NZ616832B2 - Lignin production from lignocellulosic biomass - Google Patents
Lignin production from lignocellulosic biomass Download PDFInfo
- Publication number
- NZ616832B2 NZ616832B2 NZ616832A NZ61683212A NZ616832B2 NZ 616832 B2 NZ616832 B2 NZ 616832B2 NZ 616832 A NZ616832 A NZ 616832A NZ 61683212 A NZ61683212 A NZ 61683212A NZ 616832 B2 NZ616832 B2 NZ 616832B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- lignin
- temperature
- pressure
- lignocellulosic biomass
- soluble
- Prior art date
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- 229920005610 lignin Polymers 0.000 title claims abstract description 156
- 239000002029 lignocellulosic biomass Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 18
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- 230000001603 reducing Effects 0.000 claims abstract description 28
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 36
- 239000000446 fuel Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 18
- 239000004788 BTU Substances 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- MWOOGOJBHIARFG-UHFFFAOYSA-N Vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
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- 239000002184 metal Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 8
- 230000004927 fusion Effects 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
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- 239000012071 phase Substances 0.000 description 7
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- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001590 oxidative Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000011121 hardwood Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000468 manganese oxide Inorganic materials 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese(II,III) oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 229920001542 oligosaccharide Polymers 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010882 bottom ash Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
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- 239000008103 glucose Substances 0.000 description 2
- 150000004676 glycans Polymers 0.000 description 2
- -1 hemicellulose Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- NOTVAPJNGZMVSD-UHFFFAOYSA-N Potassium oxide Chemical compound [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
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- 229910000460 iron oxide Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 238000001728 nano-filtration Methods 0.000 description 1
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229910001950 potassium oxide Inorganic materials 0.000 description 1
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another cellulosic
- Y10T428/31986—Regenerated or modified
Abstract
The disclosure relates to a method of preparing lignin from lignocellulosic biomass, comprising: providing lignocellulosic biomass at a first pressure and at a first temperature, lignocellulosic biomass comprising insoluble lignin, soluble C6 saccharides and soluble lignin, reducing said first temperature to at least about 1°C above the glass transition temperature of lignin under said first pressure then reducing the pressure in less than about 1 second to precipitate said soluble and form a mixture comprising insoluble lignin, precipitated lignin and soluble C6 saccharides. The disclosure also relates to lignin processed from lignocellulosic biomass using supercritical or near critical fluid extraction. rature to at least about 1°C above the glass transition temperature of lignin under said first pressure then reducing the pressure in less than about 1 second to precipitate said soluble and form a mixture comprising insoluble lignin, precipitated lignin and soluble C6 saccharides. The disclosure also relates to lignin processed from lignocellulosic biomass using supercritical or near critical fluid extraction.
Description
LIGNIN PRODUCTION FROM LIGNOCELLULOSIC BIOMASS
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. 61/482,479 filed May 4, 2011, the entire
disclosure of which is incorporated by reference.
FIELD OF THE INVENTION
The present invention generally relates to methods of preparing lignin from
lignocellulosic biomass. More particularly, it relates to methods of preparing lignin from
lignocellulosic biomass using rapid full or partial pressure reduction to separate and to pulverize
the lignin without fouling the equipment and with improved energy recovery.
BACKGROUND OF THE INVENTION
Existing processes delignify lignocellulosic biomass before entering the cellulose
conversion process using solvents or other chemicals. In such delignification processes, complex
equipment is typically required and is expensive to operate because of the solvent or chemical
usage and lack of recovery methods. In other existing processes, the solid conversion of
lignocellulosic biomass in pre-treatment and hydrolysis requires high temperatures to fully or
partially solubilize the lignin present. Upon cooling, the lignin precipitates from solution. The
lignin may be recovered from the process and burned for thermal energy. The particle size of the
recovered lignin may be variable and too large for efficient burning, thus requiring a separate
pulverizing step. Furthermore, as the lignin in solution cools, it becomes sticky (typically in the
glass transition temperature range of lignin, which is about 100ºC under ambient pressure) and
tends to foul the process equipment to the point of making the process inoperable. It would be
useful to have methods for providing lignin of a substantially uniform, small particle size for
improving burning efficiency, for enhanced properties for the use of lignin as a feedstock for the
production of other chemicals, and for avoiding typical equipment fouling problems. It would
206445NZ_spec_20150928_PLH
also be useful to maximize energy recovery. The methods and compositions of the present
invention are directed toward these, as well as other, important ends.
SUMMARY OF THE INVENTION
In one embodiment, the invention is directed to methods of preparing lignin from
lignocellulosic biomass, comprising:
providing lignocellulosic biomass at a first pressure and at a first temperature,
said lignocellulosic biomass comprising:
a first solid fraction comprising:
insoluble lignin; and
a first liquid fraction comprising:
soluble C saccharides; and
soluble lignin;
reducing said first temperature of said lignocellulosic biomass to a second
temperature at least about 1ºC above the glass transition temperature of lignin under said
first pressure; and
reducing said first pressure of said lignocellulosic biomass at said second
temperature to a second pressure in a time less than about 1 second to precipitate said
soluble lignin in said first liquid fraction and form a mixture comprising:
a second solid fraction comprising:
insoluble lignin; and
precipitated lignin; and
a second liquid fraction comprising:
soluble C saccharides;
wherein the average particle size of said insoluble lignin and precipitated lignin is
less than about 500 microns.
In another embodiment, the invention is directed to lignin products produced by the
methods of the invention.
206445NZ_spec_20150928_PLH
In another embodiment, the invention is directed to compositions, comprising:
lignin having an average size of no greater than about 500 micron;
wherein said lignin is processed from lignocellulosic biomass using supercritical
or near critical fluid extraction.
[0006a] More particularly, in the first aspect, the invention resides in a method of preparing
lignin from lignocellulosic biomass, comprising:
providing lignocellulosic biomass at a first pressure and at a first temperature,
said lignocellulosic biomass comprising:
a first solid fraction comprising:
insoluble lignin; and
a first liquid fraction comprising:
soluble C saccharides; and
soluble lignin;
reducing said first temperature of said lignocellulosic biomass to a second
temperature at least about 1ºC above the glass transition temperature of lignin under said
first pressure; and
reducing said first pressure of said lignocellulosic biomass at said second
temperature to a second pressure in a time less than about 1 second to precipitate said
soluble lignin in said first liquid fraction and form a mixture comprising:
a second solid fraction comprising:
insoluble lignin; and
precipitated lignin; and
a second liquid fraction comprising:
soluble C saccharides.
[0006b] Preferably, said method is continuous.
[0006c] Preferably, the further comprises:
reducing the temperature of said mixture.
206445NZ_spec_20150928_PLH
[0006d] Preferably, the method further comprises:
permitting said insoluble lignin and said precipitated lignin to separate out by
gravity.
[0006e]. Preferably, the method further comprises:
separating said second solid fraction and said second liquid fraction.
[0006f] Preferably, said second pressure is greater than atmospheric pressure.
[0006g] Preferably, the method further comprises:
reducing the second pressure to atmospheric pressure.
[0006h] Preferably, said second pressure is atmospheric pressure.
[0006i] Preferably, the method further comprises:
recovering heat using at least one heat exchanger.
[0006j] Preferably, said lignocellulosic biomass is fractionated to remove at least a portion of
C saccharides prior to said providing step.
[0006k] Preferably, the average particle size of said insoluble lignin and precipitated lignin is
less than about 500 microns.
[0006l] Preferably, said fractionation comprises a hydrothermal treatment or enzymatic
treatment.
[0006m] Preferably, said fractionation comprises hydrothermal treatment, and said hydrothermal
treatment comprises hot compressed water, subcritical water, near critical water, or
supercritical water.
[0006n] Preferably, said hydrothermal treatment further comprises an alcohol, an acid, or a base.
206445NZ_spec_20150928_PLH
[0006o] Preferably, wherein said first liquid fraction comprises water.
[0006p] Preferably, said first temperature is about 280 °C to about 375 °C.
[0006q] Preferably, wherein the temperature of said mixture is reduced to about 20 °C to about
60 °C.
[0006r] In a second aspect, the invention resides in a lignin product produced by the method
stated in paragraph [0006a].
[0006s] Preferably, wherein said lignin product is used as a fuel, tackifier, phenol formaldehyde
resin extender in the manufacture of particle board and plywood, in the manufacture of
molding compounds, urethane and epoxy resins, antioxidants, controlled-release agents,
flow control agents, cement/concrete mixing, plasterboard production, oil drilling,
general dispersion, tanning leather, road covering, vanillin production, dimethyl sulfide
and dimethyl sulfoxide production, phenol substitute in phenolic resins incorporation into
polyolefin blends, aromatic (phenol) monomers, additional miscellaneous monomers,
carbon fibers, metal sequestration in solutions, basis of gel formation, polyurethane
copolymer, and combinations thereof.
[0006t] Preferably, wherein said lignin product has an average particle size less than about 500
microns.
[0006u] Preferably, wherein said lignin product has a heating value as measured by ASTM-D240
of at least about 5,000 BTU/lb at 30% moisture content.
[0006v] Preferably, said lignin product has a heating value as measured by ASTM-D240 of at
least about 7,500 BTU/lb at 15% moisture content.
206445NZ_spec_20150928_PLH
[0006w] Preferably, said lignin product has a heating value as measured by ASTM-D240 of at
least about 8,000 BTU/lb at 5% moisture content.
[0006x] In a yet further aspect, the invention resides in a composition comprising the lignin
product stated in paragraph [0006r], wherein said composition is substantially free of
organic solvent.
[0006y] In a third aspect, the invention resides in a composition comprising,
lignin;
and ash;
wherein contents of the ash is greater than 0 wt.% but less than about 0.5 wt.%;
wherein said ash comprises at least about 18 wt.% Ca as CaO; and
wherein said ash comprises at least about 22 wt.% Fe as Fe2O3.
[0006z] Preferably, said composition has a heating value of at least about 7,500 BTU/lb at 15%
moisture content.
[0006a1] Preferably, said composition has a moisture content of about 5% to about 30%.
[0006a2] Preferably, said composition comprises less than about 0.15 % N, as measured in an
ultimate analysis.
[0006a3] Preferably, said composition comprises less than about 0.02 % S, as measured in an
ultimate analysis.
[0006a4] Preferably, said ash comprises about 29 wt.% Si as SiO2.
[0006a5] Preferably, said ash comprises about 13 wt.% S as SO3.
[0006a6] Preferably, said ash comprises about 1 wt.% P as P2O5.
206445NZ_spec_20150928_PLH
[006a7] Preferably, said composition has a softening temperature of at least about 1172 °C, as
measured in an oxidizing atmosphere.
[006a8] Preferably, said lignin has a particle size less than about 500 microns.
[006a9] Preferably, said lignin has a particle size less than about 50 microns.
[0006a10] Preferably, said lignin has a particle size of about 10 microns to about 30 microns.
[006a11] Preferably, said composition is substantially free of organic solvent.
[0006a12] Preferably, said composition is used as a fuel.
[006a13] Preferably, when said composition is used as a fuel in a combustion chamber, said
composition has a softening temperature of about 35 °C to about 65 °C above a flue gas
temperature peak at an exit of the combustion chamber.
[006a14] Preferably, in a proximate analysis, said composition has greater than 55 wt.% volatile
matter.
[006a15] Preferably, said lignin is processed from lignocellulosic biomass using supercritical or
near critical fluid extraction.
[006a16] Preferably, said supercritical or near critical fluid comprises water.
BRIEF DESCRIPTION OF THE DRAWINGS
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
206445NZ_spec_20150928_PLH
of the invention. In the drawings:
FIGURE 1 is a schematic diagram of the method of producing lignin from cellulosic
biomass in one embodiment of the invention.
FIGURE 2 is a plot of % moisture content (wet basis) as a function of cumulative
drying time in hours for lignin.
FIGURE 3 is a plot of high heating value (HHV) as a function of moisture content for
extracted lignin and filtered lignin.
DETAILED DESCRIPTION OF THE INVENTION
As employed above and throughout the disclosure, the following terms, unless
otherwise indicated, shall be understood to have the following meanings.
As used herein, the singular forms “a,” “an,” and “the” include the plural reference
unless the context clearly indicates otherwise.
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.
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
206445NZ_spec_20150928_PLH
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.
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.
As used herein, the term “saccharification” and “saccharified” refers to the breakdown
of polysaccharides to smaller polysaccharides, including oligosaccharides, and monosaccharides,
whether through hydrolysis, the use of enzymes, or other means, generally into a liquid fraction
and a solid fraction.
A supercritical fluid is a fluid at a temperature above its critical temperature and at a
pressure above its critical pressure. A supercritical fluid exists at or above its “critical point,” the
point of highest temperature and pressure at which the liquid and vapor (gas) phases can exist in
equilibrium with one another. Above critical pressure and critical temperature, the distinction
between liquid and gas phases disappears. A supercritical fluid possesses approximately the
penetration properties of a gas simultaneously with the solvent properties of a liquid.
Accordingly, supercritical fluid extraction has the benefit of high penetrability and good
solvation.
Reported critical temperatures and pressures include: for pure water, a critical
temperature of about 374.2°C, and a critical pressure of about 221 bar; for carbon dioxide, a
critical temperature of about 31°C and a critical pressure of about 72.9 atmospheres (about 1072
psig). Near-critical water has a temperature at or above about 300°C and below the critical
temperature of water (374.2°C), and a pressure high enough to ensure that all fluid is in the
206445NZ_spec_20150928_PLH
liquid phase. Sub-critical water has a temperature of less than about 300°C and a pressure high
enough to ensure that all fluid is in the liquid phase. Sub-critical water temperature may be
greater than about 250°C and less than about 300°C, and in many instances sub-critical water has
a temperature between about 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 50ºC (preferably, at least about
100ºC) but less than subcritical and at pressures such that water is in a liquid state.
As used herein, a fluid which is “supercritical” (e.g. supercritical water, supercritical
CO , 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 CO ,
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 may have a
temperature of about 250°C to about 280°C and a pressure of at least about 225 bar.
As used herein, “continuous” indicates a process which is uninterrupted for its duration,
or interrupted, paused or suspended only momentarily relative to the duration of the process.
Treatment of biomass is “continuous” when biomass is fed into the apparatus without
interruption or without a substantial interruption, or processing of said biomass is not done in a
batch process.
As used herein, “resides” indicates the length of time which a given portion or bolus of
material is within a reaction zone or reactor vessel. The “residence time,” as used herein,
including the examples and data, are reported at ambient conditions and are not necessarily
actual time elapsed.
206445NZ_spec_20150928_PLH
As used herein, the term “substantial free of” refers to a composition having less than
about 1% by weight, preferably less than about 0.5% by weight, and more preferably less than
about 0.1% by weight, based on the total weight of the composition, of the stated material.
As used herein, the term “glass transition temperature” or “Tg” means the temperature
at which an amorphous material changes from a brittle, vitreous state to a plastic state. It is
dependent upon the composition of the material being tested, including moisture content, the
extent of annealing, and the pressure exerted on the material. Glass transition temperature may
be measured by differential scanning calorimetry, thermomechanical analysis, dynamic
mechanical analysis, and the like.
As used herein, “pulverize” means providing a small particle size, such as through
spraying or atomizing, or reducing the particle size of a given material, whether or not through
the use of mechanical means.
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 sawmill and paper mill discards), and (4)
municipal waste, and their constituent parts including without limitation, lignocellulose biomass
itself, lignin, C saccharides (including cellulose, cellobiose, C oligosaccharides, C
6 6 6
monosaccharides, and C saccharides (including hemicellulose, C oligosaccharides, and C
5 5
monosaccharides).
Generally, the methods of the invention precipitate out and pulverize (provide as a
small particle size or reduce the particle size) lignin and avoid fouling of the process equipment
while maximizing heat recovery. This is accomplished by cooling the stream containing the
lignin to just above its glass transition temperature (Tg) to prevent sticking and then rapidly
dropping the pressure so that the lignin is well below its Tg at the new pressure when it
precipitates out of solution at a small particle size.
206445NZ_spec_20150928_PLH
Accordingly, in one embodiment, the invention is directed to methods of preparing
lignin from lignocellulosic biomass, comprising:
providing a lignocellulosic biomass at a first pressure and at a first temperature,
said lignocellulosic biomass comprising:
a first solid fraction comprising:
insoluble lignin; and
a first liquid fraction comprising:
soluble C saccharides; and
soluble lignin;
reducing said first temperature of said lignocellulosic biomass to a second
temperature at least about 1ºC above the glass transition temperature of lignin under said
first pressure; and
reducing said first pressure of said lignocellulosic biomass at said second
temperature to a second pressure in a time less than about 1 second to precipitate said
soluble lignin in said first liquid fraction and form a mixture comprising:
a second solid fraction comprising:
insoluble lignin; and
precipitated lignin; and
a second liquid fraction comprising:
soluble C saccharides;
wherein the average particle size of said insoluble lignin and precipitated lignin is
less than about 500 microns.
A schematic of one embodiment of the invention is shown in FIGURE 1. The lignin
slurry exits the hydrolysis process 2. It is cooled to just above its glass transition temperature to
maximize heat recovery, for example, in a pre-cooler heat exchanger 4. The lignin slurry is then
subjected to a rapid pressure drop, for example, through the pressure letdown valve 6, and
subsequently the liquid (i.e., water) content in the slurry is flash evaporated. This results in the
sudden precipitation of the soluble lignin into fine particles inside the lignin pulverizer 8. In
certain embodiments, the pulverizer is of relatively small volume to keep the slurry moving and
avoid lignin settling. In other embodiments, it may be of a large volume to permit settling of the
206445NZ_spec_20150928_PLH
lignin, which may be recovered by mechanical means, especially when using full flash. The inlet
pipe to the pulverizer may either be above, below, or to either side of the pulverizer.
Atmospheric pressure for full pressure reduction, or an intermediate pressure in the case of a
partial pressure reduction, is maintained in the pulverizer by the back pressure control valve 10.
In embodiments using full flash to atmospheric pressure, no back pressure control is needed.
Any recovered steam enters a condenser 12 (not shown) for heat recovery. Following the
pulverizer, the slurry flows through flow control 14 and then is further cooled to recover more
heat in a heat exchanger 16, and is reduced to atmospheric pressure, if not yet at atmospheric
temperature, via a pressure letdown valve 18 in the settling tank 20. In the tank, the lignin is
permitted to settle to the bottom. Finally, the slurry may be passed through a solid/liquid
filtration apparatus 22 for final separation of liquor 24 and lignin 26.
Advantages of the methods of the invention are that the pulverization (preparation of
small particles and/or reduction in average particle size) of soluble and insoluble lignin improves
handling, accelerates the drying, and improves combustion of the lignin. Another advantage of
the methods of the invention is that the glass transition phase of the lignin, both soluble and
insoluble, is avoided, to avoid fouling of the process equipment and permit pulverization of the
lignin.
In certain embodiments of the method, lignocellulosic biomass is fractionated to
remove at least a portion of C saccharides by any suitable means, including, but not limited to,
hydrothermal treatment (such as hot compressed water, subcritical, near critical, or supercritical
water, which may contain other fluids, including alcohol, acid, or base), enzymatic treatment,
and the like.
In certain embodiments of the method, the average particle size of said insoluble lignin
and precipitated lignin is less than about 500 microns.
The methods of the invention are preferably run continuously, although they may be run
as batch or semi-batch processes.
206445NZ_spec_20150928_PLH
The methods of the invention may be carried out in any suitable reactor, including, but
not limited to, a tubular reactor, a digester (vertical, horizontal, or inclined), and 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.
In certain embodiments, the method further comprises the step of reducing the
temperature of said mixture. All of the embodiments of the invention involve a temperature
reduction from the temperature at which the saccharified lignocellulosic biomass is provided,
typically about 280ºC to about 375ºC (hydrolysis temperature) to eventually ambient or near
ambient temperatures, typically about 20ºC to about 60ºC. The key of the temperature reduction
is that the temperature is reduced instantaneously across the glass transition temperature range of
the lignin to permit pulverization of the lignin.
In embodiments where there is a partial pressure reduction in the method, the second
pressure is greater than atmospheric pressure.
In embodiments where there is a full pressure reduction in the method, the second
pressure is about atmospheric pressure.
In certain embodiments, the method further comprises the step of reducing the pressure
on said mixture to a third pressure. Pressure control impacts temperature in the flashing process
where the saccharified lignocellulosic biomass is cooled in a very short period of time (e.g., less
than one second). The inlet pressure must be equal to or greater than the saturation pressure at
the given temperature so that the liquid components of fraction remain as liquids. With respect
to processing of lignocellulosic biomass, it is preferably to avoid the temperature range of about
180ºC and about 240ºC, the glass transition temperature range of lignin under typical processing
conditions. Thus, if the inlet temperature is at least the 240ºC +1ºC, then the minimum inlet
pressure needs to be about 34 bar but may be much higher. For example, it is typical to have the
inlet pressure at 40 bar. The exit temperature is determined and dependent upon the exit
pressure. If, for example, there is flash cooling of the saccharified lignocellulosic biomass down
to a temperature of 180ºC, then the exit pressure needs to equal to the saturation pressure at
206445NZ_spec_20150928_PLH
180ºC, which about 10 bar. The exit pressure is controlled by the back pressure valve, and the
exit temperature is determined by the exit pressure. If the exit pressure is changed, the exit
temperature will also change. The exit temperature is the saturation temperature at the selected
pressure.
In certain embodiments, the method further comprises the step of permitting said
insoluble lignin and said precipitated lignin, where the lignin has been pulverized (provided as a
small particle size or reduce the particle size) to separate out by gravity.
In certain embodiments, the method further comprises the step of separating said
second solid fraction and said second liquid fraction. Suitable separation methods including
filtration methods well known to those skilled in the art, such as decanter filters, filter press,
reverse osmosis and nanofiltration, centrifuge decanters, and the like.
In certain embodiments, the method further comprises the step of recovering heat using
at least one heat exchanger, for example, using a pre-cooler heat exchanger 4 or final heat
exchanger 16.
In another embodiment, the invention is directed to lignin products produced by the
methods of the invention, including fuels, such as those used in a process heat boiler. The lignin
product may also be used as a functional replacement for phenol, as a functional replacement for
polyol, or as a building block for carbon fiber. In other embodiments, the compositions of the
invention comprising lignin may be utilized in a variety of applications, including, but not
limited to, fuels, tackifiers, phenol formaldehyde resin extenders in the manufacture of particle
board and plywood, in the manufacture of molding compounds, urethane and epoxy resins,
antioxidants, controlled-release agents, flow control agents, cement/concrete mixing,
plasterboard production, oil drilling, general dispersion, tanning leather, road covering, vanillin
production, dimethyl sulfide and dimethyl sulfoxide production, phenol substitute in phenolic
resins incorporation into polyolefin blends, aromatic (phenol) monomers, additional
miscellaneous monomers, carbon fibers, metal sequestration in solutions, basis of gel formation,
polyurethane copolymer – as a renewable filler/extender, and the like.
206445NZ_spec_20150928_PLH
In another embodiment, the invention is directed to compositions, comprising:
lignin;
wherein said lignin is processed from lignocellulosic biomass using supercritical
or near critical fluid extraction.
In preferred embodiments, the composition is substantially free of organic solvent. In preferred
embodiments, the lignin product has an average particle size less than about 500 microns, more
preferably, less than 300 microns, even more preferably, less than about 250 microns, and yet
even more preferably less than about 50 microns. The particle size of the lignin may be
measured by standard sieve shaker, microscopy, light scattering, laser diffraction, and other
standard size analysis techniques.
In a preferred embodiment, the lignin has a heating value as measured by ASTM-D240
of at least about 5,000 BTU/lb at 30% moisture content. In a preferred embodiment, the lignin
has a heating value as measured by ASTM-D240 of at least about 7,500 BTU/lb at 15% moisture
content. In a preferred embodiment, the lignin has a heating value as measured by ASTM-D240
of at least about 8,000 BTU/lb at 5% moisture content.
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:
Pretreatment (fractionation) and cellulose hydrolysis processes liberate lignin from
206445NZ_spec_20150928_PLH
lignocellulosic biomass utilized as feedstock. For testing in this example, lignin samples, which
were generated from the flashing of cellulose effluent, were tested to determine heating value,
proximate, ultimate, and ash fusion temperature, ash oxide composition, moisture content, and
particle size.
Drying Rate and Moisture Content
When the lignin is separated from the flashed cellulose hydrolysis effluent glucose
stream utilizing gravity and 20 µm filter paper, it has an average moisture content between 65%
and 75%, by weight. This can be further reduced by using a centrifuge or vacuum filtration unit
to more effectively separate the solids from the mother liquor. The representative lignin sample
was obtained from the sludge collected in the bottom of the glucose product tank, whose product
was generate from multiple runs of 100 mesh wood flour at the cellulose hydrolysis conditions of
about 225 bar and 375°C. The sample was subsequently allowed to air dry to measure its drying
rate.
The results are shown in FIGURE 2. The curve indicates that the lignin dries to 10%
moisture content, by weight, settling around 5%, by weight, after approximately 105 hours. This
was drier than expected and may have been due to the location (inside plant) where the drying
experiments were conducted. Ambient conditions were warmer and drier than would be
anticipated if the lignin were dried outside where solar insulation, diurnal temperature changes,
humidity, and precipitation would be expected to keep the final moisture content between 20%
and 25%, by weight. The first 75 hours of drying follows a typical constant rate drying period
with moisture moving to the particle surface sufficiently fast to maintain a saturated condition at
the surface. This indicates that the rate of drying is controlled by the rate of heat transferred to
the evaporating surface. The lower part of the curve, from 75 to 125 hours, is typical of a
continuously changing drying rate (usually decreasing) indicating a change in the controlling
mechanism for drying. The surface area of the particle can no longer remain fully saturated and
evaporation begins shifting into the particle interior where the internal particle water diffusion
rate begins to control the drying process.
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Heating Value
The heating values of the lignin at various moisture contents were analyzed. The
heating value of a fuel is the measure of the heat released during its complete combustion with
oxygen. Any fuel will contain hydrogen, and water will be formed as a product of combustion
when hydrogen is burned in air. This generated water may remain the vapor state or condense to
liquid creating a substantial difference in the measured heat value due to the latent heat of
vaporization associated with the phase change. When determining the heat given up by a unit of
fuel, the higher (or gross) heating value (HHV) is usually reported where it is assumed than any
water generated is all condensed, thus the heating value incorporates the latent heat of
vaporization. For the lower (or net) heating value (LHV), none of the water is assumed to have
condensed and all of the products of combustion remain is the gaseous state. The HHV may be
determined using an oxygen bomb calorimeter and is expressed in terms of heat related per unit
weight of fuel (Btu/lb ). Determination of LHV may be calculated from the following equation:
206445NZ_spec_20150928_PLH
HHV = LHV + nHvp
where: HHV = fuel high heating value (Btu/lb )
LHV = fuel high heating value (Btu/lb )
n = stoichiometric mass of water generated per mass of fuel combusted
(lb /lb )
Hvp = latent heat of vaporization of water (Btu/lb )
The results of testing using an oxygen bomb calorimeter in accordance with ASTM
Method D240 are shown in FIGURE 3 for extracted lignin and filtered lignin. The heating
value data decreases with increasing moisture content. The filtered lignin is the lignin obtained
from flashing the cellulose hydrolysis effluent to atmospheric conditions. The extracted lignin
was extracted from the fractionation slurry utilizing ethanol. The average heating value for the
filtered lignin at 25% moisture content is approximately 8,200 Btu/lb.
Particle Size
Surface area/mass ratio for discrete particles is an important aspect of the lignin’s
usefulness as a fuel because it impacts combustion efficiency, boiler design, and method of
introduction of combustion air. Improperly sized fuel may not burn completely and heat energy
can be lost in the form of carbon rich bottom and/or fly ashes. Measuring particle size may be
done by classification, e.g., sieving, or by observing under a microscope a representative sample
and comparing to an appropriate scale. The average particle size was determined using a
Magnaview DC5-153 microscope and a calibrated scaling slide. The average particle diameter
observed was 10 µm to 30 µm at 37% moisture content for separated solids derived from
cellulose hydrolysis, where the solids were determined to be approximately 80% lignin.
Proximate Analysis
Proximate analysis of a fuel describes the volatiles, fixed carbon, moisture content, and
ash present in a fuel as a percentage of dry fuel weight. The percentages of volatiles and fixed
206445NZ_spec_20150928_PLH
carbon both have a direct impact on the heating value of the fuel, flame temperature, and
combustion process in general. Other than carbon and metals, all other fuels burn as a gas. The
percentage of volatiles represents the amount of fuel that would burn in the gas phase with the
remaining carbon burning as a solid on the grates or as a fine particulate. The ash content is
important in the design of air pollution control equipment, boiler grates, and bottom ash handling
equipment.
The results for a single sample are shown in Table 1.
Table 1
Sample No. % Moisture % Ash Content % Volatile % Fixed Carbon
Content Matter
1 18.57 0.44 56.75 24.24
Ultimate Analysis
Ultimate analysis of a fuel describes its elemental composition as a percentage of the
fuel sample’s dry weight. The main elements typically considered are carbon (C), hydrogen (H),
nitrogen (N), sulfur (S), and oxygen (O), and while not an element, ash. Sulfur and ash
percentages are particularly important because they are needed to accurately estimate air
emission rates for sulfur dioxides (SO ) and particulate matter (PM) for use in effective design of
air pollution control equipment and air permitting.
The results for a single sample are shown in Table 2.
Table 2
Sample No. % C % H % N % O (by % S % Ash
difference)
1 51.00 6.56 0.15 41.74 0.02 0.44
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Ash Fusion Temperature
Ash fusion temperatures are determined by viewing a mounded specimen of the fuel’s
(lignin) ash through an observation window in a high-temperature furnace in both reducing and
oxidizing atmospheres. The ash, in the form of a cone, pyramid, or cube, is heated steadily
above 1000°C to as high a temperature as possible, preferably 1600°C (2910°F). The following
temperatures are then recorded:
▪ Initial deformation temperature (IT): This is reached when the point of the mound first
begins to deform and round.
▪ Softening (spherical) temperature (ST): This is reached when the top of the mound takes
on a spherical shape, i.e., the base of the cone is equal to its height.
▪ Hemispherical temperature (HT): This is reached when the entire mound takes on a
hemispherical shape, i.e., the base of the cone is twice its height.
▪ Flow (fluid) temperature (FT): This is reached when the molten ash collapse to a
flattened button on the furnace floor, i.e., spread to a fused mass.
Generally, a temperature under reducing should be equal to or lower than the corresponding
temperature under oxidizing conditions. The difference in these temperatures generally increases
with increasing iron content in the ash. Fusion temperatures should monotonically increase in
order of IT, ST, HT, and FT.
The results for a single sample in an oxidizing atmosphere are shown in Table 3.
Table 3
Initial deformation temperature (IT): 2136°F (1169°C)
Softening (spherical) temperature (ST): 2141°F (1172°C)
Hemispherical temperature (HT): 2143°F (1173°C)
Flow (fluid) temperature (FT): 2144°F (1174°C)
A spherical temperature, a critical temperature for fuel evaluation, that is too low will
cause slagging problems in the combustion chamber of a boiler. As the ash softens and melts, it
subsequently impacts a surface within the combustion chamber where it cools and forms a glassy
206445NZ_spec_20150928_PLH
substance called clinker, which must be removed. Its removal severely impedes boiler
operations as the boiler must be shutdown. If the melted ash cools on a heat transfer surface, the
resultant layer builds up, fouling the heat exchanger decreasing its overall efficiency and thus the
boiler efficiency as well. It is preferred to have an ST of 35°C to 65°C (100°F to 150°F) above
the actual flue gas temperature peak at the combustion chamber exit to minimize the impact.
The ash fusion temperature gives an indication of its softening and melting behavior.
Ash Mineral Oxide Analysis
Ash mineral oxide composition is also useful in understanding how the ash generated
by the combustion of lignin will behave in the combustion chambers of the biomass boiler.
Composition does affect the ranges of fusion temperatures, particularly the iron levels and base
to acid oxide rations. Typical analyses determine the weight percentage of the following mineral
oxides silica (SiO ), alumina (Al O ), ferric oxide (Fe O ), titanium dioxide (TiO ), phosphorous
2 2 3 2 3 2
pentoxide (P O ), calcium oxide (CaO), magnesium oxide (MgO), manganese oxide (MnO),
sodium oxide (Na O), potassium oxide (K O), and sulfur trioxide (SO ). The silica, alumina,
2 2 3
and titanium dioxide make up the group of acidic oxides with the remaining compounds forming
the basic oxides.
The results for a single sample are shown in Table 4.
Table 4
Sample %Al %Ca %Fe %Mg %Mn %P as %K %Si %Na %Ti %S as %
No. as as as as as P O as as as as SO Sum
2 5 3
Al O CaO Fe O MgO MnO K O SiO Na O TiO
2 3 2 3 2 2 2 2
1 7.52 18.56 22.30 1.57 0.19 1.05 1.20 29.18 1.19 3.67 13.15 99.56
Table 5 shows a side-by-side comparison for a typical high-rank eastern Kentucky coal,
a typical hardwood, and the cellulose hydrolysis-derived lignin.
206445NZ_spec_20150928_PLH
Table 5
Characteristic Eastern Kentucky Coal Typical Hardwood Cellulose Hydrolysis-
derived Lignin
Heating value (Btu/lb) 13254 @ 5% MC 8839 (oven dried) 8200 @ 25% MC
Proximate Analysis
% Moisture content 1.2 45.6 18.57
% Ash 10.15 0.45 0.44
% Volatile matter 36.82 48.58 56.75
% Fixed carbon 53.03 5.52 24.24
Ultimate Analysis
% C 75.0 51.64 51.09
% H 7/0 6.26 6.56
% N 1.0 0 0.15
% S 3.0 0.009 0.02
% O (by difference) 6.2 41.45 41.74
% Ash 7.8 0.65 0.44
Ash fusion temperatures
(oxidizing)
IT (ºF) 1627 2136
ST (ºF) 1647 1652 2141
HT (ºF) 1649 2143
FT( ºF) 1649 2144
Ash mineral oxide analysis
%Al as Al O 30.67 0.03 7.52
%Ca as CaO 1.16 31.35 18.56
%Fe as Fe O 4.87 0.09 22.30
%Mg as MgO 0.42 7.57 1.57
%P as P O 0.13 0.56 1.09
%K as K O 0.99 10.25 1.20
%Si as SiO 58.20 0.13 29.18
%Na as Na O 0.17 0.06 1.18
%Ti as TiO 2.08 - 3.67
%S as SO 1.29 1.21 13.15
As can be seen, the lignin’s HHV is better than typical hardwood (allowing for moisture
content), but not quite as high as coal. However, the lignin is considered to be a relatively high
energy density fuel. With better than 55% of the lignin representing volatile matter and less than
206445NZ_spec_20150928_PLH
0.50% ash, most of the lignin is expected to combust and exit the combustion chamber in the
gaseous phase, minimizing the size of the ash handling equipment needed in the biomass boiler.
ST is much greater than the average of the hardwood. This is expected to help
minimize the impact of slagging on the combustion chamber walls. The elevated ST is likely
related to the relatively high iron and calcium content in the ash. The ash fusion temperature is
important to boiler operations and efficiency.
From an air pollution control standpoint, NO formation (specifically fuel NO ) is
expected to be minimal as the nitrogen content of the lignin is very low. The same is true for
particulate matter (PM).
Overall, the results indicate that the cellulose hydrolysis-derived lignin has fuel
properties that will allow it to be effectively combusted in a process boiler. In particular, the
HHV, % volatile matter, spherical temperature (ST), and ash mineral oxide concentrations are
particularly conducive for lignin being used as a boiler fuel.
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.
The disclosures of each patent, patent application, and publication cited or described in
this document are hereby incorporated herein by reference, in their entirety.
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.
206445NZ_spec_20150928_PLH
Claims (24)
1. A method of preparing lignin from lignocellulosic biomass, comprising: providing lignocellulosic biomass at a first pressure and at a first temperature, said lignocellulosic biomass comprising: a first solid fraction comprising: insoluble lignin; and a first liquid fraction comprising: soluble C saccharides; and soluble lignin; reducing said first temperature of said lignocellulosic biomass to a second temperature at least about 1ºC above the glass transition temperature of lignin under said first pressure; and reducing said first pressure of said lignocellulosic biomass at said second temperature to a second pressure in a time less than about 1 second to precipitate said soluble lignin in said first liquid fraction and form a mixture comprising: a second solid fraction comprising: insoluble lignin; and precipitated lignin; and a second liquid fraction comprising: soluble C saccharides.
2. A method of claim 1, wherein said method is continuous.
3. A method of claim 1, further comprising: reducing the temperature of said mixture. 206445NZ_spec_20150928_PLH
4. A method of claim 1, further comprising: permitting said insoluble lignin and said precipitated lignin to separate out by gravity.
5. A method of claim 1, further comprising: separating said second solid fraction and said second liquid fraction.
6. A method of claim 1, wherein said second pressure is greater than atmospheric pressure.
7. A method of claim 6, further comprising: reducing the second pressure to atmospheric pressure.
8. A method of claim 1, wherein said second pressure is atmospheric pressure.
9. A method of claim 1, further comprising: recovering heat using at least one heat exchanger.
10. A method of claim 1, wherein said lignocellulosic biomass is fractionated to remove at least a portion of C saccharides prior to said providing step.
11. A method of claim 1, wherein the average particle size of said insoluble lignin and precipitated lignin is less than about 500 microns.
12. A lignin product produced by the method of claim 1.
13. A lignin product of claim 12, 206445NZ_spec_20150928_PLH wherein said lignin product is used as a fuel, tackifier, phenol formaldehyde resin extender in the manufacture of particle board and plywood, in the manufacture of molding compounds, urethane and epoxy resins, antioxidants, controlled-release agents, flow control agents, cement/concrete mixing, plasterboard production, oil drilling, general dispersion, tanning leather, road covering, vanillin production, dimethyl sulfide and dimethyl sulfoxide production, phenol substitute in phenolic resins incorporation into polyolefin blends, aromatic (phenol) monomers, additional miscellaneous monomers, carbon fibers, metal sequestration in solutions, basis of gel formation, polyurethane copolymer, and combinations thereof.
14. A lignin product of claim 12, wherein said lignin product has an average particle size less than about 500 microns.
15. A lignin product of claim 12, wherein said lignin product has a heating value as measured by ASTM-D240 of at least about 5,000 BTU/lb at 30% moisture content.
16. A lignin product of claim 12, wherein said lignin product has a heating value as measured by ASTM-D240 of at least about 7,500 BTU/lb at 15% moisture content.
17. A lignin product of claim 12, wherein said lignin product has a heating value as measured by ASTM-D240 of at least about 8,000 BTU/lb at 5% moisture content.
18. A composition comprising the lignin product of claim 12, wherein said composition is substantially free of organic solvent.
19. A method of claim 10, 206445NZ_spec_20150928_PLH wherein said fractionation comprises a hydrothermal treatment or enzymatic treatment.
20. A method of claim 19, wherein said fractionation comprises hydrothermal treatment, and said hydrothermal treatment comprises hot compressed water, subcritical water, near critical water, or supercritical water.
21. A method of claim 20, wherein said hydrothermal treatment further comprises an alcohol, an acid, or a base.
22. A method of claim 1, wherein said first liquid fraction comprises water.
23. A method of claim 1, wherein said first temperature is about 280 °C to about 375 °C.
24. A method of claim 3, wherein the temperature of said mixture is reduced to about 20 °C to about 60 °C. 206445NZ_spec_20150928_PLH
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161482479P | 2011-05-04 | 2011-05-04 | |
US61/482,479 | 2011-05-04 | ||
PCT/US2012/036591 WO2012151524A2 (en) | 2011-05-04 | 2012-05-04 | Lignin production from lignocellulosic biomass |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ616832A NZ616832A (en) | 2015-11-27 |
NZ616832B2 true NZ616832B2 (en) | 2016-03-01 |
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