澳大利亚专利AU2012362936A1 Compositions comprising lignin

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专利摘要:
Compositions comprising lignin and low levels of undesirable impurities, such as compounds containing sulfur, nitrogen, or metals, are disclosed.
公开号:AU2012362936A1
申请号:U2012362936
申请日:2012-12-03
公开日:2014-07-03
发明作者:Kiran L. Kadam；Srinivas Kilambi
申请人:Renmatix Inc；
IPC主号:C08L97-00

专利说明:
WO 2013/101397 PCT/US2012/067535 COMPOSITIONS COMPRISING LIGNIN CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Application No. 61/581,865, filed December 30, 2011, and U.S. Application No. 13/472,798 filed May 16, 2012, the entire disclosures of which are incorporated herein by reference. FIELD OF THE INVENTION [0002] The present invention generally relates to compositions comprising lignin containing maximum levels of undesirable impurities, such as compounds containing sulfur, nitrogen, or metals. BACKGROUND OF THE INVENTION [0003] There are a number of processes for converting lignocellulosic biomass into liquid streams of various sugars. Certain preferred processes are based on supercritical water (SCW) or hot compressed water (HCW) technology, which offer several advantages including high throughputs, use of mixed feedstocks, separation of sugars, and avoidance of concentrated acids, microbial cultures, and enzymes. Processes using hot compressed water may have two distinct operations: pre treatment and cellulose hydrolysis. The pre-treatment process hydrolyzes the hemicellulose component of the lignocellulosic biomass and cellulose hydrolysis (CH) process hydrolyzes the cellulose fibers. The resultant five carbon (C5) and six carbon (C6) sugar streams are recovered separately. The remaining solids, which consist mostly of lignin, are preferably recovered, such as through filtration, and may be used as a fuel to provide thermal energy to the process itself or for other processes. Lignin has the combustion heat of 26.6 KJ/g, and holds highest energy among all natural polymeric compounds that contain carbon, hydrogen and oxygen. In energy, lignin is equivalent to ethanol, which also contains carbon, hydrogen and oxygen, and has the combustion heat of 30 KJ/g. However, for a given volume, lignin's combustion heat is approximately 1.5 times as much as that of ethanol, because of lignin's higher density. 1 WO 2013/101397 PCT/US2012/067535 http://www.altenergymag.com/emagazine/2009/06/lig n in-as-alternative-renewable fuel/1384). Thus, lignin serves as a useful renewable energy source. [0004] Lignocellulosic biomass contains cellulose, hemicellulose, and lignin, along with minor amounts of proteins, lipids (fats, waxes, and oils) and minerals. About two thirds of the dry mass of cellulosic materials is present as cellulose and hemicellulose with lignin making up the bulk of the remaining dry mass. Lignin is a cross-linked racemic macromolecule with a molecular masse in excess of 10,000 Daltons. It is relatively hydrophobic and aromatic in nature. The degree of polymerization in nature is difficult to measure, since it is fragmented during extraction and the molecule consists of various types of substructures that appear to repeat in a haphazard manner. Different types of lignin have been described depending on the means of isolation. "Lignin and its Properties: Glossary of Lignin Nomenclature," Dialogue/Newsletters Volume 9, Number 1, Lignin Institute, July 2001. [0005] There are three monolignol monomers, methoxylated to various degrees: p coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. K. Freudenberg & A.C. Nash (eds) (1968). Constitution and Biosynthesis of Lignin. Berlin: Springer-Verlag. These lignols are incorporated into lignin in the form of the phenylpropanoids p-hydroxyphenyl (H), guaiacyl (G), and syringal (S), respectively. W. Boerjan, J. Ralph, M. Baucher (June 2003). "Lignin bios". Ann. Rev. Plant Biol. 54 (1): 519-549. Gymnosperms have a lignin that consists almost entirely of G with small quantities of H. That of dicotyledonous angiosperms is more often than not a mixture of G and S (with very little H), and monocotyledonous lignin is a mixture of all three. Id. Many grasses have mostly G, while some palms have mainly S. All lignins contain small amounts of incomplete or modified monolignols, and other monomers are prominent in non-woody plants. J. Ralph, et al. (2001). "Elucidation of new structures in lignins of CAD- and COMT-deficient plants by NMR." Phytochem. 57 (6): 993-1003. [0006] Impurities may be introduced into lignin via processing of the lignocellulosic biomass. Since lignin compositions may be used as a fuel in the SCW or HCW process or other processes, they preferably have a low level of contaminants or impurities that contribute to health, environmental, and safety concerns. For example, it is highly desirable to have no or only a low level of compounds containing sulfur in the lignin 2 WO 2013/101397 PCT/US2012/067535 composition, as the presence of sulfur may contribute to SOx emissions, when the lignin is combusted. In other applications, low levels of sulfur may also be desirable if lignin is chemically converted through a catalytic process to a downstream product or a derivative. Low levels of sulfur within the final product may also be desirable from product acceptance criteria, or low levels of sulfur may help prevent premature catalyst deactivation for such chemical conversions. [0007] Accordingly, the invention is directed to lignin compositions having low levels of impurities, as well as other important ends. SUMMARY OF THE INVENTION [0008] In one embodiment, the invention is directed to compositions, comprising: lignin; and less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. In some embodiments, the compositions further comprise less than about 700 mg of calcium per kg of said lignin. In other embodiments, the compositions further comprise less than about 525 mg of iron per kg of said lignin. In yet other embodiments, the compositions further comprise less than about 150 mg of sulfur per kg of said lignin. In some embodiments, the compositions further comprise less than about 20 g of ash per kg of said lignin. In other embodiments, the compositions comprise less than about 2000 mg of nitrogen per kg of said lignin. In yet other embodiments, the compositions further comprise a weight ratio of the total mass of hydrogen and nitrogen to carbon of less than about 0.110. [0009] In other embodiments, the invention is directed to compositions, comprising: lignin; less than about 700 mg of calcium per kg of said lignin; less than about 525 mg of iron per kg of said lignin; and less than about 150 mg of sulfur per kg of said lignin. 3 WO 2013/101397 PCT/US2012/067535 In some embodiments, the compositions comprise less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. [0010] In yet other embodiments, the invention is directed to compositions, comprising: lignin; and less than about 700 mg of calcium per kg of said lignin. In some embodiments, the compositions comprise less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. [0011] In yet further embodiments, the invention is directed to compositions, comprising: lignin; and less than about 525 mg of iron per kg of said lignin. In some embodiments, the compositions comprise less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. [0012] In yet another embodiment, the invention is directed to compositions, comprising: lignin; and less than about 150 mg of sulfur per kg of said lignin. In some embodiments, the compositions comprise less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. DETAILED DESCRIPTION OF THE INVENTION [0013] As employed above and throughout the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings. 4 WO 2013/101397 PCT/US2012/067535 [0014] As used herein, the singular forms "a," "an," and "the" include the plural reference unless the context clearly indicates otherwise. [0015] While the present invention is capable of being embodied in various forms, the description below of several embodiments is made with the understanding that the present disclosure is to be considered as an exemplification of the invention, and is not intended to limit the invention to the specific embodiments illustrated. Headings are provided for convenience only and are not to be construed to limit the invention in any manner. Embodiments illustrated under any heading may be combined with embodiments illustrated under any other heading. [0016] The use of numerical values in the various quantitative values specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word "about." In this manner, slight variations from a stated value can be used to achieve substantially the same results as the stated value. Also, the disclosure of ranges is intended as a continuous range including every value between the minimum and maximum values recited as well as any ranges that can be formed by such values. Also disclosed herein are any and all ratios (and ranges of any such ratios) that can be formed by dividing a recited numeric value into any other recited numeric value. Accordingly, the skilled person will appreciate that many such ratios, ranges, and ranges of ratios can be unambiguously derived from the numerical values presented herein and in all instances such ratios, ranges, and ranges of ratios represent various embodiments of the present invention. [00171 As used herein, the phrase "substantially free" means have no more than about 1%, preferably less than about 0.5%, more preferably, less than about 0.1%, by weight of a component, based on the total weight of any composition containing the component. [0018] A supercritical fluid is a fluid at a temperature above its critical temperature and at a pressure above its critical pressure. A supercritical fluid exists at or above its "critical point," the point of highest temperature and pressure at which the liquid and vapor (gas) phases can exist in equilibrium with one another. Above critical pressure 5 WO 2013/101397 PCT/US2012/067535 and critical temperature, the distinction between liquid and gas phases disappears. A supercritical fluid possesses approximately the penetration properties of a gas simultaneously with the solvent properties of a liquid. Accordingly, supercritical fluid extraction has the benefit of high penetrability and good solvation. [0019] Reported critical temperatures and pressures include: for pure water, a critical temperature of about 374.20C, and a critical pressure of about 221 bar; for carbon dioxide, a critical temperature of about 31 0 C and a critical pressure of about 72.9 atmospheres (about 1072 psig). Near critical water has a temperature at or above about 300'C and below the critical temperature of water (374.20C), and a pressure high enough to ensure that all fluid is in the liquid phase. Sub-critical water has a temperature of less than about 3000C and a pressure high enough to ensure that all fluid is in the liquid phase. Sub-critical water temperature may be greater than about 2500C and less than about 3000C, and in many instances sub-critical water has a temperature between about 2500C and about 2800C. The term "hot compressed water" is used interchangeably herein for water that is at or above its critical state, or defined herein as near- critical or sub-critical, or any other temperature above about 500C (preferably, at least about 1000C) but less than subcritical and at pressures such that water is in a liquid state. [0020] As used herein, a fluid which is "supercritical" (e.g. supercritical water, supercritical C02, etc.) indicates a fluid which would be supercritical if present in pure form under a given set of temperature and pressure conditions. For example, "supercritical water" indicates water present at a temperature of at least about 374.20C and a pressure of at least about 221 bar, whether the water is pure water, or present as a mixture (e.g. water and ethanol, water and C02, etc.). Thus, for example, "a mixture of sub-critical water and supercritical carbon dioxide" indicates a mixture of water and carbon dioxide at a temperature and pressure above that of the critical point for carbon dioxide but below the critical point for water, regardless of whether the supercritical phase contains water and regardless of whether the water phase contains any carbon dioxide. For example, a mixture of sub-critical water and supercritical C02 may have a temperature of about 2500C to about 2800C and a pressure of at least about 225 bar. 6 WO 2013/101397 PCT/US2012/067535 [0021] As used herein, "lignocellulosic biomass or a component part thereof' refers to plant biomass containing cellulose, hemicellulose, and lignin from a variety of sources, including, without limitation (1) agricultural residues (including corn stover and sugarcane bagasse), (2) dedicated energy crops, (3) wood residues (including hardwoods, softwoods, sawmill and paper mill discards), and (4) municipal waste, and their constituent parts including without limitation, lignocellulose biomass itself, lignin, C6 saccharides (including cellulose, cellobiose, C6 oligosaccharides, C6 monosaccharides, C 5 saccharides (including hemicellulose, C5 oligosaccharides, and C5 monosaccharides), and mixtures thereof. [0022] As used herein, "ash" refers to the non-aqueous residue that remains after a sample is burned, and consists mostly of metal oxides. Ash content may be measured in accordance with ASTM Standard Method No. E1755-01 "Standard Method for the Determination of Ash in Biomass." This test method covers the determination of ash, expressed as the percentage of residue remaining after dry oxidation at 550 to 6000C. All results are reported relative to the 105'C oven dry weight of the sample." See also: http://www.nrel.qov/biomass/pdfs/42622.pdf and http://www.astm.orq/Standards/ El 755.htm, which are both incorporated herein by reference in their entirety. [00231 Accordingly, in one embodiment, the invention is directed to compositions, comprising: lignin; and less than about 2000 mg, preferably less than about 1775 mg, in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. [0024] In other embodiments, the invention is directed to compositions, comprising: lignin; less than about 700 mg, preferably less than about 675 mg, of calcium per kg of said lignin; less than about 525 mg, preferably less than about 505 mg, of iron per kg of said lignin; and 7 WO 2013/101397 PCT/US2012/067535 less than about 150 mg, preferably less than about 147 mg, of sulfur per kg of said lignin. [0025] In some embodiments, the compositions comprise: lignin; and less than about 700 mg, preferably less than about 675 mg, of calcium per kg of said lignin. [0026] In some embodiments, the compositions comprise: lignin; and less than about 525 mg, preferably less than about 505 mg, of iron per kg of said lignin. [0027] In some embodiments, the compositions comprise: lignin; and less than about 150 mg, preferably less than about 147 mg, of sulfur per kg of said lignin. [0028] In some embodiments, the compositions comprise less than about 2000 mg, preferably less than 1775 mg, in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn. [0029] In some embodiments, the compositions further comprise less than about 700 mg, preferably less than about 675 mg, of calcium per kg of said lignin. In other embodiments, the compositions further comprise less than about 525 mg of iron per kg of said lignin. In yet other embodiments, the compositions further comprise less than about 150 mg of sulfur per kg of said lignin. [0030] In some embodiments, the lignin has a heating value as measured by ASTM D240 and D5865 of at least about 5,000 BTU/lb, preferably at least about 7,500 BTU/lb, and more preferably, at least about 8,000 BTU/lb. 8 WO 2013/101397 PCT/US2012/067535 [0031] In some embodiments, the lignin has an average particle size less than about 500 microns. In preferred embodiments, the lignin has an average unaggregated particle size less than about 100 microns. In other preferred embodiments, the lignin has an average unaggregated particle size less than about 60 microns. [0032] In some embodiments, the lignin has a bulk density of less than about 0.35 g/cc, depending upon particle size. [0033] In some embodiments, the lignin is processed from lignocellulosic biomass optionally using supercritical, subcritical, or near critical fluid extraction or combinations thereof. [0034] In some embodiments, the composition is substantially free of organic solvent. [0035] In some embodiments, the lignin is in a powdered form. In other embodiments, the lignin is in a pelletized form. In yet other embodiments, the lignin is in a liquid form. In addition, the lignin may be in combination of these forms. [0036] In some embodiments, is present at a level of at least 30% by weight, based on the total weight of the composition, as measured by pyrolysis molecular beam mass spectrometry. [00371 In some embodiments, the weight ratio of syringyl monolignol to guaiacyl monolignol is about 2.0 to about 3.0, as measured by pyrolysis molecular beam mass spectrometry. [0038] In some embodiments, the compositions further comprise less than about 700 mg, preferably less than about 675 mg, of calcium per kg of said lignin. [0039] In some embodiments, the compositions further comprise less than about 525 mg, preferably less than about 505 mg, of iron per kg of said lignin. [0040] In some embodiments, the compositions further comprise less than about 150 mg, preferably less than about 147 mg, of sulfur per kg of said lignin. 9 WO 2013/101397 PCT/US2012/067535 [0041] In some embodiments, the levels of said elements are measured by inductively coupled plasma emission spectroscopy. [0042] In some embodiments, the compositions further comprise less than about 20 g of ash per kg of said lignin, preferably less than about 17.5 g of ash per kg of said lignin. [0043] In other embodiments, the compositions comprise less than about 2000 mg of nitrogen per kg of said lignin, preferably less than about 1900 mg of nitrogen per kg of said lignin. Nitrogen may be measured by thermal conductivity detection after combustion and reduction. [0044] In yet other embodiments, the compositions further comprise a weight ratio of the total mass of hydrogen and nitrogen to carbon of less than about 0.110, preferably less than about 0.105. Carbon, hydrogen, and nitrogen levels may be measured by thermal conductivity detection after combustion and reduction. [0045] In certain other embodiments, the compositions comprising the lignin further comprise less than a maximum of any of the elements, individually or in combination, in the table listed below: Element Level less than about (mg of element/kg of lignin) Al 50 As 16 B 3.25 Ba 3.7 Be 0.04 Cd 0.850 Co 1.25 Cr 2.0 Cu 20.0 K 45.0 Li 0.310 Mg 22.5 Mn 7.00 Mo 3.00 10 WO 2013/101397 PCT/US2012/067535 Element Level less than about (mg of element/kg of lignin) Na 61.5 Ni 1.50 P 115 Pb 10.00 Sb 9.50 Se 21.0 Si 65.0 Sn 11.00 Sr 2.25 Ti 6.00 TI 21.0 V 0.350 Zn 11.5 [0046] In further embodiments, the compositions further comprise less than about 0.5% by weight, based on the total weight of said lignin, of organic solvent, such as alcohols, including water miscible lower aliphatic C1C4 alcohols (e.g., methanol, ethanol, isopropanol, t-butanol). In preferred embodiments, the compositions contain less than about 0.1% by weight, based on the total weight of said lignin of organic solvent. In more preferred embodiments, the compositions contain substantially no organic solvent. [0047] The compositions of the invention are preferably prepared from biomass by processes employing supercritical, subcritical, and/or near critical water, preferably without the addition of acid. The processes may include pretreatment step or steps using supercritical or near critical water to separate the C5 sugars (monomers and/or oligomers) from cellulose and lignin. In the pretreatment step, suitable temperatures are about 130'C to about 250*C, suitable pressures are about 4 bars to about 100 bars, and suitable residence times are about 0.5 minutes to about 5 hours. The processes may also include a cellulose hydrolysis step or steps using supercritical or near critical water to separate the cellulose (which may processed to form C6 monomeric and/or oligomeric sugars) from the lignin. In the hydrolysis step(s), suitable temperatures are about 2500C to about 450 0 C, suitable pressures are about 40 bars to about 260 bars, and suitable residence times are about 0.1 seconds to about 3 minutes. 11 WO 2013/101397 PCT/US2012/067535 [0048] The compositions of the invention may be prepared in any suitable reactor, including, but not limited to, a tubular reactor, a digester (vertical, horizontal, or inclined), or the like. Suitable digesters include the digester system described in US-B 8,057,639, which include a digester and a steam explosion unit, the entire disclosure of which is incorporated by reference. [0049] The compositions of the invention comprising lignin may be utilized in a variety of applications, including, but not limited to, fuels, tackifiers, phenol formaldehyde resin extenders in the manufacture of particle board and plywood, in the manufacture of molding compounds, urethane and epoxy resins, antioxidants, controlled-release agents, flow control agents, cement/concrete mixing, plasterboard production, oil drilling, general dispersion, tanning leather, road covering, vanillin production, dimethyl sulfide and dimethyl sulfoxide production, phenol substitute in phenolic resins incorporation into polyolefin blends, aromatic (phenol) monomers, additional miscellaneous monomers, carbon fibers, metal sequestration in solutions, basis of gel formation, polyurethane copolymer - as a renewable filler/extender, and the like. [0050] The present invention is further defined in the following Examples, in which all parts and percentages are by weight, unless otherwise stated. It should be understood that these examples, while indicating preferred embodiments of the invention, are given by way of illustration only and are not to be construed as limiting in any manner. From the above discussion and these examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. EXAMPLES Example 1: Preparation of lignin compositions [0051] Lignin compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in a two stage process. Particulate 12 WO 2013/101397 PCT/US2012/067535 lignocellulosic biomass consisting of mixed hardwood chips of 140 mesh or less was mixed with water to form a slurry (about 20% by weight solids). The slurry was heated to a temperature of about 170-245'C and then feed into a pretreatment reactor for about 1-120 minutes under sufficient pressure to keep the water in the liquid phase. The pretreated slurry was then cooled to a temperature less than about 100 0 C under little (less than about 10 bar) or no pressure. The pretreated solids were then separated from the liquid stream using a filter press. Alternatively, the solids may be separated using a centrifugal filter pressor. The pretreated solids were then mixed with water to form a slurry and the slurry was heated to a temperature of about 150-250'C. The slurry was then subjected to supercritical water at about 374-600*C in a hydrolysis reactor for about 0.05-10 seconds under a pressure of about 230-300 bar. After exiting the hydrolysis reactor, the hydrolyzed slurry was quenched with water and then flashed to about ambient temperature and pressure to remove water. The lignin solids were then separated from the liquid stream using a centrifugal decanter and air dried. Example 2: Analysis of lignin compositions using inductively coupled plasma [0052] The dried compositions containing the lignin of Example 1 were analyzed using inductively coupled plasma emission spectroscopy. The results are shown in the table below: Sample Duplicate Sample Duplicate Sample Duplicate IPA ReotdB Reotdc Reorted element Reported Rorte Reported Repotd p Reported Rep Average conc. Coonc . n.Conc. oc (mg/kg) (mg/kg) mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) _________________________________ Al 45.5 47.8 39.1 37.5 43.6 40.4 42.3 As < 12.6 < 14.6 < 12.1 < 12.5 < 13.6 < 15.6 13.5 B 3.22 0.777 2.88 1.66 0.603 < 0.605 1.6 Ba 3.34 3.62 2.99 2.99 3.02 2.77 3.1 Be < 0.0300 < 0.0349 < 0.0288 < 0.0299 < 0.0326 < 0.0374 0.0 Ca 618 671 551 535 594 545 585.7 Cd < 0.667 < 0.777 < 0.640 < 0.665 < 0.724 < 0.830 0.7 Co < 0.972 < 1.13 < 0.933 < 0.969 < 1.05 < 1.21 1.0 Cr 1.56 1.94 1.60 1.66 1.33 1.38 1.6 Cu 5.89 8.80 7.26 7.87 6.64 19.0 9.2 Fe 465 501 313 298 351 320 374.6 K 39.1 40.4 23.7 31.1 33.1 44.1 35.3 Li < 0.245 < 0.285 < 0.235 < 0.244 < 0.266 < 0.304 0.3 Mg 21.9 22.1 18.8 19.0 18.6 19.8 20.0 Mn 5.89 6.47 5.02 4.99 4.34 4.01 5.1 Mo < 2.34 < 2.72 < 2.25 < 2.33 < 2.54 < 2.91 2.5 Na 58.7 52.0 54.6 40.7 50.6 61.0 52.9 13 WO 2013/101397 PCT/US2012/067535 Sample Duplicate Sample Duplicate Sample Duplicate lCP A ReotdB Ceore ceorted element Reported Rorte Reported Reponcd Reported Rep Average Con.nc.kg Conc. Conc.g Conc. Conc.g (mg/kg) (mg/kg) mg/kg) (mg/kg) (mg/kg) (mg/kg) Ni < 1.16 < 1.35 < 1.12 < 1.16 < 1.26 < 1.45 1.3 P < 89.9 < 105 < 86.2 < 89.6 < 97.5 < 112 96.6 Pb < 7.95 < 9.25 < 7.63 < 7.92 < 8.63 < 9.89 8.5 S 105 132 146 128 128 103 123.6 Sb < 7.46 < 8.68 < 7.16 < 7.43 < 8.09 < 9.28 8.0 Se < 16.5 < 19.2 < 15.9 < 16.5 < 18.0 < 20.6 17.8 Si 54.9 63.9 42.1 57.2 67.6 64.5 58.4 Sn 9.23 9.19 7.04 7.65 10.9 10.1 9.0 Sr 2.11 2.20 1.81 1.77 1.93 1.80 1.9 Ti 3.56 5.57 2.77 5.87 3.26 3.46 4.1 TI < 16.7 < 19.5 < 16.1 < 16.7 < 18.2 < 20.8 18.0 V < 0.260 < 0.303 < 0.250 0.332 < 0.282 < 0.324 0.3 Zn 9.79 11.0 9.28 9.86 7.48 6.37 9.0 Total Elements 1610.3 1762.1 1378.7 1347.2 1496.6 1441.4 1506.0 Example 3: Analysis of lignin for carbon, hydrogen, and nitrogen [0053] Dried compositions containing lignin were analyzed to determine the levels of ash, carbon, hydrogen, and nitrogen by thermal conductivity detection after combustion and reduction. The results are shown in the table below: Element/Material Sample 1 Sample 2 C 56.76% 57.09% H 5.46% 5.66% N 0.18% 0.19% Ash 1.1% 1.1% Ratio of N+H:C 0.099 0.102 Example 4: Lignin Characterization [0054] The NREL method for lignin (acid hydrolysis followed by gravimetric protocol in accordance with standard NREL procedures found at http:/Iwww. nrel.ciov/biomass/pdfs/42618.pdf and pyrolysis molecular beam mass spectrometry (py MBMS) were used to quantify the level of lignin in the solids, using lignin from hardwood as a standard. The results are shown in the table below: 14 WO 2013/101397 PCT/US2012/067535 Sample Lignin Weight % Lignin Weight % Syringyl/Guaiacyl from NREL Method from py-MBMS Weight Ratio from Method py-MBMS Method Hardwood 28 23.3 2.6 standard Pretreated 40-44 21.6 2.4 solids Solid residue >50 33.3 2.5 after supercritical hydrolysis [0055] When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, all combinations, and subcombinations of ranges specific embodiments therein are intended to be included. [0056] The disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference, in their entirety. [0057] Those skilled in the art will appreciate that numerous changes and modifications can be made to the preferred embodiments of the invention and that such changes and modifications can be made without departing from the spirit of the invention. It is, therefore, intended that the appended claims cover all such equivalent variations as fall within the true spirit and scope of the invention. 15

权利要求:
Claims (27)
[1] 1. A composition, comprising: lignin; and less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn.
[2] 2. A composition of claim 1, wherein said lignin has a heating value as measured by ASTM-D240 and D5865 of at least about 5,000 BTU/lb.
[3] 3. A composition of claim 1, wherein said lignin has an average particle size less than about 500 microns.
[4] 4. A composition of claim 1, wherein said lignin has a bulk density of less than about 0.35 g/cc.
[5] 5. A composition of claim 1, wherein said lignin is processed from lignocellulosic biomass optionally using supercritical, subcritical, or near critical fluid extraction or combinations thereof.
[6] 6. A composition of claim 1, wherein said composition is substantially free of organic solvent.
[7] 7. A composition of claim 1, wherein said lignin is in a powdered form.
[8] 8. A composition of claim 1, wherein said lignin is in a pelletized form. 16 WO 2013/101397 PCT/US2012/067535
[9] 9. A composition of claim 1, wherein said lignin is in a liquid form.
[10] 10. A composition of claim 1, further comprising: less than about 700 mg of calcium per kg of said lignin.
[11] 11. A composition of claim 1, further comprising: less than about 525 mg of iron per kg of said lignin.
[12] 12. A composition of claim 1, further comprising: less than about 150 mg of sulfur per kg of said lignin.
[13] 13. A composition of claim 1, wherein levels of said elements are measured by inductively coupled plasma emission spectroscopy.
[14] 14. A composition of claim 1, further comprising: less than about 20 g of ash per kg of said lignin.
[15] 15. A composition of claim 1, further comprising: less than about 2000 mg of nitrogen per kg of said lignin.
[16] 16. A composition of claim 1, further comprising: a weight ratio of the total mass of hydrogen and nitrogen to carbon of less than about 0.110.
[17] 17. A composition of claim 1, wherein said lignin is present at a level of at least 30% by weight, based on the total weight of the composition, as measured by pyrolysis molecular beam mass spectrometry. 17 WO 2013/101397 PCT/US2012/067535
[18] 18. A composition of claim 1, wherein the weight ratio of syringyl monolignol to guaiacyl monolignol is about 2.0 to about 3.0, as measured by pyrolysis molecular beam mass spectrometry.
[19] 19. A composition, comprising: lignin; less than about 700 mg of calcium per kg of said lignin; less than about 525 mg of iron per kg of said lignin; and less than about 150 mg of sulfur per kg of said lignin.
[20] 20. A composition of claim 19, further comprising: less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn.
[21] 21. A composition, comprising: lignin; and less than about 525 mg of iron per kg of said lignin.
[22] 22. A composition of claim 21, further comprising: less than about 700 mg of calcium per kg of said lignin.
[23] 23. A composition of claim 21, further comprising: less than about 2000 mg in total per kg of said lignin of elements; wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn.
[24] 24. A composition, comprising: lignin; and less than about 150 mg of sulfur per kg of said lignin.
[25] 25. A composition of claim 24, further comprising: less than about 2000 mg in total per kg of said lignin of elements; 18 WO 2013/101397 PCT/US2012/067535 wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn.
[26] 26. A composition of claim 24, further comprising: less than about 700 mg of calcium per kg of said lignin.
[27] 27. A composition of claim 24, further comprising: less than about 525 mg of iron per kg of said lignin. 19

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同族专利:

公开号 | 公开日

MY167811A|2018-09-26|

US9255188B2|2016-02-09|

SG10201610518QA|2017-02-27|

US20140039144A1|2014-02-06|

BR112014015905A8|2017-07-04|

WO2013101397A1|2013-07-04|

JP2015504111A|2015-02-05|

PH12014501323B1|2014-09-15|

US8759498B2|2014-06-24|

CA2859752A1|2013-07-04|

RU2629062C2|2017-08-24|

RU2012154209A|2014-06-20|

US9963555B2|2018-05-08|

KR20140116875A|2014-10-06|

JP6083763B2|2017-02-22|

US20160108182A1|2016-04-21|

US20130172540A1|2013-07-04|

PH12014501323A1|2014-09-15|

CA2859752C|2020-03-24|

AU2012362936B2|2016-07-07|

BR112014015905A2|2017-06-13|

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法律状态:
2016-11-03| FGA| Letters patent sealed or granted (standard patent)|

优先权:

申请号 | 申请日 | 专利标题

US201161581865P| true| 2011-12-30|2011-12-30||

US61/581,865||2011-12-30||

US13/472,798|US8759498B2|2011-12-30|2012-05-16|Compositions comprising lignin|

US13/472,798||2012-05-16||

PCT/US2012/067535|WO2013101397A1|2011-12-30|2012-12-03|Compositions comprising lignin|

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