WO2013101402A1 - Compositions comprising c5 and c6 oligosaccharides - Google Patents

Compositions comprising c5 and c6 oligosaccharides Download PDF

Info

Publication number
WO2013101402A1
WO2013101402A1 PCT/US2012/067641 US2012067641W WO2013101402A1 WO 2013101402 A1 WO2013101402 A1 WO 2013101402A1 US 2012067641 W US2012067641 W US 2012067641W WO 2013101402 A1 WO2013101402 A1 WO 2013101402A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
soluble
weight
composition
oligosaccharide
Prior art date
Application number
PCT/US2012/067641
Other languages
English (en)
French (fr)
Inventor
Daniel Clay FLOYD
Kiran L. Kadam
Srinivas Kilambi
Original Assignee
Renmatix, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=48693841&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2013101402(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Renmatix, Inc. filed Critical Renmatix, Inc.
Priority to CA2804993A priority Critical patent/CA2804993C/en
Priority to BR112014015909A priority patent/BR112014015909B1/pt
Priority to RU2012154202/15A priority patent/RU2012154202A/ru
Priority to KR1020147020083A priority patent/KR20140108300A/ko
Publication of WO2013101402A1 publication Critical patent/WO2013101402A1/en
Priority to ZA2014/04633A priority patent/ZA201404633B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B50/00—Sugar products, e.g. powdered, lump or liquid sugar; Working-up of sugar
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C13K1/04—Purifying
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K11/00—Fructose
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/002—Xylose
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/007—Separation of sugars provided for in subclass C13K
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention generally relates to compositions comprising C5 and C6 saccharides of varying degrees of polymerization and/or containing maximum levels of undesirable impurities, such as compounds containing sulfur, nitrogen, or metals, especially those processed from lignocellulosic biomass using supercritical, subcritical, and/or near critical fluid extraction.
  • 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, as its name infers, hydrolyzes the cellulose fibers.
  • CH cellulose hydrolysis
  • 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.
  • the sugar streams may be converted to ethanol through fermentation using yeast or bacteria that feed on the sugars. As the sugars are consumed, ethanol and carbon dioxide are produced.
  • the invention is directed to these compositions, as well as and other important ends.
  • the invention is directed to compositions, comprising: at least one water-soluble C6 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of elements;
  • said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
  • compositions comprising:
  • At least one water-soluble C6 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble
  • compositions comprising:
  • At least one water-soluble C6 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble
  • compositions comprising:
  • At least one water-soluble C6 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 3000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of calcium.
  • compositions comprising: at least one water-soluble C6 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 350 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of iron.
  • compositions comprising:
  • At least one water-soluble C6 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 1000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of sulfur.
  • compositions comprising:
  • the invention is directed to compositions, about 80% by weight to about 95% by weight, based on total weight of C6 saccharides present in said composition, of water-soluble C6 oligosaccharides; wherein said water-soluble C6 oligosaccharides have a degree of polymerization of about 2 to about 15.
  • compositions comprising:
  • At least one water-soluble C5 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 3700 ppm in total by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • the invention is directed to compositions, comprising: at least one water-soluble C5 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on the total weight of C5 saccharide hydrolysate in said composition, of aluminum;
  • compositions comprising: at least one water-soluble C5 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 10 ppm, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of aluminum.
  • compositions comprising:
  • At least one water-soluble C5 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 2300 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of calcium.
  • compositions comprising:
  • At least one water-soluble C5 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 50 ppm by weight, based on total weight of said water-soluble
  • compositions comprising:
  • At least one water-soluble C5 oligosaccharide hydrolysate especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 150 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of sulfur.
  • the invention is directed to methods of reducing the level of enzyme required for enzymatically hydrolyzing first water-soluble C6 saccharides having an average degree of polymerization to about 2 to about 15, preferably about 2 to about 10, and more preferably about 2 to about 6, to second water-soluble C6 saccharides having a lower average degree of polymerization than said average degree of polymerization of said first water-soluble C6 saccharides, comprising:
  • hydrolysate comprising said first water-soluble C6 saccharides and less than about 5250 ppm in total, based on total weight of water-soluble C6 saccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • the invention is directed to methods of reducing the level of enzyme required for enzymatically hydrolyzing first water-soluble C5 saccharides having an average degree of polymerization to about 2 to about 28, preferably about 2 to about 15, more preferably about 2 to about 13, even more preferably about 2 to about 6, to second water-soluble C5 saccharides having a lower average degree of polymerization than said average degree of polymerization of said first water-soluble C5 saccharides, comprising:
  • hydrolysate comprising said first water-soluble C5 saccharides and less than about 3700 ppm in total, based on total weight of water-soluble C5 saccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • FIGURE 1A is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a C6 oligosaccharide composition of one embodiment of the invention.
  • FIGURE 1 B is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a C6 oligosaccharide composition of one embodiment of the invention.
  • FIGURE 2A is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a C5 oligosaccharide composition of one embodiment of the invention.
  • FIGURE 2B is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a C5 oligosaccharide composition of one embodiment of the invention.
  • 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.
  • 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.
  • 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 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.
  • Reported critical temperatures and pressures include: for pure water, a critical temperature of about 374.2°C, and a critical pressure of about 221 bar; for carbon dioxide, a critical temperature of about 31 °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 (374.2X), 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 300°C and a pressure high enough to ensure that all fluid is in the liquid phase.
  • Sub-critical water temperature may be greater than about 250°C and less than about 300°C, and in many instances sub-critical water has a temperature between about 250X and about 280°C.
  • 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 50°C (preferably, at least about 100°C) but less than subcritical and at pressures such that water is in a liquid state.
  • a fluid which is "supercritical” indicates a fluid which would be supercritical if present in pure form under a given set of temperature and pressure conditions.
  • “supercritical water” indicates water present at a temperature of at least about 374.2°C 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 CO 2 , etc).
  • 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.
  • a mixture of sub-critical water and supercritical C0 2 may have a temperature of about 250°C to about 280X and a pressure of at least about 225 bar.
  • 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, C 6 saccharides (including cellulose, cellobiose, C e oligosaccharides, C 6 monosaccharides, C 5 saccharides (including hemicellulose, C 5 oligosaccharides, and C5 monosaccharides), and mixtures thereof.
  • 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 600°C. All results are reported relative to the 105°C oven dry weight of the sample.” See also: http://www.nrel.gov/biomass/pdfs/42622.pdf and http://www.astm.orci Standards/ E1755.htm. which are both incorporated herein by reference in their entirety.
  • degree of polymerization refers to the number of monomeric units in a macromolecule or polymer or oligomer molecule, including those monomeric units that are not identical (such as in a oligomer with different monomeric residues).
  • the degree of polymerization (DP) of the various saccharides in the compositions of the invention may be measured using gel permeation chromatography (GPC), high pressure liquid chromatography (HPLC), such as DIONEX with an electrochemical detector, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, or other conventional molecular weight determination methods.
  • the invention is directed to compositions, comprising C6 saccharides.
  • the compositions comprise: at least one water-soluble C6 oligosaccharide hydrolysate;
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • the elements are present at a level of less than about 5100 ppm in total by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition.
  • compositions comprising:
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of aluminum;
  • compositions further comprise:
  • said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
  • compositions comprising:
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble
  • compositions further comprise: less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • compositions comprising:
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 3000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of calcium.
  • compositions further comprise:
  • said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
  • compositions comprising:
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 350 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of iron.
  • compositions further comprise:
  • said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
  • compositions comprising:
  • At least one water-soluble C6 monosaccharide hydrolysate optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 1000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of sulfur.
  • compositions further comprise:
  • said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,
  • the water-soluble C6 oligosaccharide hydrolysate has a degree of polymerization of about 2 to about 15. In other embodiments, water- soluble C6 oligosaccharide hydrolysate has a degree of polymerization of about 2 to about 13. In other embodiments, water-soluble C6 oligosaccharide hydrolysate has a degree of polymerization of about 2 to about 10. In other embodiments, water- soluble C6 oligosaccharide hydrolysate has a degree of polymerization of about 2 to about 6.
  • compositions further comprise at least one water-soluble C6 monosaccharide hydrolysate.
  • the water-soluble C6 monosaccharide hydrolysate is glucose, galactose, mannose, fructose, or a mixture thereof.
  • the compositions further comprise less than about 10 ppm, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of aluminum, preferably less than about 5 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of aluminum.
  • the compositions further comprise less than about 3000 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of calcium, preferably less than about 2950 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water- soluble C6 monosaccharide hydrolysate in said composition, of calcium.
  • the compositions further comprise less than about 350 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of iron, preferably less than about 325 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of iron.
  • the compositions further comprise less than about 1000 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of sulfur, preferably less than about 975 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of sulfur.
  • the ratio of the total weight of said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate to said elements is greater than about 45:1 , preferably greater than about 47:1.
  • the level of said elements are measured by inductively coupled plasma emission spectroscopy.
  • compositions less than about 1500 mg of nitrogen per kg of total weight of water-soluble C6 saccharides, preferably less than about 1450 of nitrogen per kg of total weight of water-soluble C6 saccharides.
  • Nitrogen may be measured by thermal conductivity detection after combustion and reduction.
  • the weight ratio of the collective mass of hydrogen and nitrogen to mass of carbon present in said water- soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate is less than about 0.14.
  • Carbon, hydrogen, and nitrogen levels may be measured by thermal conductivity detection after combustion and reduction.
  • compositions comprising the C6 saccharides further comprise less than a maximum of any of the elements, individually or in combination, in the table listed below:
  • compositions comprise:
  • said water-soluble C6 oligosaccharides are present at a level of about 80% by weight to about 92.5% by weight, based on total weight of C6 saccharides present in said composition.
  • said water-soluble C6 oligosaccharides have a degree of polymerization of about 2 to about 13, preferably, about 2 to about 10, and more preferably about 2 to about 6.
  • the compositions further comprise about 5% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition, of C6 monosaccharides.
  • said water- soluble C6 oligosaccharide hydrolysate comprises:
  • compositions further comprise: about 5% by weight to about 20% by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of C6 monosaccharides.
  • compositions further comprise:
  • compositions comprise:
  • said C6 disaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.
  • said C6 trisaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.
  • said C6 tetrasaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.
  • said C6 pentasaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.
  • said C6 saccharides having at a degree of polymerization of at least about 6 are present at a level of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.
  • compositions further comprise:
  • compositions further comprise about 7.5% by weight to about 20% by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-soluble C6 monosaccharide hydrolysate in said composition, of C6 monosaccharides.
  • compositions further comprise water.
  • the water-soluble C6 oligosaccharide hydrolysate and the water-soluble C6 monosaccharide hydrolysate are processed from lignocellulosic biomass using supercritical, subcritical, or near critical fluid extraction, or a combination thereof.
  • compositions comprising C5 oligosaccharides.
  • the compositions comprise:
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 3700 ppm in total by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, 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, Tl, V, and Zn.
  • 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, Tl, V, and Zn.
  • the invention is directed to compositions, comprising: at least one water-soluble C5 oligosaccharide hydrolysate;
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of aluminum;
  • the elements are present at a level of less than about 3610 ppm in total by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • compositions comprising:
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on total weight of said water-soluble
  • compositions comprising:
  • At least one water-soluble C5 oligosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 2300 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of calcium.
  • compositions comprising:
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 50 ppm by weight, based on total weight of said water-soluble
  • compositions comprising:
  • At least one water-soluble C5 monosaccharide hydrolysate optionally, at least one water-soluble C5 monosaccharide hydrolysate; and less than about 150 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of sulfur.
  • compositions described herein further comprise:
  • 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, Tl, V, and Zn.
  • the water-soluble C5 oligosaccharide hydrolysate has a degree of polymerization of at least about 2 to about 28. In other embodiments, water-soluble C5 oligosaccharide hydrolysate has a degree of polymerization of at least about 2 to about 15. In other embodiments, water-soluble C5 oligosaccharide hydrolysate has a degree of polymerization of at least about 2 to about 10. In other embodiments, water-soluble C5 oligosaccharide hydrolysate has a degree of polymerization of at least about 2 to about 6.
  • compositions further comprise:
  • At least one water-soluble C5 monosaccharide hydrolysate at least one water-soluble C5 monosaccharide hydrolysate.
  • the water-soluble C5 monosaccharide hydrolysate is xylose, arabinose, lyxose, ribose, or a mixture thereof.
  • the compositions further comprise less than about 10 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of aluminum, preferably less than about 5 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water- soluble C5 monosaccharide hydrolysate in said composition, of aluminum.
  • the compositions further comprise less than about 2300 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of calcium, preferably less than about 2250 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water- soluble C5 monosaccharide hydrolysate in said composition, of calcium.
  • the compositions further comprise less than about 50 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of iron, preferably less than about 30 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of iron.
  • the compositions further comprise less than about 150 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of sulfur, preferably less than about 140 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of sulfur.
  • the ratio of total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition to said elements is greater than about 75:1 , preferably greater than about 80:1.
  • the water-soluble C5 oligosaccharide hydrolysate is processed from lignocellulosic biomass using supercritical, subcritical, or near critical fluid extraction, or a combination thereof.
  • the level of said elements are measured by inductively coupled plasma emission spectroscopy.
  • compositions comprise less than about 350 ppm of nitrogen per kg of total weight of water-soluble C5 saccharides, preferably less than about 325 ppm of nitrogen per kg of total weight of water-soluble C5 saccharides. Nitrogen may be measured by thermal conductivity detection after combustion and reduction.
  • the weight ratio of the collective mass of hydrogen and nitrogen to mass of carbon present in said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate is less than about 0.14.
  • Carbon, hydrogen, and nitrogen levels may be measured by thermal conductivity detection after combustion and reduction.
  • compositions comprising the C5 saccharides further comprise less than a maximum of any of the elements, individually or in combination, in the table listed below:
  • compositions comprise:
  • water-soluble C5 oligosaccharides have a degree of polymerization of about 2 to about 28.
  • said water-soluble C5 oligosaccharides are present at a level of about 80% by weight to about 90% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • said water-soluble C5 oligosaccharides have a degree of polymerization of about 2 to about 16, preferably, about 2 to about 10, and more preferably, about 2 to about 5.
  • compositions further comprise about 10% by weight, to about 25% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of C5 monosaccharides.
  • said water- soluble C5 oligosaccharide hydrolysate comprises:
  • said water-soluble C5 oligosaccharides have a degree of polymerization of about 2 to about 16, preferably, about 2 to about 10, and more preferably, about 2 to about 5.
  • the compositions further comprise about 10% by weight, to about 25% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water- soluble C5 monosaccharide hydrolysate in said composition, of C5 monosaccharides.
  • compositions further comprise about 12.5% by weight, to about 20% by weight, based on total weight of said water- soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of C5 monosaccharides.
  • said C5 disaccharides are present at a level of about 17.5% by weight to about 25% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • said C5 trisaccharides are present at a level of about 12.5% by weight to about 17.5% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • said C5 tetrasaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • said C5 pentasaccharides are present at a level of about 2.5% by weight to about 15% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • said C5 saccharides having at a degree of polymerization of at least about 6 are present at a level of about 12.5% by weight to about 30% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition.
  • compositions described herein further comprise about 10% by weight, to about 25% by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soluble C5 monosaccharide hydrolysate in said composition, of C5 monosaccharides.
  • compositions described herein further comprise water.
  • water-soluble C6 oligosaccharide hydrolysate and the water-soluble C6 monosaccharide hydrolysate are processed from lignocellulosic biomass using supercritical, subcritical, or near critical fluid extraction, or a combination thereof.
  • the invention is directed to methods of reducing the level of enzyme required for enzymatically hydrolyzing first water-soluble C6 saccharides having an average degree of polymerization to about 2 to about 15, preferably about 2 to about 10, and more preferably about 2 to about 6, to second water-soluble C6 saccharides having a lower average degree of polymerization than said average degree of polymerization of said first water-soluble C6 saccharides, comprising:
  • hydrolysate comprising said first water-soluble C6 saccharides and less than about 5250 ppm in total, based on total weight of water-soluble C6 saccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • the C6 saccharides are extracted from lignocellulosic biomass. In other embodiments, the C6 saccharides are processed from lignocellulosic biomass using supercritical, subcritical, or near critical fluid extraction, or a combination thereof.
  • the invention is directed to methods of reducing the level of enzyme required for enzymatically hydrolyzing first water-soluble C5 saccharides having an average degree of polymerization to about 2 to about 28, preferably about 2 to about 15, more preferably about 2 to about 13, even more preferably about 2 to about 6, to second water-soluble C5 saccharides having a lower average degree of polymerization than said average degree of polymerization of said first water-soluble C5 saccharides, comprising: providing a hydrolysate comprising said first water-soluble C5 saccharides and less than about 3700 ppm in total, based on total weight of water-soluble C5 saccharide hydrolysate in said composition, of elements;
  • 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, Tl, V, and Zn.
  • the compositions further comprise less than about 0.5% by weight, based on the total weight of said C5 saccharides or C6 saccharides, of organic solvent, such as alcohols, including water miscible lower aliphatic C1-C4 alcohols (e.g., methanol, ethanol, isopropanol, f-butanol).
  • organic solvent such as alcohols, including water miscible lower aliphatic C1-C4 alcohols (e.g., methanol, ethanol, isopropanol, f-butanol).
  • the compositions contain less than about 0.1 % by weight, based on the total weight of said of said C5 saccharides or C6 saccharides of organic solvent.
  • the compositions contain substantially no organic solvent.
  • 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.
  • suitable temperatures are about 130°C to about 250°C
  • suitable pressures are about 4 bars to about 100 bars
  • 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.
  • suitable temperatures are about 250°C to about 450°C
  • suitable pressures are about 40 bars to about 260 bars
  • suitable residence times are about 0.1 seconds to about 3 minutes.
  • the compositions 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.
  • compositions of the invention comprising C5 saccharides or C6 saccharides may be utilized in a wide variety of applications, where C5 and C6 sugars are conventionally utilized, including, but not limited to, the production of various chemicals and fuels using fermentative, enzymatic, catalytic, and non- catalytic (e.g., thermal decomposition) processes. Such processes are useful for preparing feedstocks for the preparation of the following non-exhaustive list:
  • fuels such as gasoline, jet fuel, butanol, and the like
  • pharmaceuticals and foods such as acetoin, alanine, arabitol, ascorbic acid, aspartic acid, citric acid, coumaric acid, fumaric acid, glycerol, glycine, kojic acid, lactic acid, lysine, malonic acid, proline, propionic acid, serine, sorbitol, succinic acid, threonine, xylitol, sugar acids (glucaric acid, gluconic acid, xylonic acids), and the like);
  • pharmaceuticals and foods such as acetoin, alanine, arabitol, ascorbic acid, aspartic acid, citric acid, coumaric acid, fumaric acid, glycerol, glycine, kojic acid, lactic acid, lysine, malonic acid, proline, propionic acid, serine, sorbitol, succinic acid, threonine, xylitol, sugar acids (glucaric
  • specialty chemicals such as acontic acid, glutamic acid, malic acid, oxalic acid, and the like
  • the C5 oligosaccharide and C6 oligosaccharide compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in a two stage process.
  • Particulate 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°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.
  • 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.
  • 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.
  • the C5 oligosaccharides and the C6 oligosaccharides streams were first concentrated to about 200 g/L, adjusted to about pH 3-4 and filtered using 0.45 micron filter.
  • Example 2 Analysis of oligosaccharide compositions using inductively coupled plasma
  • Example 3 Analysis of oligosaccharide compositions using gel permeation chromatography
  • the C5 oligosaccharide and C6 oligosaccharide compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in a two stage process as described in Example 1. The samples were then diluted ten times. The degree of polymerization was qualitatively determined, i.e., not quantifying the amount of each oligomer, using gel permeation chromatography.
  • a degree of polymerization were detected up to at least a DP of 13, with small peaks visible above DP of 13 for the C6 oligosaccharide compositions.
  • a degree of polymerization were detected up to at least a DP of 28, with small peaks visible above DP of 28 for the C5 oligosaccharide compositions.
  • Example 4 Analysis of C6 saccharide compositions using gel permeation chromatography
  • the C6 saccharide compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in a two stage process as described in Example 1. Representative samples bracketing the extremes/possibilities of feed material source (tubular reactor), reactor temperature (348.2-383.4°C), reactor residence time (0.19-1.48 seconds), and feed aqueous slurry concentration (6.4-14.77%) were selected.
  • Example 5 Analysis of C5 saccharide compositions using gel permeation chromatography
  • the C5 saccharide compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in the first stage of the two stage process as described in Example 1. Representative samples bracketing the extremes/possibilities of reactor feed concentration (10.66-13.78 weight %, reactor temperature (249-261 °C), and reactor residence time (2-3 minutes) were selected.
  • Detector 1260-RID set at 50°C Agilent and DAD (signal 214 and 270
  • Example 6 Analysis of C5 and C6 saccharide compositions using HPLC with an electrochemical detector
  • the C5 and C6 saccharide compositions of the invention were prepared using supercritical, subcritical, and near critical water extraction in the two stage process as described in Example 1. Representative samples were selected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Food Science & Technology (AREA)
  • Saccharide Compounds (AREA)
  • Fodder In General (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Cosmetics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Processing Of Solid Wastes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/US2012/067641 2011-12-30 2012-12-03 Compositions comprising c5 and c6 oligosaccharides WO2013101402A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA2804993A CA2804993C (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 oligosaccharides
BR112014015909A BR112014015909B1 (pt) 2011-12-30 2012-12-03 composição compreendendo oligossacarídeo c5 e c6 e hidrolisatos de monossacarídeo
RU2012154202/15A RU2012154202A (ru) 2011-12-30 2012-12-03 Композиции, включающие с5 и с6 олигосахариды
KR1020147020083A KR20140108300A (ko) 2011-12-30 2012-12-03 C5 및 c6 올리고당류를 포함하는 조성물
ZA2014/04633A ZA201404633B (en) 2011-12-30 2014-06-24 Compositions comprising c5 and c6 oligosaccharides

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
US201161581890P 2011-12-30 2011-12-30
US201161581878P 2011-12-30 2011-12-30
US201161581922P 2011-12-30 2011-12-30
US201161581907P 2011-12-30 2011-12-30
US61/581,907 2011-12-30
US61/581,878 2011-12-30
US61/581,890 2011-12-30
US61/581,922 2011-12-30
US13/649,395 US8894771B2 (en) 2011-12-30 2012-10-11 Compositions comprising C5 and C6 monosaccharides
US13/649,437 2012-10-11
US13/649,343 2012-10-11
US13/649,343 US20130172547A1 (en) 2011-12-30 2012-10-11 Compositions comprising c5 and c6 oligosaccharides
US13/649,294 2012-10-11
US13/649,395 2012-10-11
US13/649,294 US20130172546A1 (en) 2011-12-30 2012-10-11 Compositions comprising c5 and c6 oligosaccharides
US13/649,437 US20130167837A1 (en) 2011-12-30 2012-10-11 Compositions comprising c5 and c6 monosaccharides

Publications (1)

Publication Number Publication Date
WO2013101402A1 true WO2013101402A1 (en) 2013-07-04

Family

ID=48693841

Family Applications (4)

Application Number Title Priority Date Filing Date
PCT/US2012/067641 WO2013101402A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 oligosaccharides
PCT/US2012/067538 WO2013101399A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 monosaccharides
PCT/US2012/067644 WO2013101403A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 oligosaccharides
PCT/US2012/067537 WO2013101398A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 monosaccharides

Family Applications After (3)

Application Number Title Priority Date Filing Date
PCT/US2012/067538 WO2013101399A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 monosaccharides
PCT/US2012/067644 WO2013101403A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 oligosaccharides
PCT/US2012/067537 WO2013101398A1 (en) 2011-12-30 2012-12-03 Compositions comprising c5 and c6 monosaccharides

Country Status (15)

Country Link
US (19) US20130172546A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (4) EP3778926A3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (2) JP6325454B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
KR (4) KR20140108301A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CN (2) CN104024268A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (2) AU2012362938B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BR (4) BR112014015908A8 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (3) CA2804993C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IN (2) IN2014KN01517A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
MY (2) MY167796A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
PH (2) PH12014501321A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
RU (3) RU2012154203A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
SG (1) SG10201610821TA (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (4) WO2013101402A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (3) ZA201404633B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103604799A (zh) * 2013-10-25 2014-02-26 中国航空工业集团公司北京航空材料研究院 一种测定甘油水溶液中铬、铁、锰、镍、铜元素的方法
EP3296307A1 (en) * 2011-12-30 2018-03-21 Renmatix Inc. Compositions comprising c5 oligosaccharides
US10385140B2 (en) 2014-09-26 2019-08-20 Renmatix, Inc. Cellulose-containing compositions and methods of making same
CN114410704A (zh) * 2022-02-15 2022-04-29 上海云洛生物技术有限公司 一种生物合成玻色因的方法

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011161685A2 (en) 2010-06-26 2011-12-29 Hcl Cleantech Ltd. Sugar mixtures and methods for production and use thereof
IL206678A0 (en) 2010-06-28 2010-12-30 Hcl Cleantech Ltd A method for the production of fermentable sugars
IL207329A0 (en) 2010-08-01 2010-12-30 Robert Jansen A method for refining a recycle extractant and for processing a lignocellulosic material and for the production of a carbohydrate composition
IL207945A0 (en) 2010-09-02 2010-12-30 Robert Jansen Method for the production of carbohydrates
GB2524906B8 (en) 2011-04-07 2016-12-07 Virdia Ltd Lignocellulose conversion processes and products
WO2013055785A1 (en) 2011-10-10 2013-04-18 Virdia Ltd Sugar compositions
EP2878614A1 (en) 2012-05-03 2015-06-03 Virdia Ltd. Methods for treating lignocellulosic materials
US9200337B2 (en) * 2014-04-22 2015-12-01 Renmatix, Inc. Method for mixed biomass hydrolysis
US11078548B2 (en) 2015-01-07 2021-08-03 Virdia, Llc Method for producing xylitol by fermentation
EP3280812B1 (en) 2015-04-10 2024-02-28 Comet Biorefining Inc. Methods and compositions for the treatment of cellulosic biomass and products produced thereby
CA2985478A1 (en) 2015-05-27 2016-12-01 Virdia, Inc. Integrated methods for treating lignocellulosic material
CN107099558B (zh) * 2017-04-25 2021-06-11 华东理工大学 一种同时生物合成1，3-丙二醇和乙偶姻的新方法
EP3530743A1 (en) 2018-02-21 2019-08-28 Cambridge Glycoscience Ltd Method of production
AU2019265921B2 (en) 2018-05-10 2024-12-19 Comet Biorefining Inc. Compositions comprising glucose and hemicellulose and their use
BR112021002910A2 (pt) 2018-08-15 2021-07-20 Cambridge Glycoscience Ltd novas composições, seu uso e métodos para sua formação
EA202100279A1 (ru) 2019-05-10 2022-02-11 Комет Биорефайнинг Инк. Материалы и способы получения арабиноксилановых композиций
CN114727642B (zh) 2019-08-16 2025-02-14 剑桥糖质科学有限公司 处理生物质以生产寡糖的方法和相关组合物
EP4072318A2 (en) 2019-12-12 2022-10-19 Cambridge Glycoscience Ltd Low sugar multiphase foodstuffs
JP2023132598A (ja) * 2022-03-11 2023-09-22 日本製紙株式会社 セルロース材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4165240A (en) * 1974-10-04 1979-08-21 Cpc International Inc. Starch hydrolysate having less than 5 ppm of heavy metals
US20090176979A1 (en) * 2006-06-26 2009-07-09 Tokyo Institute Of Technology Process for production of polysaccharide and/or monosaccharide by hydrolysis of different polysaccharide
WO2010045576A2 (en) * 2008-10-17 2010-04-22 Mascoma Corporation Production of pure lignin from lignocellulosic biomass
US20100297704A1 (en) * 2009-02-18 2010-11-25 Rongxiu Li Process for biomass conversion
US20110183394A1 (en) * 2008-06-27 2011-07-28 MICROBIOGEN PTY LTDC C/O Peter Hunt & Associates Method of producing yeast biomass
US20120282655A1 (en) * 2011-05-04 2012-11-08 Renmatix, Inc. Enhanced soluble c5 saccharide yields

Family Cites Families (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635061A (en) 1948-04-13 1953-04-14 Rohm & Haas Ion-exchange purification of sugar
DE1955392B2 (de) * 1969-10-29 1978-06-22 Grain Processing Corp., Muscatine, Ia. (V.St.A.) Verfahren zur Herstellung eines Stärkehydrolysate mit einem Dextroseäquivalentwert von nicht wesentlich über 18
JPS5141451A (ja) 1974-10-04 1976-04-07 Cpc International Inc Iseikatonoseizohoho
JPS5141450A (en) * 1974-10-04 1976-04-07 Cpc International Inc Iseikatoyobudotoganjueki no shorihoho
DE2545111C3 (de) 1975-10-08 1980-07-17 Sued-Chemie Ag, 8000 Muenchen Verfahren zum zweistufigen Aufschließen von xylanhaltigen Naturprodukten zwecks Gewinnung von Xylose
US3990904A (en) 1976-05-11 1976-11-09 Sud-Chemie Ag Method for the preparation of xylose solutions
FR2445839A1 (fr) * 1979-01-08 1980-08-01 Roquette Freres Hydrolysat d'amidon eventuellement hydrogene, son procede de preparation et ses applications
DE2915026A1 (de) 1979-04-12 1980-10-30 Bayer Ag N,n-disubstituierte ethylglycin (thiol)ester, verfahren zu ihrer herstellung sowie ihre verwendung als fungizide
JPS62283988A (ja) 1986-06-02 1987-12-09 Hitachi Ltd マルトオリゴ糖の製造方法
FR2601036B1 (fr) 1986-07-07 1990-01-19 Sucre Rech & Dev Procede de liquefaction de betteraves par hydrolyse enzymatique et hydrolysat liquide obtenu
DE3909096A1 (de) * 1989-03-20 1990-09-27 Garabed Antranikian Alpha-amylase
WO1991003574A1 (en) 1989-09-01 1991-03-21 The Dow Chemical Company Process for purifying sugar solutions
JP2835894B2 (ja) * 1991-07-26 1998-12-14 農林水産省食品総合研究所長 ビフィズス菌増殖促進剤
US5424417A (en) 1993-09-24 1995-06-13 Midwest Research Institute Prehydrolysis of lignocellulose
FI97625C (fi) * 1995-03-01 1997-01-27 Xyrofin Oy Menetelmä ksyloosin kiteyttämiseksi vesiliuoksista
US5705369A (en) 1994-12-27 1998-01-06 Midwest Research Institute Prehydrolysis of lignocellulose
FI952065A0 (fi) 1995-03-01 1995-04-28 Xyrofin Oy Foerfarande foer tillvaratagande av en kristalliserbar organisk foerening
WO1996028051A1 (en) 1995-03-10 1996-09-19 Unilever Plc Batter composition
US6228177B1 (en) 1996-09-30 2001-05-08 Midwest Research Institute Aqueous fractionation of biomass based on novel carbohydrate hydrolysis kinetics
US6022419A (en) 1996-09-30 2000-02-08 Midwest Research Institute Hydrolysis and fractionation of lignocellulosic biomass
CA2627846C (en) 1999-03-23 2011-01-04 Oji Paper Co., Ltd. Process for bleaching lignocellulose pulp
AU1584201A (en) 1999-11-02 2001-05-14 Waste Energy Integrated Sytems, Llc Process for the production of organic products from lignocellulose containing biomass sources
ES2166316B1 (es) * 2000-02-24 2003-02-16 Ct Investig Energeticas Ciemat Procedimiento de produccion de etanol a partir de biomasa lignocelulosica utilizando una nueva levadura termotolerante.
KR100643817B1 (ko) * 2000-06-26 2006-11-10 유니버시티 오브 플로리다 리서치 파운데이션, 아이엔씨. 당화와 발효의 동시 수행을 위한 방법 및 조성물
CN1137140C (zh) * 2000-11-06 2004-02-04 浙江大学 纤维多糖系列试剂的同时制备方法
JP4588205B2 (ja) * 2000-12-15 2010-11-24 日本水産株式会社 キチンオリゴ糖製造方法
FI111960B (fi) 2000-12-28 2003-10-15 Danisco Sweeteners Oy Erotusmenetelmä
JP4158396B2 (ja) * 2002-03-28 2008-10-01 トヨタ自動車株式会社 乳酸エステルの製造方法および装置
WO2004013409A1 (en) 2002-07-25 2004-02-12 Coffin World Water Systems Apparatus and method for treating black liquor
BR0301678A (pt) 2003-06-10 2005-03-22 Getec Guanabara Quimica Ind S Processo para a produção de xilose cristalina a partir de bagaço de cana-de-açucar, xilose cristalina de elevada pureza produzida através do referido processo, processo para a produção de xilitol cristalino a partir da xilose e xilitol cristalino de elevada pureza assim obtido
ATE360682T1 (de) 2003-06-30 2007-05-15 Clasado Inc Neue galactooligosaccharidzusammensetzung und herstellung davon
JP5170725B2 (ja) * 2003-07-04 2013-03-27 国立大学法人佐賀大学 水溶性糖類の製造方法
JP2005270056A (ja) * 2004-03-26 2005-10-06 Hitachi Zosen Corp 加水分解物中の発酵阻害物の除去方法
BRPI0509886B1 (pt) 2004-04-13 2018-01-30 Iogen Energy Corporation Método para o processamento de uma matéria-prima lignocelulósica e obtenção de um sal inorgânico
JP2006101829A (ja) * 2004-10-08 2006-04-20 Mitsubishi Heavy Ind Ltd 糖液製造装置及び方法
JP2006223152A (ja) * 2005-02-16 2006-08-31 Hitachi Zosen Corp セルロース溶剤による溶解と加水分解の組合せによるバイオマス処理方法
US8349365B2 (en) 2005-09-27 2013-01-08 Asahi Kasei Chemicals Corporation Cellooligosaccharide-containing composition
EP1832179B1 (en) * 2005-12-20 2018-11-07 N.V. Nutricia Carbohydrate composition and flat glucose response
PT2007945E (pt) 2006-03-29 2011-04-29 Virginia Tech Intell Prop Fraccionamento de lenhocelulose à base de solventes de celulose com condições de reacção moderadas e ciclagem de reagentes
US20070254348A1 (en) 2006-04-28 2007-11-01 Theodora Retsina Method for the production of fermentable sugars and cellulose from lignocellulosic material
JP5190858B2 (ja) 2006-07-12 2013-04-24 独立行政法人農業・食品産業技術総合研究機構 多糖を含む素材からの低分子糖質等の製造法
US7670813B2 (en) 2006-10-25 2010-03-02 Iogen Energy Corporation Inorganic salt recovery during processing of lignocellulosic feedstocks
CN101611195A (zh) 2006-12-18 2009-12-23 诺维信北美公司 使经预处理的含木质纤维素的材料解毒
AU2008256938B2 (en) 2007-05-23 2013-02-28 Tate & Lyle Ingredients Americas Llc Edible composition comprising a slowly digestible or digestion resistant oligosaccharide composition
EP2198035B1 (en) 2007-07-30 2012-04-11 Kmps Financial Group, S.R.O. Method and equipment for production of glucose, ethanol, furfural, furane and lignin from renewable raw materials
FI121885B (fi) * 2007-11-09 2011-05-31 Chempolis Oy Menetelmä sokerituotteen valmistamiseksi
US8057639B2 (en) 2008-02-28 2011-11-15 Andritz Inc. System and method for preextraction of hemicellulose through using a continuous prehydrolysis and steam explosion pretreatment process
WO2009129525A2 (en) 2008-04-18 2009-10-22 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Antifungal and anti-cariogenic cellobio-oligosaccharides produced by dextransucrase
BRPI0912195A2 (pt) * 2008-05-09 2019-09-24 Cargill Inc xaropes com açúcar reduzido e baixa viscosidade, métodos de preparação e uso dos mesmos.
JP5646469B2 (ja) 2008-06-16 2014-12-24 キャンピナ・ネダーランド・ホールディング・ビー．ブイ． 熱安定な水性ラクトフェリン組成物並びにその調製及び使用
US8282738B2 (en) 2008-07-16 2012-10-09 Renmatix, Inc. Solvo-thermal fractionation of biomass
EP2310418B1 (en) * 2008-07-16 2016-03-30 Renmatix, Inc. Method of extraction of furfural and glucose from biomass using one or more supercritical fluids
US8030039B1 (en) 2008-10-14 2011-10-04 American Process, Inc. Method for the production of fermentable sugars and cellulose from lignocellulosic material
FI121237B (fi) 2008-10-21 2010-08-31 Danisco Menetelmä ksyloosin ja liukosellun tuottamiseksi
KR101657100B1 (ko) 2008-10-29 2016-09-19 삼성전자주식회사 리그노셀룰로오스계 바이오매스의 분별방법 및 분별장치
CN102282264B (zh) 2009-01-14 2014-12-03 艾欧基能源公司 从本质纤维素原料生产葡萄糖的改进方法
CN101613970B (zh) 2009-06-09 2012-10-03 上海士林纤维材料有限公司 预提取半纤维素的蔗渣溶解浆制浆方法及其产品
WO2011027389A1 (ja) * 2009-09-02 2011-03-10 川崎重工業株式会社 リグノセルロース系バイオマスからエタノールを製造する方法
JP2011078327A (ja) * 2009-10-05 2011-04-21 Gunma Univ 糖溶液からの発酵阻害物質の分離方法
JP2011087478A (ja) * 2009-10-20 2011-05-06 Akita Prefecture エタノールの製造方法
JP2011103874A (ja) * 2009-10-22 2011-06-02 Idemitsu Kosan Co Ltd バイオマスの処理方法
EP3719145A1 (en) 2010-01-19 2020-10-07 Renmatix, Inc. Production of fermentable sugars and lignin from biomass using supercritical fluids
CN101974161B (zh) * 2010-09-30 2012-10-31 中国科学院西双版纳热带植物园 一种溶解和快速水解木质纤维素生物质的方法及其设备和应用
PT106039A (pt) 2010-12-09 2012-10-26 Hcl Cleantech Ltd Processos e sistemas para o processamento de materiais lenhocelulósicos e composições relacionadas
CN102080116A (zh) 2010-12-14 2011-06-01 南京林业大学 一种采用蒸汽爆破—定向酶解制取低聚木糖的方法
WO2012155074A1 (en) 2011-05-12 2012-11-15 Virent, Inc. Process for purifying lignocellulosic feedstocks
WO2013055785A1 (en) 2011-10-10 2013-04-18 Virdia Ltd Sugar compositions
US20140256931A1 (en) 2011-10-18 2014-09-11 Bp Corporation North America Inc. Carbonaceous material for purifying lignocellulosic oligomers
US20130118483A1 (en) 2011-11-11 2013-05-16 Johnway Gao Solid lignocellulosic hydrolysate and methods to prepare a solid lignocellulosic hydrolysate
US20130172546A1 (en) 2011-12-30 2013-07-04 Renmatix, Inc. Compositions comprising c5 and c6 oligosaccharides
CN103993161B (zh) 2014-05-21 2016-11-16 攀钢集团攀枝花钢铁研究院有限公司 一种含钒物料的两段式钙化焙烧的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4165240A (en) * 1974-10-04 1979-08-21 Cpc International Inc. Starch hydrolysate having less than 5 ppm of heavy metals
US20090176979A1 (en) * 2006-06-26 2009-07-09 Tokyo Institute Of Technology Process for production of polysaccharide and/or monosaccharide by hydrolysis of different polysaccharide
US20110183394A1 (en) * 2008-06-27 2011-07-28 MICROBIOGEN PTY LTDC C/O Peter Hunt & Associates Method of producing yeast biomass
WO2010045576A2 (en) * 2008-10-17 2010-04-22 Mascoma Corporation Production of pure lignin from lignocellulosic biomass
US20100297704A1 (en) * 2009-02-18 2010-11-25 Rongxiu Li Process for biomass conversion
US20120282655A1 (en) * 2011-05-04 2012-11-08 Renmatix, Inc. Enhanced soluble c5 saccharide yields

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3296307A1 (en) * 2011-12-30 2018-03-21 Renmatix Inc. Compositions comprising c5 oligosaccharides
CN103604799A (zh) * 2013-10-25 2014-02-26 中国航空工业集团公司北京航空材料研究院 一种测定甘油水溶液中铬、铁、锰、镍、铜元素的方法
US10385140B2 (en) 2014-09-26 2019-08-20 Renmatix, Inc. Cellulose-containing compositions and methods of making same
US11440974B2 (en) 2014-09-26 2022-09-13 Renmatix, Inc. Cellulose-containing compositions and methods of making same
US11649296B2 (en) 2014-09-26 2023-05-16 Renmatix, Inc. Cellulose-containing compositions and methods of making same
CN114410704A (zh) * 2022-02-15 2022-04-29 上海云洛生物技术有限公司 一种生物合成玻色因的方法

Also Published As

Publication number Publication date
BR112014015910A2 (pt) 2017-06-13
US20180080093A1 (en) 2018-03-22
US20190338379A1 (en) 2019-11-07
WO2013101403A1 (en) 2013-07-04
CA2804993C (en) 2016-06-21
US20180066328A1 (en) 2018-03-08
US20180230559A1 (en) 2018-08-16
AU2012362938A1 (en) 2014-07-03
ZA201404632B (en) 2016-05-25
EP2797944A4 (en) 2015-09-30
EP2797943A1 (en) 2014-11-05
SG10201610821TA (en) 2017-02-27
CN104039803A (zh) 2014-09-10
EP2797943A4 (en) 2015-10-07
JP6325454B2 (ja) 2018-05-16
JP2015503558A (ja) 2015-02-02
US20200199694A1 (en) 2020-06-25
US20130167836A1 (en) 2013-07-04
IN2014KN01516A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2015-10-23
US20190106756A1 (en) 2019-04-11
MY170912A (en) 2019-09-16
WO2013101399A1 (en) 2013-07-04
RU2014131379A (ru) 2016-02-20
US20180230561A1 (en) 2018-08-16
EP3296307A1 (en) 2018-03-21
BR112014016008A8 (pt) 2017-07-04
BR112014015910A8 (pt) 2017-07-04
CN104024268A (zh) 2014-09-03
PH12014501321A1 (en) 2014-09-08
BR112014015909A8 (pt) 2017-07-04
ZA201404633B (en) 2016-06-29
US20200224284A1 (en) 2020-07-16
US20150191500A1 (en) 2015-07-09
CA2817235A1 (en) 2013-06-30
US20150191499A1 (en) 2015-07-09
AU2012362938B2 (en) 2017-11-23
CA2860704A1 (en) 2013-07-04
AU2012362942B2 (en) 2017-06-22
BR112014016008B1 (pt) 2019-09-17
BR112014015908A8 (pt) 2017-07-04
KR20140108302A (ko) 2014-09-05
BR112014015908A2 (pt) 2017-06-13
MY167796A (en) 2018-09-26
WO2013101398A1 (en) 2013-07-04
US10487369B2 (en) 2019-11-26
US9797021B2 (en) 2017-10-24
US20130167837A1 (en) 2013-07-04
ZA201404634B (en) 2016-06-29
EP2797944A1 (en) 2014-11-05
EP2797944B1 (en) 2017-10-25
PH12014501322A1 (en) 2014-09-15
US9783860B2 (en) 2017-10-10
US20130172547A1 (en) 2013-07-04
EP3296307B1 (en) 2020-07-22
US20190338378A1 (en) 2019-11-07
KR20140108300A (ko) 2014-09-05
CA2817235C (en) 2015-09-29
NZ625869A (en) 2016-04-29
PH12014501322B1 (en) 2014-09-15
US20180230560A1 (en) 2018-08-16
BR112014016008A2 (pt) 2017-06-13
KR20140109441A (ko) 2014-09-15
US20150184261A1 (en) 2015-07-02
US20150197824A1 (en) 2015-07-16
CA2804993A1 (en) 2013-06-30
BR112014015909A2 (pt) 2017-06-13
NZ625887A (en) 2016-04-29
JP2015503559A (ja) 2015-02-02
BR112014015909B1 (pt) 2019-12-17
AU2012362942A1 (en) 2014-07-03
KR20140108301A (ko) 2014-09-05
RU2012154203A (ru) 2014-06-20
US20200199693A1 (en) 2020-06-25
EP3778926A2 (en) 2021-02-17
EP3778926A3 (en) 2021-03-03
RU2012154202A (ru) 2014-06-20
US8894771B2 (en) 2014-11-25
EP2797943B1 (en) 2018-03-28
IN2014KN01517A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2015-10-23
US20130172546A1 (en) 2013-07-04

Similar Documents

Publication Publication Date Title
US10487369B2 (en) Compositions comprising C5 and C6 oligosaccarides
NZ625887B2 (en) Compositions comprising c5 and c6 monosaccharides

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2012154202

Country of ref document: RU

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2804993

Country of ref document: CA

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12863045

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20147020083

Country of ref document: KR

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112014015909

Country of ref document: BR

122 Ep: pct application non-entry in european phase

Ref document number: 12863045

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112014015909

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20140626