-rich stream to generate sugars and/or fermentation products;

d. Separating at least a part of the solid lignaceaus residue;

e. Mixing at least a portion of the lignaceaus residue with an organic solvent to form an extraction mixture; f. Subjecting the mixture to an elevated temperature and pressure and, optionally, acid;

g. Maintaining the elevated temperature and pressure for a period; and h. Recovering aromatic compounds from the solvent.

The present compositions may be subjected to organosolv processing. Any suitable organosolv processing conditions may be used herein. Various organosolv processes are known in the art. See, for example, US Patent 4,100,016; US Patent 4,764,596; US Patent 5,681 ,427; US Patent 7,465,791 ; US Patent Application 2009/0118477; US Patent

Application 2009/0062516; US Patent Application 2009/00669550; or US Patent 7,649,086. Four major "organosolv" processes are known. The first method uses ethanol/water pulping (aka the Lignol® (Alcell®) process); the second method uses alkaline sulphite anthraquinone methanol pulping (aka the "ASAM" process); the third process uses methanol pulping followed by methanol, NaOH, and anthraquinone pulping (aka the "Organocell" process); the fourth process uses acetic acid/hydrochloric acid or formic acid pulping (aka the "Acetosolv" and "Formacell" processes). A description of the Lignol® Alcell® process can be found, for example, in US Patent 4,764,596 or Kendall Pye and Jairo H. Lora, The Alcell™ Process, Tappi Journal, March 1991, pp. 1 13-117. Various disclosures exemplified by US Patent No. 7,465,791 and PCT Patent Application Publication No. WO 2007/129921, describe modifications to the Lignol® Alcell® organosolv (all references are herein incorporated by reference). The process generally comprises pulping or pre-treating a fibrous biomass feedstock with primarily an ethanol/water solvent solution under conditions that include: (a) 60% ethanol/40% water (w/w), (b) a temperature of about 180°C to about 210°C, and (c) pressure of about 20 atm to about 35 atm. In the present disclosure these conditions are referred to as "Alcell™ conditions".

While not wishing to be bound by theory it is believed that the present compositions may be suitable for processing at lower temperatures and pressures than typically used in organosolv extraction processes. In addition, it is believed that the required treatment time may be reduced. These factors can enhance the economic viability of the process.

The present organosolv processing may be adapted depending on the desired output. For example, the process may be a "Low Temperature" process. The present compositions may be subjected to pressures of about 18 bar or less. For example, 17 bar or less, 16 bar or less, 15 bar or less. The present compositions may be subjected to a temperature of from about 130°C or greater, 132°C or greater, 134°C or greater, 136°C or greater, 138°C or greater, 140°C or greater, 142°C or greater, 144°C or greater, 146°C or greater, 148°C or greater, 150°C or greater, 152°C or greater, 154°C or greater. The present compositions herein may be subjected to a temperature of from about 170°C or less, 168°C or less, 166°C or less, 165°C or less. For example, the present compositions may be subjected to a temperature of from about 155°C to about 165°C. The present compositions may be subjected to the elevated temperature for about 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, 70 minutes or more, 75 minutes or more, 80 minutes or more, 95 minutes or more, 100 minutes or more, 105 minutes or more, 110 minutes or more, 115 minutes or more, 120 minutes or more. The present compositions may be subjected to the elevated temperature for about 200 minutes or less, 195 minutes or less, 190 minutes or less, 185 minutes or less, 180 minutes or less. For example, the present compositions may be subjected to the elevated temperature for about 120 to about 180 minutes.

The present organosolv processing may be adapted depending on the desired output. The present composition preferably is subjected to pressures of about 1 bar or greater, about 5 bar or greater, about 10 bar or greater, about 15 bar or greater, about 18 bar or greater. For example, about 19 bar, about 20 bar, about 21 bar, about 22 bar, about 23 bar, about 24 bar, about 25 bar, about 26 bar, about 27 bar, about 28 bar, about 29 bar, or greater. The present composition preferably is subjected to temperatures of from about 150°C or greater, about 160°C or greater, about 170°C or greater, about 180°C or greater, about 190°C or greater, about 200°C or greater, about 210°C or greater. The present composition preferably is subjected to the elevated temperature for about 5 minutes or more, about 10 minutes or more, about 15 minutes or more, about 20 minutes or more, about 25 minutes or more, about 30 minutes or more, about 35 minutes or more, about 40 minutes or more, about 45 minutes or more, about 50 minutes or more, about 55 minutes or more, about 60 minutes or more, about 65 minutes or more. The present composition preferably is subjected to the elevated temperature for about 300 minutes or less, about 270 minutes or less, about 240 minutes or less, about 210 minutes or less, about 180 minutes or less, about 150 minutes or less, about 120 minutes or less. For example, the present composition can be subjected to the elevated temperature for about 30 to about 100 minutes. The present organosolv extraction may be a 'vapor' extraction. That is, an extraction where the solid is not fully submerged in the solvent mixture and the extraction is carried out by both a liquid and vapor phases.

The aromatic compounds may be recovered by any suitable means. For example, the solvent may be evaporated to precipitate the compounds. The compounds in the spent liquor can be recovered chromatographically followed by recrystallization or precipitation, dilution of the spent liquor with acidified water followed by filtration, centrifugation or tangential filtration, liquid/liquid extraction, among others.

The present aromatic compounds may be recovered in a single step or may be recovered in stages to provide compounds having different properties. The precipitated aromatic compounds do not seem to be sticky and are generally easy to filter.

The present compounds may be recovered for the present compositions by quenching the cooked mixture. For example, cold water may be added to the mixture in a ratio of 2 or more to 1 (H ₂ 0 to extraction mixture).

The present disclosure provides lignin derivatives which give surprisingly good properties when formulated in phenol formaldehyde resins. While not wishing to be bound by theory it is believed that the present aromatic compounds have a surprisingly low z-average molecular weight (Mz). The present disclosure provides lignin derivative having a Mz of about 3500 or less, about 3000 or less, about 2750 or less, about 2500 or less.

The present disclosure provides lignin derivatives having a number average molecular weight (Mn) of about 3000 or less, about 2000 or less, about 1000 or less, about 900 or less, about 800 or less, about 700 or less, about 600 or less.

The present disclosure provides lignin derivatives having a weight average molecular weight (Mw) of about 2000 or less, about 1800 or less, about 1600 or less, about 1400 or less, about 1300 or less.

The present disclosure provides lignin derivatives having a polydispersity of from about 0.1 to about 8; about 0.5 to about 4; from about 0.6 to about 3; from about 0.7 to about 2; from about 0.8 to about 1.5; from about 0.9 to about 1.2; about 1.

The present aromatic compounds may be used for a variety of applications such as, for example, phenol formaldehyde resins, phenol furan resins, in particular foundry resins, urea formaldehyde resins, epoxy resins, other resol or novolac resins, other resins, environmental remediation of hydrocarbon spills, remediation of other contamination, waste water treatment for recycling or reclaiming, antioxidants, wax emulsions, carbon fibres, surfactants, coatings, among others.

The present aromatic compounds may be used as precursors for furan-phenolic foundry resins or other furan resins. In foundry resins furfuryl alcohol is used in the synthesis of furan resins and the present aromatic compounds could replace phenol and/or some of the furfuryl alcohol or the resin precursor itself synthesized by reacting phenol with furfuryl alcohol. It is contemplated that any embodiment discussed in this specification can be implemented or combined with respect to any other embodiment, method, composition or aspect of the invention, and vice versa.

All citations are herein incorporated by reference, as if each individual publication was specifically and individually indicated to be incorporated by reference herein and as though it were fully set forth herein. Citation of references herein is not to be construed nor considered as an admission that such references are prior art to the present invention.

The invention includes all embodiments, modifications and variations substantially as hereinbefore described and with reference to the examples and figures. It will be apparent to persons skilled in the art that a number of variations and modifications can be made without departing from the scope of the invention as defined in the claims. Examples of such modifications include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way.

The present invention will be further illustrated in the following examples. However it is to be understood that these examples are for illustrative purposes only, and should not be used to limit the scope of the present invention in any manner.

EXAMPLES

Samples of lOOg of lignaceaus residue from a steam-explosion process followed by simultaneous saccharification and fermentation was obtained. The samples contained approximately 62-66% lignin and 25-26% carbohydrate. The mixed with an organic solvent (aqueous ethanol) to form an extraction mixture. The residue comprised The composition was placed in a vessel (Parr reactor, 2L) and subjected to an elevated temperature of 100°C, 165°C, or 200°C for a varying amount of time. The resultant extraction liquor was filtered to separate the solid residue from the liquid residue. Lignin derivatives were precipitated from the extraction liquor by drop-wise precipitation in 2x amount of water. The conditions/results are shown in the tables below.

EtOH

L:Resi Precipitated

in Acid, Final Residue Solid due Pressure Time Lignin

liquid %of liquor T(°C) (% of Lignin

(w/dry (psi) (min) (% of

% residue PH feestock) Recovered w) feestock)

(w/w)

Dry Substrate

1

1.0(1) 7.8:1 50 2.0 173 3.1 165 120 88.1 7.9 14.0

2

1.1(1) 5:1 57 2.5 400 3.0 200 80 71.7 14.6 25.8

Crushed Wet Substrate

3

1.2(1) 10:1 57 2.5 400 3.4 200 80 64.3 19.0 33.6

4

1.4(1) 10:1 70 1.5 29 3.96 100 120 73.8 11.2 19.8

5

1.5(l)stirred 10:1 70 3.0 187 3.33 165 120 64.4 16.4 29.0

6

1.6( 1 )stirred 10:1 70 4.0 186 2.88 165 120 62.5 19.5 34.4

Precipitated lignin (PL) recov/ Glc in AIL % ASL Ash in Lignin in

PL Acid dissolve PL (w/w) in PL PL PL Mn Mw Mz D

AIL Tg Number d (%) PL (%) (%) (% PL)

(%)

¹ 2.2 0.18 93.85 2.07 0.00 n/a 95.9 1001 1734 2952 1.73 122.6 18.6

2 0.86 0.18 94.15 2.37 0.03 n/a 96.5 914 1794 3274 1.96 124.2 15.7

3 0.98 0.09 92.45 2.38 0.00 0.04 94.8 946 1768 3072 1.87 117.7

4 0.84 0.20 93.63 1.46 n/a 0.02 95.1 20.5

5 0.73 0.32 93.55 1.41 n/a 0.00 95.0 21.5

6 0.82 0.16 92.73 1.26 n/a 0.00 94.0 22.1

COOR-

CO-nc CO-conj CO-tot OH-pr OH-sec OH-al OH-ph OH-tot al feedstock sample mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g

Lignaceaus

Residue RT extraction 0.53 0.69 1.22 3.17 2.72 5.89 5.06 10.94 1.56

1 -2( 1 ) 0.39 0.47 0.86 1.33 0.44 1.78 4.94 6.72 0.78

COOR- COOR- conj tot OMe O-Et b-5 b-b b-O-4

feedstock sample mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g mmol/g S/G DC

Lignaceaus

Residue RT extraction 0.17 1.72 8.25 0.00 0.25 0.33 0.72 1.63 26

1 -2( 1 ) 0.22 1.00 6.97 0.28 0.28 0.22 0.33 1.32 40

Chemical nature of the extracted lignins is similar to that of high purity lignin produced from native wood extractions.