U.S. patent application number 16/516504 was filed with the patent office on 2019-11-07 for compositions comprising c5 and c6 monosaccharides.
This patent application is currently assigned to Renmatix, Inc.. The applicant listed for this patent is Renmatix, Inc.. Invention is credited to Daniel Clay Floyd, Kiran Kadam, Srinivas Kilambi.
Application Number | 20190338379 16/516504 |
Document ID | / |
Family ID | 48693841 |
Filed Date | 2019-11-07 |
United States Patent
Application |
20190338379 |
Kind Code |
A1 |
Floyd; Daniel Clay ; et
al. |
November 7, 2019 |
COMPOSITIONS COMPRISING C5 and C6 MONOSACCHARIDES
Abstract
Compositions comprising C5 and C6 monosaccharides and low levels
of undesirable impurities, such as compounds containing sulfur,
nitrogen, or metals, are disclosed.
Inventors: |
Floyd; Daniel Clay;
(Richmond, VA) ; Kadam; Kiran; (Golden, CO)
; Kilambi; Srinivas; (Duluth, GA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Renmatix, Inc. |
King of Prussia |
PA |
US |
|
|
Assignee: |
Renmatix, Inc.
King of Prussia
PA
|
Family ID: |
48693841 |
Appl. No.: |
16/516504 |
Filed: |
July 19, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15949878 |
Apr 10, 2018 |
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16516504 |
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15827486 |
Nov 30, 2017 |
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15949878 |
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14668133 |
Mar 25, 2015 |
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15827486 |
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14659675 |
Mar 17, 2015 |
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14668133 |
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13649437 |
Oct 11, 2012 |
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14659675 |
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61581907 |
Dec 30, 2011 |
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61581890 |
Dec 30, 2011 |
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61581878 |
Dec 30, 2011 |
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61581922 |
Dec 30, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C13K 1/02 20130101; C07H
3/06 20130101; Y02E 50/16 20130101; C13K 1/04 20130101; Y02E 50/10
20130101; C13K 13/00 20130101; C13B 50/00 20130101; C13K 11/00
20130101; Y02P 20/54 20151101; Y02P 20/544 20151101; C07H 3/02
20130101; C13K 13/007 20130101; C13K 13/002 20130101 |
International
Class: |
C13K 1/02 20060101
C13K001/02; C13K 13/00 20060101 C13K013/00; C07H 3/02 20060101
C07H003/02; C13B 50/00 20060101 C13B050/00; C07H 3/06 20060101
C07H003/06; C13K 1/04 20060101 C13K001/04; C13K 11/00 20060101
C13K011/00 |
Claims
1. A composition comprising: (a) at least one water-soluble C6
monosaccharide hydrolysate, derived from cellulose; (b) at least
one water-soluble C5 monosaccharide hydrolysate and/or at least one
water-soluble C6 monosaccharide hydrolysate, derived from
hemicellulose; (c) at least one water-soluble C5 oligosaccharide
hydrolysate and/or at least one water-soluble C6 oligosaccharide
hydrolysate, derived from hemicellulose; and (d) impurities wherein
the impurities comprise a total amount by weight, based on total
weight of the composition, of (a) less than about 6750 ppm or (b)
less than about 1950 ppm of elements 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 when the composition is measured for all of
the elements.
2. The composition of claim 1, wherein the elements comprise Ca,
Cu, Fe, K, Mg, Mn, Na, P, S, and Si.
3. The composition of claim 2, further comprising: at least one
water-soluble C6 oligosaccharide hydrolysate, derived from
cellulose.
4. The composition of claim 3, wherein the at least one
water-soluble C6 oligosaccharide hydrolysate, derived from
cellulose, is selected from one of cellobiose, isomaltose,
trehalose, or a combination thereof.
5. The composition of claim 2, further comprising: glucose,
mannose, galactose, fructose, or a combination thereof.
6. The composition of claim 2, wherein the one water-soluble C5
monosaccharide hydrolysate and/or the water-soluble C6
monosaccharide hydrolysate is derived from a lignocellulose
biomass.
7. The composition of claim 2, further comprising: water.
8. The composition of claim 2, wherein the water-soluble
hydrolysates are present: at a concentration of at least 0.5 g/L;
or at a concentration of at least 200 g/L.
9. The composition of claim 2, wherein the at least one
water-soluble C6 monosaccharide hydrolysate, derived from
cellulose, is glucose.
10. The composition of claim 2, wherein at least one of the
following is satisfied: the impurities comprise less than 1925 ppm
by weight, based on the total weight of the composition, of
elements; the impurities comprise less than 300 ppm by weight,
based on the total weight of the composition, of calcium; the
impurities comprise less than 10 ppm by weight, based on the total
weight of the composition, of iron; the impurities comprise less
than 1000 ppm by weight, based on the total weight of the
composition, of sulfur.
11. The composition of claim 10, wherein: the at least one
water-soluble C5 monosaccharide hydrolysate is present and is
selected from xylose, arabinose, or a combination thereof; and/or
the at least one water-soluble C5 oligosaccharide hydrolysate is
present and is composed of monomeric units of xylose, arabinose, or
a combination thereof.
12. The composition of claim 2, wherein: the weight ratio of the
water-soluble C5 monosaccharide hydrolysate to the elements is
greater than about 95:1; and/or the weight ratio of the one
water-soluble C6 monosaccharide hydrolysate to the elements is
greater than about 30:1.
13. The composition of claim 1, wherein the impurities comprise:
less than 300 ppm by weight, based on the total weight of the
composition, of calcium; less than 10 ppm by weight, based on the
total weight of the composition, of iron; and less than 1000 ppm by
weight, based on the total weight of the composition, of
sulfur.
14. The composition of claim 13, wherein the elements comprise Ca,
Cu, Fe, K, Mg, Mn, Na, P, S, and Si.
15. The composition of claim 13, further comprising: at least one
water-soluble C6 oligosaccharide hydrolysate, derived from
cellulose.
16. The composition of claim 15, wherein the at least one
water-soluble C6 oligosaccharide hydrolysate, derived from
cellulose, is selected from one of cellobiose, isomaltose,
trehalose, or a combination thereof.
17. The composition of claim 13, further comprising: glucose,
mannose, galactose, fructose, or a combination thereof.
18. The composition of claim 13, the impurities comprise less than
1925 ppm by weight, based on the total weight of the composition,
of elements; and wherein the elements comprise Ca, Cu, Fe, K, Mg,
Mn, Na, P, S, and Si.
19. The composition of claim 2, wherein: the at least one
water-soluble C5 oligosaccharide hydrolysate, derived from
hemicellulose, is present and has a degree of polymerization of 2
to about 6; and/or the at least one water-soluble C6
oligosaccharide hydrolysate, derived from hemicellulose, is present
and has a degree of polymerization of 2 to about 6.
20. The composition of claim 2, wherein: the at least one
water-soluble C5 monosaccharide hydrolysate is present and is
selected from xylose, arabinose, or a combination thereof; and/or
the at least one water-soluble C5 oligosaccharide hydrolysate is
present and is composed of monomeric units of xylose, arabinose, or
a combination thereof.
21. The composition of claim 2, further comprising ash.
22. A composition, comprising: at least one water-soluble C6
monosaccharide hydrolysate; at least one water-soluble C5
monosaccharide hydrolysate; at least one water-soluble C5
oligosaccharide hydrolysate having a degree of polymerization of
about 2 to about 10; and impurities, wherein the impurities
comprise a total amount by weight, based on total weight of the
composition, of (a) less than about 6750 ppm or (b) less than about
1950 ppm of elements 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 when the composition is measured for all of the
elements.
23. The composition of claim 22, wherein the elements comprise Ca,
Cu, Fe, K, Mg, Mn, Na, P, S, and Si.
24. The composition of claim 23, wherein the water-soluble C6
monosaccharide hydrolysate is extracted from lignocellulosic
biomass.
25. The composition of claim 23, further comprising water.
26. The composition of claim 23, wherein at least one of the
following is satisfied: the water-soluble hydrolysates are present
at a concentration of at least 200 g/L; the water-soluble C6
monosaccharide hydrolysate is present at a concentration of at
least about 0.5 g/L; the water-soluble C5 monosaccharide
hydrolysate is present at a concentration of at least 0.5 g/L.
27. The composition of claim 23, wherein the water-soluble C6
monosaccharide hydrolysate is glucose, galactose, mannose,
fructose, or a mixture thereof.
28. The composition of claim 23, wherein the impurities comprise at
least one of: less than about 300 ppm by weight of calcium; less
than about 10 ppm by weight of iron; less than about 1000 ppm by
weight of sulfur.
29. The composition of claim 23, wherein: the weight ratio of the
water-soluble C5 monosaccharide hydrolysate to the elements is
greater than about 95:1; and/or the weight ratio of the one
water-soluble C6 monosaccharide hydrolysate to the elements is
greater than about 30:1.
30. The composition of claim 22, wherein the impurities comprise at
least one of: less than about 300 ppm by weight of calcium; less
than about 10 ppm by weight of iron; less than about 1000 ppm by
weight of sulfur.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Ser. No.
15/949,878, currently pending, which is a continuation of U.S. Ser.
No. 15/827,486, filed Nov. 30, 2017, abandoned, which is a
continuation of U.S. Ser. No. 14/668,133, filed Mar. 25, 2015,
abandoned, which is a continuation of U.S. Ser. No. 14/659,675,
filed Mar. 17, 2015, abandoned, which is a continuation of U.S.
application Ser. No. 13/649,437, filed Oct. 11, 2012, abandoned,
which claims the benefit of:
[0002] U.S. Application No. 61/581,922, filed Dec. 30, 2011;
[0003] U.S. Application No. 61/581,907, filed Dec. 30, 2011;
[0004] U.S. Application No. 61/581,878, filed Dec. 30, 2011;
and
[0005] U.S. Application No. 61/581,890, filed Dec. 30, 2011;
the entire disclosures of which are incorporated herein by
reference.
FIELD OF THE INVENTION
[0006] The present invention generally relates to compositions
comprising C5 and C6 monosaccharides 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.
BACKGROUND OF THE INVENTION
[0007] There are a number of processes for converting
lignocellulosic 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
hemicellulose component of the lignocellulosic biomass and
cellulose hydrolysis (CH) process, as its name infers, hydrolyzes
the cellulose fibers. The resultant five carbon (C5) and six carbon
(C6) sugar streams are recovered separately. The remaining solids,
which consist mostly of lignin, are preferably recovered, such as
through filtration, and may be used as a fuel to provide thermal
energy to the process itself or for other processes.
[0008] 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.
[0009] The invention is directed to these compositions, as well as
and other important ends.
SUMMARY OF THE INVENTION
[0010] In a first embodiment, the invention is directed to
compositions, comprising C6 monosaccharides. In particular, the
compositions comprise:
[0011] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0012] less than about 6750 ppm in total by weight, based on total
weight of water-soluble C6 saccharide hydrolysate in said
composition, of elements;
[0013] 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.
[0014] In certain embodiments, the compositions comprise:
[0015] at least one water-soluble C6 monosaccharide
hydrolysate;
[0016] less than about 10 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
aluminum;
[0017] less than about 350 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
calcium;
[0018] less than about 425 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
iron; and
[0019] less than about 4500 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
sulfur.
[0020] In certain embodiments, the compositions comprise:
[0021] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0022] less than about 10 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
aluminum.
[0023] In certain embodiments, the compositions comprise:
[0024] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0025] less than about 350 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
calcium.
[0026] In certain embodiments, the compositions comprise:
[0027] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0028] less than about 425 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
iron.
[0029] In certain embodiments, the compositions comprise:
[0030] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0031] less than about 4500 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
sulfur.
[0032] In other embodiments, the invention is directed to
compositions, comprising C5 monosaccharides. In particular, the
compositions comprise:
[0033] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0034] less than about 1950 ppm in total by weight, based on total
weight of water-soluble C5 saccharide hydrolysate in said
composition, of elements;
[0035] 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.
[0036] In certain embodiments, the compositions comprise:
[0037] at least one water-soluble C5 monosaccharide
hydrolysate;
[0038] less than about 5 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
aluminum;
[0039] less than about 300 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
calcium;
[0040] less than about 10 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
iron; and
[0041] less than about 1000 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
sulfur.
[0042] In certain embodiments, the compositions comprise:
[0043] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0044] less than about 5 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
aluminum.
[0045] In certain embodiments, the compositions comprise:
[0046] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0047] less than about 300 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
calcium.
[0048] In certain embodiments, the compositions comprise:
[0049] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0050] less than about 10 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
iron.
[0051] In certain embodiments, the compositions comprise:
[0052] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0053] less than about 1000 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
sulfur.
[0054] In certain embodiments, 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:
[0055] providing a hydrolysate comprising said first water-soluble
C6 saccharides and less than about 5250 ppm in total by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of elements;
[0056] 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.
[0057] In certain embodiments, 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:
[0058] providing a hydrolysate comprising said first water-soluble
C5 saccharides and less than about 3700 ppm in total by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of elements;
[0059] 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.
DETAILED DESCRIPTION OF THE INVENTION
[0060] As employed above and throughout the disclosure, the
following terms, unless otherwise indicated, shall be understood to
have the following meanings.
[0061] As used herein, the singular forms "a," "an," and "the"
include the plural reference unless the context clearly indicates
otherwise.
[0062] 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.
[0063] 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.
[0064] As used herein, the phrase "substantially free" means have
no more than about 1%, preferably less than about 0.5%, more
preferably, less than about 0.1%, by weight of a component, based
on the total weight of any composition containing the
component.
[0065] 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.
[0066] Reported critical temperatures and pressures include: for
pure water, a critical temperature of about 374.2.degree. C., and a
critical pressure of about 221 bar; for carbon dioxide, a critical
temperature of about 31.degree. C. and a critical pressure of about
72.9 atmospheres (about 1072 psig). Near critical water has a
temperature at or above about 300.degree. C. and below the critical
temperature of water (374.2.degree. 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.degree. 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.degree. C. and less than about 300.degree. C., and in many
instances sub-critical water has a temperature between about
250.degree. C. and about 280.degree. 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.degree. C.
(preferably, at least about 100.degree. C.) but less than
subcritical and at pressures such that water is in a liquid
state
[0067] As used herein, a fluid which is "supercritical" (e.g.
supercritical water, supercritical C02, etc.) indicates a fluid
which would be supercritical if present in pure form under a given
set of temperature and pressure conditions. For example,
"supercritical water" indicates water present at a temperature of
at least about 374.2.degree. 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 C02, etc). Thus, for example, "a
mixture of sub-critical water and supercritical carbon dioxide"
indicates a mixture of water and carbon dioxide at a temperature
and pressure above that of the critical point for carbon dioxide
but below the critical point for water, regardless of whether the
supercritical phase contains water and regardless of whether the
water phase contains any carbon dioxide. For example, a mixture of
sub-critical water and supercritical CO.sub.2 may have a
temperature of about 250.degree. C. to about 280.degree. C. and a
pressure of at least about 225 bar.
[0068] As used herein, "lignocellulosic biomass or a component part
thereof" refers to plant biomass containing cellulose,
hemicellulose, and lignin from a variety of sources, including,
without limitation (1) agricultural residues (including corn stover
and sugarcane bagasse), (2) dedicated energy crops, (3) wood
residues (including hardwoods, softwoods, sawmill and paper mill
discards), and (4) municipal waste, and their constituent parts
including without limitation, lignocellulose biomass itself,
lignin, C.sub.6 saccharides (including cellulose, cellobiose,
C.sub.6 oligosaccharides, C6 monosaccharides, C.sub.5 saccharides
(including hemicellulose, C.sub.5 oligosaccharides, and C.sub.5
monosaccharides), and mixtures thereof.
[0069] As used herein, "ash" refers to the non-aqueous residue that
remains after a sample is burned, and consists mostly of metal
oxides. Ash content may be measured in accordance with ASTM
Standard Method No. E1755-01 "Standard Method for the Determination
of Ash in Biomass." This test method covers the determination of
ash, expressed as the percentage of residue remaining after dry
oxidation at 550 to 600.degree. C. All results are reported
relative to the 105.degree. C. oven dry weight of the sample. See
also: Sluiter, A. et al., "Determination of Ash in Biomass,"
National Renewable Energy Laboratory (NREL) Technical Report
NREL/TP-510-42622, Jul. 17, 2005; and ASTM Standard Method No.
E1755-01 "Standard Method for the Determination of Ash in Biomass,"
2007, which are both incorporated herein by reference in their
entirety.
[0070] 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 DIONEX with an electrochemical detector, matrix-assisted
laser desorption/ionization time-of-flight (MALDI-TOF) mass
spectrometry, or other conventional molecular weight determination
methods.
C6 Monosaccharides
[0071] Accordingly, in one embodiment, the invention is directed to
compositions, comprising C6 monosaccharides. In particular
embodiments, the compositions comprise:
[0072] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0073] less than about 6750 ppm in total by weight, based on total
weight of water-soluble C6 saccharide hydrolysate in said
composition, of elements;
[0074] 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.
In certain preferred embodiments, said elements are present at a
level of less than about 6600 ppm in total by weight, based on
total weight of water-soluble C6 saccharide hydrolysate in said
composition, of said elements.
[0075] In certain embodiments, the compositions comprise:
[0076] at least one water-soluble C6 monosaccharide
hydrolysate;
[0077] less than about 10 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
aluminum;
[0078] less than about 350 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
calcium;
[0079] less than about 425 mg, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
iron; and
[0080] less than about 4500 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
sulfur.
[0081] In certain embodiments, the compositions comprise:
[0082] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0083] less than about 10 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
aluminum.
[0084] In certain embodiments, the compositions comprise:
[0085] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0086] less than about 350 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
calcium.
[0087] In certain embodiments, the compositions comprise:
[0088] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0089] less than about 425 mg, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
iron.
[0090] In certain embodiments, the compositions comprise:
[0091] at least one water-soluble C6 monosaccharide hydrolysate;
and
[0092] less than about 4500 ppm by weight, based on total weight of
water-soluble C6 saccharide hydrolysate in said composition, of
sulfur.
[0093] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions comprise:
[0094] less than about 6750 ppm in total by weight, based on total
weight of water-soluble C6 saccharide hydrolysate in said
composition, of elements;
[0095] 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.
In certain preferred embodiments, said elements are present at a
level of less than about 6600 ppm in total by weight, based on
total weight of water-soluble C6 saccharide hydrolysate in said
composition, of said elements.
[0096] In certain embodiments, the water-soluble C6 monosaccharide
hydrolysate is extracted from lignocellulosic biomass. In certain
embodiments, the water-soluble C6 monosaccharide hydrolysate is
processed from lignocellulosic biomass using supercritical,
subcritical, or near critical fluid extraction, or a combination
thereof.
[0097] In certain embodiments, the compositions further comprise
water.
[0098] In certain embodiments, the water-soluble C6 monosaccharide
hydrolysate is present at a concentration of at least about 0.5
g/L.
[0099] In certain embodiments, the C6 monosaccharide is glucose,
galactose, mannose, fructose, or a mixture thereof.
[0100] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise less than about 10 ppm by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of aluminum, preferably less than about 7.5 ppm
by weight, based on total weight of water-soluble C6 saccharide
hydrolysate in said composition, of aluminum.
[0101] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise less than about 350 ppm by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of calcium, preferably less than about 325 ppm by
weight, based on total weight of water-soluble C6 saccharide
hydrolysate in said composition, of calcium.
[0102] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise less than about 425 ppm by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of iron, preferably less than about 420 ppm by
weight, based on total weight of water-soluble C6 saccharide
hydrolysate in said composition, of iron.
[0103] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise less than about 4500 ppm by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of sulfur, preferably less than about 4425 ppm by
weight, based on total weight of water-soluble C6 saccharide
hydrolysate in said composition, of sulfur.
[0104] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
weight ratio of said water-soluble C6 monosaccharide hydrolysate to
said elements is greater than about 25:1, preferably greater than
about 30:1.
[0105] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise at least one water-soluble C6
oligosaccharide having a degree of polymerization of about 2 to
about 15, preferably about 2 to about 13, more preferably about 2
to about 10, and even more preferably about 2 to 6.
[0106] In certain preferred embodiments of the compositions
comprising the water-soluble C6 monosaccharide hydrolysate, the
compositions further comprise at least one water-soluble C5
saccharide having a degree of polymerization of about 1 to about
28, preferably about 1 to 15, more preferably about 1 to about 10,
and even more preferably about 1 to about 6.
[0107] In certain embodiments, the water-soluble C6 monosaccharide
hydrolysate is processed from lignocellulosic biomass using
supercritical, subcritical, or near critical fluid extraction, or a
combination thereof.
[0108] In certain embodiments, the level of said elements are
measured by inductively coupled plasma emission spectroscopy.
[0109] In other embodiments, the compositions comprise less 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.
[0110] In yet other embodiments, the compositions further comprise
a weight ratio of the total mass of hydrogen and nitrogen to carbon
of less than about 0.17.
[0111] In certain other embodiments, the compositions comprising
the C6 monosaccharides further comprise less than a maximum of any
of the elements, individually or in combination, in the table
listed below:
TABLE-US-00001 Level less than about (ppm or mg of element/kg of
Element C6 saccharides) As 0.25 B 1.0 Ba 1.0 Be 0.1 Cd 0.1 Co 0.25
Cr 3.25 Cu 325 K 350 Li 25 Mg 0.1 Mn 625 Mo 3.0 Na 15 Ni 0.25 P
0.25 Pb 0.35 Sb 0.25 Se 2.0 Si 0.1 Sn 0.3 Sr 0.1 Ti 0.25 Tl 1.0 V
1.0 Zn 0.1
C5 monosaccharides
[0112] Accordingly, in one embodiment, the invention is directed to
compositions, comprising C5 monosaccharides. In particular, the
compositions comprise:
[0113] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0114] less than about 1950 ppm in total by weight, based on total
weight of water-soluble C5 saccharide hydrolysate in said
composition, of elements;
[0115] 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.
In certain preferred embodiments, the elements are present at a
level of less than about 1925 ppm in total by weight, based on
total weight of water-soluble C5 saccharide hydrolysate in said
composition.
[0116] In certain embodiments, the compositions comprise:
[0117] at least one water-soluble C5 monosaccharide
hydrolysate;
[0118] less than about 5 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
aluminum;
[0119] less than about 300 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
calcium;
[0120] less than about 10 mg, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
iron; and
[0121] less than about 1000 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
sulfur.
[0122] In certain embodiments, the compositions comprise:
[0123] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0124] less than about 5 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
aluminum.
[0125] In certain embodiments, the compositions comprise:
[0126] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0127] less than about 300 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
calcium.
[0128] In certain embodiments, the compositions comprise:
[0129] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0130] less than about 10 mg, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
iron.
[0131] In certain embodiments, the compositions comprise:
[0132] at least one water-soluble C5 monosaccharide hydrolysate;
and
[0133] less than about 1000 ppm by weight, based on total weight of
water-soluble C5 saccharide hydrolysate in said composition, of
sulfur.
[0134] In certain embodiments, the compositions further
comprise:
[0135] less than about 1950 ppm in total by weight, based on total
weight of water-soluble C5 saccharide hydrolysate in said
composition, of elements;
[0136] 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.
In certain preferred embodiments, the elements are present at a
level of less than about 1925 ppm in total by weight, based on
total weight of water-soluble C5 saccharide hydrolysate in said
composition.
[0137] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise less than about 5 ppm by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of aluminum, preferably less than about 2 ppm by
weight, based on total weight of water-soluble C5 saccharide
hydrolysate in said composition, of aluminum.
[0138] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise less than about 300 ppm by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of calcium, preferably less than about 280 ppm by
weight, based on total weight of water-soluble C5 saccharide
hydrolysate in said composition, of calcium.
[0139] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise less than about 10 ppm by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of iron, preferably less than about 5 ppm by
weight, based on total weight of water-soluble C5 saccharide
hydrolysate in said composition, of iron.
[0140] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise less than about 1000 ppm by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of sulfur, preferably less than about 975 ppm by
weight, based on total weight of water-soluble C5 saccharide
hydrolysate in said composition, of sulfur.
[0141] In certain preferred embodiments, the weight ratio of said
C5 monosaccharide to said elements is greater than about 90:1,
preferably greater than about 95:1.
[0142] In certain embodiments, the compositions further comprise
water.
[0143] In certain embodiments, the water-soluble C5 monosaccharide
hydrolysate is present at a concentration of at least 0.5 g/L.
[0144] In certain embodiments, the C5 monosaccharide is xylose,
arabinose, lyxose, ribose, or a mixture thereof.
[0145] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise at least one water-soluble C5
oligosaccharide having a degree of polymerization of about 2 to
about 28, preferably about 2 to about 15, more preferably about 2
to about 10, and even more preferably about 2 to 6.
[0146] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise at least one water-soluble C6
saccharide having a degree of polymerization of about 1 to about
15, preferably about 1 to 13, more preferably about 1 to about 10,
and even more preferably about 1 to about 6.
[0147] In certain preferred embodiments of the compositions
comprising the water-soluble C5 monosaccharide hydrolysate, the
compositions further comprise at least one water-soluble C6
saccharide having a degree of polymerization of about 1 to about
15, preferably about 1 to about 13, more preferably about 1 to
about 10, and even more preferably about 1 to 6.
[0148] In certain embodiments, the water-soluble C5 monosaccharide
hydrolysate is processed from lignocellulosic biomass using
supercritical, subcritical, or near critical fluid extraction, or a
combination thereof.
[0149] In certain embodiments, the level of said elements are
measured by inductively coupled plasma emission spectroscopy.
[0150] In other embodiments, the compositions comprise less than
about 350 mg of nitrogen per kg of total weight of water-soluble C5
saccharides, preferably less than about 325 mg of nitrogen per kg
of total weight of water-soluble C5 saccharides. Nitrogen may be
measured by thermal conductivity detection after combustion and
reduction.
[0151] In yet other embodiments, the compositions further comprise
a weight ratio of the total mass of hydrogen and nitrogen to carbon
of less than about 0.17. Carbon, hydrogen, and nitrogen levels may
be measured by thermal conductivity detection after combustion and
reduction.
[0152] In certain other embodiments, the compositions comprising
the C5 monosaccharides further comprise less than a maximum of any
of the elements, individually or in combination, in the table
listed below:
TABLE-US-00002 Level less than about (ppm or mg of element/kg of
Element C5 saccharides) As 0.2 B 1.0 Ba 0.25 Be 0.1 Cd 0.1 Co 0.1
Cr 0.1 Cu 275 K 325 Li 75 Mg 0.2 Mn 35 Mo 0.25 Na 20 Ni 0.25 P 0.15
Pb 0.25 Sb 0.20 Se 3.0 Si 0.1 Sn 0.25 Sr 0.1 Ti 4.0 Tl 0.25 V 1.25
Zn 0.25
FURTHER EMBODIMENTS
[0153] In further embodiments, the compositions further comprise
less than about 0.5% by weight, based on the total weight of said
C5 monosaccharides or C6 monosaccharides, of organic solvent, such
as alcohols, including water miscible lower aliphatic
C.sub.1-C.sub.4 alcohols (e.g., methanol, ethanol, isopropanol,
t-butanol). In preferred embodiments, the compositions contain less
than about 0.1% by weight, based on the total weight of said of
said C5 monosaccharides or C6 monosaccharides of organic solvent.
In more preferred embodiments, the compositions contain
substantially no organic solvent.
[0154] The compositions of the invention are preferably prepared
from biomass by processes employing supercritical, subcritical,
and/or near critical water, preferably without the addition of
acid. The processes may include pretreatment step or steps using
supercritical or near critical water to separate the C5 sugars
(monomers and/or oligomers) from cellulose and lignin. In the
pretreatment step, suitable temperatures are about 130.degree. C.
to about 250.degree. C., suitable pressures are about 4 bars to
about 100 bars, and suitable residence times are about 0.5 minutes
to about 5 hours. The processes may also include a cellulose
hydrolysis step or steps using supercritical or near critical water
to separate the cellulose (which may processed to form C6 monomeric
and/or oligomeric sugars) from the lignin. In the hydrolysis
step(s), suitable temperatures are about 250.degree. C. to about
450.degree. 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 C5 monomers in the pretreatment step are formed by
autohydrolysis both from xylan directly and/or from C5 oligomers.
Similarly, the C6 monomers are formed in the supercritical
hydrolysis step directly from the cellulose and/or from C6
oligomers. The pretreatment step also produces small amounts of C6
sugars in oligomeric and/or monomeric form. The C5 and C6 oligomers
may be hydrolyzed to their respective monomers using acid, such as
sulfuric acid. 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 U.S. Pat. No.
8,057,639, which include a digester and a steam explosion unit, the
entire disclosure of which is incorporated by reference.
[0155] The compositions of the invention comprising C5
monosaccharides or C6 monosaccharides 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);
[0156] chemicals (such as acetic acid, acetic anhydride, acetone,
acrylic acid, adipic acid, benzene, ethanol, ethylene, ethylene
glycol, ethylene oxide, methanol, polypropylene, terephthalic acid,
toluene, xylene, 1,3-propanediol, 1,4-butanediol, and the
like);
[0157] 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);
[0158] specialty chemicals (such as acontic acid, glutamic acid,
malic acid, oxalic acid, and the like);
[0159] textile applications (such as formic acid and the like);
and
[0160] industrial intermediates (acetaldehyde, 3-hydroxypropionic
acid, 2,5-furan dicarboxylic acid, furfural, glutaric acid,
itaconic acid, levulinic acid, and the like).
[0161] In certain embodiments, 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:
[0162] providing a hydrolysate comprising said first water-soluble
C6 saccharides and less than about 5250 ppm in total by weight,
based on total weight of water-soluble C6 saccharide hydrolysate in
said composition, of elements;
[0163] 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.
In certain embodiments, 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.
[0164] In certain embodiments, 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:
[0165] providing a hydrolysate comprising said first water-soluble
C5 saccharides and less than about 3700 ppm in total by weight,
based on total weight of water-soluble C5 saccharide hydrolysate in
said composition, of elements;
[0166] 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.
In certain embodiments, the C5 saccharides are extracted from
lignocellulosic biomass. In other embodiments, the C5 saccharides
are processed from lignocellulosic biomass using supercritical,
subcritical, or near critical fluid extraction, or a combination
thereof.
[0167] 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 Monosaccharide Compositions
[0168] The C5 monosaccharide and C6 monosaccharide compositions of
the invention were prepared using supercritical, subcritical, and
near critical water extraction in a two stage process followed by
acid hydrolysis. 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.degree. 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.degree.
C. under little (less than about 10 bar) or no pressure. The
pretreated solids were then separated from the liquid stream using
a filter press. Alternatively, the solids may be separated using a
centrifugal filter pressor. The pretreated solids were then mixed
with water to form a slurry and the slurry was heated to a
temperature of about 150-250.degree. C. The slurry was then
subjected to supercritical water at about 374-600.degree. 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.
[0169] 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.
[0170] Sulfuric acid (0.3%) was added to the C5 oligosaccharides
and the C6 oligosaccharides streams in a tubular reactor at a
residence time of about 1 minute at about 200.degree. C. to
hydrolyze the oligosaccharides to their respective monosaccharides.
Alternatively, a batch autoclave at a lower temperature or a
continuously stirred agitated tank reactor may be used. The glucose
was cleaned with over liming and had acetic acid at a level of less
than about 5 g/L. The xylose was cleaned by contacting it with ion
exchange resin and had acetic acid at a level of less than about 5
g/L.
Example 2: Analysis of Monosaccharide Compositions Using
Inductively Coupled Plasma
[0171] The dried compositions containing the C5 and C6
monosaccharides of Example 1 were analyzed using inductively
coupled plasma emission spectroscopy. The results are shown in the
table below:
TABLE-US-00003 Monosaccharide Monosaccharide (glucose sample)
(xylose sample) g/liter or ppm g/liter or ppm based on total C6
based on total C5 Species saccharides saccharides Al 7.40 0.39 As
0.18 0.12 B 0.81 0.91 Ba 0.78 0.16 Be 0.00 0.00 Ca 0.08 0.02 Cd
0.07 0.02 Co 0.18 0.04 Cr 3.09 0.08 Cu 316.00 261.00 Fe 0.05 0.03 K
333.00 291.00 Li 19.50 60.00 Mg 0.03 0.12 Mn 590.00 33.60 Mo 2.09
0.18 Na 13.50 17.90 Ni 0.12 0.08 P 0.15 0.07 Pb 0.24 0.16 S 54.50
10.80 Sb 0.20 0.14 Se 1.61 2.48 Si 0.00 0.00 Sn 0.24 0.16 Sr 0.00
0.00 Ti 88.90 3.56 Tl 0.18 0.12 V 0.81 0.91 Zn 0.78 0.16
[0172] When ranges are used herein for physical properties, such as
molecular weight, or chemical properties, such as chemical
formulae, all combinations, and subcombinations of ranges specific
embodiments therein are intended to be included.
[0173] The disclosures of each patent, patent application, and
publication cited or described in this document are hereby
incorporated herein by reference, in their entirety.
[0174] 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.
* * * * *