BR112019027082A2 - nanolignocellulose compositions and processes for producing these compositions - Google Patents

Abstract

Some variations provide a new nanolignocellulose composition comprising, on a dry weight basis, ash free and acetyl free, from 35% by weight to 80% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof 15% by weight to 45% by weight of lignin and 5% by weight to 20% by weight of hemicelluloses. Hemicelluloses may contain xylan or mannan as the main component. New properties arise from the hemicellulose content that is intermediate between the high hemicellulose content of the crude biomass and the low hemicellulose content of conventional nanocellulose. The composition of nanolignocellulose is hydrophobic due to the presence of lignin. Processes for preparing and using nanolignocellulose compositions are also described.

Description

Descriptive Report of the Invention Patent for: “NANOLIGNOCELLULOSE COMPOSITIONS AND PROCESSES TO PRODUCE THESE COMPOSITIONS”

PRIORITY DATA

[001] This international patent application claims priority to US Provisional Patent Application 62 / 523,293, filed on June 22, 2017 and US patent application 16 / 014,589, filed on June 21, 2018, each of which is incorporated by reference in the present invention.

FIELD

[002] The present invention relates, in general, to nanocellulose and related materials produced by fractionation of lignocellulosic biomass and further processing of the cellulose fraction.

BACKGROUND

[003] Biomass refining (or biorefining) has become more prevalent in the industry. Cellulose fibers and sugars, hemicellulose sugars, lignin, singas, and derivatives of these intermediates are being used for the production of chemicals and fuels. In fact, now we see the commercialization of integrated biorefineries that are capable of processing received biomass in the same way that oil refineries now process crude oil. Underused lignocellulosic biomass raw materials have the potential to be much cheaper than oil,

on a carbon basis, and also much better from the point of view of the environmental life cycle.

[004] Lignocellulosic biomass is the most abundant renewable material on the planet and has long been recognized as a potential raw material for the production of chemicals, fuels and materials. Lignocellulosic biomass normally comprises mainly cellulose, hemicellulose and lignin. Cellulose and hemicellulose are natural polymers of sugars, and lignin is an aromatic / aliphatic hydrocarbon polymer that strengthens the entire biomass network. Some forms of biomass (for example, recycled materials) do not contain hemicellulose.

[005] Despite being the most available natural polymer on Earth, it is only recently that cellulose has gained prominence as a nanostructured material, in the form of nanocrystalline cellulose (NCC), nanofibrillar cellulose (NFC), and bacterial cellulose (BC). Nanocellulose is being developed for use in a wide variety of applications, such as polymer reinforcement, antimicrobial films, biodegradable food packaging, printing papers, pigments and inks, paper and cardboard packaging, barrier films, adhesives, biocomposites , wound healing, dispensing pharmaceuticals and drugs, textiles, water-soluble polymers, building materials, recyclable interior and structural components for the transport industry, rheology modifiers, low-calorie food additives, thickeners for cosmetics, binders for pharmaceutical tablets, bioactive paper, pickering stabilizers for emulsion and particulate stabilized foams, ink formulations, films for optical switching and detergents.

[006] Cellulose pulp derived from biomass can be converted into nanocellulose by mechanical processing.

Although the process may be simple, the disadvantages include high energy consumption, damage to fibers and particles due to intense mechanical treatment, and a wide distribution in the diameter and length of the fibrils.

[007] Improved processes for the production of nanocellulose from biomass at reduced energy costs are necessary in the art. In addition, improved starting materials (ie cellulose pulps derived from biomass) are needed in the art for the production of nanocellulose. For some applications, it is desirable to produce nanocellulose with high hydrophobicity.

[008] There is also a need in the art to increase the strength of weak cellulose fibers, and to improve certain properties of paper, pulp medium and cellulose pulp products.

SUMMARY

[009] Some variations provide a nanolignocellulose composition comprising, on a dry weight basis, ash free and acetyl free, from about 35% by weight to about 80% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof, from about 15% by weight to about 45% by weight of lignin, and from about 5% by weight to about 20% by weight of hemicelluloses.

Hemicelluloses may contain xylan or mannan as the main component.

[010] In certain embodiments, the composition comprises from about 40% by weight to about 70% by weight of cellulose nanofibrils, cellulose microfibrils, or a combination thereof on a dry, ash-free basis and free of acetyl.

[011] In certain embodiments, the composition comprises from about 45% by weight to about 60% by weight of cellulose nanofibrils, cellulose microfibrils, or a combination thereof on a dry, ash-free basis and free of acetyl.

[012] In certain embodiments, the composition comprises from about 20% by weight to about 40% by weight of lignin on a dry weight basis, free from ash and free from acetyl.

[013] In certain embodiments, the composition comprises from about 25% by weight to about 35% by weight of lignin on a dry weight basis, free from ash and free from acetyl.

[014] In certain embodiments, the composition comprises from about 7% by weight to about 15% by weight of hemicelluloses on a dry weight, ash-free and acetyl-free basis.

[015] In certain embodiments, the composition comprises from about 8% by weight to about 14% by weight of hemicelluloses on a dry weight, ash-free and acetyl-free basis.

[016] In some embodiments, said nanolignocellulose composition is characterized by at least 99% completion of filtration (such as 100% completion) in less than 100 minutes.

[017] The present invention also provides a cellulose pulp product or a paper product containing the disclosed nanolignocellulose composition.

[018] Some variations provide a process for producing a nanolignocellulose composition, the process comprising: (a) providing a lignocellulosic biomass feedstock; (b) digesting the raw material with a reaction solution including steam and / or hot water in a digester under reaction conditions effective to produce a digested stream containing cellulose-rich solids, hemicellulose oligomers, and lignin; (c) optionally washing the cellulose-rich solids to remove at least a portion of the hemicellulose oligomers and / or at least a portion of the lignin from the cellulose-rich solids; (d) mechanically treating cellulose-rich solids to form a nanolignocellulose composition containing cellulose nanofibrils and / or cellulose nanocrystals, hemicelluloses and lignin; and (e) recovering the nanolignocellulose composition.

[019] In some processes, the nanolignocellulose composition comprises, on a dry weight basis, free from ash and free from acetyl, from about 35% by weight to about 80% by weight of cellulose nanofibrils, cellulose microfibrils , or a combination thereof, from about 15% by weight to about 45% by weight of lignin, and from about 5% by weight to about 20% by weight of hemicelluloses.

[020] In some processes, the composition of nanolignocellulose is characterized by at least 99% completion of filtration in less than 100 minutes.

[021] The process may additionally include a cellulose pulp product or a paper product containing the nanolignocellulose composition. For example, the nanolignocellulose composition can be fed to a paper machine to produce a paper product.

BRIEF DESCRIPTION OF THE FIGURES

[022] FIG. 1A is a sample image of an example nanocellulose produced experimentally, by refining and homogenizing material produced from the extraction of biomass in hot water.

[023] FIG. 1B is an example nanocellulose SEM image produced experimentally, by refining and homogenizing material produced from the extraction of biomass in hot water.

[024] FIG. 1C is a sample image of an example nanocellulose produced experimentally, by refining and homogenizing material produced from the extraction of biomass in hot water.

[025] FIG. 2 is an optical micrograph with 40x magnification of washed nanolignocellulose produced in Example 1.

[026] FIG. 3 is an optical micrograph with 40x magnification of washed nanolignocellulose produced in Example 2.

[027] FIG. 4 is a graph of the filtration rate of the nanolignocellulose of Example 2 compared to the prior art Kraft cellulose pulp.

DETAILED DESCRIPTION OF SOME ACHIEVEMENTS

[028] This description will enable one skilled in the art to make and use the invention, and describes various embodiments, adaptations, variations, alternatives and uses of the invention. These and other embodiments, features and advantages of the present invention will become more apparent to those skilled in the art when taken with reference to the following detailed description of the invention in conjunction with any accompanying drawings.

[029] As used in this specification and the appended claims, the singular forms "one", "one" and "a" and "o" include plural referents, unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as is commonly understood by one of ordinary skill in the art to which this invention belongs. All numbers and composition ranges based on percentages are percentages by weight, unless otherwise stated. All ranges of numbers or conditions must cover any specific value contained in the range, rounded to any suitable decimal point.

[030] Unless otherwise indicated, all numbers expressing parameters, reaction conditions, concentrations of components, and so on used in the specification and in the claims should be understood as being modified in all cases by the term “ about". Suitably, unless otherwise indicated, the numerical parameters set out in the following specification and in the appended claims are approximations that may vary depending on at least one specific analytical technique.

[031] The term "comprising", which is synonymous with "including", "containing" or "characterized by" is inclusive or open and does not exclude additional elements not specified or steps in the method. “Understanding” is a technical term used in the claim language, which means that the so-called claim elements are essential, but other elements of the claim can be added and still form a construction within the scope of the claim.

[032] As used in the present invention, the term "consisting of" excludes any element, step or ingredient not specified in (a) the claim. When the expression “consists of” (or variations thereof) appears in a clause in the body of a claim, instead of immediately following the preamble, it limits only the element established in that clause; other elements are not excluded from the claim as a whole. As used in the present invention, the phrase “consisting essentially of” limits the scope of a claim to the specified elements or method steps, in addition to those that do not materially affect the basis and the new feature (s) of the claimed object.

[033] With respect to the terms "comprising", "consisting of" and "consisting essentially of", where one of these three terms is used in the present invention, the object currently disclosed and claimed may include the use of any of the other two terms . Thus, in some embodiments not explicitly mentioned, any case of "understanding" can be replaced by "consisting of" or, alternatively, "consisting essentially of".

[034] Some variations are based on the discovery of a surprisingly simple process for converting lignocellulosic biomass into nanocellulose or nanolignocellulose. The biomass can be subjected to steam or immersion in dissolved hemicelluloses in hot water. This step is followed by the mechanical refining of cellulose-rich (and lignin-rich) solids.

[035] Some variations provide a nanolignocellulose composition comprising, on a dry weight basis, ash free and acetyl free, from about 35% by weight to about 80% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof, from approximately 15% by weight to about 45% by weight of lignin, and from about 5% by weight to about 20% by weight of hemicelluloses.

[036] In various embodiments, the nanolignocellulose composition can include about (or at least about, or at most about) 30, 35, 40, 45, 50, 55, 60, 65, 75, 75, 80, 85 or 90% by weight of cellulose nanofibrils, cellulose microfibrils, or a combination thereof, based on dry weight, ash free and acetyl free.

[037] In various embodiments, the nanolignocellulose composition can include about (or at least about, or at most about) 10, 15, 20, 25, 30, 35, 40, 45 or 50% by weight of lignin, based on dry weight, free from ash and free from acetyl.

[038] In various embodiments, the nanolignocellulose composition can include about (or at least approximately or at most approximately) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19 or 20% by weight of hemicelluloses, a dry weight base, free from ash and free from acetyl. Hemicelluloses may contain xylan or mannan as the main component.

[039] A “dry weight, ash-free and acetyl-free base” means that the concentrations mentioned are (i) absolutely free of any water, not including chemically contained H-OH groups, for example, in sugar polymers; (ii) free of any ash, including loose ash (for example, sand or dirt) and bound ash (for example, metal oxides that do not easily extract from solids); and (iii) acetyl groups attached to components of hemicellulose, or free acetic acid derived from acetyl groups.

[040] In certain embodiments, the composition comprises from about 40% by weight to about 70% by weight of cellulose nanofibrils, cellulose microfibrils, or a combination thereof on a dry, ash-free basis and free of acetyl.

[041] In certain embodiments, the composition comprises from about 45% by weight to about 60% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof on a dry, ash-free basis and acetyl free.

[042] In certain embodiments, the composition comprises from about 20% by weight to about 40% by weight of lignin on a dry weight basis, free from ash and free from acetyl.

[043] In certain embodiments, the composition comprises from about 25% by weight to about 35% by weight of lignin on a dry weight basis, free from ash and free from acetyl.

[044] In certain embodiments, the composition comprises from about 7% by weight to about 15% by weight of hemicelluloses on a dry weight, ash-free and acetyl-free basis.

[045] In certain embodiments, the composition comprises from about 8% by weight to about 14% by weight of hemicelluloses on a dry weight, ash-free and acetyl-free basis.

[046] The nanolignocellulose composition may contain water as moisture or in a slurry of solids, for example. The nanolignocellulose composition, in an ash-free and acetyl-free (but wet-based) base, can contain at least about (or at least about, or at most about) 5, 10, 15, 20, 25 , 30, 35, 40, 45, 50, 60, 70, 80, 90% by weight of water or more.

[047] The nanolignocellulose composition may contain ash. The nanolignocellulose composition, on a dry weight basis and without acetyl, may contain at least about (or at least about or at most about) 0.1; 0.5; 1; 2; 3; 4; 5% by weight of ash or more.

[048] The nanolignocellulose composition may contain acetyl groups. The nanolignocellulose composition, on a dry weight basis and without ash, can contain at least about (or at least about, or at most about) 0.1; 0.5; 1.0; 1.5; 2.0; 2.5; 3.0% by weight of acetyl content or more.

[049] In some embodiments, said nanolignocellulose composition is characterized by at least 99% completion of filtration (such as 100% completion) in less than 100 minutes.

[050] The present invention also provides a cellulose pulp product or a paper product containing a disclosed nanolignocellulose composition.

[051] In some variations, a paper mill co-produces nanolignocellulose and adds that material back to its own feed load, in order to prepare a stronger sheet, or a smoother sheet, or to provide a cheaper feed load for the final paper product. In some embodiments, nanolignocellulose is produced using an existing low consistency refiner, such as a side operation at the plant or at a nearby plant. At least part of the resulting nanolignocellulose is added back to the mixture.

[052] This concept may result in the ability to use less expensive wood as the main raw material to produce cellulose pulp. Many paper mills use a mixture of hardwood and softwood to achieve a desired combination of strength and sheet formation / smoothness. In addition to replacing the most expensive raw materials, nanolignocellulose can act as a retention aid for paper machines.

Thus, a paper machine can use the function of a retention aid, and also the strength of the sheet of the same material (nanolignocellulose).

[053] The principles of the invention can be applied to any type of cellulose or plant, including chemicals (for example, AVAP®, kraft or sulfite), mechanical, thermomechanical, chemothermechanics, hydrothermal-mechanics (for example, GreenBox + ® or GP3 + ™) or other types of pulping. Chemical pulping generally degrades lignin and hemicellulose into small water-soluble molecules that can be washed from cellulose fibers without depolymerizing the cellulose fibers. AVAP® pulping removes lignin and hemicelluloses without significant sugar degradation, allowing the recovery of all major components (cellulose, hemicellulose and lignin). The various methods of mechanical pulping, such as mechanical pulping of milled and refining wood, physically tear the cellulose fibers from each other. Much of the lignin continues to adhere to the fibers. The resistance is impaired because the fibers can be cut. The related hybrid pulping methods use a combination of chemical and thermal treatment to initiate an abbreviated chemical pulping process, followed by a mechanical treatment to separate the fibers. These hybrid methods include thermomechanical and polymetromechanical pulping. Chemical and thermal treatments reduce the amount of energy subsequently required by mechanical treatment, and also reduce the amount of loss of strength suffered by the fibers.

[054] In some preferred embodiments, the invention is applied to a thermomechanical cellulose pulp mill or to a hydrothermal-mechanical cellulose pulp mill.

[055] In some embodiments, some of the thermomechanical or hydrothermal-mechanical cellulose pulps that are produced from the normal pulping operation are sent to a side nanocellulose production operation, involving mechanical refining of the thermomechanical cellulose pulp or hydrothermal-mechanical to generate nanocellulose particles (for example, cellulose nanofibrils).

Commonly owned US patent application No. 15 / 278,800 filed on September 28, 2016, entitled “PROCESSES FOR PRODUCING NANOCELLULOSE, AND NANOCELLULOSE COMPOSITIONS PRODUCED THEREFROM”, is incorporated by reference into the present invention for its thermomechanical pulp conversion teachings or hydrothermal-mechanical in nanocellulose, in some embodiments.

[056] In some variations, nanocellulose may be added to the corrugated medium cellulose pulp having inadequate strength properties, so that the resulting composite meets, or exceeds, the strength properties required for the intended application.

While the principles of these embodiments are not limited to any specific source of corrugated medium or nanocellulose, the preferred embodiments combine corrugated medium produced by steam extraction or hot water (known as GreenBox + ® technology) with nanocellulose produced by refining cellulose pulp obtained by fractioning the biomass in an acidic solvent (known as AVAP® technology).

[057] In some preferred embodiments, steam or hot water extraction of the initial biomass is employed to produce cellulose pulp, which is then refined and optionally washed to produce corrugated cellulose pulp. Refers to Commonly Owned US Patent Application No. 14 / 044,784 filed on October 2, 2013 (published as US 20140096922A1 on April 10, 2014), which is incorporated herein by reference in the present invention, for process conditions as an example for producing corrugated cellulose pulp, in various embodiments.

[058] In some embodiments, hot water extraction of the initial biomass is used to produce cellulose pulp, which is then refined to produce nanolignocellulose. As intended in the present invention, "nanolignocellulose" is a material that contains cellulose particles closely associated (i.e., chemically and / or physically) with substantial amounts of lignin and hemicellulose. Cellulose (within the nanolignocellulose particles) can include nanofibrils and / or microfibrils. The percentage of lignin (within the nanolignocellulose particles) is generally at least about 20% by weight, and the percentage of hemicellulose (within the nanolignocellulose particles) is generally at least about 5% by weight. Certain embodiments employ digestion in hot water and / or refining, as described in common US patent application No. 15 / 047,608, published as US 20160244788 on August 25, 2016, which is incorporated herein by reference in the present invention .

[059] Effective hot water extraction conditions may include contact of lignocellulosic biomass with steam (at various pressures in saturated, overheated or supersaturated form) and / or hot water. In some embodiments, the HWE step is performed using liquid hot water at a temperature of about 140-220 ° C, such as about 150 ° C, 160 ° C, 170 ° C, 175 ° C, 175 ° C , 180 ° C, 185 ° C, 190 ° C, 200 ° C or 210 ° C. In some embodiments, the HWE step is performed using liquid hot water with a residence time of about 1 minute to about 60 minutes, such as about 2.5, 2.5; 3; 3.5; 4; 5; 7.5; 10; 12.5; 15; 20; 25; 30; 35; 40; 45; 50 or 55 minutes.

[060] In certain embodiments, the lignin-coated nanocellulose (preferably lignin-coated cellulose nanofibrils) is added to the corrugated cellulose pulp. Without being limited by theory, the lignin in nanofibrils can reinforce the moisture resistance of corrugated paper. The production of nanocellulose coated with lignin is described in detail below. In some embodiments, lignin fills the voids between the fibers during pressing.

[061] Using well-known techniques, the corrugated medium product can be produced from the cellulose pulp of the modified corrugated medium (with nanocellulose).

See, for example, Twede and Selke, “Cartons, crates and corrugated board: handbook of paper and wood packaging technology,”, DEStech Publications, pages 41–56, 2005; and Foster, “Boxes, Corrugated", in The Wiley Encyclopedia of Packaging Technology, 1997, eds. Brody A and Marsh K, 2nd ed.

[062] As intended in the present invention, "nanocellulose" is broadly defined to include a range of cellulosic materials, including, but not limited to, microfibrillated cellulose (or cellulose microfibrils), nanofibrillated cellulose (or cellulose nanofibrils), microcrystalline cellulose , nanocrystalline cellulose, and particulate or fibrillated dissolving cellulose pulp.

Typically, nanocellulose, as provided in the present invention, will include particles having at least one dimension of length (e.g., diameter) on the nanometer scale.

[063] “Nanofibrillated cellulose” or equivalent “cellulose nanofibrils” means fibers or cellulose regions that contain nanometer-sized particles or fibers, or micron-sized and nanometer-sized particles or fibers. "Nanocrystalline cellulose" or equivalently "cellulose nanocrystals" means particles, regions or crystals of cellulose that contain domains sized in nanometers, or domains sized in microns and nanometers. The "micron size" includes from 1 µm to 100 µm and the "nanometer" size includes from 0.01 nm to 1000 nm (1 µm). Larger domains (including long fibers) may also be present in these materials.

[064] Certain exemplary embodiments of the invention will now be described. These embodiments are not intended to limit the scope of the invention as claimed. The order of the steps can vary, some steps can be omitted and / or other steps can be added.

The reference made in the present invention to the first stage, the second stage, etc. it is only for the purpose of illustrating some embodiments.

[065] Some variations provide a cellulose pulp product comprising cellulose and nanolignocellulose, where the nanocellulose includes cellulose nanofibrils and / or cellulose nanocrystals, and where the nanolignocellulose is derived from cellulose in a separate step from the pulping process to produce cellulose.

[066] In some embodiments, the pulping process is thermomechanical pulping or hydrothermal-mechanical pulping. The cellulose pulp product can be paper or a structural object (eg box, panel, wood products, etc.) other than paper.

[067] In preferred embodiments, the cellulose pulp product is stronger than an identical cellulose pulp product without nanolignocellulose. In some embodiments, the cellulose pulp product is softer than an identical cellulose pulp product without nanolignocellulose.

[068] The pulping process is thermomechanical pulping, in certain embodiments, and nanolignocellulose essentially consists of nanofibrils containing cellulose, lignin and hemicellulose. Nanofibrils can be produced by mechanically refining the cellulose precursor (with significant amounts of lignin and hemicelluloses) from thermomechanical pulping.

[069] Other variations provide a corrugated medium cellulose pulp composition comprising cellulose pulp and nanolignocellulose, where nanolignocellulose includes hydrophobic nanofibrils. In some embodiments, nanolignocellulose is present in a concentration of at least about 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 5% by weight or 10% by weight. weight of the composition on a dry basis. In certain embodiments, nanolignocellulose is a significant portion of the cellulose feed charge, i.e., about 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight or more .

[070] In some embodiments of the corrugated medium cellulose composition, the cellulose pulp is a mechanical cellulose pulp or thermomechanical cellulose pulp (for example, GreenBox + ® cellulose). In some embodiments, the cellulose pulp is a chemical cellulose pulp (for example, AVAP®, kraft, sulfite or soda cellulose pulp).

[071] In some embodiments, the process further comprises producing a corrugated medium product from the corrugated medium cellulose pulp composition. The first quantity of lignocellulosic biomass and the second quantity of lignocellulosic biomass can be from the same source of biomass or from different sources of biomass.

[072] In some embodiments, nanolignocellulose is hydrophobic cellulose containing lignin.

In these or other embodiments, nanolignocellulose is predominantly in the form of nanofibrils, microfibrils or a mixture thereof.

[073] In some embodiments, a system is provided to perform the process, as disclosed. The system can include a first subsystem to produce the first cellulose pulp at a first location and a second subsystem to produce nanolignocellulose at a second location other than the first location. The production of the final product can be done in one of the first or second subsystems or in another location.

[074] In some embodiments, nanolignocellulose is derived from a source of biomass selected from the group consisting of hardwood, softwood, agricultural waste and combinations thereof.

[075] In some embodiments, nanolignocellulose is obtained from the fractionation of biomass in the presence of an acid, a solvent for lignin, and water, to generate solids rich in cellulose and a liquid phase; and then mechanically refine cellulose-rich solids to generate nanolignocellulose. In certain embodiments, the acid is sulfur dioxide and the solvent is ethanol. In certain embodiments, an AVAP® process is used to produce nanolignocellulose to reinforce cellulose fibers.

[076] “Reinforcing” can be carried out by simple mixing, grinding, grinding, agitation, deposition / drying or other treatments, in various embodiments.

[077] In some embodiments, the method further comprises producing a single fiber product from cellulose fibers. In these or other embodiments, the method further comprises producing a composite from cellulose fibers. The reinforcement of weak fibers with nanolignocellulose can increase the strength in composite products and single fibers and in other products.

[078] In some embodiments, a product is made first of cellulose fibers and then the product (not the cellulose pulp) is reinforced with nanolignocellulose.

In these embodiments, if desired, reinforcement can be made for the bulk product or for selected surfaces or regions, for example.

[079] The biomass raw material can be selected from hardwood, softwood, forest waste, eucalyptus, industrial waste, pulp and paper pulp waste, consumer waste or combinations thereof. Some embodiments use agricultural residues, which include lignocellulosic biomass associated with food crops, annual grasses, energy crops or other renewable raw materials annually. Example agricultural residues include, but are not limited to, corn straw, corn fiber, wheat straw, sugar cane bagasse, sugar cane straw, rice straw, oat straw, barley straw, miscanthus, straw / energy cane residue, or combinations thereof. The process disclosed in the present invention benefits from the flexibility of the raw material; it is effective for a wide variety of cellulose-containing raw materials.

[080] As used in the present invention, "lignocellulosic biomass" means any material that contains cellulose, lignin and hemicellulose. Mixtures of one or more types of biomass can be used. In some embodiments, the biomass feedstock comprises a lignocellulosic component (such as that described above), in addition to a sucrose-containing component (for example, sugar cane or energy cane) and / or a starch component ( for example, corn, wheat, rice, etc.). Various levels of humidity can be associated with the initial biomass. The raw material for biomass need not be, but it can be, relatively dry. In general, biomass is in the form of particles or chips, but the particle size is not critical in this invention.

[081] In some embodiments, cellulose-rich solids are treated with a total mechanical energy of less than about 5,000 kilowatt-hours per ton (1 ton = 907.18 kg) of cellulose-rich solids, such as less than about 4000, 3000, 2000 or 1000 kilowatt hours per ton (1 ton = 907.18 Kg) of cellulose-rich solids.

Energy consumption can be measured in any other suitable unit. An ammeter that measures the current drawn by a motor that drives the mechanical treatment device is a way to obtain an estimate of the total mechanical energy.

[082] Mechanical treatment may employ one or more known technique (s), such as, but in no way limited to, grinding, crushing, beating, sonication or any other means to form or release nanofibrils and / or nanocrystals in cellulose. Essentially, any type of plant or device that physically separates fibers into fibrils can be used. These factories are well known in the industry and include, without limitation, Valley beaters, single disc refiners, double disc refiners, conical refiners, including wide angle and narrow angle, cylindrical refiners, homogenizers, microfluidizers and other types of grinding devices or crushing. See, for example, Smook, Handbook for Pulp & Paper Technologists, Tappi Press, 1992; and Hubbe et al., “Cellulose Nanocomposites: A Review,” BioResources 3 (3), 929-980 (2008).

[083] The extent of mechanical treatment can be monitored during the process by any of several means. Certain optical instruments can provide continuous data related to the fiber length and% fines distributions, one of which can be used to define end points for the mechanical treatment step. Time, temperature and pressure can vary during mechanical treatment. For example, in some embodiments, sonication for a period of about 5 minutes to 2 hours, at room temperature and pressure, can be used.

[084] In some embodiments, a portion of the cellulose-rich solids is converted to nanofibrils, while the rest of the cellulose-rich solids are not fibrillated. In various embodiments, about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or substantially all cellulose-rich solids are fibrillated in nanofibrils. In some embodiments, a portion of the nanofibrils is converted to nanocrystals, while the rest of the nanofibrils are not converted to nanocrystals. During drying, it is possible for some nanocrystals to come together again and form nanofibrils.

[085] After mechanical treatment, the nanocellulose material can be classified by particle size.

A portion of the material can be subjected to a separate process, such as enzymatic hydrolysis to produce glucose. This material may have good crystallinity, for example, but it may not have a desirable particle size or degree of polymerization.

[086] The process may further comprise treating cellulose-rich solids with one or more enzyme (s) or with one or more acid (s). When acids are used, they can be selected from the group consisting of sulfur dioxide, sulfurous acid, lignosulfonic acid, acetic acid, formic acid and combinations thereof. The acids associated with hemicellulose, such as acetic acid or uronic acids, can be used, alone or in conjunction with other acids. In addition, the process may include treating cellulose-rich solids with heat. In some embodiments, the process does not employ enzymes or acids.

[087] When an acid is used, the acid can be a strong acid, such as sulfuric acid, nitric acid or phosphoric acid, for example. Weaker acids can be used, under more severe temperature and / or time. Enzymes that hydrolyze cellulose (ie, cellulases) and possibly hemicellulose (ie, with hemicellulase activity) can be employed, instead of acids, or potentially in a sequential configuration before or after acid hydrolysis.

[088] In some embodiments, the process comprises enzymatically treating cellulose-rich solids to hydrolyze amorphous cellulose. In other embodiments, either sequentially before or after enzymatic treatment, the process may comprise acid treatment of cellulose-rich solids to hydrolyze amorphous cellulose.

[089] In some embodiments, the process further comprises the enzymatic treatment of crystalline cellulose. In other embodiments, either sequentially before or after enzymatic treatment, the process further comprises treatment of crystalline cellulose by treatment with acid.

[090] If desired, an enzyme treatment can be employed before, or possibly simultaneously with, mechanical treatment. However, in preferred embodiments, no enzymatic treatment is required to hydrolyze the amorphous cellulose or weaken the fiber wall structure prior to the isolation of the nanofibers.

[091] After mechanical treatment, nanolignocellulose can be recovered. The separation of cellulose nanofibrils and / or nanocrystals can be performed using a device capable of disintegrating the cell wall ultrastructure while preserving the integrity of the nanofibrils. For example, a homogenizer can be used. In some embodiments, the aggregated cellulose fibrils are recovered, having component fibrils in the range 1-100 nm wide, in which the fibrils have not been completely separated from each other.

[092] In some embodiments, the nanolignocellulose material is characterized by an average aspect ratio of particle length and width of about 10 to about 1000, such as about 15, 20, 25, 35, 50, 75, 100, 150, 200, 250, 300, 400 or 500. Nanofibrils are generally associated with higher aspect ratios than nanocrystals. Nanocrystals, for example, can have a length range of about 100 nm to 500 nm and a diameter of about 1 to 10 nm. Nanofibrils can have a length of about 2000 nm and a diameter range from 5 to 50 nm, resulting in a ratio of 40 to 400. In some embodiments, the aspect ratio is less than 50, less than 45 , less than 40, less than 35, less than 30, less than 25, less than 20, less than 15 or less than 10.

[093] Optionally, the process further comprises hydrolyzing amorphous cellulose into glucose, recovering glucose, and fermenting glucose in a fermentation product. Optionally, the process additionally comprises the recovery, fermentation or additional treatment of hemicellulose sugars derived from part of the hemicellulose. Optionally, the process additionally comprises the recovery, combustion or additional treatment of the lignin.

[094] The glucose that is generated from the hydrolysis of amorphous cellulose can be integrated into a general process to produce ethanol or another fermentation by-product. Thus, in some embodiments, the process further comprises hydrolyzing amorphous cellulose into glucose, and recovering glucose.

Glucose can be purified and sold. Or glucose can be fermented to a fermentation product, such as, but not limited to, ethanol. Glucose or a fermentation product can be recycled for intake, such as for processing hemicellulose sugar, if desired.

[095] When hemicellulosic sugars are recovered and fermented, they can be fermented to produce a monomer or precursor to it. The monomer can be polymerized to produce a polymer, which can then be combined with the nanocellulose material to form a polymer-nanocellulose composite.

[096] In some embodiments, the process further comprises chemically converting the nanolignocellulose material into one or more nanolignocellulose derivative (s). For example, nanolignocellulose derivatives can be selected from the group consisting of nanolignocellulose esters, nanolignocellulose ethers, nanolignocellulose esters, alkylated nanolignocellulose compounds, cross-linked nanolignocellulose compounds, acid-functionalized nanolignocellulose compounds, functionalized nanolignocellulose compounds base, and combinations thereof.

[097] Various types of functionalization or derivation of nanolignocellulose can be employed, such as functionalization using polymers, chemical modification of the surface, functionalization using nanoparticles (ie,

nanoparticles other than nanolignocellulose), modification with inorganic or surfactants or biochemical modification.

[098] High rates of lignin loading have been achieved in thermoplastics. Even higher load levels are achieved with well-known modifications of lignin. The preparation of useful polymeric materials containing a substantial amount of lignin has been the subject of research for over thirty years. Typically, lignin can be mixed in polyolefins or polyesters by extrusion up to 25-40% by weight, while satisfying the mechanical characteristics. In order to increase compatibility between lignin and other hydrophobic polymers, different approaches have been used. For example, chemical modification of lignin can be carried out through esterification with long-chain fatty acids.

[099] A significant factor that limits the application of light nanocellulose and that intensifies the resistance in composites is the hydrophilicity inherent to cellulose. The modification of the nanocellulose surface to provide hydrophobicity to allow uniform dispersion in a hydrophobic polymeric matrix is an active area of study.

Nanolignocellulose, as provided in the present invention, has been found to be hydrophobic.

[100] Optionally, the process for producing a hydrophobic nanolignocellulose material may additionally include chemically modifying the lignin to increase the hydrophobicity of the nanolignocellulose material.

Any known chemical modifications can be made to the lignin, to further increase the hydrophobic nature of the nanolignocellulose material provided by the embodiments of this invention.

[101] Some variations of the present invention are based on relatively simple processes for generating high viscosity compounds prepared from cellulosic biomass. High viscosity compounds act as rheological modifiers when mixed in small proportions with different fluids, such as drilling fluids, paints, etc.

[102] In hydraulic fracturing fluid formulations, particularly water-based formulations, but also for oil-based formulations, these compositions can function as gelling agents. Easy mixing and manipulation allow the customization of each reservoir characteristic. Several properties of these rheology modifiers have strong advantages when compared to products currently available on the market.

Some of these properties are: higher thermal stability, strong pesudoplasticity, thixotropic qualities and solubility in water. Another important property of these new compounds is that they are biodegradable, and their production does not involve chemicals other than biomass and water.

[103] Some variations provide a process for producing a nanocellulose material, the process comprising: (a) providing a raw material of lignocellulosic biomass; (b) digest the raw material with a reaction solution including steam and / or hot water in a digester under reaction conditions effective to produce a digested stream containing cellulose-rich solids, hemicellulose oligomers and lignin; (c) optionally washing the cellulose-rich solids to remove at least a portion of the hemicellulose oligomers and / or at least a portion of the lignin from the cellulose-rich solids; (d) mechanically treating cellulose-rich solids to form a nanocellulose material containing cellulose nanofibrils and / or cellulose nanocrystals; and (e) recovering the nanocellulose material.

[104] The process may additionally include treating cellulose-rich solids with one or more enzyme (s) (eg cellulases) or with one or more acid (s), such as sulfur dioxide, sulfurous acid,

lignosulfonic acid, acetic acid, formic acid or combinations thereof. The process may additionally include treating the cellulose-rich solids with heat. In some embodiments, steps (b) - (d) do not employ any enzymes or acids added externally.

[105] The nanocellulose material may include cellulose nanofibrils or a mixture of cellulose nanofibrils and cellulose nanocrystals. Figs. 1A-1C show SEM images of sample nanocellulose experimentally produced by refining and homogenizing material produced from the extraction of biomass in hot water.

The nanocellulose material can also include lignin, including lignin particles less than 1 micron in diameter. The process may include targeting cellulose-rich solids and / or targeting the nanocellulose material after it is produced.

[106] In some embodiments, the process further comprises the recovery, fermentation or further treatment of hemicellulose sugars derived from hemicellulose oligomers. For example, hemicellulosic sugars can be fermented to a fermentation product, such as (but not limited to) ethanol.

[107] In some embodiments, the process additionally comprises the hydrolysis of a portion of the cellulose-rich solids to glucose, the recovery of glucose, and the optional fermentation of glucose in a fermentation product, such as n-butanol or 1 , 4-butanediol.

[108] The process may additionally include recovering, combustion or additionally treating lignin that is washed from cellulose-rich solids. Part or all of the initial lignin (in the starting raw material) can become part of the nanocellulose material, which will be at least partially hydrophobic due to the presence of the lignin.

[109] In some embodiments, the process further comprises chemically converting the nanocellulose material into one or more nanocellulose derivative (s).

For example, nanocellulose derivatives can be selected from the group consisting of nanocellulose esters, nanocellulose ethers, nanocellulose esters, alkylated nanocellulose compounds, cross-linked nanocellulose compounds, acid-functionalized nanocellulose compounds, base-functionalized nanocellulose compounds , and combinations thereof.

[110] In certain embodiments, step (d) includes disk refining followed by homogenization of cellulose-rich solids. Step (d), or a portion thereof, can be carried out with a solid consistency of at least 10% by weight, such as at least 20% by weight.

[111] The process includes, in some embodiments, the explosion of cellulose fibers contained in cellulose-rich solids. The fiber explosion can be achieved using steam explosion and / or rapid pressure reduction, for example. In certain embodiments, step (d) uses an insufflation line refiner, optionally with pressure reduction.

[112] Some variations of the invention provide a process for producing a rheology modifier derived from biomass from cellulosic biomass, the process comprising: (a) providing a raw material comprising cellulosic biomass; (b) digest the raw material with a reaction solution including steam and / or hot water in a digester under reaction conditions effective to produce a digested stream containing cellulose-rich solids, hemicellulose oligomers and lignin; (c) refining cellulose-rich solids in a first high-intensity refining unit, thereby generating refined cellulose solids; (d) washing the refined cellulose solids after step (c) and / or washing the digested stream before step (c) followed by refining, thereby generating washed refined cellulose solids;

(e) gelling the refined cellulose solids washed in a second high-intensity refining unit, thus generating gelled cellulose solids; and (f) homogenize the gelled cellulose solids in a high shear homogenizer, thus generating a rheology modifier derived from biomass containing cellulose nanofibrils, cellulose nanocrystals, or a mixture of cellulose nanofibrils and cellulose nanocrystals.

[113] Optionally, the process also includes wet or dry cleaning of the raw material before step (b). Optionally, regardless of whether the raw material is cleaned or not, the process additionally comprises reducing the size of the raw material before step (b).

[114] Step (b) can be carried out at a digestion temperature of about 140 ° C to about 210 ° C. Step (b) can be carried out for a digestion time of about 5 minutes to about 45 minutes. Step (b) can be carried out at a net / solid weight ratio of about 2 to about 6.

[115] The process may include a pressure reduction by hot or cold insufflation of the digested stream, after step (b).

[116] The first high-intensity refining unit can use discs or a conical plate, for example. In various embodiments, the first high-intensity refining unit transfers energy to cellulose-rich solids in an amount from about 20 kW / ton to about 200 kW / ton (dry weight basis).

[117] The washing in step (d) can be carried out at a temperature of about 18 ° C to about 95 ° C. In some embodiments, washing in step (d) uses a pressurized screw press.

[118] The second high-intensity refining unit can use discs or a conical plate, for example. The first and second high intensity refining units preferably have different patterns with different groove and dam dimensions. In several embodiments, the second high-intensity refining unit transfers energy to the washed refined cellulose solids in an amount from about 20 kW / ton to about 200 kW / ton (dry weight basis).

[119] In some embodiments, the high shear homogenizer transfers a shear force equivalent to a shear force produced under a pressure of about 10,000 psig (68.95 MPa man.) To about 25,000 psig (172, 37 MPa man.).

[120] In some embodiments, the washed refined cellulose solids are stored for a period of time before step (e). Step (e) can be performed in a different location than steps (a) - (d). In addition, step (f) can be performed in a different location than steps (a) - (e).

[121] Other variations of the invention provide a process for producing a biomass-derived rheology modifier from cellulosic biomass, the process comprising: (a) providing a pre-treated raw material comprising cellulose-rich solids; (b) refining cellulose-rich solids in a first high-intensity refining unit, thereby generating refined cellulose solids; (c) optionally washing the refined cellulose solids after step (b) and / or optionally washing the digested stream before step (b) followed by refining, thereby generating washed refined cellulose solids; (d) gelling the refined cellulose solids washed in a second high-intensity refining unit, thus generating gelled cellulose solids; and (e) homogenize the gelled cellulose solids in a high shear homogenizer, thus generating a rheology modifier derived from biomass containing cellulose nanofibrils.

[122] In some embodiments, the pre-treated raw material is kraft cellulose pulp derived from wood or lignocellulosic biomass. In some embodiments, the pre-treated raw material is sulfite cellulose pulp derived from wood or lignocellulosic biomass. In some embodiments, the pre-treated raw material is soda cellulose pulp derived from wood or lignocellulosic biomass. In some embodiments, the pre-treated raw material is mechanical cellulose pulp derived from wood or lignocellulosic biomass. In some embodiments, the pre-treated raw material is thermomechanical pulp derived from wood or lignocellulosic biomass. In some embodiments, the pre-treated raw material is chemiomechanical cellulose pulp derived from wood or lignocellulosic biomass.

[123] The variations of the invention provide a water-based hydraulic fracturing fluid formulation or additive comprising (i) a nanocellulose material produced according to a described process or (ii) a rheology modifier derived from biomass produced according to a process as described.

[124] The variations of the invention provide an oil-based hydraulic fracturing fluid formulation or additive comprising (i) a nanocellulose material produced according to the described process or (ii) a rheology modifier derived from biomass produced from according to the process as described.

[125] Variations of the invention provide a water-based drilling fluid formulation or additive comprising (i) a nanocellulose material produced according to the described process or (ii) a biomass derived rheology modifier produced according to with the described process.

[126] Variations of the invention provide an oil-based drilling fluid formulation or additive comprising (i) a nanocellulose material produced according to the described process or (ii) a biomass derived rheology modifier produced according to the described process.

[127] Some variations provide a polymer-nanocellulose composite comprising (i) a nanocellulose material produced according to the described process or (ii) a biomass derived rheology modifier produced according to the described process. Example polymers include, but are not limited to, polylactide, poly (vinyl alcohol), polyethylene, polypropylene, etc.

[128] In some embodiments, this process creates high viscosity compounds ranging in size from 1 micron to 100 microns, such as between 15 microns and 50 microns. These new compounds produced without any chemical products (except biomass and water) can be used as rheological modifiers and, being based on cellulose, they are completely biodegradable.

[129] The process has several advantages. The project allows the process to be fully integrated into a line from the beginning of biomass to the production of high viscosity compounds. Or the process can be separated into several modules that can be located in different geographical locations.

[130] The biomass raw material can be selected from hardwood, softwood, forest residues, agricultural residues (such as sugarcane bagasse), industrial residues, consumer residues or combinations thereof.

In any of these processes, the raw material can include sucrose. In some embodiments with sucrose present in the raw material, most of the sucrose is recovered as part of the fermentable sugars.

[131] Some embodiments of the invention allow the processing of "agricultural waste", which for the current purposes is intended to include lignocellulosic biomass associated with food crops, annual grasses, energy crops or other renewable raw materials annually. Example agricultural residues include, but are not limited to, corn palette, corn fiber, wheat straw, sugar cane bagasse, rice straw, oat straw, barley straw, miscanthus, energy cane or combinations thereof. In certain embodiments, the agricultural residue is sugarcane bagasse, sugarcane bagasse, sugar cane straw or energy cane straw.

[132] In some embodiments, the process additionally comprises wet or dry cleaning of the raw material prior to step (b). In some embodiments, the process further comprises reducing the size of the raw material before step (b). The process may include size reduction, immersion in hot water, dehydration, steam treatment or other operations, upstream of the digester.

[133] Step (b) can be conducted at a digestion temperature of about 140 ° C to about 210 ° C, such as from about 175 ° C to about 195 ° C. Step (b) can be carried out for a digestion time of about 5 minutes to about 45 minutes, such as about 15 minutes to about 30 minutes. Step (b) can be conducted at a liquid / solid weight ratio of about 2 to about 6, such as about 3; 3.5; 4; 4.5 or 5.

[134] In some embodiments, the reaction solution comprises saturated, overheated or supersaturated steam. In some embodiments, the reaction solution comprises hot water.

[135] The pressure in the pressurized container can be adjusted to maintain the aqueous liquor as a liquid, a vapor or a combination thereof. Example pressures are about 1 atm to about 30 atm, such as about 3 atm, 5 atm, 10 atm or 15 atm.

[136] The residence time in the solid phase for the digester (pressurized extraction vessel) can vary from about 2 minutes to about 4 hours, from about 5 minutes to about 1 hour. In certain embodiments, the residence time of the digester is controlled in about 5 to 15 minutes, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 minutes. The residence time in the liquid phase for the digester can vary from about 2 minutes to about 4 hours, as can about 5 minutes to about 1 hour. The residence time in the vapor phase of the digester can vary from about 1 minute to about 2 hours, for example, such as about 3 minutes to about 30 minutes. The residence times in the solid phase, in the liquid phase and in the vapor phase can be practically the same, or can be controlled independently according to the reactor's engineering principles (for example, recycling and internal recirculation strategies).

[137] In some embodiments, the process further comprises reducing the pressure by hot insufflation of the digested stream after step (b).

Alternatively, a pressure reduction by cold insufflation of the digested stream, after step (b), can be employed.

[138] To reduce the pressure, an insufflation tank can be located between the digester and the refining unit.

In some embodiments, the steam is separated from the insufflation tank and the heat is recovered from at least part of the steam. Optionally, at least part of the steam is compressed and returned to the digester, and / or at least part of the steam is purged from the process. Note that an “inflation tank” should be broadly interpreted to include not just a tank, but any other device or equipment capable of allowing a pressure reduction in the process flow. Thus, an insufflation tank (or insufflation medium) can be a tank, vessel, pipe section, valve, separation device or other unit.

[139] Each mechanical refiner can be selected from the group consisting of a hot blow refiner, a hot load refiner, a disc refiner, a conical refiner, a cylindrical refiner, an in-line shredder, a homogenizer and combinations of the same. The treatment (refining) mechanically may employ one or more known technique (s), such as, but in no way limited to, grinding, grinding, beating, sonication or any other means to reduce the size of the cellulose particles. These refiners are well known in the industry and include, without limitation, Valley beaters, single disc refiners, double disc refiners,

conical refiners, including wide and narrow angles, cylindrical refiners, homogenizers, microfluidizers and other similar grinding and grinding devices. See, for example, Smook, Handbook for Pulp & Paper Technologists, Tappi Press, 1992.

[140] Refining can be conducted over a wide range of solids concentrations (consistency), including from about 2% to about 50% consistency, such as, about 3%, 4%, 5%, 6% , 7%, 8%, 9%, 10%, 11%, 12%, 15%, 20%, 30%, 35% or 40% consistency.

[141] Each mechanical refiner can be configured to transfer from about 20 to about 200 kW / ton (ie refining power in kW per ton (1 ton = 907.18 Kg) of fiber, based on the solid phase which is converted into the refined flow). In certain embodiments, the mechanical refiner is configured to transfer from about 75 to about 150 kW of refining power per ton of fiber. For example, a mechanical refiner with plates can be adjusted by changing the type of plate, clearance, speed, etc. to obtain these power inputs.

[142] The extent of mechanical treatment can be monitored during the process by any of several means. Certain optical instruments can provide continuous data related to the fiber length and% fines distributions, one of which can be used to define end points for the mechanical treatment step. Time, temperature and pressure can vary during mechanical treatment. For example, in some embodiments, sonication for a period of about 5 minutes to 2 hours, at room temperature and pressure, can be used.

[143] In some embodiments, a portion of the cellulose-rich solids is converted to fibrillated and / or gelled, while the rest of the cellulose-rich solids are not fibrillated and / or gelled. In various embodiments, about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or substantially all cellulose-rich solids are fibrillated and / or gelled.

[144] The first high-intensity refining unit can use discs or a conical plate, for example. In some embodiments, the first high-intensity refining unit transfers energy to cellulose-rich solids in an amount of about 20 kW / ton (1 ton = 907.18 kg) to about 200 kW / ton (1 ton = 907.18 Kg) (dry weight basis), as from about 75 kW / ton (1 ton = 907.18 Kg) to about 150 kW / ton (dry weight basis).

[145] In some embodiments, washing in step (d) is carried out at a temperature of about 18 ° C to about 95 ° C, such as from about 70 ° C to about 80 ° C. The wash in step (d) can use a pressurized screw press.

[146] In some embodiments, the second high-intensity refining unit uses discs or a tapered plate. The first and second high intensity refining units preferably have different patterns with different groove and dam dimensions. In some embodiments, the second high-intensity refining unit transfers energy to the washed refined cellulose solids in an amount of about 20 kW / ton (1 ton = 907.18 Kg) to about 200 kW / ton ( 1 ton = 907.18 Kg) (dry weight basis), as from about 75 kW / ton (1 ton = 907.18 Kg) to about 150 kW / ton (dry weight basis).

[147] In some embodiments, the high shear homogenizer (or other unit operation capable of imparting shear) transfers a shear force equivalent to a shear force produced under a pressure of about 1,000 psig (6.89 MPa man.) at about 50,000 psig (344.74 MPa man.), such as about 10,000 psig (68.94757 MPa man.) to about 25,000 psig (172.37 MPa man.).

[148] Washed refined cellulose solids can be stored for a period of time before step (e), which can be conducted in a different location from steps (a) - (d). In some embodiments, step (f) is not conducted in a location other than steps (a) - (e).

[149] In some embodiments, the rheology modifier derived from biomass can be characterized by a particle size (for example, fiber or fibril length or effective length) from about 1 micron to about 100 microns, such as about 1 micron to about 50 microns. In certain embodiments, the majority (such as about 50%, 60%, 70%, 80%, 90% or 95%) of the particles are in the 10-15 micron size range. The rheology modifier derived from biomass can include particles smaller than 5 microns, such as 4, 3, 2, 1 micron (s) or less (i.e., nanoparticles). The width of the particles can be less than 1 micron. Particles larger than 100 microns, such as 150, 200, 250, 300, 400, 500 microns or more, may be present.

[150] In some embodiments, the biomass-derived rheology modifier may be characterized by a particle size (e.g., effective length or length) of less than about 10 microns, such as about 9, 8, 7, 6, 5, 4, 3, 2, 1 micron (s) or less. In certain embodiments, the nanocellulose particle length is about 900, 800, 700, 600, 500, 400, 300, 200, 100 nm or less. In these or other embodiments (including lengths greater than 1 micron), the diameter of the nanocellulose particles can be from about 3 nm to about 1000 nm, such as from about 5 nm to about 500 nm, or about 10 nm to about 200 nm or about

5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400 or 450 nm. In some of these embodiments, nanoparticles (or a portion of them) can be characterized as nanocrystals.

[151] Rheology-modifying compounds are mainly cellulose-based polymers, with some microcrystalline form like nanocellulose, including part of the initial biomass lignin in the structure. In some embodiments, the properties of the compound are predominantly hydrophilic, allowing strong stability of the water-based drilling fluid and water-based fracturing fluids. In some embodiments with suitable lignin content and high intensity refining, the compounds are hydrophobic, moderately hydrophobic, or a combination of hydrophilic and hydrophobic.

[152] The present disclosure provides a water-based hydraulic fracturing fluid formulation or additive comprising a rheology modifier derived from biomass produced according to the processes described in the present invention.

[153] The present disclosure provides an oil-based hydraulic fracturing fluid formulation or additive comprising a biomass-derived rheology modifier produced according to the processes described in the present invention.

[154] The present disclosure provides a water-based drilling fluid formulation or additive comprising a rheology modifier derived from biomass produced according to the processes described in the present invention.

[155] The present disclosure provides an oil-based drilling fluid formulation or additive comprising a biomass-derived rheology modifier produced according to the processes described in the present invention.

[156] The process may additionally include the removal of one or more fermentation inhibitor (s) (such as acetic or furfural acid) by removal. This removal can be carried out by treating the hydrolyzed cellulose stream before fermentation. Alternatively, or in addition, removal can be carried out in a stream after digestion, such as in the insufflation line.

[157] The process in some embodiments further comprises a stage of fermentation of the fermentable sugars, contained in the liquid phase derived from the initial digestion, in a diluted fermentation product. The process may further comprise concentration and purification of the fermentation product. The fermentation product can be selected from ethanol, n-butanol, 1,4-butanediol, succinic acid, lactic acid or combinations thereof, for example. In addition, a solid stream containing lignin can be removed, either before fermentation or downstream of fermentation.

[158] One step may include hydrolyzate conditioning to remove some or most of the volatile acids and other fermentation inhibitors. Evaporation can include flash evaporation or removal to remove sulfur dioxide, if present, before removing volatile acids.

The evaporation step is preferably carried out below the acetic acid dissociation pH of 4.8, and more preferably a selected pH of about 1 to about 2.5.

In some embodiments, additional evaporation steps can be employed. These additional evaporation steps can be carried out under different conditions (for example, temperature, pressure and pH) in relation to the first evaporation step.

[159] In some embodiments, some or all of the evaporated organic acids can be recycled, such as steam or condensate, to the first stage (cooking stage) to assist in the removal of hemicelluloses or minerals from biomass. This recycling of organic acids, such as acetic acid, can be optimized along with process conditions that can vary depending on the amount recycled, to improve cooking efficiency.

[160] One step may include recovering fermentable sugars, which can be stored, transported or processed. One step may include fermenting the fermentable sugars in a co-product (the primary product being a rheology modifier).

[161] One step may include the preparation of solid waste (containing lignin) for combustion. This step can include refining, grinding, fluidizing, compacting and / or pelleting the extracted and dried biomass. Solid residues can be fed to a refiller in the form of fine powder, loose fiber, granules, briquettes, extruded or any other suitable form. Using known equipment, solid waste can be extruded through a pressurized chamber to form uniformly sized granules or briquettes.

[162] After fermentation, residual solids (such as distillation background product) can be recovered, either burned in solid form or in slurry, or recycled to be combined in the biomass granules.

The use of residual fermentation solids may additionally require removal of minerals. Generally, any remnants of solids can be used for burning, after concentration of the distillation bottom products.

[163] Alternatively, or in addition, the process may include recovering residual solids as a fermentation by-product in solid, liquid or slurry form. The fermentation by-product can be used as a fertilizer or fertilizer component, as it will normally be rich in potassium, nitrogen and / or phosphorus.

[164] The process can be continuous, semi-continuous or batch. When continuous or semi-continuous, the removal column can be operated in countercurrent, concurrent or a combination thereof.

[165] The process may further comprise bleaching cellulose-rich solids prior to a refining step and / or as part of refining. Alternatively, or in addition, the process may further comprise bleaching of the refined material, the gelled material or the homogenized material. Any known targeting technology or sequence can be employed, including enzymatic targeting.

[166] Rheology modifiers, as provided in the present invention, can be incorporated into drilling fluids, drilling fluid additives, fracturing fluids and fracturing fluid additives. Rheology modifiers can be present in a wide variety of concentrations, such as from about 0.001 wt% to about 10 wt% or more, for example, about 0.01 wt%, 0.05 wt% weight, 0.1% by weight, 0.5% by weight, 1% by weight or 2% by weight.

[167] The invention, in some variations, is related to a group of cellulosic compounds that can be used in different applications. One of the applications is to use them as intensifiers for drilling fluid products. Rheology modifiers can serve as one or more functions in drilling fluids. For example, the rheology modifier can serve as a gelling agent to increase viscosity, or a viscosifier in general. The rheology modifier can serve as a friction reducer. In addition, rheology modifiers can be a perforation polymer, displacing other polymers or adding to them.

[168] Drilling fluids are fluids used in drilling in the natural gas and oil industries, as well as in other industries that use large drilling equipment. Drilling fluids are used to lubricate, provide hydrostatic pressure, keep the drill cool, and keep the hole as clean as possible from drilling cuts. Rheology modifiers provided in the present invention are suitable as additives for such drilling fluids.

[169] In some embodiments, enzymes can be used as a "reducer" with compositions to decrease rheology modifiers after a period of time or under certain conditions (for example, temperature or pH).

[170] In some embodiments, lignosulfonates are incorporated to enhance lubrication in drilling applications. In addition, the ability of lignosulfonates to reduce the viscosity of mineral pastes can be beneficial in oil drilling muds.

[171] In some embodiments, native lignin or unsulfonated lignin, or derivatives of unsulfonated lignin, are incorporated into the compositions.

[172] The embodiments provide a drilling fluid additive comprising rheology modifiers.

[173] Some embodiments provide a drilling fluid additive comprising rheology modifiers, wherein the additive additionally comprises lignosulfonates.

[174] Some embodiments provide a drilling fluid additive comprising rheology modifiers, wherein the additive further comprises unsulfonated lignin.

[175] Some embodiments provide a drilling fluid additive comprising rheology modifiers, wherein the additive further comprises a crosslinking agent.

[176] Some embodiments provide a drilling fluid additive comprising crosslinked rheology modifiers and lignosulfonates.

[177] Some embodiments provide drilling fluids comprising drilling fluid additives, as disclosed. The drilling fluid can be a water-based drilling fluid, an oil-based drilling fluid, or a water-based / oil-based hybrid drilling fluid.

[178] In various embodiments, the drilling fluid further comprises one or more of a weighting material derived from biomass, a filtering agent derived from biomass, a rheological control agent derived from biomass, a pH control derived from biomass, a lost circulation material derived from biomass, a surface activity modifier derived from biomass, a lubricant derived from biomass, and a flocculant derived from biomass and / or a stabilizer derived from biomass.

[179] In some variations, the invention provides a method of using a drilling fluid additive, the method comprising combining a drilling fluid additive as disclosed in a base fluid to generate a drilling fluid. In some variations, the invention provides a method that comprises the introduction of a drilling fluid additive disclosed directly or indirectly into a geological formation.

[180] In some variations, a drilling method includes introducing a drilling fluid additive directly or indirectly into a geological formation, where the drilling fluid additive includes an enzyme for effective degelification. In related variations, a drilling method includes introducing a drilling fluid additive directly or indirectly into a geological formation and, subsequently, introducing an enzyme for degelification under effective conditions.

[181] Some variations provide a process for producing a drilling fluid additive, the process comprising refining biomass under effective pretreatment conditions and refining conditions to generate a drilling fluid additive, as disclosed. In some embodiments, effective pre-treatment conditions include the generation of lignosulfonic acids. Optionally, at least a portion of the lignosulfonic acids is not removed and remains present in the drilling fluid additive. In certain embodiments, the drilling fluid additive comprises a liquid slurry derived from the process. For example, the slurry may contain rheological modifiers derived from biomass, as well as water and pretreatment chemicals (such as acids, solvents, etc.).

[182] Another application of these compositions is to use them as intensifiers for hydraulic fracturing fluid products. The improvement in this purpose is mainly due to the impact on friction reduction, improved pumping of lift agents at a higher rate, reduced pressure and predictable viscosity at high temperatures. Additionally, these products are completely biodegradable; they are produced from biomass, and are less susceptible to bio-encrustation, as could be other products, such as those derived from galactomannan.

[183] Rheology modifiers can be cross-linked for robust gelation in fracturing fluids. In some embodiments, crosslinking of rheology modifiers results in a stronger gel with more hydration.

[184] Ashes derived from biomass (from the biomass structure) or sand (from washing) can be used as a supporting agent to displace the mined silica.

[185] The present invention, in other variations, provides fracturing fluid additives.

[186] Some embodiments provide a fracturing fluid additive comprising rheology modifiers.

[187] Some embodiments provide a fracturing fluid additive comprising rheology modifiers, wherein the additive additionally comprises lignosulfonates.

[188] Some embodiments provide a fracturing fluid additive comprising rheology modifiers, wherein the additive additionally comprises unsulfonated lignin.

[189] Some embodiments provide a fracturing fluid additive comprising rheology modifiers, wherein the additive additionally comprises a crosslinking agent.

[190] Some embodiments provide a fracturing fluid additive comprising crosslinked rheology modifiers and lignosulfonates.

[191] Some embodiments provide a fracturing fluid comprising the fracturing fluid additive, as disclosed. The fracturing fluid can be a water-based fracturing fluid, an oil-based fracturing fluid or a water-based / oil-based hybrid fracturing fluid.

[192] The fracturing fluid may additionally include, in addition to a disclosed fracturing fluid additive, one or more of a biomass-derived acid (such as acetic acid, formic acid, levulinic acid and / or lignosulfonic acid), an inhibitor corrosion agent derived from biomass (such as lignin or a derivative of lignin), a friction reducer derived from biomass (such as lignosulfonate or a derivative of lignosulfonate), a clay control agent derived from biomass, a crosslinking agent derived from biomass, a biomass derived scale inhibitor, a biomass derived reducer, a biomass derived iron control agent, a biomass derived biocide (eg biomass hydrolyzate) and / or a source derived from recycled water biorefinery or recovered. Normally, the fracturing fluid carries, includes or must be combined with a support agent, which can be a support agent derived from biomass (such as ash contained in the structure of the biomass and / or sand, ash or dirt collected with biomass) .

[193] Some variations of the invention provide a method of using a fracturing fluid additive, the method comprising combining a fracturing fluid additive disclosed in a base fluid to generate a fracturing fluid. Some methods include introducing a fracturing fluid additive directly or indirectly into a geological formation.

[194] In some variations, a process for producing a fracturing fluid additive comprises refining the biomass under effective pretreatment conditions and refining conditions to generate a fracturing fluid additive, as disclosed. In some embodiments, pre-treatment conditions include the generation of lignosulfonic acids, which optionally are not completely removed and are present in the fracturing fluid additive. In some embodiments, the fracturing fluid additive comprises a liquid slurry derived from the process. For example, the slurry may contain rheological modifiers derived from biomass, as well as water and pretreatment chemicals (for example, solvents, acids, bases and so on).

[195] The rheology modifiers of some embodiments are characterized by an average degree of cellulose polymerization from about 100 to about 2000, such as from about 400 to about 1200 or from about 500 to about 800 In certain embodiments, rheology modifiers are free of enzymes.

[196] The present disclosure is in no way limited to rheology modifiers. The material produced by the multiple refining steps (after pre-treatment of the biomass), as disclosed, can be used in a wide variety of applications. For example, the rheology modifier can be incorporated into the product selected from the group consisting of a structural object, a foam, an airgel, a polymer compound, a carbon compound, a film, a coating, a coating precursor, a chain or tension conveyor, a filter, a membrane, a catalyst, a catalyst substrate, a coating additive, a paint additive, an adhesive additive, a cement additive, a paper coating, a thickening agent, a rheological modifier , an additive for a drilling fluid and combinations or derivatives thereof.

[197] Some embodiments provide products with applications for sensors, catalysts, antimicrobial materials, current energy transport and storage capabilities. Cellulose crystals have the ability to assist in the synthesis of metal and semiconductor chains.

[198] Some embodiments provide composites containing refined cellulose and a material containing carbon, such as (but not limited to) lignin, graphite, graphene or carbon airgel.

[199] Cellulose crystals can be coupled with the stabilizing properties of surfactants and exploited for the manufacture of architectures of various semiconductor materials.

[200] The reactive surface of the -OH side groups in refined cellulose facilitates the grafting of chemical species to obtain different surface properties. The surface functionalization allows the adaptation of the particle surface chemistry to facilitate self-assembly,

controlled dispersion over a wide range of matrix polymers, and control of particle-particle and matrix-particle bond strength. Composites can be transparent, have greater tensile strength than cast iron, and have a very low coefficient of thermal expansion.

Potential applications include, but are not limited to, barrier films, antimicrobial films, transparent films, flexible displays, reinforcement fillers for polymers, biomedical implants, dispensers for pharmaceuticals, drugs, fibers and textiles, molds for electronic components, membranes for separation, batteries, supercapacitors, electroactive polymers and many others.

[201] Other applications suitable for the present invention include reinforced polymers, adhesives, fibers and high-strength spun textiles, advanced composite materials, barrier films and other properties, additives for coatings, paints, varnishes, adhesives, optical devices switchable products, pharmaceuticals and drug dispensing systems, bone replacement and teeth repair, improved paper, packaging and construction products, food and cosmetic additives, catalysts and hydrogels.

[202] Aerospace and transport composites can benefit from these rheology modifiers. Automotive applications include cellulose composites with polypropylene, polyamide (for example, nylon) or polyesters (for example, PBT).

[203] Rheology modifiers provided in the present invention may be suitable as additives to enhance the strength of renewable and biodegradable composites. Cellulosic fibrillar structures can function as a binder between two organic phases to improve fracture toughness and prevent the formation of cracks for application in packaging, construction materials, utensils, and renewable fibers.

[204] The rheology modifiers provided in the present invention can be additives and substrates that enhance the stable dimensional and transparent resistance for application in flexible displays, flexible circuits, printable electronic components and flexible solar panels. Cellulose is incorporated into the substrate - the leaves are formed by vacuum filtration, dried under pressure and calendered, for example. In a plate structure, cellulose acts as a glue between the load aggregates. The calendered sheets formed are smooth and flexible.

[205] Rheology modifiers provided in the present invention may be suitable for composite and cement additives, allowing for the reduction of cracks and greater toughness and strength. Cellular and foamed cellulose-concrete hybrid materials allow for lightweight structures with reduced cracking and increased strength.

[206] The intensification of the resistance with cellulose increases the bonding area and the bonding strength for application on high-strength, high-volume, high-load paper and board, with enhanced moisture and oxygen barrier properties. The pulp and paper pulp industry, in particular, can benefit from the rheology modifiers provided in the present invention.

[207] Porous cellulose can be used for cellular bioplastics, insulation and plastics and bioactive membranes and filters. Highly porous cellulose materials are generally of high interest in the manufacture of filtration media, as well as for biomedical applications, for example, in dialysis membranes.

[208] Rheology modifiers provided in the present invention may be suitable as additives to improve the durability of the paint, protecting paints and varnishes from friction caused by UV radiation.

[209] Rheology modifiers provided in the present invention are suitable as thickening agents in food and cosmetic products. Rheology modifiers can be used as a thixotropic, biodegradable and dimensionally stable thickener (stable against temperature and addition of salt). The rheology modifying materials provided in the present invention may be suitable as a Pickering stabilizer for emulsions and stabilized particle foam.

[210] The large surface area of these rheology modifiers in combination with their biodegradability makes them attractive materials for highly porous and mechanically stable airgel.

[211] In some embodiments, the process comprises forming a structural object that includes nanolignocellulose material, or a derivative thereof.

[212] In some embodiments, the process comprises forming a foam or airgel that includes the nanolignocellulose material, or a derivative thereof.

[213] In some embodiments, the process comprises combining the nanolignocellulose material, or a derivative thereof, with one or more other materials to form a composite. For example, the other material may include a polymer selected from polyolefins, polyesters, polyurethanes, polyamides or combinations thereof. Alternatively, or in addition, the other material may include carbon in a number of ways.

[214] In some embodiments, the process comprises forming a film comprising the nanolignocellulose material, or a derivative thereof. The film is optically transparent and flexible, in certain embodiments.

[215] In some embodiments, the process comprises forming a coating or coating precursor comprising the nanolignocellulose material, or a derivative thereof. In some embodiments, the product containing nanolignocellulose is a paper coating.

[216] In some embodiments, the product containing nanolignocellulose is configured as a catalyst, catalyst substrate or cocatalyst. In some embodiments, the product containing nanolignocellulose is electrochemically configured to carry or store an electric current or voltage.

[217] In some embodiments, the product containing nanolignocellulose is incorporated into a filter, membrane or other separation device.

[218] In some embodiments, the product containing nanolignocellulose is incorporated as an additive in a coating, paint or adhesive. In some embodiments, the product containing nanolignocellulose is incorporated as a cement additive.

[219] In some embodiments, the product containing nanolignocellulose is incorporated as a thickening agent or rheological modifier. For example, the product containing nanolignocellulose may be an additive in a drilling fluid, such as (but not limited to) an oil recovery fluid and / or a gas recovery fluid or a fracturing fluid.

[220] A product containing nanolignocellulose may include any of the disclosed nanolignocellulose compositions. Many products containing nanolignocellulose are possible. For example, a product containing nanolignocellulose can be selected from the group consisting of a structural object, a foam, an airgel, a polymer composite, a carbon composite, a film, a coating, a coating precursor, a chain conveyor or voltage, a filter, a membrane, a catalyst, a catalyst substrate, a coating additive, an ink additive, an adhesive additive, a cement additive, a paper coating, a thickening agent, a rheological modifier, an additive for a drilling fluid and combinations or derivatives thereof.

[221] Certain products containing nanolignocellulose provide high transparency, good mechanical resistance and / or barrier properties to intensified gases (for example, O2 or CO2), for example. Certain products containing nanolignocellulose containing hydrophobic nanocellulose materials provided in the present invention may be useful as anti-wetting and anti-freeze coatings, for example.

[222] Some embodiments provide products containing nanolignocellulose with applications for sensors, catalysts, antimicrobial materials, current capacities for transport and power storage.

[223] Some embodiments provide composites containing nanolignocellulose and a material containing carbon, such as (but not limited to) lignin, carbon black, graphite, graphene or carbon airgel.

[224] The reactive surface of the -OH side groups in nanolignocellulose facilitates the grafting of chemical species to obtain different surface properties. The surface functionalization allows the adaptation of the particle surface chemistry to facilitate self-assembly, controlled dispersion within a wide range of matrix polymers and control of the particle-particle and matrix-particle bond strength. Composites can be transparent, have greater tensile strength than cast iron, and have a very low coefficient of thermal expansion.

Potential applications include, but are not limited to, barrier films, antimicrobial films, transparent films, flexible displays, reinforcement fillers for polymers, biomedical implants, dispensers for pharmaceuticals, drugs, fibers and textiles, molds for electronic components, membranes separators, batteries, supercapacitors, electroactive polymers and many others.

[225] Other applications of nanolignocellulose suitable for the present invention include reinforced polymers, fibers and high-strength spun textiles, advanced composite materials, barrier films and other properties, additives for coatings, paints, varnishes and adhesives, optical devices switchable products, pharmaceuticals and drug dispensing systems, bone replacement and teeth repair, improved paper, packaging and construction products, food and cosmetic additives, catalysts and hydrogels.

[226] Aerospace and automotive applications include nanolignocellulose composites with polypropylene, polyamide (for example, nylon) or polyesters (for example, PBT).

[227] The nanolignocellulose materials provided in the present invention are suitable as additives to enhance the strength of renewable and biodegradable composites. Cellulosic nanofibrillary structures can function as a binder between two organic phases for improved fracture toughness and prevent the formation of cracks for use in packaging, building materials, appliances, and renewable fibers.

[228] The nanolignocellulose materials provided in the present invention are suitable as additives and substrates that enhance the transparent and dimensional strength,

for application on flexible displays, flexible circuits, printable electronic components, and flexible solar panels. Nanolignocellulose is incorporated into the substrate - the leaves are formed by vacuum filtration, dried under pressure and calendered, for example. In a sheet structure, nanocellulose acts as a glue between the load aggregates. The calendered sheets formed are smooth and flexible.

[229] The nanolignocellulose materials provided in the present invention are suitable for composite and cement additives, allowing reduction of cracks and increased toughness and strength. Cellular hybrid materials of sparkling nanolignocellulose-concrete, with reduced cracks and increased strength.

[230] The intensification of the resistance with nanolignocellulose increases the bonding area and the bonding strength for application on high-strength, high-volume, high-load paper and cardboard, with enhanced barrier properties to moisture and oxygen. The paper and cellulose industry, in particular, can benefit from the nanolignocellulose materials provided in the present invention.

[231] Nanofibrillated cellulose nanopaper has a higher density and mechanical tensile properties than conventional paper. It can also be optically transparent and flexible, with low thermal expansion and excellent oxygen barrier characteristics. The functionality of the nanopaper can be further expanded with the incorporation of other entities, such as carbon nanotubes, nano clay or a conductive polymer coating.

[232] Rojo et al., “Comprehensive elucidation of the effect of residual lignin on the physical, barrier, mechanical and surface properties of nanocellulose films,” Green Chem., 2015, 17, 1853-1866, is hereby incorporated by reference in present invention.

[233] Porous nanolignocellulose can be used for cellular bioplastics, insulation and plastics and bioactive membranes and filters. Highly porous materials are generally of high interest in the manufacture of filtration media, as well as for biomedical applications, for example, in dialysis membranes.

[234] The nanolignocellulose materials provided in the present invention are suitable as coating materials with an oxygen barrier and affinity for wood fibers for application in food packaging and printing papers.

[235] The nanolignocellulose materials provided in the present invention are suitable as additives to improve the durability of the paint, protecting paints and varnishes from friction caused by UV radiation.

[236] The nanolignocellulose materials provided in the present invention are suitable as thickening agents in food and cosmetic products. Nanolignocellulose can be used as a thixotropic, biodegradable and dimensionally stable thickener (stable against temperature and the addition of salt). The nanolignocellulose materials provided in the present invention are suitable as a Pickering stabilizer for emulsions and stabilized particle foam.

[237] The large surface area of these nanolignocellulose materials in combination with their biodegradability makes them attractive materials for highly porous and mechanically stable aerogels.

[238] The present invention also provides systems configured for the execution of the disclosed processes and compositions produced from them. Any current generated by the disclosed processes can be partially or completely recovered, purified or further treated and / or traded or sold.

[239] In this detailed description, reference has been made to various embodiments of the invention and to non-limiting examples related to how the invention can be understood and practiced. Other embodiments that do not provide all the features and advantages presented in the present invention can be used, without departing from the spirit and scope of the present invention. This invention incorporates routine experimentation and optimization of the methods and systems described in the present invention. Such modifications and variations are considered to be within the scope of the invention defined by the claims.

[240] All publications, patents and patent applications cited in this specification are incorporated herein by reference in their entirety, as if each publication, patent or patent application was specifically and individually presented in the present invention.

[241] Where the methods and steps described (a) s above indicate certain events that occur in a certain order, those skilled in the art will recognize that the order of certain steps can be modified and that these changes are in accordance with the variations of the invention . In addition, some of the steps can be performed simultaneously in a parallel process when possible, as well as performed sequentially.

[242] Therefore, insofar as there are variations of the invention, which are in the spirit of the disclosure or equivalent to the inventions found in the attached claims, it is intended that this patent also covers those variations. The present invention is to be limited only by what is claimed.

EXAMPLES Example 1: Nanolignocellulose Produced from Soft Wood.

[243] The softwood shavings (pine) are processed in a pilot steam gun digester at a temperature of 185 ° C and 20 minutes, resulting in a cellulose pulp yield of about 80%. The cellulose pulp is passed through a pilot plant disc refiner to defibrillate the cooked chips at a drainage rate of 100. The cellulose pulp drainage rate provides a measure of the rate at which a diluted pulp suspension of cellulose can be drained (see TAPPI T221 “Pulp Drainage Time”). The cellulose pulp is then passed through a laboratory scale homogenizer three times to an 80-85% fines target, to produce unwashed nanolignocellulose. The percentage of fines (refined material) can be increased with more passes of the homogenizer. The unwashed nanolignocellulose is washed with water three times at 60 ° C for 30 min at about 2, 1 and 1 kg of water per kg of cellulose pulp, to produce washed nanolignocellulose.

[244] FIG. 2 shows an optical micrograph with 40x magnification of the washed nanolignocellulose produced in this example.

[245] Nanolignocellulose in this example is a combination of precipitated lignin particles (with a diameter of about 50 to 300 nanometers), lignocellulose nanofibrils (with lengths of about 500 nanometers, widths of about 10 to 500 nanometers and lengths of tens of microns), and fine lignocellulose (with length <76 microns and width <5 microns).

[246] Washed solids are analyzed for composition. The total carbohydrate is about 66.8% by weight of solids. Glucan is 54% by weight, xylan is 9.2% by weight, galacatane is 1.3% by weight, arabinane is 0.6% by weight and mannan is 1.7% by weight . The concentration of the acetyl groups is 1.9% by weight in the solids. The total lignin is 35.8% by weight, of which 33.3% by weight (in solids) is Klason's lignin and 2.5% by weight (in solids) is acid-soluble lignin.

[247] A liquid phase analysis shows 0.98% by weight of glucose, 7.44% by weight of xylose, 0.42% by weight of galactose, 0.35% by weight of arabinose and 0.79% by weight. mannose weight, all sugars being a percentage of the original total solids (% in wood). Formic acid is 0.07% by weight, acetic acid is 0.28% by weight, HMF is 0.02% by weight, furfural is 0.02% by weight and dissolved lignin is 1, 82% by weight, again being a percentage of the total original solids.

Example 2: Nanolignocellulose produced from hardwood.

[248] Wood chips are processed in a pilot steam gun digester at a temperature of 185 ° C and 15 minutes, resulting in a cellulose pulp yield of around 80%. The cellulose pulp is passed through a pilot plant disc refiner to defibrillate the cooked chips at about drainage rate

100. The cellulose pulp is then passed through a laboratory scale homogenizer three times to an 80-85% fines target, to produce unwashed nanolignocellulose. The percentage of fines (refined material) can be increased with more passes of the homogenizer. The unwashed nanolignocellulose is washed with water three times at 60 ° C for 30 min at about 2, 1 and 1 kg of water per kg of cellulose pulp, to produce washed nanolignocellulose.

[249] FIG. 3 shows an optical micrograph with 40x magnification of the washed nanolignocellulose produced in this example.

[250] The cellulose pulp produced in this example is also passed through the homogenizer 7 times, resulting in 92% fines. This is compared to the bleached softwood Kraft pulp, refined by Masuko, 14 passages, 93% fines per area. FIG. 4 is a graph of the filtration rate of this nanolignocellulose compared to the prior art Kraft cellulose pulp. Filtration is Buchner filtration at 0.8% by weight of total solids, with an initial volume of 450 ml (the total available filtrate is 430 ml based on 17% of total solids in the nanocellulose pad). The filter paper is Whatman 4 (pore size 20-25 µm).

[251] FIG. 4 shows a considerably higher filtration rate for this nanolignocellulose versus bleached Kraft fibrils. In particular, nanolignocellulose has essentially 100% filtration completion in less than 100 minutes. Due to the high lignin content, the water retention value and drainage of nanolignocellulose fibrils is much higher than that of pure cellulose fibrils. This is believed to be a key performance attribute for the use of nanolignocellulose in a paper machine.

Claims (11)

1. Nanolignocellulose composition characterized by the fact that it comprises, on a dry weight basis, free from ash and free from acetyl, from about 35% by weight to about 80% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof, from about 15% by weight to about 45% by weight of lignin, and from about 5% by weight to about 20% by weight of hemicelluloses. 2. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 40% by weight to about 70% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof in a dry weight base, free from ash and free from acetyl. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 45% by weight to about 60% by weight of cellulose nanofibrils, cellulose microfibrils or a combination thereof in a dry weight base, free from ash and free from acetyl. 4. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 20% by weight to about 40% by weight of lignin, on a dry weight basis, free from ash and acetyl free. 5. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 25% by weight to about 35% by weight of lignin, on a dry weight basis, free from ash and acetyl free. 6. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 7% by weight to about 15% by weight of hemicelluloses on a dry, ash-free and free weight basis of acetyl. 7. Nanolignocellulose composition according to claim 1, characterized in that said composition comprises from about 8% by weight to about 14% by weight of hemicelluloses on a dry, ash-free and free weight basis of acetyl. 8. Nanolignocellulose composition according to claim 1, characterized by the fact that said hemicelluloses contain xylan as the main component. 9. Nanolignocellulose composition according to claim 1, characterized by the fact that said hemicelluloses contain mannan as the main component. 10. Nanolignocellulose composition according to claim 1, characterized by the fact that said nanolignocellulose composition is qualified by at least 99% completion of filtration in less than 100 minutes. 11. Cellulose pulp product or paper product characterized by the fact that it contains the composition of nanolignocellulose as defined in claim 1.