# US 2014/0154756 A1 · Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom

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- Number: US 2014/0154756 A1
- Document ID: US20140154756A1
- Status: Published application
- Kind: A1
- Application number: 14/092,906
- Filed: 2013-11-27
- Published: 2014-06-05
- Earliest claimed: 2012-11-30
- Assignees: API Intellectual Property Holdings, LLC
- Applicants: API Intellectual Property Holdings, LLC
- Inventors: Kimberly NELSON; Theodora RETSINA; Vesa PYLKKANEN; Ryan O'CONNOR
- Web page: https://patentgrep.com/patent/US20140154756A1

## CPC

- C08B 15/08: Fractionation of cellulose, e.g. separation of cellulose crystallites
- C07G 1/00: Low-molecular-weight derivatives of lignin (high-molecular-weight derivatives of lignin {C08H6/00})
- C08B 15/00: Preparation of other cellulose derivatives or modified cellulose {, e.g. complexes}
- C08B 15/02: Oxycellulose; Hydrocellulose; {Cellulosehydrate, e.g. microcrystalline cellulose}
- C08B 37/0057: {beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof}
- C08H 8/00: Macromolecular compounds derived from lignocellulosic materials {(pretreatment thereof B27N)}
- C08L 1/02: Cellulose; Modified cellulose
- C12P 7/04: acyclic
- C12P 7/10: substrate containing cellulosic material
- C12P 7/14: Multiple stages of fermentation; Multiple types of microorganisms or re-use of microorganisms
- C12P 7/16: Butanols
- C12P 7/28: Acetone-containing products
- C12P 7/46: Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
- C12P 7/56: Lactic acid
- C12P 19/02: Monosaccharides (2-ketogulonic acid C12P7/60)
- C12P 19/14: produced by the action of a carbohydrase {(EC 3.2.x)}, e.g. by alpha-amylase {, e.g. by cellulase, hemicellulase}
- C13K 1/02: obtained by saccharification of cellulosic materials (manufacture of fodder A23K10/32)
- D21C 3/04: with acids, acid salts or acid anhydrides {(D21C3/003 and D21C3/222 take precedence)}
- D21C 3/06: sulfur dioxide; sulfurous acid; bisulfites {sulfites}
- D21C 3/20: with organic solvents {or in solvent environment}
- D21C 5/00: Other processes for obtaining cellulose, e.g. cooking cotton linters (obtaining fibres for spinning D01C); {Processes characterised by the choice of cellulose-containing starting materials}
- D21C 5/005: {Treatment of cellulose-containing material with microorganisms or enzymes}
- D21C 9/002: {by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives}
- D21C 9/007: {by mechanical or physical means}
- D21C 9/10: Bleaching {; Apparatus therefor}
- D21C 11/0007: {Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for (volatile compounds obtained by decomposition of spent liquors in order to regenerate them D21C11/125; compounds obtained by fractionating the liquors in order to regenerate them D21C11/0042)}
- D21H 11/18: Highly hydrated, swollen or fibrillatable fibres
- C12P 2201/00: Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
- C12P 2203/00: Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 40/40: Production or processing of lime, e.g. limestone regeneration of lime in pulp and sugar mills
- C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21)
- C07G: COMPOUNDS OF UNKNOWN CONSTITUTION (sulfonated fats, oils or waxes of undetermined constitution C07C309/62)
- C08H: DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS (polysaccharides C08B; natural rubber C08C; natural resins or their derivatives C09F; bituminous materials C10)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- C13K: SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES (chemically synthesised sugars or sugar derivatives C07H; polysaccharides, e.g. starch, derivatives thereof C08B; malt C12C; fermentation or enzyme-using processes for preparing compounds containing saccharide radicals C12P19/00; production of sucrose C13B)
- D21C: PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21H: PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Processes disclosed are capable of converting biomass into high-crystallinity nanocellulose with surprisingly low mechanical energy input. In some variations, the process includes fractionating biomass with an acid (such as sulfur dioxide), a solvent (such as ethanol), and water, to generate cellulose-rich solids and a liquid containing hemicellulose and lignin; and mechanically treating the cellulose-rich solids to form nanofibrils and/or nanocrystals. The total mechanical energy may be less than 500 kilowatt-hours per ton. The crystallinity of the nanocellulose material may be 80% or higher, translating into good reinforcing properties for composites. The nanocellulose material may include nanofibrillated cellulose, nanocrystalline cellulose, or both. In some embodiments, the nanocellulose material is hydrophobic via deposition of some lignin onto the cellulose surface. Optionally, sugars derived from amorphous cellulose and hemicellulose may be separately fermented, such as to monomers for various polymers. These polymers may be combined with the nanocellulose to form completely renewable composites.

## Claims

### Claim 1

A process for producing a nanocellulose material, said process comprising:
(a) providing a lignocellulosic biomass feedstock;
(b) fractionating said feedstock in the presence of an acid, a solvent for lignin, and water, to generate cellulose-rich solids and a liquid containing hemicellulose and lignin;
(c) mechanically treating said cellulose-rich solids to form cellulose fibrils and/or cellulose crystals, thereby generating a nanocellulose material having a crystallinity of at least 60%; and
(d) recovering said nanocellulose material.

### Claim 2 (depends on 1)

The process of claim 1, wherein said acid is selected from the group consisting of sulfur dioxide, sulfurous acid, sulfur trioxide, sulfuric acid, lignosulfonic acid, and combinations thereof.

### Claim 3 (depends on 2)

The process of claim 2, wherein said acid is sulfur dioxide.

### Claim 4 (depends on 1)

The process of claim 1, wherein during step (c), said cellulose-rich solids are treated with a total mechanical energy of less than about 1000 kilowatt-hours per ton of said cellulose-rich solids.

### Claim 5 (depends on 4)

The process of claim 4, wherein said total mechanical energy is less than about 500 kilowatt-hours per ton of said cellulose-rich solids.

### Claim 6 (depends on 5)

The process of claim 5, wherein said total mechanical energy is from about 100 kilowatt-hours to about 400 kilowatt-hours per ton of said cellulose-rich solids.

### Claim 7 (depends on 1)

The process of claim 1, wherein step (c) further comprises treatment of said cellulose-rich solids with one or more enzymes.

### Claim 8 (depends on 1)

The process of claim 1, wherein step (c) further comprises treatment of said cellulose-rich solids with one or more acids.

### Claim 9 (depends on 8)

The process of claim 8, wherein said one or more acids are selected from the group consisting of sulfur dioxide, sulfurous acid, lignosulfonic acid, acetic acid, formic acid, and combinations thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein step (c) further comprises treatment of said cellulose-rich solids with heat.

### Claim 11 (depends on 1)

The process of claim 1, wherein step (c) does not employ any enzymes or acids.

### Claim 12 (depends on 1)

The process of claim 1, said process further comprising bleaching said cellulose-rich solids prior to step (c) and/or as part of step (c).

### Claim 13 (depends on 1)

The process of claim 1, said process further comprising bleaching said nanocellulose material during step (c) and/or following step (c).

### Claim 14 (depends on 1)

The process of claim 1, wherein said crystallinity of said nanocellulose material is at least 70%.

### Claim 15 (depends on 14)

The process of claim 14, wherein said crystallinity of said nanocellulose material is at least 80%.

### Claim 16 (depends on 15)

The process of claim 15, wherein said crystallinity of said nanocellulose material is at least 85%.

### Claim 17 (depends on 1)

The process of claim 1, wherein said nanocellulose material comprises nanofibrillated cellulose.

### Claim 18 (depends on 1)

The process of claim 1, wherein said nanocellulose material comprises nanocrystalline cellulose.

### Claim 19 (depends on 1)

The process of claim 1, wherein said nanocellulose material comprises nanofibrillated cellulose and nanocrystalline cellulose.

### Claim 20 (depends on 1)

The process of claim 1, wherein said nanocellulose material is characterized by an average degree of polymerization from about 100 to about 1500.

### Claim 21 (depends on 20)

The process of claim 20, wherein said nanocellulose material is characterized by an average degree of polymerization from about 300 to about 700.

### Claim 22 (depends on 20)

The process of claim 20, wherein said nanocellulose material is characterized by an average degree of polymerization from about 150 to about 250.

### Claim 23 (depends on 1)

The process of claim 1, said process further comprising hydrolyzing amorphous cellulose into glucose in step (b) and/or step (c), recovering said glucose, and optionally fermenting said glucose to a fermentation product.

### Claim 24 (depends on 1)

The process of claim 1, said process further comprising recovering, fermenting, or further treating hemicellulosic sugars derived from said hemicellulose.

### Claim 25 (depends on 24)

The process of claim 24, said process further comprising fermenting said hemicellulosic sugars to produce a monomer or precursor thereof; polymerizing said monomer to produce a polymer; and combining said polymer and said nanocellulose material to form a polymer-nanocellulose composite.

### Claim 26 (depends on 1)

The process of claim 1, said process further comprising recovering, combusting, or further treating said lignin.

### Claim 27 (depends on 1)

The process of claim 1, wherein said nanocellulose material is at least partially hydrophobic via deposition of at least some of said lignin onto a surface of said cellulose-rich solids during step (b).

### Claim 28 (depends on 1)

The process of claim 1, wherein said nanocellulose material is at least partially hydrophobic via deposition of at least some of said lignin onto a surface of said nanocellulose material during step (c) or step (d).

### Claim 29 (depends on 1)

The process of claim 1, said process further comprising chemically converting said nanocellulose material to one or more nanocellulose derivatives.

### Claim 30 (depends on 29)

The process of claim 29, wherein said nanocellulose derivatives are selected from the group consisting of nanocellulose esters, nanocellulose ethers, nanocellulose ether esters, alkylated nanocellulose compounds, cross-linked nanocellulose compounds, acid-functionalized nanocellulose compounds, base-functionalized nanocellulose compounds, and combinations thereof.

### Claim 31

A process for producing a nanocellulose material, said process comprising:
(a) providing a lignocellulosic biomass feedstock;
(b) fractionating said feedstock in the presence of sulfur dioxide, a solvent for lignin, and water, to generate cellulose-rich solids and a liquid containing hemicellulose oligomers and lignin, wherein the crystallinity of said cellulose-rich solids is at least 70%, wherein SO2 concentration is from about 10 wt % to about 50 wt %, fractionation temperature is from about 130° C. to about 200° C., and fractionation time is from about 30 minutes to about 4 hours;
(c) mechanically treating said cellulose-rich solids to form cellulose fibrils and/or cellulose crystals, thereby generating a nanocellulose material having a crystallinity of at least 70%; and
(d) recovering said nanocellulose material.

### Claim 32 (depends on 31)

The process of claim 31, wherein said SO2 concentration is from about 12 wt % to about 30 wt %.

### Claim 33 (depends on 31)

The process of claim 31, wherein said fractionation temperature is from about 140° C. to about 170° C.

### Claim 34 (depends on 31)

The process of claim 31, wherein said fractionation time is from about 1 hour to about 2 hours.

### Claim 35 (depends on 31)

The process of claim 31, wherein during step (b), a portion of said lignin deposits onto a surface of said cellulose-rich solids, thereby rendering said cellulose-rich solids at least partially hydrophobic.

### Claim 36

A process for producing a hydrophobic nanocellulose material, said process comprising:
(a) providing a lignocellulosic biomass feedstock;
(b) fractionating said feedstock in the presence of an acid, a solvent for lignin, and water, to generate cellulose-rich solids and a liquid containing hemicellulose and lignin, wherein a portion of said lignin deposits onto a surface of said cellulose-rich solids, thereby rendering said cellulose-rich solids at least partially hydrophobic;
(c) mechanically treating said cellulose-rich solids to form cellulose fibrils and/or cellulose crystals, thereby generating a hydrophobic nanocellulose material having a crystallinity of at least 60%; and
(d) recovering said hydrophobic nanocellulose material.

### Claim 37 (depends on 36)

The process of claim 36, wherein said acid is selected from the group consisting of sulfur dioxide, sulfurous acid, sulfur trioxide, sulfuric acid, lignosulfonic acid, and combinations thereof.

### Claim 38 (depends on 36)

The process of claim 36, wherein during step (c), said cellulose-rich solids are treated with a total mechanical energy of less than about 1000 kilowatt-hours per ton of said cellulose-rich solids.

### Claim 39 (depends on 38)

The process of claim 38, wherein said total mechanical energy is less than about 500 kilowatt-hours per ton of said cellulose-rich solids.

### Claim 40 (depends on 36)

The process of claim 36, wherein said crystallinity of said nanocellulose material is at least 70%.

### Claim 41 (depends on 40)

The process of claim 40, wherein said crystallinity of said nanocellulose material is at least 80%.

### Claim 42 (depends on 36)

The process of claim 36, wherein said nanocellulose material comprises nanofibrillated cellulose, nanocrystalline cellulose, or both nanofibrillated and nanocrystalline cellulose, and wherein said nanocellulose material is characterized by an average degree of polymerization from about 100 to about 1500.

### Claim 43 (depends on 42)

The process of claim 42, wherein said nanocellulose material is characterized by an average degree of polymerization from about 300 to about 700.

### Claim 44 (depends on 42)

The process of claim 42, wherein said nanocellulose material is characterized by an average degree of polymerization from about 150 to about 250.

### Claim 45 (depends on 36)

The process of claim 36, said process further comprising chemically modifying said lignin to increase hydrophobicity of said nanocellulose material.

### Claim 46

A process for producing a nanocellulose-containing product, said process comprising:
(a) providing a lignocellulosic biomass feedstock;
(b) fractionating said feedstock in the presence of an acid, a solvent for lignin, and water, to generate cellulose-rich solids and a liquid containing hemicellulose and lignin;
(c) mechanically treating said cellulose-rich solids to form cellulose fibrils and/or cellulose crystals, thereby generating a nanocellulose material having a crystallinity of at least 60%; and
(d) incorporating at least a portion of said nanocellulose material into a nanocellulose-containing product.

### Claim 47 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product consists essentially of said nanocellulose material.

### Claim 48 (depends on 46)

The process of claim 46, wherein step (d) comprises forming a structural object that includes said nanocellulose material, or a derivative thereof.

### Claim 49 (depends on 46)

The process of claim 46, wherein step (d) comprises forming a foam or aerogel that includes said nanocellulose material, or a derivative thereof.

### Claim 50 (depends on 46)

The process of claim 46, wherein step (d) comprises combining said nanocellulose material, or a derivative thereof, with one or more other materials to form a composite.

### Claim 51 (depends on 50)

The process of claim 50, wherein said one or more other materials includes a polymer selected from polyolefins, polyesters, polyurethanes, polyamides, or combinations thereof.

### Claim 52 (depends on 50)

The process of claim 50, wherein said one or more other materials includes carbon.

### Claim 53 (depends on 46)

The process of claim 46, wherein step (d) comprises forming a film comprising said nanocellulose material, or a derivative thereof.

### Claim 54 (depends on 53)

The process of claim 53, wherein said film is optically transparent and flexible.

### Claim 55 (depends on 46)

The process of claim 46, wherein step (d) comprises forming a coating or coating precursor comprising said nanocellulose material, or a derivative thereof.

### Claim 56 (depends on 55)

The process of claim 55, wherein said nanocellulose material is at least partially hydrophobic via deposition of at least some of said lignin onto a surface of said cellulose-rich solids during step (b).

### Claim 57 (depends on 55)

The process of claim 55, wherein said nanocellulose material is at least partially hydrophobic via deposition of at least some of said lignin onto a surface of said nanocellulose material during step (c) or step (d).

### Claim 58 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is configured electrochemically for carrying or storing an electrical current or voltage.

### Claim 59 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is incorporated into a filter, membrane, or other separation device.

### Claim 60 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is incorporated as an additive into a coating, paint, or adhesive.

### Claim 61 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is configured as a catalyst, catalyst substrate, or co-catalyst.

### Claim 62 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is incorporated as a cement additive.

### Claim 63 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is a paper coating.

### Claim 64 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is incorporated as a thickening agent or rheological modifier.

### Claim 65 (depends on 46)

The process of claim 46, wherein said nanocellulose-containing product is incorporated as an additive in a drilling fluid.

### Claim 66 (depends on 64)

The process of claim 64, wherein said drilling fluid is an oil recovery fluid and/or a gas recovery fluid.