COMPOSITIONS COMPRISING C5 AND C6 OLIGOSACCHARIDES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of:

U.S. Application No. 61/581 ,890 filed December 30, 2011 ;

U.S. Application No. 61/581 ,878 filed December 30, 201 ;

U.S. Application No. 61/581 ,907 filed December 30, 2011 ;

U.S. Application No. 61/581 ,922 filed December 30, 2011;

U.S. Application No. 13/649,343 filed October 1 1 , 2012;

U.S. Application No. 13/649,294 filed October 11 , 2012;

U.S. Application No.13/649,395 filed October 11 , 2012; and

U.S. Application No.13/649,437 filed October 11 , 2012;

the entire disclosures of which are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] 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 Signoceiluiosic biomass using supercritical, subcritical, and/or near critical fluid extraction.

BACKGROUND OF THE INVENTION

[0003] There are a number of processes for converting lignoceliuSossc biomass into liquid streams of various fermentable 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 hemicellu!ose component of the Signoceiluiosic biomass and cellulose hydrolysis (CH) process, as its name infers, hydrolyzes the cei!uiose fibers. The resultant five carbon (05) and six carbon (C6) sugar streams are recovered separately. The remaining solids, which consist mostly of Signin, 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.

[0004] Among their many uses, 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.

[0005] The invention is directed to these compositions, as well as and other important ends.

SUMMARY OF THE INVENTION

[0006] In one embodiment, the invention is directed to compositions, comprising: at least one water-soluble 06 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;

optionally, at least one water-soluble 06 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 06 monosaccharide hydrolysate in said composition, of elements;

wherein said elements are A!, As, B, Ba, Be, Ca, Cd, Co, Or, Cu, Fe, K, Li,

Mg, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

[0007] In another embodiment, the invention is directed to compositions, comprising:

at least one water-soluble 06 oligosaccharide hydrolysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critical fluid extraction;

optionally, at least one water-soluble C6 monosaccharide hydrolysate; and less than about 10 ppm by weight, based on iota! weight of said water-soiub!e C6 oligosaccharide hydroiysate and said ater-soiub!e C6 monosaccharide hydroiysate in said composition, of aluminum:

less than about 3000 ppm by weight, based on total weight of said water- solubie C6 oiigosacchande hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of calcium;

less than about 350 ppm by weight, based on total weight of said water- solubie C6 oligosaccharide hydroiysate and said water-soiuble C6 monosaccharide hydroiysate in said composition, of iron; and

less than about 1000 ppm by weight based on total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of su!fur.

[0008} In other embodiments, the invention is directed to compositions, comprising:

at least one water-soluble C6 oligosaccharide hydroiysate, especially those hydrolysates processed from lignocellu!osic biomass using supercritical or near critical fluid extraction;

optionally, at least one water-soluble C6 monosaccharide hydroiysate: and less than about 10 ppm by weight, based on total weight of said water-soluble

C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of aluminum.

[0009] in a further embodiment, the invention is directed to compositions, comprising:

at least one water-soluble C6 oligosaccharide hydroiysate, especially those hydrolysates processed from lignocellu!osic biomass using supercritical or near critica! fluid extraction:

optionally, at least one water-soluble C6 monosaccharide hydroiysate: and less than about 3000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of calcium. [0010] !n yet other embodiments, the invention is directed to compositions, comprising:

at least one water-soluble C6 oiigosaccharide hydroiysate, especially those hydrolysates processed from lignocellu!osic biomass using supercritical or near critical fluid extraction;

optionally, at least one water-soluble C6 monosaccharide hydroiysate; and less than about 350 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of iron.

[0011] In another embodiment, the invention is directed to compositions, comprising:

at least one water-soluble C6 oligosaccharide hydroiysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near critica! fluid extraction;

optionally, at least one water-soluble C6 monosaccharide hydroiysate; and less than about 1000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of sulfur.

[0012] In yet another embodiment, the invention is directed to compositions, comprising:

about 10% by weight to about 25% by weight, based on total weight of C6 saccharides present in said composition, of C6 disaccharides;

about 10% by weight to about 25% by weight, based on total weight of C6 saccharides present in said composition, of C6 trisaccharides;

about 10% by weight to about 25% by weight, based on total weight of C6 saccharides present in said composition, of C6 tetrasaccharides;

about 10% by weight to about 25% by weight, based on total weight of C6 saccharides present in said composition, of C6 pentasaccharides; and

about 10% by weight to about 50% by weight, based on total weight of C6 saccharides present in said composition, of C6 saccharides having at a degree of polymerization of at least about 8. [0013] Sn further embodiments, the invention is directed to compositions, comprising:

about 80% by weight to about 95% by weight, based on total weight of C6 saccharides present in said composition, of water-soiubie C6 oiigosaccharides;

wherein said water-soiubie C6 oiigosaccharides have a degree of poiymerization of about 2 to about 15.

[0014] in other embodiments, the invention is directed to compositions, comprising:

at ieast one water-soiubie C5 oligosaccharide hydroiysate, especiai!y those hydrolysates processed from iignoceliuiosic biomass using supercritical or near critical fluid extraction;

optionally, at Ieast one water-soiubie C5 monosaccharide hydroiysate; and less than about 3700 ppm in total by weight, based on total weight of said water-solubie C5 oligosaccharide hydroiysate and said water-soiubie C5 monosaccharide hydroiysate in said composition, of elements;

wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, JVlg, n, Mo, Na, Hi, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TS, V, and Zn.

[0015] In one embodiment, the invention is directed to compositions, comprising: at ieast one water-soiubie C5 oligosaccharide hydroiysate, especiaily those hydrolysates processed from Iignoceliuiosic biomass using supercritical or near critical fluid extraction;

optionally, at Ieast one water-soluble C5 monosaccharide hydroiysate; and less than about 10 ppm by weight, based on the total weight of C5 saccharide hydroiysate in said composition, of aluminum:

less than about 2300 ppm by weight, based on the total weight of C5 saccharide hydroiysate in said composition, of calcium;

less than about 50 ppm by weight, based on the total weight of C5 saccharide hydroiysate in said composition, of iron; and

less than about 150 ppm by weight, based on the total weight of C5 saccharide hydroiysate in said composition, of sulfur. [0016] In further embodiments, the invention is directed to compositions, comprising:

at least one water-soiubie C5 oiigosacchande hydroiysate, especially those hydrofysates processed from iignocelluiosic biomass using supercriticai or near criticai fluid extraction;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 10 ppm, based on total weight of said water-solubie C5 oligosaccharide hydroiysate and said water-so!uble C5 monosaccharide hydroiysate in said composition, of aluminum.

[0017] In yet further embodiments, the invention is directed to compositions, comprising:

at least one water-solubie C5 oligosaccharide hydroiysate, especially those hydrolysates processed from lignocellulosic biomass using supercritical or near criticai fluid extraction;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 2300 ppm by weight based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soiubSe C5 monosaccharide hydroiysate in said composition, of calcium.

[0018] In another embodiment, the invention is directed to compositions, comprising:

at least one water-solubie C5 oiigosacchande hydroiysate, especially those hydrolysates processed from lignoceliulosic biomass using supercritical or near critical fiuid extraction;

optionaily, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 50 ppm by weight, based on total weight of said water-solubie

C5 oiigosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of iron.

[0019] in yet another embodiment, the invention is directed to compositions, comprising: at ieast one water-soiuble C5 oiigosaccharide hydroiysate, especially those hydrolysates processed from lignoceliuiosic biomass using supercritical or near critical fluid extraction;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 150 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soiubie C5 monosaccharide hydroiysate in said composition, of sulfur.

[0020] in certain embodiments, the invention is directed to methods of reducing the level of enzyme required for enzymaticaily hydroiyzing first water-soiuble C6 saccharides having an average degree of polymerization to about 2 to about 15, preferabl about 2 to about 10, and more preferably about 2 to about 8, 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:

providing a hydroiysate comprising said first water-soluble C6 saccharides and less than about 5250 ppm in total, based on total weight of water-soluble C6 saccharide hydroiysate in said composition, of elements;

wherein said elements are A!, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

[0021] in certain embodiments, the invention is directed to methods of reducing the level of enzyme required for enzymaticaily hydroiyzing first water-soiuble C5 saccharides having an average degree of polymerization to about 2 to about 28, preferably about 2 to about 15, more preferabiy about 2 to about 13, even more preferabl about 2 to about 6, to second water-soiubie C5 saccharides having a lower average degree of polymerization than said average degree of polymerization of said first water-soiubie C5 saccharides, comprising:

providing a hydroiysate comprising said first water-soluble C5 saccharides and less than about 3700 ppm in total, based on total weight of water-soluble C5 saccharide hydroiysate in said composition, of elements;

wherein said elements are AS, 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. In the drawings:

[0023] 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.

[0024] FIGURE 1 B is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a 06 oligosaccharide composition of one embodiment of the invention.

[0025] FIGURE 2A is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a 05 oligosaccharide composition of one embodiment of the invention.

[0026] FIGURE 2B is a scan from a DIONEX high pressure liquid chromatography device with an electrochemical detector of a 05 oligosaccharide composition of one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0027] As employed above and throughout the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.

[0028] As used herein, the singular forms "a," "an," and "the" include the plural reference unless the context clearly indicates otherwise.

[0029] 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.

[0030] 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.

[0031] As used herein, the phrase "substantially free" means have no more than about 1%, preferabl 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.

[0032] 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 Iiquid and gas phases disappears. A supercritical fluid possesses approximately the penetration properties of a gas simultaneously with the solvent properties of a Iiquid. Accordingly, supercritical fluid extraction has the benefit of high penetrability and good solvation. [0033] Reported critica! temperatures and pressures include: for pure water, a critical temperature of about 374.2°C, and a critica! pressure of about 221 bar; for carbon dioxide, a critica! 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 (374.2°C), 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-critica! 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 250" C and about 280° C. 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 50°C (preferably, at least about 100°C) but less than subcritical and at pressures such that water is In a liquid state.

[0034] As used herein, a fluid which is "supercritical" (e.g. supercritical water, supercritical CO ₂ , 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 374.2 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 00% 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 Ci¾ may have a temperature of about 250°C to about 280°C and a pressure of at least about 225 bar.

[0035] As used herein, "lignoce!lulosic biomass or a component part thereof refers to plant biomass containing cellulose, hemicellu!ose, and Signin from a variety of sources, including, without limitation (1 ) agricultural residues (including cor 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, SignoceHuiose biomass itseif, !ignin, Cg saccharides {including ce!!u!ose, cellobiose, Ce oligosaccharides, C _& monosaccharides, C ₅ saccharides (including hemicellulose, C ₅ oligosaccharides, and C5 monosaccharides), and mixtures thereof.

[0036] 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 AST 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 . n ei . qov/biomass/pdf s/42622. pdf and http:/ www. astm.org/Standards/ E1755.htm. which are both incorporated herein by reference in their entirety.

[0037] As used herein, "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 D!ONEX with an electrochemical detector, matrix-assisted laser desorption/ionization time-of-fiight (MALD!-TOF) mass spectrometry, or other conventional molecular weight determination methods.

OS Saccharides

[0038] Accordingly, in one embodiment, the invention is directed to compositions, comprising C6 saccharides. In particular embodiments, the compositions comprise: at least one water-soluble C6 oligosaccharide 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; wherein said e!ements are At, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TI, V, and Zn.

in certain embodiments, the elements are present at a levei of less than about 5100 ppm in total by weight, based on total weight of said water-soiub!e C6 oiigosacchande hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition.

[0039] In another embodiment, the invention is directed to compositions, comprising:

at ieast one water-soluble C6 oiigosacchande hydroiysate;

optionally, at Ieast one water-soluble C6 monosaccharide hydroiysate; and less than about 10 ppm by weight, based on total weight of said water-so!ubie C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of aluminum;

less than about 3000 ppm by weight based on total weight of said water- solubie C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of calcium;

less than about 350 ppm by weight, based on total weight of said water- solubie C6 oligosaccharide hydroiysate and said water-soiuble C6 monosaccharide hydroiysate in said composition, of iron; and

less than about 1000 ppm by weight, based on total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soiuble C6 monosaccharide hydroiysate in said composition, of sulfur.

Sn certain preferred embodiments, such compositions further comprise:

less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of elements;

wherein said elements are At, 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.

[0040] Sn other embodiments, the invention is directed to compositions, comprising:

at Ieast one water-soluble C6 oligosaccharide hydroiysate;

optionaily, at Ieast one water-soluble C6 monosaccharide hydroiysate; and less than about 10 ppm by weight, based on total weight of said water- soiubie C6 oiigosaccharide hydrolysate and said ater-solub!e C6 monosaccharide hydroiysaie in said composition, of aluminum.

in certain preferred embodiments, such compositions further comprise:

less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oiigosaccharide hydrolysate and said water-soiuble C8 monosaccharide hydroiysaie in said composition, of elements;

wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,

Mg, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TS, V, and Zn.

[0041] !n a further embodiment, the invention is directed to compositions, comprising:

at ieast one water-soluble C6 oiigosaccharide hydrolysate;

optionally, at Ieast one water-sol ubie C6 monosaccharide hydroiysaie; and less than about 3000 ppm by weight based on total weight of said water- soluble C6 oiigosaccharide hydroiysaie and said waier-so!ubie C6 monosaccharide hydrolysate in said composition, of ca!cium.

in certain preferred embodiments, such compositions further comprise:

less than about 5250 ppm in total by weight, based on total weight of said water-soluble C6 oiigosaccharide hydrolysate and said water- sol ubie C6 monosaccharide hydroiysaie in said composition, of elements;

wherein said elements are AS, 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, TS, V, and Zn.

[0042] in yet other embodiments, the invention is directed to compositions, comprising:

at ieast one water-soluble C6 oiigosaccharide hydrolysate;

optionally, at Ieast one water-soluble C6 monosaccharide hydro!ysate; and less than about 350 ppm by weight, based on total weight of said water- solub!e C6 oligosaccharide hydro!ysate and said water-soiuble C6 monosaccharide hydrolysate in said composition, of iron.

in certain preferred embodiments, such compositions further comprise: less than about 5250 ppm in total by weight, based on total weight of said water-soiub!e C6 oiigosacchande hydroiysate and said water-sol ub!e C6 monosaccharide hydroiysate in said composition, of elements;

wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, g, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

[0043] in another embodiment, the invention is directed to compositions, comprising:

at !east one water-soluble C6 oligosaccharide hydroiysate;

optionally, at least one water-soluble C6 monosaccharide hydroiysate; and less than about 1000 ppm by weight, based on total weight of said water- solubie C6 oiigosacchande hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of su!fur.

!n certain preferred embodiments, such compositions further comprise:

less than about 5250 ppm in total by weight, based on total weight of said water-soiuble C6 oiigosacchande hydroiysate and said water-soiuble C6 monosaccharide hydroiysate in said composition, of elements;

wherein said elements are AS, 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.

[0044] In certain embodiments, the water-soluble C6 oiigosacchande hydroiysate has a degree of polymerization of about 2 to about 15. In other embodiments, water- soluble C6 oligosaccharide hydroiysate has a degree of polymerization of about 2 to about 13. in other embodiments, water-soluble C6 oligosaccharide hydroiysate has a degree of poiymerization of about 2 to about 10. In other embodiments, water- soluble C6 oligosaccharide hydroiysate has a degree of polymerization of about 2 to about 6.

[0045] In certain embodiments, the compositions further comprise at least one water-soluble C6 monosaccharide hydroiysate.

[0046] in certain embodiments, the water-soluble C6 monosaccharide hydroiysate is glucose, galactose , mannose, fructose, or a mixture thereof. [0047] In certain embodiments, the compositions further comprise less than about 10 ppm, based on total weight of said water-solubie C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of aSuminum, preferably less than about 5 ppm by weight, based on total weight of said water-soiuble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of aluminum.

[0048] In certain embodiments, the compositions further comprise less than about 3000 ppm by weight, based on total weight of said water-sol ub!e C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of calcium, preferably less than about 2950 ppm by weight, based on total weight of said water-solubie C6 oligosaccharide hydroiysate and said water- soluble C6 monosaccharide hydroiysate in said composition, of calcium.

[0049] In certain embodiments, the compositions further comprise less than about 350 ppm by weight, based on total weight of said water-solubie C6 oligosaccharide hydroiysate and said water-solub!e C6 monosaccharide hydroiysate in said composition, of iron, preferably less than about 325 ppm by weight, based on total weight of said water-soluble C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of iron.

[0050] In certain embodiments, the compositions further comprise less than about 1000 ppm by weight, based on total weight of said water-solub!e C6 oligosaccharide hydroiysate and said water-soluble C6 monosaccharide hydroiysate in said composition, of sulfur, preferably less than about 975 ppm by weight, based on total weight of said water-solub!e C6 oligosaccharide hydroiysate and said water-soiuble C6 monosaccharide hydroiysate in said composition, of sulfur.

[0051] in certain embodiments, wherein the ratio of the total weight of said water- soluble C6 oligosaccharide hydroiysate and said water-soiuble C6 monosaccharide hydroiysate to said elements is greater than about 45:1 , preferably greater than about 47:1. [0052] In certain embodiments, the level of said elements are measured by inductively coupled plasma emission spectroscopy.

[0053] In other embodiments, the compositions iess than about 1500 mg of nitrogen per kg of total weight of water-soluble C6 saccharides, preferably less than about 1450 mg of nitrogen per kg of total weight of water-soluble C6 saccharides. Nitrogen may be measured by thermal conductivity detection after combustion and reduction.

[0054] In yet other embodiments of the compositions, 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 iess than about 0.14. Carbon, hydrogen, and nitrogen levels may be measured by thermal conductivity detection after combustion and reduction.

[0055] In certain other embodiments, the 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:

Level fess than about

Element {ppm or mg of element/kg

of C6 saccharides)

Se 0.6

Si 85.0

Sn 0.25

Sr 5.0

Ti 0.05

TI 0.7

V 0.05

Zn 65

[0056] In another embodiment, the compositions comprise:

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-soiubie C6 oligosaccharides have a degree of polymerization of about 2 to about 15.

Sn certain embodiments, said water-soluble C6 oligosaccharides are present at a Ievei of about 80% by weight to about 92.5% by weight, based on total weight of C6 saccharides present in said composition. in certain embodiments of the composition, said water-soluble C6 oligosaccharides have a degree of poiymerization of about 2 to about 13, preferably, about 2 to about 10, and more preferably about 2 to about 6. Sn certain embodiments, the compositions further comprise about 5% by weight to about 20% by weight, based on totaS weight of C6 saccharides present in said composition, of C6 monosacch arides .

[0057] In certain embodiments of the compositions described herein, said water- soluble C6 oligosaccharide hydrolysate comprises:

about 10% by weight to about 25% 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 di saccharides;

about 10% by weight to about 25% 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 trisaccharides;

about 10% by weight to about 25% by weight, based on total weight of said water-soluble C6 oligosaccharide hydrolysate and said water-solub!e C6 monosaccharide hydrolysate in said composition, of C6 tetrasaccharides; about 10% b weight to about 25% by weight, based on total weight of said water-soluble C6 oligosaccharide hydroSysate and said water-sol ub!e C6 monosaccharide hydroSysate in said composition, of C6 pentasaccharides; and

about 10% by weight to about 50% by weight, based on total weight of said water-soiuble C6 oligosaccharide hydroSysate and said water-soluble C6 monosaccharide hydroSysate in said composition, of CO saccharides having at a degree of polymerization of at least about 6.

In certain embodiments, the compositions further comprise:

about 5% by weight to about 20% by weight, based on total weight of said water-soluble C6 oligosaccharide hydroSysate and said water-soluble CO monosaccharide hydroSysate in said composition, of C6 monosaccharides, in certain embodiments, the compositions further comprise:

about 7.5% by weight to about 20% by weight, based on total weight of said water-soiuble CO oligosaccharide hydrolysate and said water-soluble CO monosaccharide hydroSysate in said composition, of C6 monosacchari d es.

[0058] in other embodiments, the compositions comprise:

about 10% by weight to about 25% by weight, based on total weight of CO saccharides present in said composition, of C6 disaccharides;

about 10% by weight to about 25% by weight, based on total weight of C6 saccharides present in said composition, of C6 trisaccharides;

about 10% by weight to about 25% by weight, based on total weight of CO saccharides present in said composition, of C6 tetrasaccha ides;

about 10% by weight to about 25% by weight, based on total weight of C6 sacchandes present in said composition, of CO pentasaccharides; and

about 10% by weight to about 50% by weight, based on totaS weight of C6 saccharides present in said composition, of C6 saccharides having at a degree of polymerization of at least about 0.

[0059] in other embodiments of the compositions, said CO disaccharides are present at a level of about 10% by weight to about 20% by weight, based on total weight of CO sacchandes present in said composition. [0060] in other embodiments of the compositions, said C6 trisaccha rides are present at a !evei of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.

[0061] In other embodiments of the compositions, said C6 tetrasaccha rides are present at a ievei of about 10% by weight to about 20% by weight, based on totai weight of C6 saccharides present in said composition.

[0062] In other embodiments of the compositions, said C6 pentasaccharides are present at a ievei of about 10% by weight to about 20% by weight, based on total weight of C6 saccharides present in said composition.

[0063] In other embodiments of the compositions, said C6 saccharides having at a degree of polymerization of at least about 6 are present at a ievei of about 10% by weight to about 20% by weight, based on totai weight of C6 saccharides present in said composition.

[0064} in other embodiments, the compositions further comprise:

about 5% b weight to about 20% by weight, based on totai weight of said water-so!ubie C6 oligosaccharide hydro! ysate and said water-solub!e C6 monosaccharide hydroiysate in said composition, of C6 monosaccharides, in certain embodiments, the compositions further comprise about 7.5% by weight to about 20% by weight, based on total weight of said water-so!ubie C6 oligosaccharide hydroiysate and said water-sol ubie C6 monosaccharide hydroiysate in said composition, of C6 monosaccharides.

[0065} in other embodiments, the compositions further comprise water.

[0066] In certain embodiments, the water-soluble C6 oiigosaccharide hydroiysate and the water-soluble C6 monosaccharide hydroiysate are processed from iignoceliuiosic biomass using supercritical, subcriticai, or near criticai f!uid extraction, or a combination thereof. C5 Saccharides

[0067] Accordingly, in one embodiment, the invention is directed to compositions, comprising C5 oligosaccharides. Sn particular, the compositions comprise:

at least one water-soluble C5 oligosaccharide hydroiysate:

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 3700 ppm in total by weight, based on total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of elements;

wherein said elements are A!, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li,

Mg, n _: Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, TL V, and Zn.

[0068] In one embodiment, the invention is directed to compositions, comprising: at least one water-soluble C5 oligosaccharide hydroiysate;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 10 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of aluminum;

less than about 2300 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of calcium;

less than about 50 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of iron; and

less than about 150 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of sulfur.

Sn certain embodiments, the elements are present at a level of less than about 3810 ppm in total by weight, based on total weight of said water-soluble C5 oiigosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition.

[0069] in further embodiments, the invention is directed to compositions, comprising: at least one water-sol ubie C5 oligosaccharide hydroiysate;

optionally, at least one water-so!ubie C5 monosaccharide hydroiysate; and less than about 10 ppm by weight, based on total weight of said water-soluble

C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of aluminum.

[0070] In yet further embodiments, the invention is directed to compositions, comprising:

at least one water-soluble C5 oligosaccharide hydroiysate;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 2300 ppm by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-solubie C5 monosaccharide hydroiysate in said composition, of calcium.

[0071] In another embodiment, the invention is directed to compositions, comprising:

at ieast one water-soiub!e C5 oligosaccharide hydroiysate:

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 50 ppm by weight, based on total weight of said water-soluble

C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of iron.

[0072] in yet another embodiment, the invention is directed to compositions, comprising:

at Ieast one water-soluble C5 oiigosaccharide hydroiysate;

optionally, at least one water-soluble C5 monosaccharide hydroiysate; and less than about 150 ppm by weight, based on total weight of said water- soluble C5 oiigosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of sulfur.

[0073] In certain embodiments, the compositions described herein further comprise: less than about 3700 ppm by weight in total, based on total weight of said water-soluble C5 oligosaccharide hydroSysate and said water-sol ub!e C5 monosaccharide hydroSysate in said composition, of elements;

wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, g, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

[0074] in certain embodiments, the water-soluble C5 oligosaccharide hydrolysate has a degree of polymerization of at least about 2 to about 28. Sn other embodiments, water-soluble C5 oligosaccharide hydrolysate has a degree of poSymerization of at least about 2 to about 15. In other embodiments, water-soluble C5 oligosaccharide hydroSysate has a degree of polymerization of at least about 2 to about 10. In other embodiments, water-soluble C5 oligosaccharide hydroSysate has a degree of poSymerization of at least about 2 to about 6.

[0075] Sn certain embodiments, the compositions further comprise:

at least one water-soluble C5 monosaccharide hydrolysate.

[0076] in certain embodiments, the water-soluble C5 monosaccharide hydrolysate is xylose, arabinose, !yxose, ribose, or a mixture thereof.

[0077] Sn certain embodiments, 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 hydroSysate in said composition, of aluminum.

[0078] In certain embodiments, the compositions further comprise Sess than about 2300 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydrolysate and said water-soSub!e 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. [0079] !n certain embodiments, the compositions further comprise iess than about 50 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soiub!e C5 monosaccharide hydroiysate in said composition, of iron, preferably !ess than about 30 ppm by weight, based on total weight of said water-solub!e C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of iron.

[0080] in certain embodiments, the compositions further comprise iess than about 150 ppm by weight, based on tota! weight of said water-soiubie C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of sulfur, preferably less than about 140 ppm by weight, based on total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soiubie C5 monosaccharide hydroiysate in said composition, of sulfur.

[0081] In certain embodiments, the ratio of total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition to said elements is greater than about 75:1 , preferably greater than about 80:1.

[0082] In certain embodiments, the water-soluble C5 oligosaccharide hydroiysate is processed from iignocei!uiosic biomass using supercritical, subcritical, or near critical fluid extraction, or a combination thereof.

[0083] In certain embodiments, the level of said elements are measured by inductively coupled plasma emission spectroscopy.

[0084] In other embodiments, the 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 C6 saccharides. Nitrogen may be measured by thermal conductivity detection after combustion and reduction.

[0085] In yet other embodiments of the compositions, the weight ratio of the collective mass of hydrogen and nitrogen to mass of carbon present in said water- soluble C5 oligosaccharide hydroiysate and said water-soiuble C5 monosaccharide hydroiysate is less than about 0.14. Carbon, hydrogen, and nitrogen ieveis may be measured by thermal conductivity detection after combustion and reduction.

[0086] In certain other embodiments, the compositions comprising the C5 saccharides further comprise iess than a maximum of any of the elements, individually or in combination, in the table listed below:

[0087] in another embodiment, the compositions comprise:

about 75% by weight to about 90% by weight, based on total weight of said water-soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydro!ysate in said composition, of water-soluble C5 oligosaccharides;

wherein said water-soSub!e C5 oligosaccharides have a degree of polymerization of about 2 to about 28.

In certain embodiments, 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 hydro! ysate and said water-soluble C5 monosaccharide hydrolysate in said composition. In certain embodiments of the 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. In certain embodiments, 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.

[0088] In certain embodiments of the compositions described herein, said water- soluble C5 oligosaccharide hydrolysate comprises:

about 15% 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, of C5 di saccharides:

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, of C5 trisaccharides;

about 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 tetrasaccharides;

about 2% 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 pentasaccharides; and

about 10% by weight, to about 35% 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 saccharides having at a degree of polymerization of at least about 6. In certain embodiments of the 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. In certain embodiments, the compositions further comprise about 10% by weight, to about 25% by weight, based on total weight of said water-soluble C5 oiigosaccharide hydroiysate and said water- soluble C5 monosaccharide hydroiysate in said composition, of C5 monosaccharides. In certain embodiments, the compositions further comprise about 12.5% by weight, to about 20% by weight, based on total weight of said water- soluble C5 oligosaccharide hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition, of C5 monosaccharides.

[0089] In certain embodiments of the compositions described herein, 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 hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition.

[0090] In certain embodiments of the compositions described herein, 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 hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition.

[0091] In certain embodiments of the compositions described herein, 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 hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition.

[0092] In certain embodiments of the compositions described herein, 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 hydroiysate and said water-soluble C5 monosaccharide hydroiysate in said composition.

[0093] In certain embodiments of the compositions described herein, 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-soiuble C5 oligosaccharide hydroSysate and said water-solub!e C5 monosaccharide hydrolysate in said composition.

[0094] In certain embodiments, the compositions described herein further comprise about 10% by weight, to about 25% by weight, based on total weight of said water-soluble C5 oligosaccharide hydroSysate and said water-soluble C5 monosaccharide hydroSysate in said composition, of C5 monosaccharides.

[0095] In certain embodiments, the compositions described herein further comprise water.

[0096] In certain embodiments, the water-soiuble C6 oligosaccharide hydrolysate and the water-soiuble C6 monosaccharide hydrolysate are processed from iignoceliuiosic biomass using supercritical, subcriticaS, or near critical fluid extraction, or a combination thereof .

Further embodiments

[0097] In certain embodiments, the invention is directed to methods of reducing the level of enzyme required for enzymatica!ly hydrolyzing first water-soiuble 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 poiymerization of said first water-soluble C6 saccharides, comprising:

providing a hydroSysate comprising said first water-soluble C6 saccharides and less than about 5250 ppm in total, based on total weight of water-soiuble C6 saccharide hydrolysate in said composition, of elements;

wherein said elements are At, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, , Li, g, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

In certain embodiments, the C6 saccharides are extracted from Iignoceliuiosic biomass. Sn other embodiments, the C6 saccharides are processed from SignoceiluSosic biomass using supercritical, subcriticaS, or near critical fluid extraction, or a combination thereof. [0098] In certain embodiments, the invention is directed to methods of reducing the levei of enzyme required for enzymaticaily 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 Sower average degree of polymerization than said average degree of polymerization of said first water-soluble C5 saccharides, comprising:

providing a hydro!ysate 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;

wherein said elements are Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, g, n, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, Tl, V, and Zn.

[0099] In further embodiments, 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, isopropanoi, r-butanol). In preferred embodiments, 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, in more preferred embodiments, the compositions contain substantially no organic solvent.

[0100] The compositions of the invention are preferably prepared from biomass by processes employing supercritical. subcriticaS, 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 iignin. Sn 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 ceS!u!ose hydrolysis step or steps using supercritical or near critical water to separate the cellulose (which may processed to form C6 monomeric and/or o!igomeric sugars) from the Iignin. In the hydrolysis step(s), suitable temperatures are about 250" C to about 450" C, suitable pressures are about 40 bars to about 260 bars, and suitable residence times are about 0.1 seconds to about 3 minutes. The compositions may be prepared in any suitable reactor, including, but not Hmited to, a tubular reactor, a digester (vertica!, 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.

[0101] The compositions of the invention comprising C5 saccharides or C6 saccharides ma 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);

chemicals (such as acetic acid, acetic anhydride, acetone, acrylic acid, adipic acid, benzene, ethano!, ethylene, ethylene glycol, ethylene oxide, methanol, polypropylene, terephthalic acid, toluene, xylene, 1 ,3-propanediol, 1 ,4-butanedio!, 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);

specialty chemicals (such as acontic acid, glutamic acid, malic acid, oxalic acid, and the like);

textile applications (such as formic acid and the like); and

industrial intermediates (aceta!dehyde, 3-hydroxypropionic acid, 2,5-furan dicarfooxyiic acid, furfural, gSutaric acid, itaconic acid, ievulinic acid, and the like).

[0102] 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 oligosaccharide compositions

[01031 The C5 oligosaccharide and C6 oligosaccharide compositions of the invention were prepared using supercritical subcritica!, and near critical water extraction in a two stage process. Particulate !ignoce!lulosic 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. 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 150-250X. The slurry was then subjected to supercritica! 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.

[0104] 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

[0105] The dried compositions containing the C5 and C6 oligosaccharides of Example 1 were analyzed using inductively coupled plasma emission spectroscopy. The results are shown in the table below:

Example 3: Analysis of oligosaccharide compositions using ge! permeation chromatography

[0106] The C5 oligosaccharide and C6 oligosaccharide compositions of the invention were prepared using supercritical subcriticai, 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.

[0107] As can be seen in FIGURES 1A and 1B, a degree of polymerization (DP) were detected up to at least a DP of 13, with small peaks visible above DP of 13 for the C6 oligosaccharide compositions. As can be seen in FIGURES 2A and 2B, a degree of polymerization (DP) 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

[0108] The C6 saccharide compositions of the invention were prepared using supercritical, subcriticai, 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 (tubuiar 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.

[0109] The representative samples were analyzed using gel permeation chromatography. The area under each peak (indicating an individual mer unit in the saccharide) was measured to calculate weight % of each mer unit, based on the total weight of C6 saccharides present in the sample. The results are shown in the following table: Sample C6 C6 C6 C6 C6 C6 monosaccharides disacehari es irisaccharides tetrsaee iarides pentasaccharides hexasaee arides t veight } ( eig i {weig %> t veight ) +

(wetght )

1-1033 15.3 19.8 15.4 15.2 12.1 22.2

2-1448 19.3 19.1 18.9 5,6 14.7 12.4

3-1252 8.9 1 .3 13.3 12.4 16.6 37.5

4-2125 16.8 17.1 17.1 5.4 15.9 17.8

5-2344 13.689 16.444 15.454 14.945 12.652 26.816

6-1600 7.914 10.087 11.397 13.024 12.71 44.867

Example 5: Analysis of C5 saccharide compositions using gel permeation chromatography

[0110] 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.

[0111] The representative samples were analyzed using gei permeation chromatography (details below).

GPC Agilent HPLC System Configuration

Auto Sampler 1260 ASL

Pump 1260 isocratie pump Agilent

Heater 1260 TCC

Degasser 1260 degasser

Mobile Phase Dl water

Column Ultrahydrogel-120, 250, 500 from Waters

(injection vol 25 μΙ, Size 7.8 X 300mm) temp 30°C

Flow Rate 0.5 mS/min; run time of 80 minutes

Detector 1260-RID set at 50°C Agilent and DAD (signal 214 and 270 nm)

[0112] The area under each peak (indicating an individual mer unit in the saccharide) was measured to calculate weight % of each mer unit, based on the total weight of C5 saccharides present in the sample. The results are shown in the following table: Sample C5 C5 C5 C5 C5 C5 monosaccharides disscc arkies tcisacchaiides tetrsacchsricfes pen Sasaccbaric!es >hexas3cc arkies fweight%) {weight%} {weight%} (wetghi%>

7-0458 18.2 24.4 16.3 14.1 11 ,8 15.3

8-0550 17.0 21.8 16.2 11.6 13,0 20.3

9-0S47 16.1 23.5 18.1 10.7 4.5 27.1

10- 17.2 23.6 17 6 10.4 9.4 21.9 2144

11- 13.3 20.4 13.9 17.4 9.3 25.4 2242

12- 13.4 19.3 14.7 13.0 9.5 30.1 2348

Example 6: Analysis of C5 and C6 saccharide compositions using HPLC with an electrochemical detector

[0113] The C5 and C6 saccharide compositions of the invention were prepared using supercritical, subcriticai, and near critica! water extraction in the two stage process as described in Example 1. Representative samples were selected.

[0114] The representative samples were analyzed using DIONEX HPLC (details below).

Dionex System Thermo Scientific Configuration

Auto Sampler AS-AP

Pump !CS-5000 DP (dual pulse)

Mobile Phase 100 m NaOH (sodium hydrohyde) + deionized water

100 mM NaOH (sodium hydrohyde) + 1 NaOAc

(sod

acetate)

Column/Heater CarboPac PA 200 3 X 250 mm temp 30°C

with guard column CarboPac PA 200 3 X 250 mm

(injection vol 10 μΙ) and compartment temperature 30 'C

Fiow Rate 0.5 ml/min; run time of 70 minutes

Detector ICS-5000 DC Electro chemical detector

The results are averaged and shown in the tables below

DiQNEX averaged results

(with and without quench post cettuSose hydroiysis; quench at lEMTC)

[0116] When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, ali combinations, and subcombinations of ranges specific embodiments therein are intended to be included.

[0117] The disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference, in their entirety.

[0118] 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.