Patent Publication Number: US-2013252292-A1

Title: Biomass extraction process

Description:
This application is a continuation of PCT/CA2011/001021, filed Sep. 7, 2011; which claims the priority of U.S. Provisional Application No. 61/380,675, filed Sep. 7, 2010. The contents of the above-identified applications are incorporated herein by reference in their entireties. 
    
    
     FIELD 
     This disclosure relates to an organosolv process for the extraction of materials from lignocellulosic biomass. This disclosure further relates to the chemicals and their derivatives extracted from biomass, uses, apparatus, methods, and the like. In an embodiment the material extracted is levulinic acid. 
     BACKGROUND 
     For environmental, economic, and resource security reasons, there is an increasing 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 variety of ways. In particular, the cellulose and hemicellulose in plant matter may desirably be separated out and fermented into fuel grade alcohol, synthetic biodiesel, fuel grade butanol, xylitol, succinic acid, and other useful materials. And the lignin component, which makes up a significant fraction of species such as trees and agricultural waste, has huge potential as a useful source of aromatic chemicals for numerous industrial applications. 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. 
     Organosolv processes are well known in the art. See, for example, U.S. Pat. No. 4,100,016; U.S. Pat. No. 4,764,596; U.S. Pat. No. 5,681,427; U.S. Pat. No. 7,465,791; US Patent Application 2009/0118477; US Patent Application 2009/0062516; US Patent Application 2009/00669550; or U.S. Pat. No. 7,649,086. Four major “organosolv” pulping processes have been tested on a trial basis. 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 U.S. Pat. No. 4,764,596 or Kendall Pye and Jairo H. Lora, The Alcell™ Process, Tappi Journal, March 1991, pp. 113-117 (the documents 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. Derivatives of native lignin are fractionated from the biomass into the pulping liquor which also receives solubilised hemicelluloses, other carbohydrates and other components such as resins, phytosterols, terpenes, organic acids, phenols, carbohydrate degradation products and derivatives of these products such as levulinic acid, formic acid, 5-hydromethyl furfural (5-HMF), furfural, and tannins. Organosolv pulping liquors comprising the fractionated derivatives of native lignin and other components from the fibrous biomass feedstocks, are often called “black liquors”. Various disclosures exemplified by U.S. Pat. No. 7,465,791 and PCT Patent Application Publication No. WO 2007/129921, describe modifications to the Lignol® Alcell® organosolv. 
     Organosolv processes, particularly the Lignol® Alcell® process, can be used to separate highly purified lignin derivatives and other useful materials from biomass. Such processes may therefore be used to exploit the potential value of the various components making up the biomass. 
     Despite these advantages, organosolv processes have to date met with limited commercial success. This may be due to a variety of reasons such as, for example, the fact that organosolv extraction typically involves higher pressures than other industrial methods and are thus more complex and energy intensive. Moreover, organosolv extraction processes can result in the production of self-precipitated lignins or lignins with poor solubility in the cooking liquor (SPLs), particularly when using softwood biomass but also when other types of biomass are used. SPLs can attach to metal surfaces causing equipment to be fouled and are difficult to remove. Furthermore, the necessity of restricting operating conditions to those which produce a fermentable carbohydrate stream or a high quality fibre has limited the type and utility of the lignin stream. Consequently, although large scale commercial viability was demonstrated many years ago from a technical and operational perspective, organosolv biomass extraction has not, to date, been widely adopted. 
     Due to toxicity, regulatory, renewability or supply security issues many manufacturers of chemical products are seeking alternatives to their current technologies. For example, formaldehyde-based resins such as phenol formaldehyde (PF), urea formaldehyde and melamine formaldehyde are extremely common and used for a variety of purposes such as manufacturing of housing and furniture panels such as medium density fibreboard (MDF), oriented strand board (OSB), plywood, and particleboard. Concerns about the toxicity of formaldehyde have led regulatory authorities to mandate a reduction of formaldehyde emissions (e.g. California Environmental Protection Agency Airborne Toxic Control Measure (ATCM) to Reduce Formaldehyde Emissions from Composite Wood Products, Apr. 26, 2007). It has been proposed to use lignin-cellulosic materials in PF resins (see, for example, U.S. Pat. No. 5,173,527). 
     However, large-scale commercial application of the extracted lignin derivatives, particularly those isolated in traditional pulping processes employed in the manufacture of pulp and paper, has been limited due to, for example, the inconsistency of their chemical and functional properties. This inconsistency can be due to changes in feedstock supplies or the particular extraction/generation/recovery conditions required to keep the fibre quality in accordance with market demands. These issues are further complicated by the variety of the molecular structures of lignin derivatives produced by the various extraction methods and the difficulty in performing reliable routine analyses of the structural conformity and integrity of recovered lignin derivatives. 
     SUMMARY OF THE INVENTION 
     The present disclosure provides a process for the extraction of materials from lignocellulosic biomass. Such materials may include lignin derivatives as well as process-derived bioaromatic molecules (PBMs) which can be defined as ensembles of organic molecules, primarily aromatic in nature, which are derived from biomass. Non-limiting examples of PBMs are products of condensation between furan derivatives and levulinic acids, phenol or phenol-like monomers or oligomers with ethanol, furan, and levulinates or formiates, and others. 
     An embodiment of the present process comprises treating a lignocellulosic biomass in the presence of a solvent and under conditions suitable to form a slurry. The process separates at least a part of the aromatic compounds from the biomass, such aromatic compounds being useful for a variety of industrial purposes. 
     The present disclosure further provides a jacketed pressure reactor equipped with or without mechanical mixing for extraction of materials from a lignocellulosic biomass. 
     The present disclosure further provides certain compounds that may be extracted from lignocellulosic by means of the present process. 
     The present disclosure further provides certain uses of compounds that may be extracted from lignocellulosic by means of the present process. 
     The present disclosure further provides methods for improving the yield of valuable chemicals produced as the result of a biomass extraction process. 
     As used herein, the term “biorefining” refers to the production of bio-based products (e.g. lignin derivatives) from biomass. 
     As used herein, the term “organosolv” refers to bio-refinery processes wherein the biomass is subject to an extraction step using an organic solvent at an elevated temperature. 
     As used herein, the term “native lignin” refers to lignin in its natural state, in plant material. 
     As used herein, the terms “lignin derivatives” and “derivatives of native lignin” refer to lignin material extracted from lignocellulosic biomass. Usually, such material will be a mixture of chemical compounds that are generated during the extraction process. 
     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. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  shows a typical Lignol® lignin (Alcell®) organosolv process; 
         FIG. 2  shows a flow diagram of an embodiment of the present process; 
         FIGS. 3  shows crude oil remediation with MAC-I and MAC-II; 
         FIG. 4  shows GC-MS Analysis of the FILTRATE (Agilent 7000B GC-MS); 
         FIG. 5  shows LC/QTOF Analysis of the FILTRATE (ES+TOF, SB-CN Column); 
         FIG. 6  shows an overlaid chromatogram for compounds listed in Table 10; 
         FIG. 7  shows  13 C quantitative NMR of the CONCENTRATE from aspen; 
         FIG. 8  shows  13 C quantitative NMR of the PURIFIED MAC-I from aspen; 
         FIG. 9  shows  13 C Quantitative NMR of the MAC-II from aspen. 
     
    
    
     DETAILED DESCRIPTION 
     The present disclosure provides an extraction process. The present disclosure provides a process for the extraction of materials from lignocellulosic biomass. Such materials include lignin derivatives as well as other process-derived bioaromatic materials (PBMs) which can be defined as ensembles of organic molecules, primarily aromatic in nature, which are derived from biomass (e.g. mixes of aromatic compounds (MACs)). These materials may be useful as potential to replacements for one or more than one petrochemical in industrial chemical products and may also potentially be used to enhance the performance of the end-chemical products. Examples of PBMs include the products of condensation between furan derivatives and levulinic acids, phenol or phenol-like monomers or oligomers with ethanol, furan, and levulinates or formiates, and others. The present disclosure further provides a method of producing levulinic acid with a certain yield. The present disclosure further provides a method of making ethyl levulinate via a biomass extraction process. 
     The present process comprises mixing an organic solvent with a lignocellulosic biomass under such conditions that a slurry is formed. As used herein, the term “slurry” refers to particles of biomass at least temporarily suspended in a solvent. 
     In one embodiment the present process comprises:
         (a) placing a lignocellulosic material in an extraction vessel;   (b) mixing the lignocellulosic material with an organic solvent to form an extraction mixture;   (c) subjecting the mixture to a temperature and pressure such that a slurry is formed;   (d) maintaining the elevated temperature and pressure for a period;   (e) recovering aromatic compounds from the solvent.       

     It has been found that the present process produces high yields of precipitable compounds suitable for a range of applications. The slurries produced in the present process are easy to pump and filter in order to separate the precipitable substances from the insoluble material. Typical organosolv processes involve liquids/solids separation of fibrous biomass material and spent liquor or liquid stream after the pretreatment stage, washing of the fibrous solids, circulation of pretreatment liquor through a heat exchanger, and flashing of the spent liquor. The present process requires none of these steps although a flashing step may optionally be included. In addition, the present process can be run with the help of mechanical mixing which facilitates heat and mass transfer and allows for faster reaction rates and higher yields. The mechanical mixing is not generally started at the beginning of the process but once the biomass has been partially slurried to avoid excessive energy consumption that would otherwise be needed to achieve mixing. 
     In one embodiment the present process comprises:
         (a) placing a lignocellulosic material in an extraction vessel;   (b) mixing the lignocellulosic material with an organic solvent and an acid catalyst to form an extraction mixture;   (c) subjecting the mixture to a temperature and pressure such that a slurry is formed;   (d) maintaining the elevated temperature and pressure for a period;   (e) separating at least part of the liquid potion of the slurry from the insoluble portion;   (f) recovering aromatic compounds from the solvent.       

     The extraction mixture slurry herein preferably has a viscosity of 1500 cps or less, 1000 cps or less, 800 cps or less, 600 cps or less, 400 cps or less, 200 cps or less, 100 cps or less (viscosity measurements made using viscometer Viscolite 700 (Hydramotion Ltd., Malton, York YO17 6YA England). 
     The present extraction mixture 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 extraction mixture 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 extraction mixture 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 extraction mixture 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 extraction mixture can be subjected to the elevated temperature for about 30 to about 100 minutes. 
     The present extraction mixture preferably comprise about 40% or more, about 42% or more, about 44% or more, about 46% or more, about 48% or more, about 50% or more, about 52% or more, about 54% or more, organic solvent such as ethanol. 
     The present extraction mixture preferably comprises about 80% or less, about 70% or less, about 68% or less, about 66% or less, about 64% or less, about 62% or less, about 60% or less, organic solvent such as ethanol. 
     For example, the present extraction mixture may comprise about 45% to about 65%, about 50% to about 60% organic solvent such as ethanol. 
     The present extraction mixture preferably has a pH of about 1.0 or greater, about 1.2 or greater, about 1.4 or greater, about 1.6 or greater, about 1.8 or greater. The present extraction mixture preferably has a pH of from about 3 or lower, about 2.8 or lower, about 2.6 or lower, about 2.4 or lower, about 2.2 or lower. For example, the extraction mixture may have a pH of from about 1.5 to about 2.5. For example, from about 1.6 to about 2.3. 
     The pH of the extraction mixture may be adjusted by any suitable means. For example, from about 0.1% or greater, about 0.2% or greater, about 0.3% or greater, about 0.4% or greater, by weight, of acid may be added to the extraction mixture. From about 5% or lower, about 4% or lower, about 3% or lower, by weight, of acid (based on dry weight wood) may be added to the biomass. The starting pH of the extraction mixture is the pH of the mixture of the extraction solution after it has been incubated with the biomass for a few minutes. Some biomass species, such as corn stover, are basic and can partially neutralize the acid while some biomass species are acidic and can further lower the pH. 
     The weight ratio of solvent to biomass in the present extraction mixture may be from about 10:1 to about 4:1, about 9:1 to about 4.5:1, about 8:1 to about 5:1, from about 7:1 to about 5.5:1. For example the ratio may be about 6:1. 
     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. For example, the solvent may be a mix of ethanol &amp; water. The solvent mix might be preheated before being added to the extraction vessel. 
     The present biomass may optionally be subjected to several solvent washes prior to or even after the aforementioned extraction process. For example, such washes may be under milder process conditions than the above extraction process. These solvent washes may be used to remove useful compounds from the biomass and/or to imbue the compounds that result from the organosolv extraction process with certain properties. These additional solvent washes may utilize any suitable solvent such as, for example, water, acetone, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, acetonitrile, dimethyl sulphoxide, hexane, diethyl ether, methylene chloride, carbon tetrachloride, formic acid, acetic acid, formamide, benzene, methanol, ethanol, propanol, butanol, catechol, or mixtures thereof. 
     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 l); 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 crassiflora ); 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; Ipê; 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 ); Jacarand{acute over (;)}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; Okoumé; Oregon Myrtle; California Bay Laurel; Pear; Poplar (e.g. P. balsamifera, P. nigra, Hybrid Poplar ( Populus×canadensi )); 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. 
     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 banksiana, 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. 
     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, 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. 
     Typical organosolv processes can be very sensitive to biomass quality requiring higher quality feedstocks and avoiding certain feedstocks which result in fouling of the apparatus. The present process seems have a reduced sensitivity and thus does not suffer from the same restrictions in terms of biomass and may allow for processing low value biomass residues such as sawdust, tree needles, hog fuel, bark, newspaper, fruit peels, rice hulls, and low quality wood chips among others. 
     The liquid portion of the extraction mixture may be separated from the solid portion by any suitable means. For example, the slurry may be passed through an appropriately sized filter, centrifugation followed by decanting or pumping of the supernatant, tangential ultrafiltration, evaporation alone or solvent extraction followed by evaporation, among others. 
     The aromatic compounds may be recovered from the liquid portion of the extraction mixture 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 extraction mixture 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 a process of producing PBMs in high yields. For example, the present disclosure can provide yields of PBMs (MAC-I, MAC-II) greater than the theorectical maximum of lignin in the biomass feedstock material as calculated on a weight percentage. The present yield of PBMs may be about 90%, about 95%, about 100%, about 105%, about 110%, about 115%, or greater, of the theoretical maximum yield of lignin in the biomass. That is, the yield of PBMs is approaching or greater than that of the theoretical maximum yield of lignin. The yield of PBMs and the theoretical maximum yield of lignin may be calculated by methods well known to the person of skill in the art. 
     The present disclosure provides lignin derivatives which have advantageous z-average molecular weights. While not wishing to be bound by theory it is believed that the present aromatic compounds having low z-average molecular weight (Mz) give surprisingly good properties when formulated in phenol formaldehyde resins. 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 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 fibers, 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. 
     The present dissolved or slurried biomass contains extractives, carbohydrates, modified phenolic compounds, modified carbohydrates, carbohydrate &amp; lignin degradation products, ethyl levulinate, and/or ethyl formiate etc. This mixture may be concentrated off the filtrate, for example, by evaporation during the solvent recovery process or after the solvent recovery process (after distilling off the solvent) producing a concentrate. Ethyl levulinate can be recovered by vacuum distillation since its boiling point is 93-94° C./18 mmHg. The distilled product can be useful for cosmetic applications or as a raw material for chemical reactions including conversion into a biofuel such as methylTHF or can be used as is as a fuel oxygenating agent, it can also be used in the synthesis of renewable polymers such as biodegradable ketals. 
     The present disclosure provides a method of producing high yields of levulinic acid, ethyl levulinate or other esters. For example, after biomass extraction unreacted levulinic acid and ethanol is present in significant quantities in the acidified water-diluted spent liquor. The stoichiometric yield of levulinic acid may be about 10 or greater, about 20% or greater, about 30% or greater, about 40% or greater, about 50% or greater, about 60% or greater, about 70% or greater. These substances may be reacted, for example, with a commercial esterase such as Novozym 435® (Novozymes North America Inc., Franklinton, N.C., USA) to produce ethyl levulinate. The esterase may be immobilised and therefore easy to recycle. The reaction is relatively fast (60-120 min) and can be run at 50-70° C. and atmospheric pressure. The pH of the diluted spent liquor can be adjusted for optimal enzyme performance. By operating at relatively low temperatures (50-70° C.), by-product formation can be kept to a minimum, reducing downstream purifications costs. Moreover if one would prefer not to distill the ethanol in the diluted spent liquor but to recover it in form of ethyl levulinate, one could add more levulinic acid to the diluted spent liquor (enrich it) and with the help of the esterase (e.g. Novozym 435®) convert ethanol and levulinic acid to ethyl levulinate. Ethyl levulinate is a more valuable product than ethanol. Other commercial enzymes may be used for this purpose including, for instance, Lipase QML6, Resinase HT, Lipozyme RM IM, Lipex 100L, Lipozyme TL IM or combinations thereof. Experimental esterases may be used such as those produced by fungal or bacterial strains e.g.  Bacillus subtilis, Trichoderma reesei, Penicillium funiculosum, Aspergillus niger, Chrysosporium lucknowense, Candida antarctica, Rhizomucor miehei, Thermomyces lanuginosa,  among others. For this purpose, one would preferentially use esterases or lipases showing esterase activity and tolerant to the presence of ethanol in the concentrations typical for water-diluted spent liquors (&gt;10% wt.). 
     The stoichiometric yield of levulinic acid (LVAC) from the cellulosic fraction of wood can be calculated from the relative molecular weights of the components in the following manner: 
     
       
         
           
             
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                    
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                    
                   
                       
                   
                    
                   of 
                    
                   
                       
                   
                    
                   glucose 
                    
                   
                       
                   
                    
                   in 
                    
                   
                       
                   
                    
                   units 
                    
                   
                       
                   
                    
                   in 
                    
                   
                       
                   
                    
                   cellulose 
                 
               
               = 
               
                 
                   
                     1 
                      
                     
                         
                     
                      
                     mol 
                      
                     
                       / 
                     
                      
                     mol 
                     × 
                     116 
                      
                     
                         
                     
                      
                     gm 
                      
                     
                       / 
                     
                      
                     mol 
                   
                   
                     164 
                      
                     
                         
                     
                      
                     gm 
                      
                     
                         
                     
                      
                     glucose 
                      
                     
                       / 
                     
                      
                     mol 
                      
                     
                         
                     
                      
                     cellulose 
                   
                 
                 = 
                 
                   70.7 
                    
                   % 
                 
               
             
           
         
       
     
     Previously observed LVAC yields from in Organolsolv production methods were less than 2% of theoretical. Even dedicated, non-Organosolv LVAC production processes project up to 40% of theoretical. The yields seen in this process are substantially above what was expected. 
     Another useful product present in the spent liquor is diphenolic acid which is currently considered a viable non-harmful substitute of the estrogenic bisphenol A (BPA) commonly used in manufacturing plastics. The concentrate or the filtrate before concentrating it can then be processed, for instance, by anaerobic digestion into biogas be burnt for energy production. The calorific value of the solids in this concentrate can be greater than 10,000 BTU/Lb solids according to oxygen calorimetric analysis. Alternatively, the concentrate can be used as a raw material for production of valuable fine or specialty chemicals. A range of valuables chemicals such as ethyl levulinates, ethyl formiates, levulinic acid, furfural, furfural derivatives and others have been detected in the concentrate. 
     The present disclosure provides for a lower temperature pre-organosolv stage that can be incorporated in the process so that valuable extractives are isolated from biomass before running the process under more severe liquefying conditions. For instance, when processing softwoods rosin acids and terpenoids can be produced at this stage by extraction with benzene or other alternative solvents. Pre-extraction can be particularly attractive when biorefining tree bark, leaves and needles. This pre-organosolv stage is particularly efficient when processing low quality feedstocks such as sawdust or tree needles and it can be run with the same solvent used in the biomass organosolv stage or with a different solvent depending on the targeted compounds to be extracted from the biomass. 
     The present disclosure provides an extraction vessel. The vessel preferably has a means for causing the circulation of the extraction mixture/slurry such as an internal mixing element and/or combined with injected steam. The vessel preferably has a means for causing the extraction mixture/slurry to be heated such as a heating jacket. The extraction vessel is preferably a jacketed pressure reactor. A jacketed pressure reactor has not been used for organosolv extraction due to its unsuitability for traditional organosolv processes. However, the ability to use off-the-shelf technology for organosolv extraction reduces the technical and commercial hurdles facing the adoption of the technology. 
     This present process may be deployed in a high pressure jacketed industrial chemical reactor made of an alloy resistant to hot acid such as Hastelloy® B® (registered trademark of Haynes International and it refers to nickel-molybdenum corrosion-resistant alloys) or Inconal® (registered trademark of Special Metals Corporation and it refers to a family of austenitic nickel-chromium-based superalloys) or in other high pressure steel reactors, such as stainless steel 316L, coated by Teflon® or other acid-resistant coatings or protected by electrochemical corrosion mitigation methods such as anodic and cathodic protection systems supplied by companies such as Corrosion Service (Markham, ON, Canada). The process can be deployed, for instance, in a readily available 250 gal Hastelloy B reactor or in a 3,000 gal scale Inconal reactor or in larger ones located in a fine chemicals facility. 
     The present process does not require several of the apparatus that is usually required in organosolv processes such as Accumulators, Recirculation Pumps &amp; Heaters, Pulp Washers, and Specialized Flow-Thru Digesters which represents a considerable capital saving. 
     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 
     Example 1 
     An extraction was performed according to the system of  FIG. 2 . 700 g of aspen ( Populus tremuloides ) chips were added to a 8-L 316L stainless steel jacketed pressure reactor (Parr Instrument Company, Moline, Ill., USA). 4200 g of solvent (57% ethanol, 42.75% tap H 2 0 and 0.25% H 2 SO 4 ) was added to the chips to give an extraction mixture having a 6:1 solvent to wood weight ratio. The pH of the mixture was 2.02. 
     The mixture was heated with hot oil circulated thru a jacket to a temperature of 200° C. The pressure inside the reactor was 29 bar. A low viscosity slurry was formed. The slurry was dischargeable by gravity thru a bottom discharge valve. The mixture was not stirred. The heating was maintained for 65 minutes. 
     After heating the extraction mixture was drained and filtered with a coarse paper filter. The solids recovered by filtration were air-dried, manually milled and stored in a sealed container. The yield of this first aromatic product (MAC-I) was about 14% of the total dry weight biomass processed. The filtered extraction liquid (spent liquor) was then diluted with acidified water (˜pH 2.0) at 4:1 weight water to spent liquor ratio causing the second mix of aromatic products (MAC-II) to precipitate. The precipitate was recovered by filtration similarly to MAC-I, air-dried and stored. The yield of MAC-II was about 22%. The total yield of recovered MACs was about 36%. The ethanol was recovered by rotary evaporation of the filtrate liquid yielding a 2× concentrated solution. This last step performed in a rectification column would be more efficient and would yield ˜1.2× concentrate. 
     Results 
     The aromatic compounds (MACs/PBMs) show lower average molecular weights (Mn), lower amounts of various oxygenated aliphatic structures (ethers and aliphatic hydroxyls) and lower S/G ratio than Alcell® lignins. 2D HSQC NMR analysis (not shown) and quantitative  13 C NMR spectra ( FIGS. 8 and 9 ) show incorporation of furfural and levulinic acid derivatives into MACs. Furfural, 5-ethoxymethyl furfural, ethyl levulinate, ethyl formiate and levulinic acid seem to be produced by the present process as the main products of carbohydrate degradation. 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Chemical Characteristics of Aspen MAC-I, Aspen MAC-II, and Purified Aspen MAC-I compared to Alcell ® Lignin 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 Product Yield 
                 Lignin Content 
                 CO_nc 
                 CO_conj 
                 CO_tot 
                 OH_pr 
                 OH_sec 
                 OH_al 
                 OH_ph 
                 OH_tot 
               
            
           
           
               
               
               
               
            
               
                   
                 % on wood 
                 % 
                 mmol/g 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 MAC I 
                 14.0 
                 69.7 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
               
               
                 MAC II 
                 22.0 
                 95.4 
                 1.33 
                 1.24 
                 2.58 
                 0.75 
                 nd 
                 0.75 
                 4.63 
                 5.38 
               
               
                 PURIFIED MAC I 
                 10.0 
                 91.4 
                 1.70 
                 1.02 
                 2.73 
                 1.14 
                 nd 
                 1.14 
                 2.91 
                 4.05 
               
               
                 ALCELL ® Lignin 
                 14.0 
                 97.0 
                 0.93 
                 0.58 
                 1.51 
                 1.35 
                 1.09 
                 2.44 
                 4.68 
                 7.12 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 COOR_al 
                 COOR_con 
                 COOR_tot 
                 OMe 
                 OEt 
                 S 
                 G 
                 H 
                   
               
            
           
           
               
               
               
            
               
                   
                 mmol/g 
                 SG_Ratio 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 MAC I 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
               
               
                 MAC II 
                 0.94 
                 0.13 
                 1.06 
                 4.34 
                 0.59 
                 1.84 
                 2.94 
                 0.63 
                 0.63 
               
               
                 PURIFIED MAC I 
                 0.91 
                 0.09 
                 1.00 
                 2.99 
                 0.68 
                 1.00 
                 1.64 
                 0.55 
                 0.61 
               
               
                 ALCELL ® Lignin 
                 1.03 
                 0.19 
                 1.22 
                 6.44 
                 0.42 
                 2.79 
                 2.31 
                 0.38 
                 1.21 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 BETA_5 
                 BETA_BETA 
                 BETA_O_4 
                 DC 
                 Mn 
                 Mw 
                 Mz 
                   
                 Ash 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 mmol/g 
                 % 
                 g/mol 
                 D 
                 % 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 MAC I 
                 N/A 
                 N/A 
                 N/A 
                 N/A 
                 343 
                 2883 
                 5906 
                 8.40 
                 3.35 
               
               
                   
                 MAC II 
                 0.00 
                 0.03 
                 0.00 
                 54 
                 599 
                 1329 
                 2379 
                 2.22 
                 0.10 
               
               
                   
                 PURIFIED MAC I 
                 0.00 
                 0.02 
                 0.00 
                 71 
                 281 
                 2644 
                 5562 
                 9.38 
                 0.10 
               
               
                   
                 ALCELL ® Lignin 
                 0.19 
                 0.19 
                 0.45 
                 43 
                 863 
                 1908 
                 3906 
                 2.22 
                 0.06 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Carbohydrate, Ash, and Acid-Insoluble Solids (AIS), and Acid-Soluble Solids (ASS) in MACs and their fractions 
               
            
           
           
               
               
            
               
                   
                 Percent Content on Dry Basis 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Biomass Fraction 
                 Arabinan 
                 Galactan 
                 Glucan 
                 Xylan 
                 Mannan 
                 AIS* 
                 ASS** 
                 Ash 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 ACETONE-PURIFIED MAC I 
                 0.01 
                 0.01 
                 1.45 
                 0 
                 0.07 
                 90.84 
                 0.55 
                 0.21 
               
               
                 ACETONE-INSOLUBLES MAC-I 
                 0.05 
                 0.05 
                 65.92 
                 0.09 
                 0.03 
                 21.26 
                 0.4 
                 10.92 
               
               
                 MAC I 
                 0.02 
                 0.01 
                 19.47 
                 0.01 
                 0.09 
                 72.46 
                 0.62 
                 3.34 
               
               
                 MAC II 
                 0 
                 0 
                 0.23 
                 0 
                 0.01 
                 92.93 
                 2.46 
                 0 
               
               
                   
               
               
                 *AIS—Acid-Insoluble Solids (Mostly Aromatic Compounds); 
               
               
                 **ASS—Acid-Soluble Solids (Mostly Aromatic Compounds 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Elemental Analysis of Aspen MACs 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 C 
                 H 
                 N 
                 S 
                 O* 
               
            
           
           
               
               
            
               
                   
                 % Content by wt. 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 MAC-I* 
                 61.72 
                 4.81 
                 0.16 
                 1.80 
                 31.51 
               
               
                 ACETONE-INSOLUBLES 
                 44.87 ± 0.55 
                 4.80 ± 0.06 
                 0.10 ± 0.01 
                 2.93 ± 0.04 
                 47.30 
               
               
                 MAC-I 
               
               
                 ACETONE-SOLUBLES 
                 68.94 ± 0.01 
                 4.81 ± 0.03 
                 0.18 ± 0.01 
                 1.31 ± 0.03 
                 24.76 
               
               
                 MAC-I 
               
               
                 MAC-II 
                 69.09 ± 0.02 
                 4.90 ± 0.54 
                 0.16 ± 0.01 
                 0.62 ± 0.01 
                 25.23 
               
               
                   
               
               
                 *Calculated values 
               
            
           
         
       
     
     1) The FILTRATE and CONCENTRATE 
     The FILTRATE is the solution obtained after filtration of the precipitated MAC II. The MAC II is precipitated from the black liquor containing slurried biomass by dilution with acidified water. Surprisingly, very low concentration of carbohydrates was observed in the FILTRATE (Table 4) indicating that carbohydrates were degraded during the present process. However, significant concentrations of useful chemicals, such as levulinic acid derivatives and furfural, were detected in the FILTRATE. 
     Recovery of ethanol from the FILTRATE was achieved after evaporation of about one half of the solution when the process is run in a rotary evaporator. Under these conditions, volatile components, such as furfural, 5-HMF, partially acetic and formic acids, will be also evaporated to a greater or lesser degree depending on distillation conditions. About 25% of the organic compounds in the FILTRATE seems to be volatile. 
     For analytical purposes, the FILTRATE was evaporated to dryness and the resulting re-dissolved CONCENTRATE was analysed by high resolution NMR techniques ( FIG. 7 , Table 6). The major components of the CONCENTRATE are derivatives of levulinic acid and furfural derivatives (5-HMF). A significant number of reaction products were ethylated, either as ethers or esters. As expected from the FILTRATE HPLC analysis (Table 4), the amount of carbohydrates observed in the NMR spectra was rather low. Significant amounts of carbohydrates are apparently converted to hydroxy- and saccharinic acids. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Chemical Composition of the FILTRATE 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 HMF (g/L) 
                 Furfural (g/L) 
                 Acetic Acid (g/L) 
                 Levulinic acid (g/L) 
                 Lactic Acid (g/L) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 0.61 
                 0.01 
                 2.28 
                 2.11 
                 0.03 
                 1.29 
                 1.02 
                 0.00 
                 0.28 
                 1.53 
                 0.00 
                 0.24 
                 0.15 
                 0.00 
                 2.63 
               
            
           
           
               
               
               
               
               
            
               
                 Arabinose (g/L) 
                 Galactose (g/L) 
                 Glucose (g/L) 
                 Mannose (g/L) 
                 Xylose (g/L) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.98 
                 0.02 
                 2.32 
                 0.04 
                 0.00 
                 1.37 
                 0 
                 0 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Chemical Composition of the CONCENTRATE 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
                 Average 
                 STDEV 
                 CV (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 HMF (g/L) 
                 Furfural (g/L) 
                 Acetic Acid (g/L) 
                 Levulinic acid (g/L) 
                 Lactic Acid (g/L) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 1.19 
                 0.02 
                 1.30 
                 0.18 
                 0.00 
                 1.07 
                 1.49 
                 0.00 
                 0.25 
                 2.80 
                 0.01 
                 0.26 
                 0.27 
                 0.01 
                 2.51 
               
            
           
           
               
               
               
               
               
            
               
                 Arabinose (g/L) 
                 Galactose (g/L) 
                 Glucose (g/L) 
                 Mannose (g/L) 
                 Xylose (g/L) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 1.82 
                 0.04 
                 2.34 
                 0.07 
                 0.00 
                 4.82 
                 0 
                 0 
                 0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 NMR analysis of the CONCENTRATE. Distribution of carbon atoms of various types (% of total carbon) 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                 COOR—_al + 
                   
                 Aromatic + 
                 Oxygenated 
                 OMe 
                 Saturated 
                   
                   
               
               
                 CO_nc 
                 CO_conj 
                 furfur.der. 
                 COOR_con. 
                 aliphatic 
                 aliphatic 1   
                 (+HMF) 
                 aliphatic 2   
                 EtO— 
                 Total 
               
               
                   
               
               
                 9.00 
                 1.62 
                 15.00 
                 0.63 
                 25.01 
                 18.02 
                 3.83 
                 20.03 
                 6.86 
                 100 
               
               
                   
               
               
                   1 carbon with aliphatic hydroxyl and ether type 
               
               
                   2 CH 3 —, CH 2 —and CH—(not oxygenated) 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Integration Peak List GC-MS Analysis of the FILTRATE 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                   
                 Area 
                 Confirmed 
                   
               
               
                 Peak 
                 RT 
                 Area 
                 % 
                 ID* 
                 Library Match** 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 4.908 
                 1135152972 
                 20.7 
                 Ethanol 
                   
               
               
                 2 
                 5.892 
                 5327648 
                 0.10 
                   
                 Methyl Acetate 
               
               
                 3 
                 7.029 
                 6922947 
                 0.13 
                   
                 1,1-Dimethoxy 
               
               
                   
                   
                   
                   
                   
                 ethane 
               
               
                 4 
                 7.654 
                 13323996 
                 0.24 
                   
                 Ethyl Acetate 
               
               
                 5 
                 8.481 
                 112719972 
                 2.1 
                 Acetic Acid 
               
               
                 6 
                 13.349 
                 655761415 
                 12.0 
                 Furaldehyde 
               
               
                 7 
                 15.174 
                 353738837 
                 6.5 
                   
                 substitued Furan 
               
               
                 8 
                 15.976 
                 37371490 
                 0.68 
                   
                 substitued Furan 
               
               
                 9 
                 16.248 
                 194903728 
                 3.6 
                   
                 poor match 
               
               
                 10 
                 17.485 
                 1074126495 
                 19.6 
                   
                 likely Ethyl 
               
               
                   
                   
                   
                   
                   
                 Levuinate 
               
               
                 11 
                 18.243 
                 209840574 
                 3.8 
                 Levulinic 
               
               
                   
                   
                   
                   
                 Acid 
               
               
                 12 
                 19.285 
                 22227732 
                 0.41 
                   
                 Levoglusenone 
               
               
                 13 
                 19.360 
                 24382265 
                 0.45 
                   
                 poor match 
               
               
                 14 
                 20.207 
                 15143646 
                 0.28 
                   
                 substitued Furan 
               
               
                 15 
                 20.390 
                 1396888395 
                 25.5 
                   
                 5-Ethoxymethyl 
               
               
                   
                   
                   
                   
                   
                 Furfural 
               
               
                 16 
                 21.337 
                 219302450 
                 4.0 
                 5- 
               
               
                   
                   
                   
                   
                 Hydoxymethyl 
               
               
                   
                   
                   
                   
                 Furfural 
               
               
                   
               
               
                 Notes: 
               
               
                 *Confirmed by retention time and spectral matching with pure compound 
               
               
                 **NIST library used for all compounds except WILEY library used for peak #15 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Semi-quantitative concentration of confirmed by 
               
               
                 GC-MS compounds in the FILTRATE 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 Concentration in 
                   
               
               
                   
                 Compound 
                 Filtrate 
                 Units 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Ethanol 
                 13.5 
                 % (v/v) 
               
               
                   
                 Acetic Acid 
                 0.52 
                 % (v/v) 
               
               
                   
                 Furaldehyde 
                 1.8 
                 % (v/v) 
               
               
                   
                 Levulinic 
                 1.1 
                 % (v/v) 
               
               
                   
                 Acid 
               
               
                   
                 5-HMF 
                 0.55 
                 % (m/v) 
               
               
                   
                 Vanillin 
                 0.03 
                 % (m/v) 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Formulas for suggested compounds searched against acquired data on LC/QTOF of the FILTRATE. 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                   
                 Diff (Tgt, 
                 Score 
               
               
                 Cpd 
                 Name 
                 RT 
                 Formula (Tgt) 
                 Height 
                 Area 
                 Mass 
                 ppm) 
                 (Tgt) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 1 
                 Glyceric Acid 
                 1.86 
                 C3H6O4 
                 11,321 
                 50,602 
                 106.0262 
                 −3.8 
                 46.9 
               
               
                 2 
                 D-Glucuronic Acid 
                 1.86 
                 C6H10O7 
                 18,921 
                 48,205 
                 194.0426 
                 −0.3 
                 47.6 
               
               
                 3 
                 D-Gluconic Acid 
                 1.92 
                 C6H12O7 
                 22,961 
                 122,346 
                 196.0582 
                 −0.6 
                 61.0 
               
               
                 5 
                 2-Hydroxypropionic 
                 2.08 
                 C3H6O3 
                 4,128,421 
                 27,556,200 
                 90.0316 
                 −1.0 
                 99.8 
               
               
                 6 
                 Lactic Acid 
                 2.08 
                 C3H6O3 
                 4,128,421 
                 27,556,200 
                 90.0316 
                 −1.0 
                 99.8 
               
               
                 7 
                 Mannose 
                 2.08 
                 C6H12O6 
                 4,539,014 
                 29,783,073 
                 180.0633 
                 −0.5 
                 99.8 
               
               
                 8 
                 Galactose 
                 2.08 
                 C6H12O6 
                 4,539,014 
                 29,783,073 
                 180.0633 
                 −0.5 
                 99.8 
               
               
                 9 
                 Glucose 
                 2.08 
                 C6H12O6 
                 4,539,014 
                 29,783,073 
                 180.0633 
                 −0.5 
                 99.8 
               
               
                 10 
                 Acetic Acid 
                 2.08 
                 C2H4O2 
                 4,087,666 
                 26,852,460 
                 60.0210 
                 −1.6 
                 99.8 
               
               
                 14 
                 D-Arabinonic Acid 
                 2.25 
                 C5H10O6 
                 19,262 
                 245,755 
                 166.0474 
                 −1.8 
                 47.3 
               
               
                 15 
                 Xylitol (Other Sugar Alcohols) 
                 2.26 
                 C5H12O5 
                 21,798 
                 120,856 
                 152.0687 
                 1.7 
                 81.9 
               
               
                 16 
                 Diethyl Ester Hydroxy butanedioic 
                 2.45 
                 C6H10O5 
                 2,400,216 
                 20,488,667 
                 162.0530 
                 1.3 
                 98.3 
               
               
                 17 
                 1,6-anhydroglucose 
                 2.45 
                 C6H10O5 
                 2,400,216 
                 20,488,667 
                 162.0530 
                 1.3 
                 98.3 
               
               
                 18 
                 Ethyl Ester 2-Furancarboxylic acid 
                 2.76 
                 C7H8O3 
                 198,069 
                 1,027,049 
                 140.0472 
                 −0.8 
                 97.6 
               
               
                 19 
                 Ethyl Methyl Ester Butanedioic acid 
                 2.94 
                 C7H12O4 
                 259,217 
                 1,249,775 
                 160.0735 
                 −0.2 
                 86.7 
               
               
                 20 
                 2-Hydroxy-3-methyl-2-cyclopenten-1-one 
                 3.01 
                 C6H8O2 
                 27,165 
                 134,204 
                 112.0527 
                 2.1 
                 77.8 
               
               
                 22 
                 Methyl Furfural (Furfural Derivatives) 
                 4.03 
                 C6H6O2 
                 444,363 
                 10,009,028 
                 110.0371 
                 2.6 
                 99.3 
               
               
                 23 
                 5-Methyl-2-furancarboxaldehyde 
                 4.03 
                 C6H6O2 
                 444,363 
                 10,009,028 
                 110.0371 
                 2.6 
                 99.3 
               
               
                 24 
                 Ethyl Lactate 
                 4.04 
                 C5H10O3 
                 381,392 
                 3,471,968 
                 118.0631 
                 1.2 
                 98.8 
               
               
                 25 
                 ISTD - Dicamba 
                 4.05 
                 C8H6Cl2O3 
                 103,733 
                 631,772 
                 219.9688 
                 −2.5 
                 96.6 
               
               
                 26 
                 5-Hydroxymethylfurfural 
                 4.18 
                 C6H6O3 
                 2,812,068 
                 50,578,798 
                 126.0318 
                 0.5 
                 99.7 
               
               
                 27 
                 p-Hydroxybenzoic Acid 
                 4.36 
                 C7H6O3 
                 57,933 
                 702,997 
                 138.0313 
                 −3.1 
                 86.6 
               
               
                 28 
                 Furfural 
                 4.54 
                 C5H4O2 
                 251,552 
                 4,055,605 
                 96.0215 
                 3.4 
                 99.1 
               
               
                 29 
                 Ethyl Ester 2-Hydroxy butanoic acid 
                 4.62 
                 C6H12O3 
                 69,593 
                 709,947 
                 132.0787 
                 0.1 
                 99.4 
               
               
                 30 
                 2-Methoxy phenol 
                 4.92 
                 C7H8O2 
                 652,893 
                 13,420,475 
                 124.0525 
                 0.3 
                 99.8 
               
               
                 33 
                 Ethyl Levulinate 
                 5.77 
                 C7H12O3 
                 2,165,364 
                 20,705,326 
                 144.0781 
                 −3.5 
                 98.3 
               
               
                 35 
                 2,6-Dimethoxy Phenol (Syringol) 
                 6.64 
                 C8H10O3 
                 2,454,849 
                 50,498,178 
                 154.0627 
                 −1.6 
                 81.7 
               
               
                 36 
                 Isoeugenol (2-methoxy-4-propenyl) phenol 
                 6.66 
                 C10H12O2 
                 26,483 
                 185,183 
                 164.0832 
                 −3.1 
                 67.0 
               
               
                 39 
                 Syringaldehyde 
                 7.15 
                 C9H10O4 
                 531,113 
                 4,786,853 
                 182.0577 
                 −1.1 
                 99.2 
               
               
                 40 
                 Succinic Acid 
                 7.26 
                 C4H6O4 
                 8,655 
                 45,958 
                 118.0269 
                 2.2 
                 84.2 
               
               
                 41 
                 ISTD - 2,4-DP 
                 7.62 
                 C9H8Cl2O3 
                 59,499 
                 301,263 
                 233.9849 
                 −0.5 
                 99.1 
               
               
                 44 
                 ISTD - MCPB 
                 9.32 
                 C11H13ClO3 
                 269,397 
                 1,307,195 
                 228.0543 
                 −4.3 
                 86.4 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Formulas resulting from Molecular Feature Extraction and Molecular Formula Generator. 
               
               
                 MS-mode, positive ion, using SB-CN column and LC/QTOF. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                 Diff 
                   
               
               
                   
                   
                   
                   
                 Mass 
                   
                 (MFG, 
                 Score 
               
               
                 Cpd 
                 RT 
                 Height 
                 Mass 
                 (MFG) 
                 Formula (MFG) 
                 ppm) 
                 (MFG) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 1 
                 1.81 
                 667632 
                 214.0739 
                 214.0736 
                 C4H14N4O4S 
                 −1.4 
                 80.6 
               
               
                 2 
                 1.96 
                 45021 
                 183.0384 
                 183.0388 
                 C5H13NO2S2 
                 1.9 
                 47.0 
               
               
                 3 
                 1.96 
                 23845 
                 199.0160 
                 199.0159 
                 C5H13NOS3 
                 −0.5 
                 47.6 
               
               
                 10 
                 2.06 
                 859938 
                 218.0192 
                 218.0190 
                 C15H6S 
                 −0.8 
                 75.9 
               
               
                 11 
                 2.07 
                 2046818 
                 202.0447 
                 202.0451 
                 C4H6N6O4 
                 1.7 
                 94.3 
               
               
                 12 
                 2.08 
                 375893 
                 382.1091 
                 382.1084 
                 C10H18N6O10 
                 −1.7 
                 92.4 
               
               
                 13 
                 2.08 
                 35777 
                 184.0347 
                 184.0347 
                 C12H8S 
                 −0.4 
                 47.6 
               
               
                 14 
                 2.09 
                 1465486 
                 197.0900 
                 197.0899 
                 C6H15NO6 
                 −0.2 
                 47.5 
               
               
                 15 
                 2.09 
                 145433 
                 162.0525 
                 162.0528 
                 C6H10O5 
                 1.9 
                 86.4 
               
               
                 17 
                 2.24 
                 647979 
                 242.1050 
                 242.1049 
                 C6H18N4O4S 
                 −0.4 
                 85.4 
               
               
                 18 
                 2.39 
                 17546 
                 114.0319 
                 114.0317 
                 C5H6O3 
                 −1.9 
                 47.4 
               
               
                 20 
                 2.42 
                 1312362 
                 208.0944 
                 208.0947 
                 C8H16O6 
                 1.4 
                 74.1 
               
               
                 21 
                 2.43 
                 1422495 
                 162.0527 
                 162.0528 
                 C6H10O5 
                 0.6 
                 80.0 
               
               
                 24 
                 2.45 
                 464169 
                 482.2293 
                 482.2298 
                 C20H38N2O9S 
                 1.0 
                 81.1 
               
               
                 25 
                 2.45 
                 18811 
                 435.1664 
                 435.1657 
                 C29H25NOS 
                 −1.7 
                 46.8 
               
               
                 26 
                 2.45 
                 903515 
                 230.0768 
                 230.0764 
                 C6H10N6O4 
                 −2.0 
                 81.3 
               
               
                 27 
                 2.46 
                 895524 
                 438.1721 
                 438.1710 
                 C14H26N6O10 
                 −2.4 
                 88.7 
               
               
                 28 
                 2.46 
                 107771 
                 446.1578 
                 446.1577 
                 C23H26O9 
                 −0.2 
                 75.9 
               
               
                 31 
                 2.47 
                 2292217 
                 225.1211 
                 225.1212 
                 C8H19NO6 
                 0.7 
                 94.7 
               
               
                 32 
                 2.55 
                 45418 
                 172.0731 
                 172.0736 
                 C8H12O4 
                 2.6 
                 46.6 
               
               
                 33 
                 2.6 
                 1845952 
                 116.0476 
                 116.0473 
                 C5H8O3 
                 −2.4 
                 88.0 
               
               
                 35 
                 2.75 
                 33302 
                 386.0889 
                 386.0892 
                 C14H26O6S3 
                 0.6 
                 47.6 
               
               
                 36 
                 2.76 
                 200852 
                 139.0632 
                 139.0633 
                 C7H9NO2 
                 1.0 
                 87.7 
               
               
                 37 
                 2.79 
                 20763 
                 128.0473 
                 128.0473 
                 C6H8O3 
                 0.2 
                 47.6 
               
               
                 39 
                 2.79 
                 95316 
                 382.1740 
                 382.1740 
                 C18H26N2O7 
                 0.0 
                 84.0 
               
               
                 40 
                 2.79 
                 88559 
                 184.0732 
                 184.0736 
                 C9H12O4 
                 1.8 
                 47.0 
               
               
                 41 
                 2.95 
                 240808 
                 142.0631 
                 142.0630 
                 C7H10O3 
                 −0.5 
                 47.6 
               
               
                 42 
                 3 
                 147823 
                 352.1637 
                 352.1634 
                 C17H24N2O6 
                 −0.8 
                 84.5 
               
               
                 43 
                 3.02 
                 36344 
                 130.0631 
                 130.0630 
                 C6H10O3 
                 −0.9 
                 47.2 
               
               
                 44 
                 3.26 
                 46909 
                 146.0575 
                 146.0579 
                 C6H10O4 
                 2.6 
                 47.0 
               
               
                 45 
                 3.38 
                 12453 
                 102.0317 
                 102.0317 
                 C4H6O3 
                 −0.4 
                 47.2 
               
               
                 46 
                 3.48 
                 125369 
                 253.1526 
                 253.1525 
                 C10H23NO6 
                 −0.4 
                 86.5 
               
               
                 47 
                 3.51 
                 88350 
                 346.1378 
                 346.1376 
                 C14H22N2O8 
                 −0.7 
                 85.0 
               
               
                 48 
                 3.53 
                 361865 
                 190.0839 
                 190.0841 
                 C8H14O5 
                 1.0 
                 86.6 
               
               
                 49 
                 3.75 
                 67235 
                 253.1529 
                 253.1525 
                 C10H23NO6 
                 −1.3 
                 84.5 
               
               
                 50 
                 3.97 
                 147917 
                 190.0840 
                 190.0841 
                 C8H14O5 
                 0.6 
                 85.9 
               
               
                 51 
                 3.98 
                 50719 
                 172.0733 
                 172.0736 
                 C8H12O4 
                 1.8 
                 47.4 
               
               
                 53 
                 4.03 
                 233108 
                 253.1529 
                 253.1525 
                 C10H23NO6 
                 −1.4 
                 83.0 
               
               
                 55 
                 4.05 
                 14681 
                 221.9667 
                 221.9665 
                 C7H10S4 
                 −0.8 
                 47.1 
               
               
                 56 
                 4.06 
                 121416 
                 236.1265 
                 236.1269 
                 C11H24OS2 
                 1.6 
                 45.8 
               
               
                 57 
                 4.12 
                 42500 
                 444.1351 
                 444.1355 
                 C22H24N2O6S 
                 0.9 
                 72.1 
               
               
                 58 
                 4.12 
                 2156399 
                 126.0318 
                 126.0317 
                 C6H6O3 
                 −0.5 
                 99.4 
               
               
                 59 
                 4.2 
                 106857 
                 114.0682 
                 114.0681 
                 C6H10O2 
                 −0.8 
                 47.4 
               
               
                 60 
                 4.44 
                 28142 
                 156.0785 
                 156.0786 
                 C8H12O3 
                 1.2 
                 47.4 
               
               
                 62 
                 4.61 
                 31824 
                 202.0837 
                 202.0841 
                 C9H14O5 
                 2.1 
                 46.3 
               
               
                 63 
                 4.62 
                 80491 
                 142.0627 
                 142.0630 
                 C7H10O3 
                 1.8 
                 47.2 
               
               
                 66 
                 4.91 
                 118051 
                 140.0472 
                 140.0473 
                 C7H8O3 
                 0.9 
                 47.5 
               
               
                 67 
                 4.94 
                 257983 
                 246.1368 
                 246.1368 
                 C14H18N2O2 
                 0.0 
                 86.1 
               
               
                 68 
                 4.95 
                 636096 
                 123.0684 
                 123.0684 
                 C7H9NO 
                 0.3 
                 87.9 
               
               
                 69 
                 5.02 
                 64528 
                 374.1691 
                 374.1689 
                 C16H26N2O8 
                 −0.4 
                 83.5 
               
               
                 70 
                 5.13 
                 161387 
                 156.0786 
                 156.0786 
                 C8H12O3 
                 0.4 
                 87.2 
               
               
                 72 
                 5.25 
                 15961 
                 206.1150 
                 206.1154 
                 C9H18O5 
                 2.0 
                 46.3 
               
               
                 73 
                 5.27 
                 302915 
                 170.0941 
                 170.0943 
                 C9H14O3 
                 1.4 
                 79.2 
               
               
                 75 
                 5.51 
                 96651 
                 224.0681 
                 224.0685 
                 C11H12O5 
                 1.5 
                 86.6 
               
               
                 76 
                 5.55 
                 69074 
                 264.1124 
                 264.1123 
                 C14H12N6 
                 −0.3 
                 86.5 
               
               
                 79 
                 5.63 
                 275465 
                 208.0733 
                 208.0736 
                 C11H12O4 
                 1.1 
                 96.8 
               
               
                 80 
                 5.76 
                 277398 
                 374.1692 
                 374.1689 
                 C16H26N2O8 
                 −0.8 
                 67.4 
               
               
                 81 
                 5.77 
                 91178 
                 333.1425 
                 333.1424 
                 C14H23NO8 
                 −0.4 
                 83.4 
               
               
                 83 
                 5.78 
                 2063231 
                 144.0783 
                 144.0786 
                 C7H12O3 
                 2.7 
                 94.4 
               
               
                 84 
                 5.79 
                 2260283 
                 98.0370 
                 98.0368 
                 C5H6O2 
                 −2.0 
                 99.2 
               
               
                 85 
                 5.86 
                 70292 
                 176.1043 
                 176.1049 
                 C8H16O4 
                 2.9 
                 75.3 
               
               
                 86 
                 5.89 
                 81710 
                 292.1061 
                 292.1059 
                 C14H16N2O5 
                 −0.7 
                 86.0 
               
               
                 87 
                 5.89 
                 100465 
                 203.0581 
                 203.0582 
                 C11H9NO3 
                 0.6 
                 47.5 
               
               
                 88 
                 5.93 
                 240159 
                 190.0838 
                 190.0841 
                 C8H14O5 
                 1.8 
                 83.5 
               
               
                 89 
                 5.98 
                 33072 
                 214.1201 
                 214.1205 
                 C11H18O4 
                 2.1 
                 46.0 
               
               
                 90 
                 5.98 
                 14485 
                 214.0840 
                 214.0841 
                 C10H14O5 
                 0.8 
                 47.4 
               
               
                 91 
                 6.07 
                 99753 
                 200.1045 
                 200.1049 
                 C10H16O4 
                 1.9 
                 84.8 
               
               
                 92 
                 6.08 
                 65770 
                 218.1154 
                 218.1154 
                 C10H18O5 
                 0.0 
                 47.0 
               
               
                 94 
                 6.12 
                 44199 
                 188.1043 
                 188.1049 
                 C9H16O4 
                 3.0 
                 46.2 
               
               
                 95 
                 6.15 
                 141468 
                 142.0630 
                 142.0630 
                 C7H10O3 
                 0.1 
                 47.6 
               
               
                 96 
                 6.18 
                 77101 
                 184.1099 
                 184.1099 
                 C10H16O3 
                 0.0 
                 86.8 
               
               
                 98 
                 6.26 
                 102662 
                 264.1473 
                 264.1474 
                 C14H20N2O3 
                 0.5 
                 86.7 
               
               
                 101 
                 6.35 
                 246774 
                 266.1264 
                 266.1267 
                 C13H18N2O4 
                 0.8 
                 79.0 
               
               
                 104 
                 6.39 
                 16420 
                 236.0680 
                 236.0685 
                 C12H12O5 
                 2.0 
                 47.6 
               
               
                 105 
                 6.39 
                 38784 
                 188.1043 
                 188.1049 
                 C9H16O4 
                 2.7 
                 47.0 
               
               
                 107 
                 6.46 
                 2003564 
                 168.0782 
                 168.0786 
                 C9H12O3 
                 2.9 
                 82.9 
               
               
                 125 
                 6.49 
                 1794382 
                 108.0212 
                 108.0211 
                 C6H4O2 
                 −1.0 
                 87.2 
               
               
                 126 
                 6.49 
                 1851472 
                 171.0894 
                 171.0895 
                 C8H13NO3 
                 0.9 
                 93.6 
               
               
                 131 
                 6.51 
                 82397 
                 151.0994 
                 151.0997 
                 C9H13NO 
                 2.0 
                 47.1 
               
               
                 132 
                 6.6 
                 73136 
                 200.1046 
                 200.1049 
                 C10H16O4 
                 1.3 
                 78.8 
               
               
                 133 
                 6.61 
                 678120 
                 180.0783 
                 180.0786 
                 C10H12O3 
                 1.8 
                 81.6 
               
               
                 136 
                 6.63 
                 84897 
                 215.0940 
                 215.0946 
                 C13H13NO2 
                 2.7 
                 46.1 
               
               
                 137 
                 6.63 
                 112734 
                 188.1043 
                 188.1049 
                 C9H16O4 
                 2.9 
                 86.8 
               
               
                 138 
                 6.64 
                 114439 
                 209.1048 
                 209.1052 
                 C11H15NO3 
                 2.0 
                 46.9 
               
               
                 140 
                 6.68 
                 54699 
                 170.0575 
                 170.0579 
                 C8H10O4 
                 2.4 
                 46.6 
               
               
                 142 
                 6.72 
                 79975 
                 229.0734 
                 229.0739 
                 C13H11NO3 
                 2.0 
                 85.4 
               
               
                 144 
                 6.8 
                 2267396 
                 210.0889 
                 210.0892 
                 C11H14O4 
                 1.4 
                 96.1 
               
               
                 146 
                 6.9 
                 89431 
                 194.0575 
                 194.0579 
                 C10H10O4 
                 2.1 
                 86.3 
               
               
                 147 
                 6.9 
                 56959 
                 188.1043 
                 188.1049 
                 C9H16O4 
                 2.8 
                 46.1 
               
               
                 148 
                 6.91 
                 74982 
                 282.1211 
                 282.1216 
                 C13H18N2O5 
                 1.8 
                 82.4 
               
               
                 149 
                 6.91 
                 160260 
                 224.0682 
                 224.0685 
                 C11H12O5 
                 1.2 
                 86.5 
               
               
                 151 
                 6.97 
                 46660 
                 268.0946 
                 268.0947 
                 C13H16O6 
                 0.5 
                 69.8 
               
               
                 152 
                 6.99 
                 21815 
                 340.1649 
                 340.1648 
                 C17H20N6O2 
                 −0.4 
                 46.7 
               
               
                 154 
                 7 
                 96334 
                 222.0889 
                 222.0892 
                 C12H14O4 
                 1.4 
                 66.9 
               
               
                 156 
                 7.07 
                 23382 
                 280.0951 
                 280.0954 
                 C7H16N6O4S 
                 0.9 
                 47.1 
               
               
                 157 
                 7.09 
                 33682 
                 224.1049 
                 224.1049 
                 C12H16O4 
                 −0.4 
                 47.1 
               
               
                 158 
                 7.09 
                 27798 
                 220.0739 
                 220.0736 
                 C12H12O4 
                 −1.3 
                 47.0 
               
               
                 159 
                 7.14 
                 78389 
                 240.0998 
                 240.0998 
                 C12H16O5 
                 −0.3 
                 47.6 
               
               
                 160 
                 7.14 
                 18953 
                 200.0683 
                 200.0685 
                 C9H12O5 
                 0.9 
                 46.9 
               
               
                 161 
                 7.15 
                 37545 
                 256.1310 
                 256.1318 
                 C6H20N6O3S 
                 2.8 
                 47.4 
               
               
                 162 
                 7.15 
                 52307 
                 314.1841 
                 314.1842 
                 C15H26N2O5 
                 0.3 
                 80.0 
               
               
                 163 
                 7.16 
                 135614 
                 168.0419 
                 168.0423 
                 C8H8O4 
                 2.1 
                 47.3 
               
               
                 164 
                 7.17 
                 512388 
                 182.0577 
                 182.0579 
                 C9H10O4 
                 1.3 
                 90.0 
               
               
                 165 
                 7.18 
                 262272 
                 180.0782 
                 180.0786 
                 C10H12O3 
                 2.5 
                 85.7 
               
               
                 167 
                 7.18 
                 26272 
                 282.1108 
                 282.1110 
                 C7H18N6O4S 
                 0.9 
                 46.5 
               
               
                 168 
                 7.19 
                 34152 
                 112.0523 
                 112.0524 
                 C6H8O2 
                 0.9 
                 47.6 
               
               
                 169 
                 7.2 
                 89287 
                 156.0782 
                 156.0786 
                 C8H12O3 
                 2.7 
                 86.3 
               
               
                 170 
                 7.2 
                 102326 
                 268.0948 
                 268.0954 
                 C6H16N6O4S 
                 2.1 
                 60.7 
               
               
                 171 
                 7.2 
                 54538 
                 326.1476 
                 326.1478 
                 C15H22N2O6 
                 0.6 
                 82.9 
               
               
                 172 
                 7.2 
                 174899 
                 208.0733 
                 208.0736 
                 C11H12O4 
                 1.2 
                 86.6 
               
               
                 173 
                 7.21 
                 112017 
                 254.1155 
                 254.1154 
                 C13H18O5 
                 −0.3 
                 77.1 
               
               
                 174 
                 7.27 
                 307888 
                 154.0855 
                 154.0855 
                 C6H10N4O 
                 0.0 
                 68.0 
               
               
                 176 
                 7.28 
                 167901 
                 196.1094 
                 196.1099 
                 C11H16O3 
                 2.7 
                 57.3 
               
               
                 177 
                 7.29 
                 60478 
                 376.1635 
                 376.1634 
                 C19H24N2O6 
                 −0.2 
                 82.1 
               
               
                 178 
                 7.31 
                 282762 
                 292.1057 
                 292.1059 
                 C14H16N2O5 
                 0.7 
                 77.8 
               
               
                 179 
                 7.32 
                 231447 
                 234.0526 
                 234.0528 
                 C12H10O5 
                 0.9 
                 86.3 
               
               
                 180 
                 7.35 
                 62364 
                 192.0781 
                 192.0786 
                 C11H12O3 
                 2.8 
                 84.0 
               
               
                 183 
                 7.37 
                 105420 
                 222.0888 
                 222.0892 
                 C12H14O4 
                 1.8 
                 82.1 
               
               
                 184 
                 7.38 
                 88675 
                 204.0419 
                 204.0423 
                 C11H8O4 
                 1.7 
                 47.6 
               
               
                 185 
                 7.4 
                 279916 
                 224.1047 
                 224.1049 
                 C12H16O4 
                 0.5 
                 86.7 
               
               
                 187 
                 7.42 
                 16749 
                 241.1309 
                 241.1314 
                 C12H19NO4 
                 2.1 
                 47.0 
               
               
                 189 
                 7.42 
                 80787 
                 234.0889 
                 234.0892 
                 C13H14O4 
                 1.2 
                 85.3 
               
               
                 190 
                 7.43 
                 43796 
                 336.1681 
                 336.1685 
                 C17H24N2O5 
                 1.2 
                 81.1 
               
               
                 192 
                 7.43 
                 90392 
                 266.1154 
                 266.1154 
                 C14H18O5 
                 0.1 
                 83.8 
               
               
                 193 
                 7.43 
                 195797 
                 324.1687 
                 324.1685 
                 C16H24N2O5 
                 −0.7 
                 84.7 
               
               
                 194 
                 7.44 
                 145053 
                 156.0783 
                 156.0786 
                 C8H12O3 
                 2.4 
                 86.8 
               
               
                 195 
                 7.44 
                 128759 
                 200.1046 
                 200.1049 
                 C10H16O4 
                 1.3 
                 83.7 
               
               
                 196 
                 7.45 
                 30103 
                 126.0678 
                 126.0681 
                 C7H10O2 
                 2.0 
                 47.2 
               
               
                 197 
                 7.5 
                 97725 
                 196.0733 
                 196.0736 
                 C10H12O4 
                 1.3 
                 73.3 
               
               
                 198 
                 7.5 
                 33873 
                 226.0837 
                 226.0841 
                 C11H14O5 
                 1.7 
                 45.9 
               
               
                 201 
                 7.56 
                 272457 
                 220.0735 
                 220.0736 
                 C12H12O4 
                 0.2 
                 47.6 
               
               
                 202 
                 7.56 
                 78441 
                 236.1046 
                 236.1049 
                 C13H16O4 
                 0.9 
                 79.1 
               
               
                 203 
                 7.58 
                 31965 
                 398.2008 
                 398.2013 
                 C14H30N4O9 
                 1.3 
                 65.2 
               
               
                 206 
                 7.59 
                 40534 
                 364.2145 
                 364.2151 
                 C23H28N2O2 
                 1.6 
                 73.5 
               
               
                 207 
                 7.62 
                 213882 
                 165.1149 
                 165.1154 
                 C10H15NO 
                 2.8 
                 86.1 
               
               
                 208 
                 7.66 
                 30040 
                 196.0734 
                 196.0736 
                 C10H12O4 
                 1.0 
                 47.0 
               
               
                 209 
                 7.66 
                 59702 
                 334.1730 
                 334.1740 
                 C14H26N2O7 
                 2.9 
                 76.2 
               
               
                 210 
                 7.66 
                 267931 
                 276.1204 
                 276.1209 
                 C12H20O7 
                 1.7 
                 82.7 
               
               
                 212 
                 7.67 
                 42902 
                 422.2052 
                 422.2053 
                 C21H30N2O7 
                 0.4 
                 79.3 
               
               
                 213 
                 7.68 
                 81055 
                 230.1150 
                 230.1154 
                 C11H18O5 
                 2.0 
                 81.8 
               
               
                 214 
                 7.68 
                 122070 
                 184.0731 
                 184.0736 
                 C9H12O4 
                 2.3 
                 85.1 
               
               
                 215 
                 7.71 
                 30402 
                 208.0735 
                 208.0736 
                 C11H12O4 
                 0.4 
                 47.5 
               
               
                 216 
                 7.72 
                 17308 
                 438.1998 
                 438.2002 
                 C21H30N2O8 
                 1.0 
                 47.3 
               
               
                 217 
                 7.74 
                 81345 
                 474.1999 
                 474.2002 
                 C24H30N2O8 
                 0.7 
                 75.2 
               
               
                 218 
                 7.74 
                 239384 
                 416.1476 
                 416.1478 
                 C15H24N6O6S 
                 0.4 
                 87.0 
               
               
                 219 
                 7.75 
                 83447 
                 222.0889 
                 222.0892 
                 C12H14O4 
                 1.5 
                 82.4 
               
               
                 220 
                 7.76 
                 61898 
                 310.1522 
                 310.1529 
                 C15H22N2O5 
                 2.1 
                 77.1 
               
               
                 221 
                 7.76 
                 128048 
                 269.1269 
                 269.1277 
                 C14H15N5O 
                 3.0 
                 76.1 
               
               
                 222 
                 7.77 
                 60768 
                 324.1694 
                 324.1699 
                 C17H20N6O 
                 1.3 
                 85.0 
               
               
                 223 
                 7.77 
                 29042 
                 186.1252 
                 186.1256 
                 C10H18O3 
                 2.1 
                 46.9 
               
               
                 224 
                 7.77 
                 32943 
                 266.1158 
                 266.1154 
                 C14H18O5 
                 −1.2 
                 47.6 
               
               
                 225 
                 7.81 
                 34827 
                 204.1359 
                 204.1362 
                 C10H20O4 
                 1.2 
                 46.4 
               
               
                 226 
                 7.82 
                 140557 
                 218.0577 
                 218.0579 
                 C12H10O4 
                 1.1 
                 86.2 
               
               
                 227 
                 7.84 
                 166902 
                 240.0994 
                 240.0998 
                 C12H16O5 
                 1.4 
                 86.1 
               
               
                 228 
                 7.87 
                 22918 
                 264.0998 
                 264.0998 
                 C14H16O5 
                 −0.3 
                 47.3 
               
               
                 229 
                 7.88 
                 445734 
                 252.0998 
                 252.0998 
                 C13H16O5 
                 −0.1 
                 47.3 
               
               
                 230 
                 7.89 
                 555848 
                 206.0578 
                 206.0579 
                 C11H10O4 
                 0.6 
                 76.6 
               
               
                 231 
                 7.89 
                 191377 
                 310.1529 
                 310.1529 
                 C15H22N2O5 
                 0.0 
                 98.8 
               
               
                 232 
                 7.9 
                 262182 
                 318.1107 
                 318.1103 
                 C17H18O6 
                 −1.2 
                 82.9 
               
               
                 233 
                 7.9 
                 837172 
                 376.1632 
                 376.1634 
                 C19H24N2O6 
                 0.6 
                 83.4 
               
               
                 235 
                 7.93 
                 56215 
                 180.0784 
                 180.0786 
                 C10H12O3 
                 1.3 
                 80.3 
               
               
                 236 
                 7.94 
                 87309 
                 190.0629 
                 190.0630 
                 C11H10O3 
                 0.7 
                 85.7 
               
               
                 238 
                 7.97 
                 103809 
                 238.1205 
                 238.1205 
                 C13H18O4 
                 0.0 
                 83.8 
               
               
                 239 
                 7.97 
                 61786 
                 378.1783 
                 378.1791 
                 C19H26N2O6 
                 2.1 
                 80.0 
               
               
                 240 
                 7.99 
                 38187 
                 308.1264 
                 308.1267 
                 C9H20N6O4S 
                 0.8 
                 46.7 
               
               
                 241 
                 7.99 
                 46360 
                 234.0890 
                 234.0892 
                 C13H14O4 
                 0.9 
                 70.5 
               
               
                 242 
                 7.99 
                 41842 
                 402.1681 
                 402.1692 
                 C23H22N4O3 
                 2.7 
                 76.1 
               
               
                 243 
                 8 
                 350002 
                 224.0867 
                 224.0871 
                 C12H16O2S 
                 1.9 
                 53.4 
               
               
                 244 
                 8 
                 79232 
                 303.1682 
                 303.1682 
                 C14H25NO6 
                 0.1 
                 82.3 
               
               
                 246 
                 8.01 
                 77219 
                 344.1946 
                 344.1947 
                 C16H28N2O6 
                 0.3 
                 85.0 
               
               
                 247 
                 8.01 
                 138286 
                 460.2211 
                 460.2210 
                 C24H32N2O7 
                 −0.4 
                 80.9 
               
               
                 248 
                 8.04 
                 53264 
                 210.0891 
                 210.0892 
                 C11H14O4 
                 0.4 
                 75.1 
               
               
                 249 
                 8.04 
                 37667 
                 214.1205 
                 214.1205 
                 C11H18O4 
                 0.0 
                 47.6 
               
               
                 250 
                 8.04 
                 68132 
                 202.1203 
                 202.1205 
                 C10H18O4 
                 1.0 
                 47.3 
               
               
                 251 
                 8.05 
                 279070 
                 340.1634 
                 340.1634 
                 C16H24N2O6 
                 0.0 
                 88.4 
               
               
                 252 
                 8.05 
                 607167 
                 299.1374 
                 299.1369 
                 C14H21NO6 
                 −1.7 
                 96.4 
               
               
                 253 
                 8.06 
                 39365 
                 282.1108 
                 282.1110 
                 C7H18N6O4S 
                 0.8 
                 46.2 
               
               
                 254 
                 8.06 
                 84081 
                 268.1313 
                 268.1311 
                 C14H20O5 
                 −0.7 
                 66.4 
               
               
                 255 
                 8.06 
                 34815 
                 422.2051 
                 422.2053 
                 C21H30N2O7 
                 0.6 
                 80.5 
               
               
                 256 
                 8.09 
                 87464 
                 254.1155 
                 254.1154 
                 C13H18O5 
                 −0.2 
                 84.8 
               
               
                 257 
                 8.09 
                 40292 
                 274.0843 
                 274.0841 
                 C15H14O5 
                 −0.8 
                 76.3 
               
               
                 258 
                 8.1 
                 53826 
                 320.1346 
                 320.1347 
                 C20H20N2S 
                 0.4 
                 75.5 
               
               
                 259 
                 8.1 
                 36107 
                 262.0847 
                 262.0848 
                 C7H14N6O3S 
                 0.5 
                 47.2 
               
               
                 260 
                 8.13 
                 27528 
                 246.1465 
                 246.1467 
                 C12H22O5 
                 1.1 
                 47.2 
               
               
                 262 
                 8.15 
                 73051 
                 182.0943 
                 182.0943 
                 C10H14O3 
                 −0.3 
                 46.9 
               
               
                 264 
                 8.16 
                 71030 
                 267.1134 
                 267.1140 
                 C10H21NO5S 
                 2.4 
                 45.4 
               
               
                 265 
                 8.17 
                 20859 
                 264.1000 
                 264.0998 
                 C14H16O5 
                 −0.9 
                 47.4 
               
               
                 270 
                 8.2 
                 137097 
                 210.0895 
                 210.0892 
                 C11H14O4 
                 −1.2 
                 85.0 
               
               
                 271 
                 8.21 
                 41570 
                 274.0847 
                 274.0855 
                 C16H10N4O 
                 2.7 
                 79.4 
               
               
                 272 
                 8.22 
                 68468 
                 198.0893 
                 198.0892 
                 C10H14O4 
                 −0.5 
                 47.3 
               
               
                 273 
                 8.22 
                 35701 
                 254.1157 
                 254.1161 
                 C6H18N6O3S 
                 1.6 
                 46.5 
               
               
                 274 
                 8.23 
                 35243 
                 248.1052 
                 248.1049 
                 C14H16O4 
                 −1.3 
                 65.8 
               
               
                 276 
                 8.23 
                 20359 
                 334.1436 
                 334.1430 
                 C19H18N4O2 
                 −1.8 
                 47.6 
               
               
                 277 
                 8.24 
                 50688 
                 420.1903 
                 420.1910 
                 C22H24N6O3 
                 1.7 
                 79.9 
               
               
                 278 
                 8.24 
                 48903 
                 284.1748 
                 284.1749 
                 C15H20N6 
                 0.4 
                 47.5 
               
               
                 279 
                 8.24 
                 44692 
                 346.1525 
                 346.1529 
                 C18H22N2O5 
                 1.2 
                 76.7 
               
               
                 280 
                 8.24 
                 29775 
                 458.2048 
                 458.2035 
                 C36H26 
                 −3.0 
                 71.4 
               
               
                 281 
                 8.24 
                 15663 
                 362.1383 
                 362.1381 
                 C13H26N6S3 
                 −0.5 
                 47.6 
               
               
                 282 
                 8.27 
                 49146 
                 262.0845 
                 262.0841 
                 C14H14O5 
                 −1.4 
                 78.9 
               
               
                 283 
                 8.27 
                 129134 
                 320.1369 
                 320.1372 
                 C16H20N2O5 
                 0.9 
                 84.9 
               
               
                 284 
                 8.27 
                 298798 
                 166.0629 
                 166.0630 
                 C9H10O3 
                 0.5 
                 84.1 
               
               
                 285 
                 8.28 
                 60890 
                 354.1789 
                 354.1791 
                 C17H26N2O6 
                 0.5 
                 84.6 
               
               
                 286 
                 8.28 
                 44217 
                 338.1840 
                 338.1842 
                 C17H26N2O5 
                 0.5 
                 76.4 
               
               
                 288 
                 8.29 
                 30555 
                 250.0839 
                 250.0841 
                 C13H14O5 
                 0.9 
                 47.6 
               
               
                 290 
                 8.31 
                 118093 
                 288.1000 
                 288.0998 
                 C16H16O5 
                 −0.7 
                 80.8 
               
               
                 291 
                 8.32 
                 22374 
                 278.0797 
                 278.0797 
                 C7H14N6O4S 
                 0.0 
                 47.0 
               
               
                 292 
                 8.33 
                 53356 
                 266.1155 
                 266.1154 
                 C14H18O5 
                 −0.3 
                 62.1 
               
               
                 293 
                 8.35 
                 128557 
                 448.1854 
                 448.1854 
                 C23H32N2O3S2 
                 0.0 
                 83.3 
               
               
                 294 
                 8.35 
                 24715 
                 390.1324 
                 390.1323 
                 C21H26O3S2 
                 −0.1 
                 47.5 
               
               
                 295 
                 8.36 
                 520623 
                 176.0470 
                 176.0473 
                 C10H8O3 
                 2.0 
                 68.2 
               
               
                 296 
                 8.36 
                 106427 
                 318.1105 
                 318.1103 
                 C17H18O6 
                 −0.4 
                 84.2 
               
               
                 297 
                 8.37 
                 67809 
                 406.1746 
                 406.1753 
                 C21H22N6O3 
                 1.9 
                 71.0 
               
               
                 298 
                 8.37 
                 413127 
                 348.1215 
                 348.1209 
                 C18H20O7 
                 −1.7 
                 87.5 
               
               
                 299 
                 8.41 
                 137899 
                 194.0941 
                 194.0943 
                 C11H14O3 
                 0.9 
                 86.0 
               
               
                 300 
                 8.41 
                 269699 
                 222.0891 
                 222.0892 
                 C12H14O4 
                 0.4 
                 70.0 
               
               
                 301 
                 8.43 
                 132981 
                 188.1408 
                 188.1412 
                 C10H20O3 
                 2.6 
                 47.3 
               
               
                 303 
                 8.44 
                 86910 
                 240.1354 
                 240.1362 
                 C13H20O4 
                 3.0 
                 83.5 
               
               
                 304 
                 8.45 
                 85973 
                 504.2467 
                 504.2472 
                 C26H36N2O8 
                 1.0 
                 78.6 
               
               
                 305 
                 8.45 
                 31782 
                 458.2047 
                 458.2035 
                 C36H26 
                 −2.7 
                 72.8 
               
               
                 306 
                 8.45 
                 58518 
                 248.1045 
                 248.1049 
                 C14H16O4 
                 1.7 
                 78.6 
               
               
                 307 
                 8.45 
                 69609 
                 288.0992 
                 288.0998 
                 C16H16O5 
                 1.8 
                 82.0 
               
               
                 308 
                 8.48 
                 251454 
                 226.0841 
                 226.0841 
                 C11H14O5 
                 0.2 
                 81.9 
               
               
                 309 
                 8.48 
                 11209 
                 432.1870 
                 432.1865 
                 C18H32N4O4S2 
                 −1.2 
                 47.6 
               
               
                 312 
                 8.51 
                 155396 
                 238.1209 
                 238.1205 
                 C13H18O4 
                 −1.7 
                 85.4 
               
               
                 313 
                 8.51 
                 48488 
                 320.1356 
                 320.1347 
                 C20H20N2S 
                 −2.6 
                 72.0 
               
               
                 314 
                 8.51 
                 33514 
                 262.0847 
                 262.0848 
                 C7H14N6O3S 
                 0.5 
                 45.3 
               
               
                 315 
                 8.52 
                 33022 
                 286.0847 
                 286.0841 
                 C16H14O5 
                 −2.1 
                 47.6 
               
               
                 316 
                 8.52 
                 52482 
                 344.1331 
                 344.1332 
                 C13H20N4O7 
                 0.2 
                 71.3 
               
               
                 318 
                 8.54 
                 32361 
                 568.2414 
                 568.2421 
                 C30H36N2O9 
                 1.2 
                 73.5 
               
               
                 319 
                 8.55 
                 35134 
                 502.2310 
                 502.2315 
                 C26H34N2O8 
                 1.0 
                 73.5 
               
               
                 320 
                 8.55 
                 13759 
                 338.1374 
                 338.1366 
                 C17H22O7 
                 −2.5 
                 47.6 
               
               
                 324 
                 8.57 
                 60165 
                 362.1371 
                 362.1379 
                 C20H18N4O3 
                 2.3 
                 80.6 
               
               
                 325 
                 8.57 
                 11738 
                 490.2211 
                 490.2203 
                 C26H34O9 
                 −1.7 
                 47.3 
               
               
                 327 
                 8.6 
                 33004 
                 406.1744 
                 406.1753 
                 C21H22N6O3 
                 2.4 
                 76.3 
               
               
                 330 
                 8.65 
                 108312 
                 220.1101 
                 220.1099 
                 C13H16O3 
                 −0.7 
                 47.6 
               
               
                 331 
                 8.66 
                 29225 
                 152.0835 
                 152.0837 
                 C9H12O2 
                 1.7 
                 47.2 
               
               
                 332 
                 8.67 
                 85178 
                 224.1046 
                 224.1049 
                 C12H16O4 
                 1.1 
                 73.4 
               
               
                 333 
                 8.67 
                 626807 
                 216.1356 
                 216.1362 
                 C11H20O4 
                 2.5 
                 78.6 
               
               
                 334 
                 8.7 
                 50955 
                 308.1703 
                 308.1696 
                 C11H24N4O6 
                 −2.2 
                 57.1 
               
               
                 335 
                 8.72 
                 56253 
                 272.1618 
                 272.1624 
                 C14H24O5 
                 2.0 
                 79.6 
               
               
                 336 
                 8.74 
                 172488 
                 234.0887 
                 234.0892 
                 C13H14O4 
                 2.1 
                 85.9 
               
               
                 337 
                 8.75 
                 57396 
                 338.1836 
                 338.1842 
                 C17H26N2O5 
                 1.6 
                 82.7 
               
               
                 338 
                 8.75 
                 51503 
                 254.1512 
                 254.1518 
                 C14H22O4 
                 2.2 
                 74.1 
               
               
                 339 
                 8.76 
                 38516 
                 502.2313 
                 502.2315 
                 C26H34N2O8 
                 0.3 
                 74.8 
               
               
                 340 
                 8.76 
                 32572 
                 444.1799 
                 444.1798 
                 C25H24N4O4 
                 −0.3 
                 74.1 
               
               
                 341 
                 8.77 
                 50814 
                 514.1959 
                 514.1965 
                 C27H26N6O5 
                 1.1 
                 77.9 
               
               
                 342 
                 8.8 
                 30040 
                 518.2258 
                 518.2246 
                 C38H30O2 
                 −2.4 
                 73.3 
               
               
                 344 
                 8.82 
                 48533 
                 402.1788 
                 402.1791 
                 C21H26N2O6 
                 0.7 
                 79.8 
               
               
                 345 
                 8.82 
                 21607 
                 320.1734 
                 320.1736 
                 C17H24N2O4 
                 0.6 
                 46.4 
               
               
                 346 
                 8.82 
                 32764 
                 346.1422 
                 346.1423 
                 C12H22N6O4S 
                 0.3 
                 47.6 
               
               
                 347 
                 8.83 
                 157016 
                 234.0891 
                 234.0892 
                 C13H14O4 
                 0.3 
                 47.3 
               
               
                 350 
                 8.87 
                 53536 
                 154.0995 
                 154.0994 
                 C9H14O2 
                 −0.8 
                 47.6 
               
               
                 351 
                 8.87 
                 110608 
                 214.1566 
                 214.1569 
                 C12H22O3 
                 1.3 
                 86.9 
               
               
                 352 
                 8.89 
                 211908 
                 200.1409 
                 200.1412 
                 C11H20O3 
                 1.6 
                 86.8 
               
               
                 353 
                 8.93 
                 78082 
                 276.1360 
                 276.1362 
                 C16H20O4 
                 0.6 
                 83.4 
               
               
                 354 
                 8.94 
                 53539 
                 476.2162 
                 476.2172 
                 C25H28N6O4 
                 2.1 
                 78.1 
               
               
                 355 
                 8.94 
                 78313 
                 384.1578 
                 384.1586 
                 C23H20N4O2 
                 2.2 
                 82.1 
               
               
                 356 
                 8.94 
                 19203 
                 418.1655 
                 418.1643 
                 C16H30N6OS3 
                 −2.7 
                 47.6 
               
               
                 357 
                 8.94 
                 314680 
                 488.2523 
                 488.2523 
                 C26H36N2O7 
                 −0.1 
                 95.7 
               
               
                 358 
                 8.94 
                 62748 
                 202.1565 
                 202.1569 
                 C11H22O3 
                 2.1 
                 47.4 
               
               
                 360 
                 8.98 
                 114312 
                 430.2012 
                 430.2005 
                 C25H26N4O3 
                 −1.7 
                 88.9 
               
               
                 362 
                 9.03 
                 63568 
                 372.1577 
                 372.1573 
                 C21H24O6 
                 −1.1 
                 82.2 
               
               
                 363 
                 9.06 
                 49596 
                 236.1049 
                 236.1049 
                 C13H16O4 
                 −0.3 
                 47.5 
               
               
                 365 
                 9.07 
                 32191 
                 435.1903 
                 435.1907 
                 C23H25N5O4 
                 0.9 
                 76.6 
               
               
                 366 
                 9.07 
                 133368 
                 476.2162 
                 476.2159 
                 C24H32N2O8 
                 −0.8 
                 97.1 
               
               
                 367 
                 9.11 
                 135166 
                 430.2020 
                 430.2025 
                 C21H34O7S 
                 1.3 
                 93.7 
               
               
                 369 
                 9.14 
                 23340 
                 230.1514 
                 230.1518 
                 C12H22O4 
                 1.8 
                 46.8 
               
               
                 370 
                 9.15 
                 46146 
                 400.1882 
                 400.1886 
                 C23H28O6 
                 1.0 
                 77.5 
               
               
                 371 
                 9.19 
                 48238 
                 214.1565 
                 214.1569 
                 C12H22O3 
                 1.7 
                 47.0 
               
               
                 372 
                 9.25 
                 51996 
                 274.1781 
                 274.1780 
                 C14H26O5 
                 −0.3 
                 47.6 
               
               
                 373 
                 9.26 
                 80933 
                 198.1616 
                 198.1620 
                 C12H22O2 
                 1.8 
                 83.3 
               
               
                 374 
                 9.3 
                 30748 
                 532.2773 
                 532.2785 
                 C28H40N2O8 
                 2.1 
                 73.9 
               
               
                 375 
                 9.3 
                 33591 
                 462.2344 
                 462.2341 
                 C28H34N2O2S 
                 −0.7 
                 68.3 
               
               
                 377 
                 9.33 
                 61953 
                 430.2088 
                 430.2079 
                 C27H30N2OS 
                 −2.2 
                 69.7 
               
               
                 379 
                 9.35 
                 33176 
                 520.2411 
                 520.2421 
                 C26H36N2O9 
                 1.9 
                 77.5 
               
               
                 381 
                 9.41 
                 27133 
                 594.2570 
                 594.2577 
                 C32H38N2O9 
                 1.2 
                 71.3 
               
               
                 382 
                 9.41 
                 40414 
                 442.2099 
                 442.2104 
                 C24H30N2O6 
                 1.1 
                 75.8 
               
               
                 383 
                 9.44 
                 43958 
                 596.2729 
                 596.2734 
                 C32H40N2O9 
                 0.8 
                 74.4 
               
               
                 384 
                 9.47 
                 28859 
                 386.1729 
                 386.1723 
                 C14H30N2O8S 
                 −1.6 
                 45.2 
               
               
                 385 
                 9.47 
                 90502 
                 444.2258 
                 444.2260 
                 C24H32N2O6 
                 0.5 
                 81.6 
               
               
                 386 
                 9.54 
                 84204 
                 336.2048 
                 336.2049 
                 C18H28N2O4 
                 0.3 
                 85.2 
               
               
                 387 
                 9.65 
                 50092 
                 300.1937 
                 300.1937 
                 C16H28O5 
                 −0.1 
                 47.6 
               
               
                 388 
                 9.66 
                 91069 
                 358.2468 
                 358.2468 
                 C18H34N2O5 
                 −0.2 
                 84.9 
               
               
                 389 
                 9.66 
                 106582 
                 317.2203 
                 317.2202 
                 C16H31NO5 
                 −0.1 
                 82.0 
               
               
                 390 
                 9.67 
                 426025 
                 244.1675 
                 244.1675 
                 C13H24O4 
                 −0.1 
                 83.7 
               
               
                 392 
                 9.87 
                 95939 
                 350.2206 
                 350.2206 
                 C19H30N2O4 
                 −0.1 
                 85.0 
               
               
                 393 
                 9.96 
                 19195 
                 258.1831 
                 258.1831 
                 C14H26O4 
                 0.0 
                 47.6 
               
               
                 394 
                 10.14 
                 220483 
                 278.1518 
                 278.1518 
                 C16H22O4 
                 0.1 
                 86.1 
               
               
                 395 
                 10.14 
                 65839 
                 204.0782 
                 204.0786 
                 C12H12O3 
                 2.0 
                 85.3 
               
               
                 396 
                 10.15 
                 43349 
                 283.2146 
                 283.2147 
                 C16H29NO3 
                 0.7 
                 74.3 
               
               
                 397 
                 10.32 
                 36335 
                 302.2246 
                 302.2246 
                 C20H30O2 
                 0.0 
                 83.2 
               
               
                 398 
                 10.46 
                 90642 
                 304.2403 
                 304.2402 
                 C20H32O2 
                 −0.2 
                 85.0 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Suggested Compounds in FILTRATE from LC/QTOF Analysis 
               
            
           
           
               
               
               
            
               
                 # Formula 
                 Mass 
                 Cpd 
               
               
                   
               
            
           
           
               
               
               
            
               
                 C6H12O6 
                 180.06339 
                 Glucose 
               
               
                 C8H8O3 
                 152.04734 
                 Vanillin 
               
               
                 C5H10O5 
                 150.05282 
                 Arabinose 
               
               
                 C6H12O6 
                 180.06339 
                 Mannose 
               
               
                 C5H10O5 
                 150.05282 
                 Xylose 
               
               
                 C6H12O6 
                 180.06339 
                 Galactose 
               
               
                 C5H4O2 
                 96.02113 
                 Furfural 
               
               
                 C6H6O3 
                 126.03169 
                 5-Hydroxymethylfurfural 
               
               
                 C2H4O2 
                 60.02113 
                 Acetic Acid 
               
               
                 C2H6O 
                 46.04186 
                 Ethanol 
               
               
                 C5H8O3 
                 116.04734 
                 Levulinic Acid 
               
               
                 C3H6O3 
                 90.03169 
                 Lactic Acid 
               
               
                 C7H12O3 
                 144.07864 
                 Ethyl Levulinate 
               
               
                 CH2O2 
                 46.00548 
                 Formic Acid 
               
               
                 C4H6O4 
                 118.02661 
                 Succinic Acid 
               
               
                 C6H6O2 
                 110.03678 
                 Methyl Furfural (Furfural Derivatives) 
               
               
                 C2H4O3 
                 76.01604 
                 Hydroxy Acids (Glycolic Acid) 
               
               
                 C6H12O7 
                 196.05830 
                 D-Gluconic Acid 
               
               
                 C12H22O12 
                 358.11113 
                 Cellobionic Acid 
               
               
                 C5H10O6 
                 166.04774 
                 D-Arabinonic Acid 
               
               
                 C4H8O5 
                 136.03717 
                 D-Erythronic Acid 
               
               
                 C2H2O3 
                 74.00039 
                 Glyoxylic Acid 
               
               
                 C6H10O7 
                 194.04265 
                 D-Glucuronic Acid 
               
               
                 C2H4O3 
                 76.01604 
                 Glycolic Acid 
               
               
                 C3H6O3 
                 90.03169 
                 2-Hydroxypropionic 
               
               
                 C3H6O4 
                 106.02661 
                 Glyceric Acid 
               
               
                 C4H4O4 
                 116.01096 
                 3,4-Dihydroxybutyric Acid 
               
               
                 C6H10O8 
                 210.03757 
                 Glucaric Acid 
               
               
                 C5H12O5 
                 152.06847 
                 Xylitol (Other Sugar Alcohols) 
               
               
                 C9H10O4 
                 182.05791 
                 Syringaldehyde 
               
               
                 C7H6O3 
                 138.03169 
                 p-Hydroxybenzoic Acid 
               
               
                 C6H6O 
                 94.04186 
                 Phenol 
               
               
                 C8H10O3 
                 154.06299 
                 2,6-Dimethoxy Phenol (Syringol) 
               
               
                 C10H12O2 
                 164.08373 
                 Isoeugenol (2-methoxy-4-propenyl) phenol 
               
               
                 C7H8O2 
                 124.05243 
                 2-Methoxy phenol 
               
               
                 C18H36O2 
                 284.27153 
                 Ethyl ester of hexadecanoic acid 
               
               
                 C6H12O3 
                 132.07864 
                 Ethyl Ester 2-Hydroxy butanoic acid 
               
               
                 C20H40O2 
                 312.30283 
                 Ethyl ester octadecanoic acid 
               
               
                 C19H32O2 
                 292.24023 
                 Methyl ester 9,12,15-Octadecatrienoic 
               
               
                   
                   
                 acid 
               
               
                 C7H12O4 
                 160.07356 
                 Ethyl Methyl Ester Butanedioic acid 
               
               
                 C8H14O4 
                 174.08921 
                 Diethyl Ester Butandioic acid (Diethyl 
               
               
                   
                   
                 Succinate) 
               
               
                 C20H38O2 
                 310.28718 
                 Ethyl Oleate 
               
               
                 C7H8O3 
                 140.04734 
                 Ethyl Ester 2-Furancarboxylic acid 
               
               
                 C17H34O2 
                 270.25588 
                 Methyl Ester Hexadecanoic acid 
               
               
                 C6H10O5 
                 162.05282 
                 Diethyl Ester Hydroxy butanedioic 
               
               
                 C6H8O2 
                 112.05243 
                 2-Hydroxy-3-methyl-2-cyclopenten-1-one 
               
               
                 C8H6O3Cl2 
                 219.96940 
                 ISTD - Dicamba 
               
               
                 C9H9O3Cl 
                 200.02402 
                 ISTD - MCPA 
               
               
                 C9H8O3Cl2 
                 233.98505 
                 ISTD - 2,4-DP 
               
               
                 C10H11O3Cl 
                 214.03967 
                 ISTD - MCPP 
               
               
                 C11H13O3Cl 
                 228.05532 
                 ISTD - MCPB 
               
               
                 C9H10N4O2S2 
                 270.02452 
                 ISTD - Sulfamethizole 
               
               
                 C12H14N4O2S 
                 278.08375 
                 ISTD - Sulfamethazine 
               
               
                 C10H9N4O2SCl 
                 284.01347 
                 ISTD - Sulfachloropyridazine 
               
               
                 C12H14N4O4S 
                 310.07358 
                 ISTD - Sulfadimethoxine 
               
               
                 C5H10O3 
                 118.06299 
                 Ethyl Lactate 
               
               
                 C6H6O2 
                 110.03678 
                 5-Methyl-2-furancarboxaldehyde 
               
               
                 C11H14O3 
                 194.09429 
                 2,6-Dimethoxy-4-(2-propenyl)-phenol 
               
               
                 C6H10O5 
                 162.05282 
                 1,6-anhydroglucose 
               
               
                 H2O4S 
                 97.96738 
                 Sulphuric acid 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 12 
               
             
            
               
                   
               
               
                 Average molecular masses, polydispersity and glass transition points 
               
               
                 of ASPEN MACs 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Mn 
                 Mw 
                 Mz 
                   
                 Tg 
               
            
           
           
               
               
               
               
            
               
                 Aromatic Mixes (MACs) 
                 g/moL 
                 D 
                 ° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 MAC II 
                 601 
                 1331 
                 2381 
                 2.22 
                 69.14 
               
               
                 MAC II 
                 597 
                 1326 
                 2377 
                 2.22 
                 67.51 
               
               
                 MAC I 
                 335 
                 2855 
                 5859 
                 8.52 
                 N/A 
               
               
                 MAC I 
                 351 
                 2911 
                 5953 
                 8.28 
                 N/A 
               
               
                 ACETONE-INSOLUBLES 
                 581 
                 2787 
                 5733 
                 4.8 
                 N/A 
               
               
                 MAC I 
               
               
                 ACETONE-INSOLUBLES 
                 582 
                 2805 
                 5794 
                 4.82 
                 N/A 
               
               
                 MAC I 
               
               
                 ACETONE-SOLUBLES 
                 281 
                 2643 
                 5561 
                 9.38 
                 102.85 
               
               
                 MAC I 
               
               
                 ACETONE-SOLUBLES 
                 281 
                 2644 
                 5562 
                 9.37 
                 N/A 
               
               
                 MAC I 
               
               
                   
               
            
           
         
       
     
     Synthesis of MAC-Phenol-Formaldehyde (LPF) Resins for Wood Composites 
     LPF Resins were synthesized from a 40/60 MAC/Phenol mixture, and at a Phenol:Formaldehyde molar ratio of 1:2.55. 
     Reagents &amp; equipment used for the synthesis method:
     12.76 g 50% NaOH solution (Fisher Scientific, CAS 1310-73-2, Cat#SS410-4)   42.4 g 37% Formaldehyde solution (Fisher Scientific, CAS 50-00-0, Cat#F79-4)   19.28 g Phenol (Fisher Scientific, CAS 108-95-2, Cat#A91I-212)   32.71 g Nanopure water (18.2 MΩ*cm or better)   12.85 g MACs produced by Lignol Innovations, Ltd., Burnaby, BC, Canada   250 ml 3-neck round bottom flasks   Small condenser   Corning brand thermocouple   Rubber stoppers   Rubber stoppers with a hole punched in center to accept a thermocouple   Teflon covered magnetic stir bar   Hot-stirring plates   Medium crystallizing dish that fit the 250 ml round bottom flask   1 big crystallizing dish   Small plastic funnel   100 ml beaker   1 small glass funnel   3-50 ml volumetric flasks with glass stoppers   2 pieces of connecting tubing for the condensers   2 clamps for the flasks and condensers   Metal stand   Weighing dish   Portable Viscolite viscometer from Hydramotion Ltd. (York, England)   

     The reagents were weighed and synthesis resin reactors were set-up by connecting the condensers with the tubing in series, clamping the round bottom flask on top of the crystallizing dish, sitting on a hot-stirring plate. Thermocouples were inserted through rubber stoppers and placed in the centre joint of the flask. The clamped condenser was placed in one of the side joints of the flask. A magnetic stir bar was placed in the flask. On another hot-stirring plate a big crystallizing dish was placed containing the jar with solid phenol. Sufficient hot water was added to the crystallizing dish to cover the level of solid phenol in the jar. The water was heated to approximately 70-80° C. in order to melt the phenol. 
     While the phenol was melting, 100 mL beaker and a small glass funnel were heated in a 105° C. oven. Hot water was added in the crystallizing dishes containing the flasks, and the hotplate temperature set to 55° C. When the phenol was molten and the hotplate had achieved 55° C., the phenol was removed from the hot water bath. 19.3 g of molten phenol was added to the hot, 100 mL beaker. Liquid phenol was poured through the hot glass funnel into the round bottom flask. 
     Over 10-15 minutes 12.85 g of MAC was added in small amounts to the flasks through a small plastic funnel. Stirring speed was 300 rpm and as the mixture viscosity increased the stirring speed was gradually be increased to 340 rpm. 
     The stirring speed was reduced to 300 rpm. 32.71 g of deionized water and 12.76 g 50% NaOH solution was poured into the flask. The temperature may increase due to the exothermic nature of the reaction. Once the reaction temperature was stabilized at 55° C. the mixture was left to stand for 10 additional minutes then 42.4 g 37% formaldehyde solution was slowly added. The temperature was increased to 70° C. and left for it to stabilize (approx. 10 mins). Once the temperature had stabilized, the hotplate was set to 75° C. After the reaction achieved 75° C. it was held for 3 hours. The hotplate maintained the reaction temperature throughout the experiment. The water level was monitored and hot water added as necessary. The level was kept above the resin level within the flask. 
     After 3 h at 75° C., the reaction temperature was increased to 80° C. and, after stabilization, maintained for 2.5 hours. The level of water in crystallizing dishes was monitored to ensure it did not drop below that of the resin in the flasks. 
     A few minutes before the 2 h 30 minutes are done, prepare 2 big crystallizing dishes with cold water. After 2 h30 min at 80° C., the hotplate was adjusted to 35° C., and the flask with the condenser raised above the crystallizing dish. The dish with hot water was removed and poured away. A big crystallizing dish with cold water was placed on the hot plate and the flask with the condenser lowered in the cold water bath. More cold water was poured in until the flask is immersed up to the joints&#39; level in cold water. The flask was kept immersed, under continuous stirring and in cold water, until the temperature in the reaction mixture stabilized at 35° C. The reaction was then removed from the cold water bath. The bond strength (also called “shear strength”) of MAC-PF resins was tested by the ABES method (Wescott, J. M., Birkeland, M. J., Traska, A. E., New Method for Rapid Testing of Bond Strength for Wood Adhesives, Heartland Resource Technologies Waunakee, Wis., U.S.A. and Frihart, C. R. and Dally, B. N., USDA Forest Service, Forest Products Laboratory, Madison, Wis., U.S.A., Proceedings 30 th  Annual Meeting of The Adhesion Society, Inc., Feb. 18-21, 2007, Tampa Bay, Fla., USA) under the following conditions: sliced aspen strands: 117 mm×20 mm×0.8 mm (conditioned at 50% HR &amp; 20° C.), bonding area: 20 mm×5 mm, press temperature: 150° C., press pressure: 2 MPa, press time: 90 seconds. Ten replicates for each resin sample were run. The average bond strength in MPa of ten replicates was then normalized dividing by the grams loaded resin per square centimeter of bonding area to yield the Normalized Bond Strength (NBS) or normalized shear strength. 
     
       
         
           
               
             
               
                 TABLE 13 
               
             
            
               
                   
               
               
                 Bond strength performance of the MACs PF Resins 
               
               
                 (40% phenol replacement) compared to Alcell ®-Lignin PF_Resins 
               
            
           
           
               
               
            
               
                   
                 Normalized Bond Strength 
               
               
                   
                 at 150° C.* 
               
               
                   
                 MPa * cm 2 /g resin 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 MAC-I PF Resin 
                 3,700 ± 273 
               
               
                   
                 MAC-II PF Resin 
                 3,108 ± 355 
               
               
                   
                 ACETONE-SOLUBLE MAC-I PF 
                 3,229 ± 235 
               
               
                   
                 Resin 
               
               
                   
                 Alcell ®-Lignin PF_Resin 
                 3,079 ± 244 
               
               
                   
                   
               
               
                   
                 *Average of 10 replicates at 40% phenol replacement level