Carbonaceous materials having modified physical and chemical properties, and methods for producing and using them.

Abstract

This specification discloses carbonaceous materials exhibiting properties and characteristics useful for their use in the formation of composite materials. In certain embodiments, the carbonaceous material has a carbon content of 85% by weight or more, 150m 2 / g~500m 2 This includes surface area in the range of / g and oil absorption values ​​in the range of 50g / 100g to 100g / 100g. Methods for producing and using carbonaceous materials, including the formation of composite polymer compositions, are also disclosed.

Description

Technical Field

[0001] Cross - reference to related applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 455,522, filed Mar. 29, 2023, and U.S. Provisional Patent Application No. 63 / 525,306, filed Jul. 6, 2023, each of which is hereby incorporated by reference in its entirety.

[0002] This disclosure relates to carbonaceous materials, composite polymer compositions containing carbonaceous materials, rubber - containing products containing carbonaceous materials, compositions containing carbonaceous materials, and methods of manufacturing carbonaceous materials.

Background Art

[0003] Carbon black can typically be produced by the pyrolysis (e.g., incomplete combustion) of hydrocarbons from fuel / synthesis feedstocks. Carbon black is a highly versatile material. The particles of carbon black have a complex structure and can form aggregates and agglomerated particles. However, such particles can have a small diameter (e.g., in the nanometer range), which enables carbon black to absorb and scatter light, giving rise to the "black" color from which its name is derived. Depending on the color and concentration of carbon black, when used as a pigment in inks, paints, and other matrices, it can produce a deep, intense black coloration.

[0004] Carbon black can also function as a reinforcing filler in polymer products such as rubber tires, belts, and hoses. Due to the aspect ratio and particle structure of carbon black, a reinforcing network of particles is formed within the polymer matrix. This results in a more durable material and can also improve the rigidity, dimensional stability, and load - bearing capacity of the polymer matrix.

[0005] Conventional carbon black (including the methods used to produce it) is associated with environmental and health considerations. In some cases, carbon black is produced by the incomplete combustion of fossil fuels such as petroleum products, coal tar, or natural gas. This can contribute to greenhouse gas emissions and resource consumption. Fossil-based carbon black may also contain polycyclic aromatic hydrocarbons (PAHs), which are known to be carcinogenic. Therefore, improved methods are needed to produce and use materials that avoid these drawbacks. [Overview of the project]

[0006] The aspects disclosed in this disclosure are advantageous in that they provide carbonaceous materials produced from biomass feedstock. In some aspects of this disclosure, the carbonaceous materials produced from biomass feedstock contain a carbon content of 85% by weight or more. In some aspects, the carbonaceous materials are 150m 2 / g~500m 2 This further includes surface area in the range of / g, and / or oil absorption values ​​in the range of 50g / 100g to 100g / 100g.

[0007] Certain disclosed embodiments relate to methods for producing carbonaceous materials of the Disclosure. In some embodiments, the method comprises obtaining a carbonophilic material from a biomass feedstock and post-treating the carbonophilic material, the carbonophilic material may include a portion of the unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin compounds, or combinations thereof. In some embodiments, the post-treating of the carbonophilic material provides the carbonaceous material according to the Disclosure by at least partially deoxygenating the carbonophilic material. In independent embodiments, the post-treating of the carbonophilic material does not involve treating the carbonophilic material with an activator.

[0008] The aforementioned purposes, features, and advantages of this disclosure, as well as other purposes, features, and advantages, will become more apparent from the following detailed description, which will proceed with reference to the accompanying drawings. [Brief explanation of the drawing]

[0009] [Figure 1A] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 1B] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 1C] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 1D] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 1E] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 1F] Images A through F are SEM microscope images of carbonophilic materials manufactured from 100% Southern Pine raw materials. [Figure 2A] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2B] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2C]A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2D] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2E] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2F] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2G]A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2H] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 2I] A–I are SEM micrographs of examples of carbonophilic and carbonaceous materials (A–G) and comparative materials (H and I) according to embodiments of the present disclosure. A and C show SEM micrographs of carbonophilic materials produced from a lignin-free raw material (A) containing 100% corn starch and a lignin-containing raw material (C) containing 100% Southern pine wood. B and D–G show SEM micrographs of carbonaceous materials obtained from specific parent materials. H and I show images of comparative materials lacking the structural features shown by the materials of the present disclosure. [Figure 3] Several different properties of carbon black, including surface function, porosity and surface area, primary particle size, aggregated particle size, and aggregated structure, are schematically shown. [Figure 4] This is a schematic diagram illustrating one disclosed example, which includes a system for converting biomass feedstock into carbonophilic materials that can be converted into the carbonaceous materials of this disclosure. [Figure 5]This is a schematic diagram illustrating one disclosed example, which includes a system for converting biomass feedstock into carbonophilic materials containing lignin and / or humicin. [Figure 6] The 1D CP MAS solid-state 13C NMR spectra of examples of post-treated carbonophilic materials, particularly carbonophilic materials obtained from parent materials heat-treated at different temperatures, are shown. [Figure 7] Figure 6 shows the Raman spectra of the carbonaceous material obtained after post-treatment (e.g., heat treatment under an inert gas at different temperatures) using a 785 nm wavelength laser. [Figure 8A] A to C show the Raman BET, STSA, and pore surface area of ​​examples of carbonaceous materials disclosed herein, depending on the temperature. [Figure 8B] A to C show the Raman BET, STSA, and pore surface area of ​​examples of carbonaceous materials disclosed herein, depending on the temperature. [Figure 8C] A to C show the Raman BET, STSA, and pore surface area of ​​examples of carbonaceous materials disclosed herein, depending on the temperature. [Figure 9] The nitrogen physicoadsorption isotherms for examples of carbonaceous materials disclosed herein are shown. Here, black circles represent adsorption and white circles represent desorption, compared to carbonophilic materials and commercially available carbon black, N660. [Figure 10A] Figures A and B show the pore size distribution (A) and cumulative pore volume (QSDFT, slit pore model, adsorption branching, B) obtained from the nitrogen physicoadsorption data in Figure 9. [Figure 10B] Figures A and B show the pore size distribution (A) and cumulative pore volume (QSDFT, slit pore model, adsorption branching, B) obtained from the nitrogen physicoadsorption data in Figure 9. [Figure 11] The 1D quantitative direct polarization (DP) MAS solid-state 13C NMR spectra are shown using a carbonophilic material produced from a lignin-free raw material containing 13C-enriched glucose, with the proposed molecular structures of humins present in the carbonophilic material derived from the lignin-free raw material annotated. [Figure 12]Figure 11 shows the NMR spectrum of a carbonophilic material produced from a lignin-containing raw material containing 13C-enriched lignocellulose biomass, superimposed with the 1D quantitative DP MAS solid 13C NMR spectrum, where each spectrum is normalized and, as a result, each spectrum has a similar overall integral to facilitate comparison. The NMR spectrum is annotated with chemical moieties corresponding to the structures present in the carbonophilic material. [Figure 13] Figure 11 shows the aromatic region of the 2D 13C-13C CP-INADEQUATE solid-state NMR spectrum of a carbonophilic material produced from a lignin-free raw material. This shows the NMR signature of humins in the aromatic region of the 2D NMR spectrum (e.g., 100–165 ppm SQ 13C chemical shift and 210–310 ppm DQ 13C chemical shift). [Figure 14] Figure 12 shows the aromatic region of the 2D 13C-13C CP-INADEQUATE solid-state NMR spectrum of a carbonophilic material produced from a lignin-containing raw material. This shows a characteristic NMR relationship corresponding to lignin. [Figure 15] This document presents an example of MDR rheology for SBR cured packages with varying levels of TBBS accelerators, which further comprises carbonaceous material obtained from a carbonophilic material produced from 100% Southern Pine, subsequently heat-treated at 850°C for 2 hours and then dry-media-milled. [Figure 16] This paper shows tensile stress / strain for two examples of carbonaceous materials obtained from carbonophilic materials that were heat-treated for different periods and milled using a dry medium. [Figure 17A] A and B are SEM micrographs of examples of the addition of carbonaceous material. A shows an SEM micrograph of carbonaceous material obtained from heat-treated carbonophilic material milled in dry medium for 4 minutes. B shows an SEM micrograph of heat-treated carbonophilic material milled in dry medium for 40 minutes. [Figure 17B]A and B are SEM micrographs of examples of the addition of carbonaceous material. A shows an SEM micrograph of carbonaceous material obtained from heat-treated carbonophilic material milled in dry medium for 4 minutes. B shows an SEM micrograph of heat-treated carbonophilic material milled in dry medium for 40 minutes. [Figure 18] The dynamic modulus data of carbonaceous materials obtained from heat-treated carbonophilic materials subjected to media milling are shown, compared to gum rubber samples and N660 samples. [Figure 19] Examples of tensile stress / strain data based on carbonaceous materials obtained from carbonophilic materials jet-milled using different classifier rotation speeds are shown. For comparison, (i) a sample obtained from N660 carbon black and (ii) a sample obtained from carbonaceous materials exposed to 40 minutes of media milling are also shown. [Figure 20] Examples of tensile stress / strain data are shown, based on carbonaceous materials obtained from jet-milled carbonophilic materials under different conditions and extracted from the cyclone or baghouse collector of the jet-milling apparatus. For comparison, (i) a sample obtained from N660 carbon black and (ii) a sample obtained from carbonaceous materials obtained from carbonophilic materials exposed to 40 minutes of media milling are also shown. [Figure 21] Tensile stress / strain data for examples of carbonaceous materials based on Baghouse carbonaceous material blended with N660 carbon black at packing concentrations of 5%, 10%, 20%, 30%, and 40% are shown. Here, the average of the data derived from N660 carbon black is shown for comparison. [Figure 22] Additional example tensile stress / strain data based on cyclone carbonaceous materials derived from carbonophilic materials obtained from CS / HW blends are shown. Here, the carbonaceous materials are blended with N660 carbon black at packing concentrations of 5%, 10%, and 20%, and the average of the data derived from N660 carbon black is shown for comparison. [Figure 23]This section compares tensile stress / strain data for examples of polymer materials, including different types of fillers: (i) N660 carbon black, (ii) carbonaceous material obtained by post-treating a carbonophilic material derived from 100% wood raw materials (labeled "100% SP"), (iii) carbonaceous material obtained by post-treating a carbonophilic material derived from a CS / wood blend (labeled "65 / 35 CS / HW"), and (iv) carbonaceous material obtained by post-treating a carbonophilic material derived from 100% corn starch (labeled "100% CS"). [Figure 24] This section compares tensile stress / strain data for examples of polymer materials containing carbonaceous material, namely, carbonaceous material obtained by post-treating carbonophilic materials derived from different types of fillers, namely (i) N660 carbon black, (ii) N990 carbon black, and (ii) corn starch, in amounts of 5%, 10%, 20%, and 100%. [Figure 25] This is a graph of tanδ measured for various blends of N660 with different levels of jet-milled carbonaceous material. [Figure 26] This graph shows the tensile storage modulus measured for various blends of jet-milled carbonaceous material with different levels of N660. [Figure 27] This graph shows the tensile loss modulus measured for various blends of N660 with different levels of jet-milled carbonaceous material. [Modes for carrying out the invention]

[0010] I. Abbreviations 1D: One dimension. 2D: Two-dimensional. AFEX: Ammonia fiber explosion. atm: 1 atmosphere. avg: average. barg: gauge pressure (bar). BH: Bug House. BR: Bonding rubber. C6: A molecule containing six carbon atoms. CP-INADEQUATE: Cross-polarization-two-dimensional nuclear magnetic resonance. CS: Cornstarch. CY: Cyclone. D50 value: In particle size distribution, the D50 value represents the particle size where 50% of the cumulative mass of particles is smaller and 50% is larger. D90 value: In particle size distribution, the D90 value represents the particle size where 90% of the cumulative mass of particles is smaller and 10% is larger. DOE: Experimental plan. DP: Direct polarization. HW: Hardwood. MAS: Magic Corner Rotation. nm: nanometer. OAN: Oil Absorption Rate (also called "oil absorption value"). OCC: Corrugated cardboard waste paper / Cardboard waste paper. ONP: Newspaper waste paper. P: Reaction pressure. Pa: Pascal pressure. PAH: Polycyclic aromatic hydrocarbon. ppm: parts per million. psi: pounds per square inch. SA: Surface area. SBR: Styrene-butadiene rubber. SEM: Scanning Electron Microscope SP: Southern Pine. ssNMR: Solid state nuclear magnetic resonance. TBBS: N-tert-butyl-benzothiazole sulfonamide. UV: Ultraviolet light. Weight %: Percentage by weight.

[0011] II. Overview of Terms, Scope, and Definitions Both the general description above and the detailed description below are illustrative and explanatory only and are not intended to limit the scope of this disclosure.

[0012] Where used herein, the singular form includes the plural form unless otherwise specified. For example, where used herein, the singular forms "a," "an," and "the" also include the plural form unless otherwise indicated by the context. Similarly, any singular term used herein also means the plural form, and vice versa, unless otherwise indicated by the context.

[0013] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this disclosure pertains. Similar or equivalent methods and materials may be used in the implementation or testing of this disclosure, but suitable methods and materials are described below. Materials, methods, and examples are illustrative and not intended to be limiting unless otherwise indicated. Other features of this disclosure are evident from the following detailed description and claims.

[0014] Numerical range disclosures should be understood to refer to each individual point within the range, including the endpoint, unless otherwise stated. Unless otherwise indicated, all numbers representing properties such as component amounts, molecular weights, percentages, etc., as used herein or in the claims, are understood to be modified by the term "approximately." Thus, unless otherwise implicitly or explicitly indicated, or unless the context is better understood and more clearly interpreted by those skilled in the art (in the interest of this disclosure), non-numerical properties such as amorphous, continuous, crystalline, and homogeneous are understood to be modified by the term "substantially," meaning to a considerable degree or extent. Thus, unless otherwise implicitly or explicitly indicated, the numerical parameters and / or non-numerical properties described are approximations and may depend on the desired properties to be sought, the detection limits under standard test conditions / methods, the limits of the processing method, and / or the nature of the parameters or properties. To directly and explicitly distinguish the examples from the prior art discussed, the disclosed numbers are not approximations unless the word "approximately" is explicitly stated.

[0015] As used herein, the term “or any combination thereof” refers to all permutations and combinations of the listed items preceding it. For example, “A, B, C, or any combination thereof” is intended to include at least A, B, C, AB, AC, BC, or ABC, and also BA, CA, CB, ACB, CBA, BCA, BAC, or CAB, where the order is important in the particular context. Continuing this example, combinations that explicitly include repetitions of one or more items or terms are explicitly included, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, etc.

[0016] The term "activator" refers to a high surface area (e.g., 500m²). 2 This refers to a reactive chemical agent used to form an impregnating material, such as an impregnating carbon material having a surface area greater than / g. In aspects of this disclosure, an activator is a chemical substance that is actively added to a carbonophilic material to impregnate the material and from which activated carbon is formed. Activators may include bases, acids, metal halides, ureas, or combinations thereof that are actively added to promote the impregnation of the carbonophilic material. Aspects of the products and methods disclosed herein do not involve the use of an activator. None of the acids, bases, metal halides, and / or ureas that may be disclosed for use in the preparation of carbonophilic materials according to this disclosure are activators and are not added to promote impregnation for the formation of activated carbon.

[0017] The term “biomass feedstock” generally refers to any plant or plant-derived material consisting of relatively high-oxygen organic compounds, such as carbohydrates, that can be used as a starting material for producing the carbonaceous materials disclosed herein. In some aspects of this disclosure, the biomass feedstock includes lignin-free materials, which are described in more detail below. In some more specific aspects, the biomass feedstock includes plant-based lignin-free materials. In other aspects of this disclosure, the biomass feedstock includes lignin-containing materials, which are described in more detail below.

[0018] The term "carbonaceous material" generally refers to a material that contains carbon, is obtained from a carbonophilic material through post-treatment, and has a lower oxygen content than the carbonophilic material. In some examples, carbon is the main component (e.g., carbon accounts for more than 80% by weight of the carbonaceous material). In some aspects of this disclosure, the carbonaceous material has a carbon content of 85% by weight or more, 150m 2 / g~500m 2 This includes surface area in the range of / g, and oil absorption values ​​in the range of 50g / 100g to 100g / 100g.

[0019] The term "carbon black" generally refers to carbon materials produced by the incomplete combustion of coal tar or petroleum products, and does not include the carbonaceous materials as defined in this disclosure.

[0020] The term "carbon content" generally refers to the amount of carbon in a substance. In the examples disclosed herein, the carbon content can be determined by elemental analysis in accordance with DIN 51732.

[0021] The term "cellulose" generally refers to naturally occurring polysaccharides that have approximately 70 to 10,000 or more β(1→4) linked D-glucose units in a linear chain. Cellulose has the general formula (C6H 10 O5) n It has. [ka] Cellulose is a component of plant cell walls. Approximately one-third of plants are composed of cellulose. Wood contains about 50% cellulose by weight. Cellulose polymers can be characterized by their degree of polymerization, which is the number of monomer units, i.e., glucose units. Cellulose polymers can contain hundreds to thousands of glucose units. For example, the degree of polymerization can range from about 1000 for wood pulp to about 3500 for cotton fibers. Cellulose can be broken down into glucose by hydrolysis or by the enzyme cellulase.

[0022] The term "composite polymer composition" generally refers to a solid composed of two or more constituent materials having different physical and / or chemical properties, which, when combined, produce a material in which each substance retains its identity and the whole exhibits the desired properties. "Retaining its identity" means that the individual materials remain separate and distinct within the composite structure. A composite is not a solid solution or simple physical mixture of its constituent materials. In other words, each particle in the composite contains regions or domains of two or more constituent materials.

[0023] The term "curing" generally refers to the chemical process that results in the formation of polymer chains. The curing process may involve linking monomeric units, dimeric units, oligomeric units, or combinations thereof together. Additionally, the curing process may include crosslinking between polymer chains or between segments of polymer chains.

[0024] The term "deoxygenation" generally refers to a chemical process that results in the removal of oxygen atoms or molecules from the composition of a substance.

[0025] The term "derivative" generally refers to a compound derived from a similar compound, or a compound that could be expected to arise from another compound if, for example, one atom were replaced by another atom or group of atoms.

[0026] The term "dispersion" generally refers to a system in which particles are dispersed within a continuous phase of different compositions. A solid dispersion is a system in which at least one solid component is dispersed within another solid component. A molecular dispersion is a system in which at least one component is uniformly or substantially uniformly dispersed at the molecular level throughout another component.

[0027] The term "elastomer" generally refers to polymer materials that can recover their original shape after being stretched. Examples of elastomers include, but are not limited to, natural rubber (e.g., gum rubber), synthetic rubber (such as neoprene, isoprene rubber, silicone rubber, and butyl rubber), and thermoplastic elastomers (TPEs).

[0028] The term “filler” generally refers to a substance added to a polymer to modify its properties. In some aspects of this disclosure, the filler includes particulate materials dispersed in a continuous phase of different compositions. In some more specific aspects of this disclosure, the filler includes carbonaceous materials, carbon black, or a combination thereof.

[0029] The term "furan" generally refers to heterocyclic organic compounds that contain a five-membered aromatic ring with four carbon atoms and one oxygen atom.

[0030] The term "solidification" generally refers to the formation of a solid material by cooling it. An example of solidification is the solidification of a thermoplastic polymer by cooling it below its melting point or glass transition temperature.

[0031] The term “heat treatment” generally refers to exposing a material to a temperature higher than its ambient temperature in order to alter its physical and / or chemical properties. In some aspects of this disclosure, heat treatment includes heating a carbonaceous material to 300°C or higher, for example, 300°C to 1000°C or higher.

[0032] The term "humin" generally refers to polymeric materials that are insoluble in water and contain high molecular weight furan derivatives. Humins are typically dark-colored solids formed through a series of complex chemical reactions, including ring-opening, dehydration, and condensation, and can be produced by the decomposition of carbohydrates and other organic compounds present in biomass.

[0033] The term "lignin" generally refers to a complex organic polymer that is a major component of plant cell walls. Lignin provides structural support to plants and helps transport water from the roots to the leaves. Lignin consists of heterogeneous and irregular polymer networks of aromatic alcohols known as monolignols, such as coniferyl alcohol, synapyl alcohol, and p-coumaryl alcohol.

[0034] The term "lignin-containing material" generally refers to materials that contain lignin. Examples of lignin-containing materials include wood, grass, and paper products.

[0035] The term "lignin-free material" generally refers to a material that is substantially free of lignin. Examples of lignin-free materials include plant-derived carbohydrates, such as glucose and cellulose.

[0036] The term "macromolecule" generally refers to polymers that have a relatively large molecular weight or structure compared to their monomer units.

[0037] The term "matrix" generally refers to a polymer material in which filler materials are mixed or dispersed.

[0038] The term "milling" generally refers to a physical process of reducing the size of a solid. Milling can include crushing, shredding, or cutting a solid to produce smaller fragments or particles. Examples of milling processes include jet milling, ball milling, media milling, grinding, classifier milling, or a combination of these.

[0039] The term "part" generally refers to a fragment of a molecule or a portion of a complex.

[0040] The term "oil absorption value" generally refers to a measure of a material's ability to absorb oil or other nonpolar liquids. The oil absorption value can be determined according to ASTM D2414-15 "Standard test method for carbon black - Oil absorption amount (OAN)".

[0041] The term "carbonophilic material" generally refers to a carbonaceous material produced from a process in which biomass feedstock is exposed to acid, but prior to any post-treatment step according to the method described herein.

[0042] The term "particulate material" generally refers to a material containing one or more discrete masses. The term "particle" is generally understood to mean a very small or negligible mass of material.

[0043] The term "polycyclic aromatic hydrocarbon" or "PAH" generally refers to hydrocarbon molecules that contain multiple aromatic rings.

[0044] The term "polymer" generally refers to molecules of repeating structural units (e.g., monomers) that are formed through chemical reactions, i.e., polymerization.

[0045] The term “post-processing” generally refers to performing chemical or physical processes on a carbonophilic material after it has been manufactured in order to provide a carbonaceous material according to the embodiments of this disclosure. In independent embodiments, post-processing does not involve exposing a carbonophilic product to an activator.

[0046] The term "prepolymer material" generally refers to a chemical composition and / or compound containing polymerizable reactive functional groups. Examples of prepolymer materials include partially polymerized resins containing reactive functional groups such as epoxy, polyester, isocyanate, or polyurethane. Other examples of prepolymer materials include partially polymerized silicone compounds having reactive functional groups such as vinyl-terminated or hydride-terminated siloxane chains. Still other examples of prepolymer materials include polyamide prepolymers, also known as nylon prepolymers, which may contain amine and carboxylic acid functional groups. Prepolymer materials often serve as a starting point for further polymerization reactions, to which crosslinking agents, catalysts, or other additives are added to form polymer products with desired properties.

[0047] The term "primary particle" generally refers to the smallest unit of material that forms larger aggregates or aggregated particles. In some embodiments, primary particles are non-discrete and fused at constricted portions of the particles.

[0048] The term "rubber" generally refers to a type of elastomer material. In some cases, rubber exists naturally, for example in the form of latex. Rubber can also be synthesized, either additionally or alternatively, by polymerization of various monomers such as styrene, butadiene, and isoprene.

[0049] The term "rubber-containing products" generally refers to devices / equipment or compositions of materials containing rubber. Some examples of rubber-containing products include automobile tires, industrial belts and hoses, seals, and gaskets.

[0050] The term "tensile strength" generally refers to a measure of the maximum amount of tensile (pulling) stress that a material can withstand before it breaks or fractures. This represents the material's resistance to being pulled apart or stretched under tension. Tensile strength is usually expressed in units of force per unit area, such as pounds per square inch (psi).

[0051] The term "thermoplastic polymer" generally refers to a material that can be heated and softened multiple times. Examples of thermoplastic polymers include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, and polycarbonate. In some aspects of this disclosure, thermoplastic polymers include thermoplastic elastomers. Examples of thermoplastic elastomers include styrene-based block copolymers (e.g., styrene-butadiene-styrene and styrene-ethylene-butylene-styrene), thermoplastic polyurethanes, thermoplastic olefins (e.g., ethylene propylene diene monomer rubber, polyethylene, and polypropylene), and thermoplastic vulcanized rubbers.

[0052] The term "disordered layered carbon" generally refers to a material in which carbon atoms are arranged in layers. In disordered layered carbon, the layers of carbon atoms are not aligned with each other. The carbon layers can be randomly oriented or, otherwise, may lack long-range order. This disordered structure gives rise to properties that are different from those of more ordered structures such as graphite.

[0053] III. Summary As introduced above, carbon black materials are versatile. However, the production of carbon black involves environmental and health considerations. To address these problems and other drawbacks associated with conventional carbon black materials, the present disclosure provides a carbonaceous material produced from biomass feedstocks that can be used to replace conventional carbon black materials. In some aspects of the present disclosure, the carbonaceous material comprises a carbon content of 85 wt% or more. In further additional aspects, the carbonaceous material has a surface area in the range of 150 m 2 / g to 500 m 2 / g. In further additional aspects, the carbonaceous material exhibits an oil absorption value in the range of 50 g / 100 g to 100 g / 100 g. Further features of the carbonaceous materials of the present disclosure are described herein. Advantageously, the production of the carbonaceous materials disclosed herein results in less carbon emissions than conventional fossil-based carbon black. In an independent aspect, the carbonaceous material has no detectable level of PAHs or has a level of PAHs below the detectable limit, reducing the adverse health effects associated with conventional carbon black materials.

[0054] IV. Carbonaceous Materials The chemical structures of the carbonophilic materials used to produce the carbonaceous materials according to this disclosure are highly functionalized and relatively hydrophilic compared to carbonaceous materials. Some composite polymer materials require hydrophobic fillers and / or fillers with relatively fewer oxygen-containing groups than the carbonophilic materials. Therefore, the carbonophilic materials can be post-treated to form the carbonaceous materials according to this disclosure by at least partially deoxygenating them. While not limited to a single theory, it is currently believed that post-treatment promotes the formation of more hydrophobic, turbidity-like surfaces.

[0055] In some embodiments, the chemical structure of carbonaceous materials may include unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, or any combination thereof. An example of a macromolecular furan derivative is humin. Humins are macromolecules with a polymeric furan-type structure. While not theoretically bound, one possible mechanism is that humins may be formed as a result of ring-opening hydrolysis and crosslinking and / or branching of furan. As will be described in more detail below, humins are insoluble and may remain in the solid phase along with unreacted biomass during the production of carbonaceous materials. In some embodiments, carbonaceous materials derived from lignin-containing biomass are dominated by lignin-based moieties, indicating the presence of unreacted lignin, partially decomposed lignin, lignin derivatives, or combinations thereof.

[0056] In some aspects of this disclosure, the carbonaceous material is in the form of a particulate material. The particles of the carbonaceous material (before post-treatment) can have a wide variety of textures / characteristics on different length scales. For example, a carbonaceous material derived from wood may have several particles with a size of 0.1 to 10 mm, which are roughly the same shape as the particles of the wood raw material, as shown in Figures 1A and 1B. However, the carbonaceous material may have an average particle size of 30 nm to 100 nm (or 3 × 10⁻¹⁶). -5 mm~1×10 -4It also contains primary particles in the range of mm). Figures 1C and 1D show enlarged views of the carbonophilic materials in Figures 1A and 1B, respectively, where the primary particles are more clearly visible. Figures 1E and 1F show additional views of the carbonophilic materials in Figures 1A and 1B, respectively, where they show the layered, hierarchical nature of the structure of the carbonophilic material. This hierarchical structure can be maintained within the carbonaceous material obtained from the parent material. Materials obtained using specific methods known in the art do not form such a hierarchical structure. For example, by exposing a biomass feedstock according to this disclosure, such as corn starch, to processing conditions of methods known in the art, including concentrated HCl, a material lacking individual particles and any hierarchical structure can be produced, as can be seen in Figures 2H to 2I.

[0057] In some embodiments, the primary particles present in the carbonophilic material used to produce the carbonaceous material are 100 nm or larger, but typically have a D50 value of less than 1 micrometer. In some embodiments, the primary particles present in the carbonophilic material are 200 nm or larger, but typically have a D50 value of less than 1 micrometer. Figure 2A shows an example of a carbonophilic material derived from a raw material containing corn starch. The carbonophilic material in Figure 2A has primary particle D50 of 236 nm. Figure 2B shows an example of a carbonaceous material obtained from the parent material in Figure 2A by heat treatment of the parent material and then media milling.

[0058] In contrast, primary particles present in carbonaceous materials obtained from lignin-containing raw materials may be smaller than those in carbonaceous materials obtained from lignin-free raw materials. Figure 2C shows a carbohydrate material derived from a raw material containing southern pine. Figure 2D shows the carbohydrate material obtained from the carbohydrate material of Figure 2C before media milling, and Figure 2E shows the carbohydrate material after media milling. The carbohydrate material of Figure 2C has primary particles D50 with a diameter of 45 nm. Some products formed from lignin-containing raw materials may contain primary particles with diameters ranging from 10 nm to 100 nm, as shown in Figures 1A to 1F. This difference in primary particle size can also affect the surface area (SA) of the material. In some embodiments, the SA is 10 to 100 nm.2 Within the range of / g, lignin-free raw materials produce materials with a smaller surface area, while lignin-containing raw materials produce materials with a larger SA. For example, the carbonophilic material in Figure 2A is 10m 2 / g~20m 2 / g, for example, 12-16m 2 It has SA in / g. The carbonaceous material in Figure 2B is approximately 50-90m 2 It has SA of / g

[0059] The ability to modify the morphology of carbonaceous materials as disclosed herein is advantageous for obtaining materials that can replace or complement conventional carbon black. Several types of carbon black exist, which can be broadly classified into three categories based on particle size: reinforcing, semi-reinforcing, and unreinforcing. Reinforcing carbon black generally contains relatively small particles, typically ranging in size from about 20 to 100 nm. Reinforcing carbon black is characterized by its ability to improve the tensile strength, tear resistance, and abrasion resistance of polymers such as rubber materials. Unreinforcing carbon black generally contains larger particles, typically exceeding 200 nm. This type of carbon black does not significantly affect the mechanical properties of composite materials, but may contribute to other properties such as conductivity or UV protection. Semi-reinforced carbon black lies between the reinforced and unreinforced types, with particle sizes typically ranging from about 100 to 200 nm. It offers moderate reinforcement compared to reinforced and unreinforced carbon black, but can provide a balance between strength and flexibility. By adjusting the particle size, carbonaceous materials can be used to replace and / or complement all three grades of carbon black.

[0060] In some embodiments, the carbonaceous material is 150m 2 / g~600m 2 / g, for example, 150m 2 / g~550m 2 / g, or 150m 2 / g~500m 2 / g, or 150m 2 / g~450m2 / g, or 150m 2 / g~400m 2 / g, or 150m 2 / g~350m 2 It has a surface area in the range of / g. In a further embodiment, the carbonaceous material is 150m 2 / g~330m 2 It has a surface area in the range of / g. The carbonaceous material has a level of porosity that can be achieved by heat-treating the parent carbonaceous material. This porosity can increase the surface area (SA) of the carbonaceous material compared to the parent material. For example, the SA of a parent carbonaceous material derived from SP is 57-89m². 2 The range is within / g, which is 270-295m in carbonaceous material after heat treatment, media milling, and application of an activator to the parent material. 2 It increases to / g. In this example, SA is 140m without milling. 2 / g~200m 2 The value is / g. In this particular example, the heat treatment was performed at 1000°C. In some other embodiments, a lower temperature (e.g., 850°C) is used, either 380m before milling. 2 / g~430m 2 SA values ​​of / g can be provided, up to 500m after milling (e.g., media milling). 2 SA values ​​in / g can be provided. The SA of carbonophilic materials derived from CS is 12-16m 2 The range is / g, which is 315m in carbonaceous material after heat treatment and media milling of the parent material. 2 It increases to / g. Before milling, in this example it was 259m 2 The values ​​for / g were obtained. The SA of carbonophilic materials derived from CS / HW was 45-64m 2 The range is / g, which is 170-185m in carbonaceous material after heat treatment and milling (e.g., jet milling) of the parent material. 2 The concentration increases to / g. Figures 2F and 2G show images of carbonaceous materials obtained by heat treatment and jet milling of carbonophilic materials derived from CS / HW. Here, Figure 2F shows the cyclone portion of the carbonaceous material, and Figure 2G shows the baghouse portion.

[0061] In some aspects of this disclosure, the carbonaceous material has an oil absorption value in the range of 50 g / 100 g to 100 g / 100 g, for example, 50 g / 100 g to 99 g / 100 g, or 60 g / 100 g to 95 g / 100 g, or 60 g / 100 g to 90 g / 100 g, or 60 g / 100 g to 85 g / 100 g, or 60 g / 100 g to 80 g / 100 g, or 60 g / 100 g to 75 g / 100 g. In some specific aspects, the oil absorption value is in the range of 57 g / 100 g to 75 g / 100 g, including 71 g / 100 g to 75 g / 100 g, 65 g / 100 g to 80 g / 100 g, and 65 g / 100 g to 75 g / 100 g. The oil absorption value or oil absorption amount (OAN) measures the amount of oil that can be added to a material to achieve a percolation network. For example, the oil absorption value of a 100% CS-derived carbonaceous material is 65.4 g / 100 g. This indicates the structure of the carbonaceous material (in this case, the structure refers to the branching state of the aggregate particles). For comparison, the OAN of N660 is 91.4 g / 100 g, the OAN of a 100% SP heat-treated carbonaceous material ranges from 71.9 to 74.4 g / 100 g, and the OAN of a CS / HW-derived carbonaceous material is 7.9 g / 100 g.

[0062] Compared to carbon black, the carbonaceous material of this disclosure is more carbon-negative in its production. Furthermore, the raw materials used to produce the carbonaceous material have a carbon intensity (CI) of -1.7 kg CO2 per kg of carbonaceous material (anhydrous basis), while fossil fuel-derived furnace carbon black has a historical average CI of +2.4 kg CO2 per kg of carbon black produced. Fossil-based ASTM-grade carbon black also contains high levels of PAHs, which are known carcinogens. PAHs have not been detected in the disclosed carbonaceous material (i.e., PAH content is below the detection limits, such as 0 mg / kg to less than 0.5 mg / kg, 0 mg / kg to less than 0.4 mg / kg, 0 mg / kg to less than 0.3 mg / kg, or 0 mg / kg to less than 0.2 mg / kg) and are expected to be absent due to the high temperatures of the heat treatment process. The disclosed carbonaceous material also exhibits superior performance compared to other bio-based solutions and superior performance compared to current carbon black in terms of sustainability.

[0063] In some embodiments of this disclosure, the carbonaceous material has a carbon content of 85% by weight or more, for example, 85% to 100% by weight, or 90% to 100% by weight, or 95% to 100% by weight. In some embodiments, the carbonaceous material has a carbon content of more than 90% by weight, for example, 91% by weight, or 92% by weight, or 93% by weight, or 94% by weight, or 95% by weight, or 96% by weight, or 97% by weight, or 98% by weight, or 99% by weight. In some embodiments, these carbon content values ​​can be obtained by heat-treating the parent carbonaceous material described herein at a temperature of 850°C or higher (e.g., 850°C to 1000°C). For example, in some embodiments, a carbonaceous material derived from Southern Pine (SP) heat-treated at 1000°C has a carbon content in the range of 93-95%. In another exemplary embodiment, a carbonaceous material derived from CS / HW has a carbon content in the range of 91-96%. The carbon content can be used as a substitute value for the deoxygenation level and hydrophobicity, and this can be adjusted by changing the conditions of the heat treatment step.

[0064] In some representative embodiments, the carbonaceous material is obtained from a carbonophilic material heat-treated at a temperature of 850°C (or higher), and the carbonaceous material has a carbon content of 85% by weight or more, 150m 2 / g~500m 2 It has a surface area in the range of / g and an oil absorption value in the range of 50g / 100g to 100g / 100g. In a further additional typical embodiment, the carbonaceous material is obtained from a carbonophilic material heat-treated at a temperature of 850°C (or higher), and the carbonaceous material has a carbon content of 90% by weight or more, 150m 2 / g~330m 2 It has a surface area in the range of / g and an oil absorption value in the range of 50g / 100g to 80g / 100g.

[0065] V. Use of carbonaceous materials The carbonaceous materials disclosed herein can be used as raw materials for a wide range of applications. Suitability for applications may, in some embodiments, depend on the properties of the carbonaceous material, such as primary particle size, aggregated particle size, surface area / porosity, surface function / hydrophobicity, and / or aggregated structure.

[0066] Carbonaceous materials can be used as a platform for a variety of carbon products (including carbon black substitutes and / or complements). The form of the carbonaceous material plays a role in its ability to be used in several products and / or functions, such as fillers for composite materials. The form of the carbonaceous material can be influenced by several factors, including, but are not limited to, the feedstock, reaction time, temperature, acid concentration, brine concentration, organic-to-aqueous phase ratio, reactor shape, impeller design, impeller stirring speed, feedstock load, and other factors.

[0067] The adjustable form of the carbonaceous material, including adjustable primary particle size, allows the carbonaceous material to be designed to function similarly to various carbon black grades (e.g., N660 carbon black, N990 carbon black, carcass-grade carbon black, tread-grade carbon black, etc.), as well as other specialty blacks containing different degrees of hydrophilicity or oxygen content. Therefore, the carbonaceous material disclosed herein can be used as a substitute (for reinforced and unreinforced applications, as well as for colorant applications) and / or a complement (e.g., for use with carbon black). In some independent embodiments, the carbonaceous material can be used as activated carbon and / or fuel. Furthermore, the hydrophobicity of the carbonaceous material can be adjusted, thereby improving its compatibility with various solvents.

[0068] In certain aspects of this disclosure, the carbonaceous materials according to this disclosure are used as fillers for composite polymer materials, such as reinforcing fillers in elastomers. The carbonaceous materials may exhibit desirable properties exhibited by carbon black. Some such properties are shown in Figure 3 and may include, but are not limited to, surface properties, porosity, primary particle size, aggregated particle size, and / or aggregated structure.

[0069] Using the carbonaceous materials disclosed herein and the methods described herein, it is possible to compound approximately 20 grams of unpelletized material with SBR. The composite material reinforces the unfilled material (e.g., gum rubber). This specification demonstrates that blending carbonaceous materials with N660 can achieve similar performance, although not necessarily superior. In certain embodiments, 100% substitution of carbonaceous materials and N660 in SBR rubber has been shown to reinforce the unfilled gum rubber.

[0070] VI. Manufacturing of carbonaceous materials Figure 4 shows a block diagram of an exemplary system and method for converting biomass feedstock into carbonaceous materials according to the present disclosure. In the example of Figure 4, biomass 102 is added to reactor 100 and brought into contact with an organic solvent 104 and an aqueous acid 106 (e.g., hydrochloric acid). The contents of reactor 100 are heated and stirred at a reaction temperature suitable for converting at least a portion of the cellulose and / or hemicellulose in the biomass into products such as furan and furan derivatives.

[0071] After the reaction is complete, in step 120, the reaction mixture is separated into an organic phase 112 and an aqueous phase 114 at the separation temperature. Unreacted biomass, insoluble humic acid, and carbonophilic material 122, which may contain other materials, remain with the aqueous phase 114. If the biomass 102 contains lignin, as will be described in more detail below, the carbonophilic material may further contain a lignin portion, as shown in Figure 5.

[0072] A. Feedstock The feedstock used to produce a carbonophilic material generally refers to the starting material used to produce the carbonophilic material, which is then converted into the carbonaceous material of this disclosure. Suitable feedstock may include any material containing sugars. In certain embodiments, the feedstock includes cellulosic biomass such as lignocellulose and other cellulosic materials. Non-limiting examples of feedstock include glucose, glucan, cellulose, lignocellulose, hemicellulose, starch, sucrose, or any mixture thereof.

[0073] In some embodiments, the feedstock comprises six-carbon (C6) sugars and / or five-carbon (C5) monosaccharides. The terms “six-carbon sugars” or “C6 sugars” generally refer to sugars whose monomer units have six carbon atoms. The terms “five-carbon sugars” or “C5 sugars” generally refer to sugars whose monomer units have five carbon atoms. The feedstock may comprise monosaccharides, disaccharides, polysaccharides, or any mixture thereof. In one embodiment of this disclosure, the feedstock comprises one or more C6 monosaccharides. In another embodiment of this disclosure, the feedstock comprises disaccharides or polysaccharides comprising monomer units having six carbon atoms. It should be understood that the monomer units may be the same or different.

[0074] In one embodiment, the feedstock comprises monosaccharides. Suitable examples of monosaccharides include glucose, fructose, and any other isomers thereof. In another embodiment, the feedstock comprises disaccharides. Suitable examples of disaccharides include sucrose. In yet another embodiment, the feedstock comprises polysaccharides. Examples of polysaccharides include cellulose, hemicellulose, cellulose acetate, and chitin. In yet another embodiment, the feedstock comprises mixtures of monosaccharides, disaccharides, and polysaccharides. For example, in one embodiment of the present disclosure, the feedstock may comprise glucose, sucrose, cellulose, or any combination thereof. In another embodiment of the present disclosure, the feedstock comprises glucan, starch (e.g., corn starch), cellulose, hemicellulose, another anhydrous sugar, or any combination thereof.

[0075] In some embodiments, the feedstock comprises C6 sugars selected from glucose, fructose (e.g., high-fructose corn syrup), cellobiose, sucrose, lactose, and maltose, or their isomers (including any stereoisomers thereof), or any mixture thereof. In one embodiment, the feedstock comprises glucose, or its dimers or polymers, or their isomers. In another embodiment, the feedstock comprises fructose, or its dimers or polymers, or their isomers. In yet another embodiment of the present disclosure, the feedstock is a sugar composition. For example, the sugar composition may comprise a single sugar or a mixture of sugars such as fructose, glucose, sucrose, lactose, and maltose.

[0076] The feedstocks suitable for use in the production of carbonophilic materials may also include derivatives of the sugars described above. In some embodiments, the feedstocks may include aldoses, ketoses, or any mixture thereof. In some embodiments, the feedstocks may include C6 and / or C5 aldoses, C6 and / or C5 ketoses, or any mixture thereof.

[0077] In some embodiments, the feedstock comprises an aldose or any polymer thereof. In one embodiment of the present disclosure, the feedstock comprises a C6 aldose or any polymer thereof. A suitable example of an aldose is glucose. In another embodiment of the present disclosure, the feedstock comprises a polyaldose.

[0078] In other embodiments, the feedstock comprises a ketose or any polymer thereof. In yet another embodiment, the feedstock comprises a C6 ketose or any polymer thereof. A suitable example of a ketose is fructose. In yet another embodiment of the present disclosure, the feedstock comprises a polyketose.

[0079] In yet another embodiment, the feedstock comprises a mixture of C6 aldose and C6 ketosis. For example, in one embodiment of the present disclosure, the feedstock may comprise glucose and fructose.

[0080] In some embodiments, if the feedstock contains sugar, the sugar may exist in an open-chain form, a cyclic form, or a mixture thereof. Those skilled in the art will recognize that if the feedstock contains glucose, the open-chain form of the glucose used may exist in equilibrium with several cyclic isomers during the reaction.

[0081] In other embodiments, if the feedstock contains sugar, the sugar may exist as any stereoisomer or as a mixture of stereoisomers. For example, in some embodiments, the feedstock may contain D-glucose, L-glucose, or a mixture thereof. In other embodiments, the feedstock may contain D-fructose, L-fructose, or a mixture thereof.

[0082] In one aspect of this disclosure, the raw material includes a hexose, a monosaccharide having six carbon atoms and chemical formula C4H 12 It contains O6. The hexose may include aldohexose or ketohexose, or mixtures thereof. The hexose may be in open-chain form, cyclic form, or mixtures thereof. The hexose may include any stereoisomer, or mixtures of stereoisomers. Suitable hexoses include, for example, glucose, fructose, galactose, mannose, allose, altrose, growth, idose, talose, psicose, sorbose, and tagatose, or any mixtures thereof.

[0083] The raw materials used to produce carbonophilic materials can be obtained from any commercially available source. For example, those skilled in the art will recognize that cellulose and hemicellulose can be found in biomass (e.g., cellulosic biomass or lignocellulosic biomass). Thus, in some embodiments, the raw materials include biomass, which can be any plant or plant-derived raw material composed of relatively oxygen-rich organic compounds such as carbohydrates, and also containing a wide variety of other organic compounds. As mentioned above, some of these raw materials (e.g., wood, grass, corrugated cardboard, etc.) also contain lignin. Biomass may also include other materials such as inorganic salts and clay.

[0084] Biomass can be pretreated to help make sugars in the biomass more readily available by disrupting the crystalline structure of cellulose and hemicellulose and decomposing the lignin structure (if present). Examples of pretreatment include mechanical treatment (e.g., shredding, pulverization, grinding), concentrated acid, dilution acid, SO2, alkali, hydrogen peroxide, wet oxidation, steam explosion, ammonia fiber explosion (AFEX), supercritical CO2 explosion, liquid hot water, and organic solvent treatment.

[0085] Biomass can originate from a variety of sources. For example, biomass can be derived from agricultural raw materials (e.g., corn kernels, corn cobs, corn stalks and leaves, rice husks, peanut shells, and spent grains), processing waste (e.g., paper sludge), and recycled cellulose materials (e.g., corrugated cardboard, recycled corrugated cardboard / paper waste (OCC), recycled newspaper (ONP), and mixed paper). Other suitable examples of biomass include straw, paper mill wastewater, newspaper printing paper, municipal solid waste, wood chips, sawdust, thinned wood, cut branches, reeds, switchgrass, sorghum, bagasse, compost, wastewater biosolids, plant waste, and food / feed processing residues.

[0086] Any combination of the feedstocks described herein may be used. For example, in one aspect of this disclosure, the feedstocks may include glucose, corn kernels, and wood chips. In another aspect of this disclosure, the feedstocks may include wood chips and corrugated cardboard. In yet another aspect of this disclosure, the feedstocks may include bagasse and corrugated cardboard. In yet another aspect of this disclosure, the feedstocks may include empty fruit clusters. In yet another aspect of this disclosure, the feedstocks may include wood chips and corrugated cardboard. In yet another aspect of this disclosure, the feedstocks are essentially made from or consist of corn starch. In aspects in which the feedstocks are essentially made from corn starch, the feedstocks do not contain or do not contain other types of biomass species from which the carbonophilic material may be derived.

[0087] B. acid In some embodiments, the acid used to produce the carbonophilic material is a halogen-containing acid. Such an acid has the formula HX, where X is a halogen. However, it will be understood that any other suitable acid may also be used. Other examples of suitable acids include halogen-containing mineral acids or halogen-containing organic acids. Mixtures of acids may also be used. Some examples of suitable acids include hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, or hydrofluorobolic acid. Any combination of the acids described herein may be used.

[0088] Therefore, the acids used herein may be obtained from any commercially available source or may be produced in situ by providing a suitable reagent for the reaction mixture. For example, hydrochloric acid can be produced in situ in the reaction mixture by providing sulfuric acid and sodium chloride to the reaction mixture.

[0089] In other embodiments, the acid supplied to the reactor or reaction mixture is a gaseous acid. For example, at least a portion of such gaseous acid may be dissolved in the reaction mixture, or partially dissolved, to produce an aqueous solution of the acid.

[0090] The concentrations of the acids used herein may vary depending on several factors, including the type of raw materials used. In some embodiments, concentrated acids are used. For example, a person skilled in the art would recognize that concentrated hydrochloric acid is 12M. In other embodiments, the acids used to produce the materials disclosed herein may be less than 12M, 11.5M or less, 11M or less, 10.5M or less, 10M or less, 9.5M or less, 9M or less, 8.5M or less, 8M or less, 7.5M or less, 7M or less, 6.5M or less, 6M or less, 5.5M or less, 5M or less, 4.5M or less, 4M or less, 3.5M or less, 3M or less, 2.5M or less, 2M or less, 1.5M or less, and more. Alternatively, it has a concentration of 1M or less, or 0.25M-10M, 0.25M-9M, 0.25M-8M, 0.25M-7M, 0.25M-6M, 0.25M-5M, 0.5M-10M, 0.5M-9M, 0.5M-8M, 0.5M-7M, 0.5M-6M, 0.5M-5M, 1M-10M, 1M-9M, 1M-8M, 1M-7M, 1M-6M, 1M-5M, 1M-4M, or 2M-4M.

[0091] C. Salt Salts are optionally used in the production of the carbonophilic material used to obtain the disclosed carbonaceous material. The salts may comprise one or more inorganic salts and / or one or more organic salts. "Inorganic salt" generally refers to a composite of a positively charged species and a negatively charged species, neither of which contains elemental carbon. "Organic salt" generally refers to a composite of a positively charged species and a negatively charged species, at least one of which contains elemental carbon.

[0092] The choice of salt used may vary depending on the reaction conditions, as well as the acid and solvent used. In some embodiments, the salt is an inorganic salt. In some embodiments, the salt is a halogen-containing acid. Examples of salts that may be used in specific embodiments include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts. Any combination of acids described herein may be used.

[0093] The concentration of salt(s) can vary. In some embodiments, the concentration of salt(s) is greater than 5M, greater than 6M, greater than 7M, greater than 8M, greater than 9M, or greater than 10M, or between 5M and 20M, 5M and 15M, 5.5M and 10M, 7M and 10M, or between 7.5M and 9M, or approximately 10M, approximately 11M, approximately 12M, approximately 13M, approximately 14M, or approximately 15M. In other embodiments, the salt(s) are present in the aqueous phase at a concentration of approximately 0.1% to 50% (w / w).

[0094] The acids used herein may be obtained from any commercially available source or may be produced in situ to provide reagents suitable for reaction mixtures. For example, certain reagents in the presence of hydrochloric acid can undergo ion exchange to produce chloride salts used to produce carbonophilic materials.

[0095] D. cold In some embodiments, a solvent is used in a method for producing a carbonophilic material. The solvent can be obtained from any source, including any commercially available source.

[0096] Any suitable solvent capable of forming a liquid / liquid two-phase system in the reaction mixture may be used, resulting in one phase being primarily organic and the other primarily aqueous.

[0097] The solvent may also be selected based on its dipole moment, which is a measure of the solvent's polarity. The dipole moment of a liquid can be measured with a dipolemeter. In some embodiments, the solvents used herein have a dipole moment of less than 20.1D, 20D or less, 18D or less, or 15D or less.

[0098] The solvent may also be selected based on its boiling point. In some embodiments, the solvent has a boiling point of at least 110°C, at least 150°C, or at least 240°C.

[0099] The solvent may consist of one solvent or a mixture of solvents. For example, in some embodiments, the solvent may consist of one or more alkylphenyl solvents, one or more alkyl solvents (e.g., dealkyl solvents), one or more ester solvents, one or more aromatic solvents, one or more silicone oils, or a combination or mixture thereof. In other embodiments, the solvent may consist of one or more hydrocarbons, one or more halogenated hydrocarbons, one or more ethers, one or more halogenated ethers, one or more cyclic ethers, one or more amides, one or more silicone oils, or any combination or mixture thereof.

[0100] In some embodiments, the solvent includes paraxylene, mesitylene, naphthalene, anthracene, toluene, dodecylbenzene, pentylbenzene, hexylbenzene, and other alkylbenzenes (e.g., Wibaryl® A, Wibaryl® B, Wibaryl® AB, Wibaryl® F, Wibaryl® R, Cepsa Petrepar® 550-Q, Cepsa Petrepar® 900-Q, Santovac® 5, Santovac® 7, Marlican®, Synnaph AB3, Synnaph AB4), sulfolane, hexadecane, heptadecane, octadecane, eicosane, henaicosane, docosane, tricosane, tetracosane, or any combination or mixture thereof.

[0101] It should be understood that solvents may be classified into one or more of the classes listed herein. For example, solvents may include paraxylene, which is an alkylphenyl solvent and an aromatic solvent.

[0102] In some embodiments, the solvent includes water.

[0103] Combinations or mixtures of solvents may also be used. In some embodiments, an ether solvent can be combined with one or more of the other types of solvents described above.

[0104] The solvent used may vary depending on the type and amount of feedstock used. For example, in some embodiments, the mass-to-volume ratio of feedstock to solvent is 1 g to 30 g of feedstock per 100 mL of solvent.

[0105] Furthermore, it is understood that any description of the solvent used to produce the carbonaceous material may be combined with any description of the acid and salt, just as each and every combination may be listed individually. For example, in some embodiments, the acid is hydrochloric acid, the salt is lithium chloride or calcium chloride, or a combination thereof, and the solvent is an alkylphenyl solvent.

[0106] E. Reaction conditions As used herein, “reaction temperature” and “reaction pressure” refer to the temperature and pressure at which the reaction takes place to produce a carbonophilic material, respectively.

[0107] In some embodiments of the step of producing a carbonaceous material, the reaction temperature is at least 15°C, at least 25°C, at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 115°C, at least 120°C, at least 125°C, at least 130°C, at least 135°C, at least 140°C, at least 145°C, at least 150°C, at least 175°C, at least 200°C, at least 250°C, or at least 300°C. In other embodiments, the reaction temperature is 110°C to 300°C, 110°C to 250°C, 150°C to 300°C, or 110°C to 250°C.

[0108] In some embodiments, the reaction pressure is 0.1 atm to 10 atm. In other embodiments, the reaction pressure is atmospheric pressure.

[0109] It should be understood that temperature can be expressed in degrees Celsius (°C) or kelvin (K). Those skilled in the art will be able to convert the temperatures described herein from one unit to another. Pressure may also be expressed as gauge pressure (barg), which refers to pressure in bars above ambient pressure or atmospheric pressure. Pressure can also be expressed in bars, atmospheric pressure (atm), pascals (Pa), or pounds per square inch (psi). Those skilled in the art will be able to convert the pressures described herein from one unit to another.

[0110] The reaction temperature and reaction pressure of the steps for producing carbonaceous materials can also be expressed as a relationship. For example, in one aspect of this disclosure, the reaction temperature T is expressed in Kelvin and the reaction pressure P is expressed in psi, where 10 <Ln[P / (1psi)]+2702 / (T / (1K))<13である。

[0111] The residence time also varies depending on the reaction conditions and the desired yield. Residence time refers to the average time it takes to produce a carbonophilic material from the reaction mixture. In some embodiments of the steps for producing the carbonophilic material, the residence time is at least 360 minutes, at least 240 minutes, at least 120 minutes, at least 60 minutes, at least 30 minutes, at least 20 minutes, at least 10 minutes, at least 5 minutes, or at least 2 minutes.

[0112] F. Isolation In some embodiments, a method is provided for producing a carbonaceous material by combining feedstock, an acid, and optionally a salt to form a reaction mixture, generating a carbonophilic material from at least a portion of the reaction mixture, and isolating the carbonophilic material. As described above, the carbonophilic material may include unreacted feedstock and may also include humins, carbohydrate moieties, and / or lignin moieties.

[0113] Referring again to Figure 4, the generated carbonophilic material is isolated in step 122. Any suitable technique known in the art, such as filtration and centrifugation, can be used to isolate the carbonophilic material. For example, solid-liquid separation techniques such as filtration and centrifugation may be used to isolate the generated carbonophilic material.

[0114] G. Post-processing In some embodiments, the carbonophilic material 122 in Figure 4 is post-treated to deoxygenate the carbonophilic material at least partially to provide a carbonaceous material. In some examples, the post-treatment of the carbonophilic material includes heat-treating the carbonophilic material at a suitable temperature to convert at least a portion of the carbonophilic material into a carbonaceous material.

[0115] In some embodiments, heat treatment of a carbonophilic material involves heating the carbonophilic material to a temperature in the range of 300°C to 1000°C. It will also be understood that the carbonophilic material may be heat-treated at any other suitable temperature. Other examples of suitable temperatures may be below 300°C or above 1000°C. By heat-treating a carbonophilic material at a temperature within this range (e.g., at least 350°C to 500°C), at least a portion of the carbonophilic material may be converted into a chaotic carbon-like structure.

[0116] In some embodiments, the carbonophilic material is heat-treated in an inert atmosphere, for example, using argon or nitrogen. However, it should be understood that in some embodiments, the argon or nitrogen atmosphere may contain trace amounts of oxygen.

[0117] There are also applications for special carbon blacks that require materials with higher hydrophilicity and / or higher oxygen content. The carbonaceous materials described herein are well suited to meeting these specifications. In some embodiments, the high oxygen content present in the resulting carbide-philic material (e.g., carbide-philic material 122 in Figure 4) allows the carbonaceous material to be used to produce fillers with desired (e.g., intermediate) oxygen-containing group levels. This can be achieved by modifying the heat treatment of the carbide-philic material. In some embodiments, the heat treatment is modified to be performed at a relatively lower temperature and / or for a shorter time than that used to deoxygenate the carbide-philic material, as will be described in more detail below.

[0118] In some embodiments of this disclosure, the carbonaceous material has a carbon content of 85% by weight or more, for example, 85% to 100% by weight, or 90% to 100% by weight, or 95% to 100% by weight. In some embodiments, the carbonaceous material has a carbon content of more than 90% by weight, for example, 91% by weight, or 92% by weight, or 93% by weight, or 94% by weight, or 95% by weight, or 96% by weight, or 97% by weight, or 98% by weight, or 99% by weight. In some embodiments, these carbon content values ​​can be obtained by heat-treating the parent carbonaceous material at a temperature of 850°C or higher (e.g., 850°C to 1000°C). For example, in some embodiments, a carbonaceous material derived from Southern Pine (SP) heat-treated at 1000°C has a carbon content in the range of 93-95%. In another exemplary embodiment, a carbonaceous material derived from CS / HW has a carbon content in the range of 91-96%. The carbon content can be used as a substitute value for the deoxygenation level and hydrophobicity, and this can be adjusted by changing the conditions of the heat treatment step.

[0119] Figure 6 shows cross-polarization / magic angle rotation (CP / MAS) solids of carbonaceous materials heat-treated at different temperatures under nitrogen gas. 13The 13C NMR spectrum is shown. The abundant functional groups in the initially generated (before heat treatment) carbonophilic material strongly influence the chemical environment of carbon atoms within the carbonophilic material, resulting in a heterogeneous spectrum up to at least 550°C.

[0120] In some embodiments, at least partial deoxygenation of a carbonophilic material into a carbonaceous material occurs at 350°C to 550°C, where a random layered structure can be obtained. The formation of the random layered structure can be evaluated using Raman spectroscopy, for example, as shown in Figure 7. 13 Observing both 13C NMR and carbonaceous materials with increased carbon structure / content closer to that of N660 carbon black, it is possible to obtain carbonaceous materials at or near 850°C.

[0121] Figures 8A to 8C show the formation of pore structures in response to temperature and their subsequent partial collapse. This finding suggests that carbonaceous materials themselves are spontaneously activated at relatively mild temperatures (approximately 550°C) without the application of activators (up to 500m). 2 This reveals that ( / g). Nitrogen physicoadsorption isotherms are shown in Figure 9, and in addition, pore size distribution and cumulative pore volume are shown in Figures 10A and 10B. Carbonaceous material samples obtained from heat-treated parent materials (i.e., 550°C and 850°C) show high adsorption and low relative pressure, indicating a large abundance of micropores, and exhibit hysteresis at medium to high relative pressures, indicating the presence of mesopores. Carbon black does not contain micropores or mesopores. Instead, the outer surface of the carbon black contributes mainly to its surface area. The pore size distribution shows that the resulting micropores are less than 1 nm in diameter. The cumulative pore volume indicates the presence of mesopores, but these do not appear to be ordered, as evidenced by the absence of substantial peaks in the pore size distribution data for 2-30 nm.

[0122] H. Additional processing steps As described herein, the carbonaceous materials according to this disclosure are produced by post-processing a carbonophilic material obtained from a biomass feedstock. A method for producing the carbonophilic material, along with the characteristics of the parent material, is described in more detail below. In addition to the post-processing described herein, the resulting carbonophilic material may be subjected to one or more additional processing steps to provide the carbonaceous material of this disclosure. For example, in some embodiments, the resulting carbonaceous material may be washed after heat treatment of the carbonophilic material. In one embodiment of this disclosure, the resulting carbonaceous material may be washed by acid washing, water washing, or a combination thereof. For example, in one embodiment of this disclosure, the carbonaceous material may be washed with acid. The acid used to wash the resulting carbonaceous material may be called a “washing acid” or acid washing agent. In some embodiments, the washing acid is an aqueous acid solution. A suitable acid may be, for example, hydrochloric acid. The washing acid is not an activator and is not used for impregnation of the carbonaceous material.

[0123] In other embodiments, the carbonaceous material may be cleaned with an organic detergent, an aqueous detergent, a brine, or an alkaline detergent.

[0124] In other embodiments, the resulting carbonaceous material may be dried, with or without washing the carbonaceous material as described above. For example, in one embodiment of the present disclosure, the resulting carbonaceous material may be washed after heat treatment, followed by a drying step.

[0125] In some aspects of this disclosure, the aggregate particle size of carbonaceous materials can be reduced through one or more physical processes such as milling, sieving, shearing, and cavitation. Examples of suitable milling methods include jet milling, ball milling, media milling, vari milling, hammer milling, or a combination thereof. Further details regarding milling and applications of milled carbonaceous materials are described below in more detail.

[0126] Furthermore, in some embodiments, a carbonaceous material is combined with a prepolymer material that has been cured and / or solidified in the presence of the carbonaceous material to form a composite polymer composition. In some embodiments, the prepolymer material comprises (i) a mixture of styrene and butadiene, or (ii) isoprene. In this way, the prepolymer material forms an elastomer upon curing and / or solidification. Other examples of suitable materials include thermoplastic polymers and natural rubber. Other examples of rubber materials may include ethylene propylene diene monomer rubber and butyl rubber.

[0127] As described above, composite polymer materials can also be manufactured using blends of two or more chemically specific filler materials. For example, a carbonaceous material can be mixed with carbon black obtained from a non-biomass source to form a compound filler for composite polymers. In some embodiments, the carbonaceous material is present as the first filler material in an amount ranging from 0 to 100% by weight of the filler material, for example, 0 to 95% by weight, 0 to 90% by weight, 0 to 85% by weight, 0 to 80% by weight, 0 to 75% by weight, 0 to 70% by weight, 0 to 65% by weight, 0 to 60% by weight, 0 to 55% by weight, 0 to 50% by weight, 0 to 45% by weight, or 0 to 40% by weight. For example, as will be described in more detail below, a blend of carbonaceous material and N660 carbon black in a 40:60 weight ratio within a styrene-butadiene rubber (SBR) matrix results in a composite polymer material with a tensile strength of 2500 psi or more (e.g., 2500 psi to 3500 psi, etc.), which is greater than that of a composite material filled with N660 carbon black alone. In some embodiments, the tensile strength is measured using ASTM D412. In additional embodiments, the carbonaceous material of this disclosure may have an elongation in the range of 200% to 600%, e.g., 300% to 600%, 400% to 600%, or 500% to 600%. In some embodiments, the elongation is in the range of 400% to 500%.

[0128] VII. Overview of Multiple Embodiments This specification discloses embodiments of carbonaceous materials produced from biomass supply materials, wherein the carbonaceous material has a carbon content of 85% by weight or more and 150m 2 / g~500m 2 This includes surface area in the range of / g, and oil absorption values ​​in the range of 50g / 100g to 100g / 100g.

[0129] In any or all of the above embodiments, the biomass supply material includes lignin-free material, lignin-containing material, or a combination thereof.

[0130] In any or all of the above embodiments, the biomass supply material includes corn starch, wood material, or a combination thereof.

[0131] In any or all of the above embodiments, the biomass supply material is corn starch.

[0132] In any or all of the above embodiments, the carbonaceous material further comprises a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, and / or lignin-derived compounds, or a combination thereof.

[0133] In any or all of the above embodiments, the macromolecule furan derivative is a humine.

[0134] In any or all of the above embodiments, the oil absorption value is in the range of 65g / 100g to 80g / 100g.

[0135] In any or all of the above embodiments, the carbonaceous material is in the form of a particulate material comprising primary particles having (i) a D50 value of 200 nm or more, or (ii) a D50 value of 30 nm to 100 nm.

[0136] In any or all of the above embodiments, the carbonaceous material is obtained by heat-treating a carbonophilic material at a temperature of 800°C to 1000°C.

[0137] In any or all of the above embodiments, the carbonaceous material is obtained by heat-treating a carbonophilic material at a temperature of 850°C.

[0138] In any or all of the above embodiments, the carbonaceous material contains less than 0.5 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

[0139] In any or all of the above embodiments, the carbonaceous material contains less than 0.2 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

[0140] This specification also discloses embodiments of composite polymer compositions comprising a polymer matrix and a filler material dispersed within the polymer matrix, wherein at least a portion of the filler material comprises a first filler component which is a carbonaceous material in any or all of the embodiments described above.

[0141] In any or all of the above embodiments, the filler material further comprises a second filler component which is chemically different from the first filler component.

[0142] In any or all of the above embodiments, the second filler component includes carbon black obtained from a non-biomass-based raw material.

[0143] In any or all of the above embodiments, the first filler component is present in an amount ranging from 0% to 60% by weight.

[0144] In any or all of the above embodiments, the composite polymer composition has a tensile strength of 2500 psi or more.

[0145] In any or all of the above embodiments, the polymer matrix comprises a thermoplastic polymer or an elastomer.

[0146] In any or all of the above embodiments, the polymer matrix comprises one or more of styrene-butadiene rubber or natural rubber.

[0147] In any or all of the above embodiments, the first filler component is the carbonaceous material described in any or all of the above embodiments.

[0148] This specification also discloses embodiments of rubber-containing products comprising any or all of the composite polymer compositions described in the embodiments described above.

[0149] In any or all of the above embodiments, the rubber-containing product is a tire.

[0150] This specification also discloses embodiments of compositions comprising a prepolymer material and a filler material dispersed within the prepolymer material, wherein at least a portion of the filler material comprises a first filler component which is any or all of the carbonaceous materials described above.

[0151] In any or all of the above embodiments, the prepolymer material comprises (i) a mixture of styrene and butadiene, or (ii) isoprene.

[0152] Furthermore, this specification discloses embodiments of a method for producing carbonaceous materials, the method comprising obtaining a carbonophilic material from a biomass feedstock, wherein the carbonophilic material comprises a portion of the unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin compounds, or a combination thereof, and post-treating the carbonophilic material to deoxygenate it at least partially to obtain a carbonaceous material, wherein the post-treatment of the carbonophilic material does not include treating the carbonophilic material with an activator.

[0153] In any or all of the above embodiments, post-treatment of the carbonophilic material includes heat treatment of the carbonaceous material.

[0154] In any or all of the above embodiments, heat treatment of the carbonophilic material includes heating the carbonophilic material at a temperature in the range of 300°C to 1000°C.

[0155] In any or all of the above embodiments, post-treatment of the carbonophilic material includes converting at least a portion of the carbonophilic material into randomly structured carbon.

[0156] In any or all of the above embodiments, the carbonaceous material is a particulate material, and the method further includes reducing the aggregate particle size of the carbonaceous material.

[0157] In any or all of the above embodiments, post-treatment of the carbonophilic material includes heat treatment of the carbonaceous material.

[0158] In any or all of the above embodiments, milling includes jet milling, ball milling, media milling, or a combination thereof.

[0159] In any or all of the above embodiments, the method comprises combining a carbonaceous material with a prepolymer material, and curing and / or solidifying the prepolymer material in the presence of the carbonaceous material to form a composite polymer composition.

[0160] In any or all of the above embodiments, forming a composite polymer includes forming a rubber-containing product.

[0161] In any or all of the above embodiments, the carbonaceous material has a carbon content of 85% by weight or more, and 150m 2 / g~500m 2 This includes surface area in the range of / g, and oil absorption values ​​in the range of 50g / 100g to 100g / 100g. [Examples]

[0162] VIII. Examples Aspects of this teaching can be further understood by considering the following examples. While these examples are used for experimental demonstration, those skilled in the art will recognize that this embodiment is not limited to any of these small molecules or molecular weight ranges. The teachings herein enable those skilled in the art to prepare and use a variety of carbonaceous materials.

[0163] Synthesis of moist carbonophilic materials. The reaction from biomass to carbonaceous materials was carried out in a pilot 80-gallon reactor, with a target reaction temperature range of 135–145°C and a reaction time of 10–24 minutes. The target concentrations in the aqueous phase were typically 2 M HCl, 5.5 M CaCl2, and 13 M total Cl. The mass fraction of feedstock in the aqueous phase was typically in the range of 10–23 wt%, consisting of both a single feedstock (cornstarch or wood only) or a blend of feedstocks (cornstarch and wood combined). The "aqueous phase" is defined as the total water, CaCl2, and HCl in the reactor. The organic-to-aqueous ratio was in the range of 1.6–2.2. Note that both hardwood and softwood of various wood species were tested. The process steps were similar, but variations arose in the specific amounts of feedstock added.

[0164] Drying and Carbonization. 56 kg of moist carbonaceous material with a moisture content of 80% wetness (%wb) was placed in the furnace system. The system was subjected to a nitrogen purge cycle to inactivate the furnace environment. Next, nitrogen was introduced into the system at a set flow rate (50 standard liters per minute (slpm)) while maintaining a slight positive pressure (760-860 Torr). The system was heated to 175°C at 2.5°C / min, followed by a drying step with an isothermal period of 12 hours. Next, the system was heated to 200°C at 0.2°C / min, followed by an isothermal period of 2 hours to confirm that the material was dry. Next, the system was heated to 530°C at 2.75°C / min, followed by isothermal maintenance for 2 hours. Next, the system was raised to 1000°C at 7°C / min and isothermal maintenance for 4 hours to ensure complete carbonization. The system was powered off and the equipment was allowed to cool to ambient temperature, which took approximately 12 hours.

[0165] Jet milling. In the examples described herein, 200–1200 g of carbonaceous material was fed into an Alpine jet mill at a rate of 1–5 kg / hour. A grinding gas pressure of 70–110 psi and a classifier speed of 12,000–22,000 rpm were used. A two-stage particle collection system consisting of a cyclone and a baghouse was used. Both the cyclone and baghouse fractions were collected and tested separately. It should be noted that these conditions may depend on the mill used. For example, it may be used to use a higher feed rate in a mill with a larger classifier at a different grinding gas pressure and / or lower speed.

[0166] Rubber compounding. The following ASTM standards were used: ASTM D3182: Metering and mixing (TPE / rubber and plastic blends); ASTM D5289: Vulcanization using a rotary curing meter (MDR) - rheometer; ASTM D412: Original physics - tensile stress and strength of rubber; ASTM D3182: Molding and curing standard plaque or slab 6”×6; and ASTM D5992: DMA - Metrabib - strain sweep at room temperature. The cured packages compounded using these standards were used according to Table 1A. [Table 1]

[0167] NMR: 13 We purchased C-enriched D-glucose from Cambridge Isitope Laboratory, Inc. (CAS: 110187-42-3). 13 We received C-concentrated hybrid poplar (Populus alba × grandidentata) from Professor Jenny Mortimer of the Joint BioEnergy Institute (USA). Young rooted poplar cuttings (4 weeks old) were transferred to a 12L plastic container containing 11L of Hoagland nutrient solution (pH 6.0). Poplar biomass 13 C enrichment is 13 C atmosphere and controlled growth conditions (28°C, 70% humidity, 155 μmol m³)-2 s -1 The experiment was conducted in a self-constructed growth chamber equipped with 18 hours of lighting. Poplar 13 The plants were grown in a growth chamber of C for 68 days and then harvested.

[0168] The reaction was carried out using GC headspace vials with crimped caps. In two separate vials, 13 C-concentrated glucose (269 mg) and 13 245 mg of 14C-enriched lignocellulose biomass was packed into the vial with the same stirring bar. 1.25 mL of brine / acid solution and 2.00 mL of toluene were added. The vial was tightly capped and placed in a heating block set to 130°C behind a blast shield. The vial was heated for 22.5 minutes with a stirring speed of 1000 rpm. The reaction mixture was rapidly cooled in an ice bath. No weight loss was measured (less than 0.005 g), indicating no material leakage from the vial during the reaction. The reaction slurry was filtered through a filtration funnel equipped with 10 micrometer polyethylene frit (Chemglass) to collect the solid product, which was washed three times with 5 mL of toluene and three times with 5 mL of water. The solid product was then transferred to an aluminum pan covered with aluminum foil and placed in a 90°C oven to dry for approximately 48 hours. The solid product was then directly loaded onto a solid-state NMR rotor for molecular structure investigation.

[0169] In the examples in Figures 11 and 12, 13 C-concentrated glucose and 13 Carbonophilic materials for parallel comparison were produced by reacting C-enriched poplar biomass in parallel. A quantitative one-dimensional (1D) model is illustrated in Figure 11. 13 According to the 1C direct polarization (DP) SSNMR spectrum, 13 C-concentrated glucose-derived carbonophilic material ( 13CThe furan subunit (-Glu-HTC) exhibits a predominantly characteristic chemical shift at 151.1 ppm, 144.7 ppm, 121.3 ppm, and 111.5 ppm. This represents the two α-carbons, the bonded β-carbon, and the β-carbon of the furan subunit. Carbonyl and carboxylate groups are also detected in the chemical shift region, at 210–190 ppm and 183–167 ppm, respectively. Aliphatic carbon bonds of the furan subunit are detected in the chemical shift region of 53–10 ppm.

[0170] On the other hand, Figure 12 shows, 13 C-enriched poplar biomass-derived carbonophilic material ( 13 Quantitative 1D of C-Bio-HTC 13 The C DP ssNMR spectrum is shown. This is, 13 It has a different dominant chemical shift compared to C-Glu-HTC. 13 The aromatic region of the C-Bio-HTC spectrum is characterized by the regions of chemical shifts representing the arene rings of lignin subunits, e.g., S3 / 5, G3, G1, G2, S2 / 6, and methoxyl carbons at 153.1 ppm, 146.5 ppm, 128.8 ppm, 115.6 ppm, 105.3 ppm, and 56.0 ppm. 13 C-Bio-HTC also shows a significant peak in the carboxylic acid carbon chemical shift region, but the dominant chemical shift is 13 It is slightly different from the carboxylic acid carbon in C-Glu-HTC. Furthermore, 13 C-Bio-HTC is 13 Compared to C-Glu-HTC, it was not detected as strongly in the carbonyl carbon region, which is why. 13 This may indicate that humins are present in little to no form in C-Bio-HTC.

[0171] Furthermore, 2D 13C-13C correlated CP-INADEQUATE NMR experiments were also performed. 13 C-Glu-HTC and 13 The analysis was performed using both C-Bio-HTC (Figures 13 and 14, respectively), and good resolution was obtained for heavily overlapping peaks in the aromatic region. 13 C-Glu-HTC and13 This provides additional evidence regarding separate details about the molecular structure of C-Bio-HTC. 13 The CP-INADEQUETE spectrum of C-Glu-HTC shows five major types of furan structural environments, and no significant evidence of aromatic ring structure is found. However, 13 The molecular structure of C-Bio-HTC is dominated by seven identified lignin-derived arene ring structures (three types of G units, two types of S units, and two types of oxidized S units), and no furan structure is observed. This is consistent with the results shown by the 1D spectra in Figures 5 and 6.

[0172] Figure 6 shows examples of 1-D CP MAS solids of post-treated matrix carbonaceous materials, particularly carbonaceous materials obtained from parent materials heat-treated at different temperatures. 13 The 13C NMR spectrum is shown. The spectrum provides a broad indicator of the relative abundance of heteroatoms (e.g., oxygen) in the carbonaceous material. Heat treatment of the carbonaceous material at higher temperatures simultaneously results in greater deoxygenation of the carbonaceous material than simultaneous heat treatment at lower temperatures. Deoxygenation is indicated by the relative smoothing of the NMR spectrum because the chemical diversity of the carbonaceous material decreases and the remaining carbonaceous material is converted into chaotic carbon. In typical examples, the oxygen content was changed to the values ​​shown in Table 1B. [Table 2]

[0173] The molecular structures of carbonophilic materials generated from lignin-free raw materials and lignocellulosic biomass raw materials were respectively subjected to magic angle rotation (MAS). 13 The study was conducted using 13C solid-state nuclear magnetic resonance (ssNMR). 13Using lignocellulosic biomass enriched with 13C, we generated carbonophilic materials whose molecular structure could be directly explored by ssNMR. Carbonophilic materials generated from lignin-containing feedstocks have a different molecular structure from carbonophilic materials generated from lignin-free feedstocks such as glucose and corn starch. The molecular structure of carbonophilic materials derived from lignin-free feedstocks is mainly composed of humins, which are dominated by furan subunits having aliphatic bonds and carbonyl and carboxylate groups, as shown in Figure 11. In contrast, the molecular structure of carbonophilic materials derived from lignin-containing biomass is dominated by lignin-based moieties, such as the arene ring subunit shown in Figure 12. These lignin-based moieties may indicate the presence of unreacted lignin, lignin degradation products, lignin-based moieties with modified interunit bonds, or combinations thereof.

[0174] The inherent surface activity of the carbonaceous materials disclosed herein is beneficial in various specialty applications such as coatings and inks. Certain functional surface activities can provide improved reinforcement compared to furnace carbon black. This may be beneficial in addressing the less complex structures of the carbonaceous materials disclosed herein (since the structure of carbon black provides reinforcement through the entanglement of rubber chains in the free volume of carbon black aggregates). In addition, rCB (recycled carbon black) has certain limitations compared to the disclosed carbonaceous materials due to its higher ash content. Higher ash content means higher silica and zinc content, which can reduce the tear strength of the reinforced rubber.

[0175] Figure 7 shows the Raman spectra of the carbonaceous material from Figure 6 obtained after post-treatment (e.g., heat treatment under an inert gas at different temperatures). The Raman spectra indicate that the carbonaceous material transitions from a resin to a randomly layered carbon structure at 350-550°C.

[0176] In one example, a carbonaceous material was dry-media-milled to produce a first set of carbon black substitute samples. The carbonaceous material was compounded with SBR using the curing package described in Table 1C, provided in the examples of this disclosure. In some embodiments, a marching modulus was observed, which may indicate that the accelerator loading was too low. The accelerator used was N-tert-butyl-benzothiazole sulfonamide (TBBS). While not limited to a single operating theory, the marching modulus is thought to be attributable to either the microporosity of the heat-treated material (resulting in physioadsorption of TBBS) or the abundance of oxygen-containing functional groups (resulting in neutralization and / or chemiadsorption of TBBS). Figure 15 shows the MDR rheology of SBR curing with different levels of TBBS. 1.9 phr of TBBS was found to yield a T90 curing time similar to that of N660, which has a "typical" curing profile. Therefore, 1.9 phr of TBBS was used when compounding the carbonaceous material. [Table 3]

[0177] After the curing package is determined, routine testing of the carbonaceous material as a filler can be initiated. Figure 16 shows the tensile stress / strain curves of N660, gum rubber, and two carbonaceous material samples that were dry-media-milled for different durations. Both carbonaceous material samples were found to withstand significantly higher stresses than gum rubber, indicating that these samples reinforce the rubber. Table 2 shows formulation data comparing carbonaceous materials milled for 4 minutes and 40 minutes, as well as N660. At low strain (≤200%), the 4-minute milled sample withstood higher stresses than the 40-minute sample. However, in some embodiments, the 4-minute sample fractured at relatively low strains. The 40-minute milled sample yielded lower stresses than N660 throughout the test, although in certain embodiments, the elongation at fracture was comparable. While not limited to a single theory, the difference in performance between the two carbonaceous material samples may be due to the size and structure of the aggregates. As shown in Figure 17A, the maximum particle size of the carbonaceous material milled for 4 minutes is approximately 26 micrometers. In the sample milled for 40 minutes, the maximum particle size, as shown in Figure 17B, is 8 micrometers. For comparison, N660 carbon black has aggregated particles D90 of approximately 0.4 micrometers. It was surprising that 8-micrometer particles possessed a tensile strength comparable to that of N660. In some cases, particles larger than 1 micrometer may cause point defects in the rubber matrix, leading to reduced elongation at the fracture point (observed in some aspects of the 4-minute milled sample). While not bound by theory, the 40-minute milled sample, being sufficiently milled, may have any remaining tubular structures derived from the wood feed material converted into fragments (e.g., tube walls), which, due to their plate-like morphology, may be sheared during the rubber / carbonaceous material mixing process. [Table 4]

[0178] Table 2 shows that the OAN structure of the 4-minute milled sample is close to that of N660 (97 compared to 90g oil / 100g carbon, respectively). The 40-minute milled sample has an OAN of 57g oil / 100g carbon. The larger structure in the 4-minute milled sample may explain the low strain and good reinforcement (stress), and the lower reinforcement across the entire stress / strain range in the 40-minute milled sample. Figure 18 shows the dynamic modulus data for these samples. The relatively high storage modulus of the 4-minute milled sample indicates strong inter-filler interactions, likely due to the higher particle structure.

[0179] Other processes for particle size reduction were investigated. In particular, heat-treated carbonaceous materials were ground using a counter-air jet mill (e.g., an Alpine mill). Tensile stress-strain data from one attempt to combine carbonaceous material produced from Alpine jet milling with SBR are shown in Figure 19. The RPM rate indicates the classifier speed. Some samples showed relatively low tensile strength and elongation at break. These samples were taken only from the cyclone of the milling apparatus, which may explain the narrow center of the particle size distribution (approximately 8 micrometers).

[0180] Different alpine milling systems were tested, and both cyclone and baghouse materials were recovered. Baghouse material is usable because it may be finer (and potentially contain a higher proportion of primary particles) than cyclone material. The design of experiment (DOE) was performed by varying the chamber pressure and air classifier speed. The resulting baghouse and cyclone particle sizes and fractions are shown in Table 3. The baghouse particle size did not appear to be significantly affected by the grinding conditions. However, both the size of the material in the cyclone and the overall fraction reaching the baghouse were affected by the milling conditions. Higher air classification speeds resulted in lower D90 in the cyclone and a larger proportion of baghouse material. This is because the classifier speed primarily indicates the degree to which the particles are ground (faster classification speeds result in finer grinding). Cyclones can block airborne particles down to a certain size. Therefore, typically, the more the material is ground, the smaller the larger particle size end (D90) of the classifier's particle size distribution becomes, and the proportion of material that is too small to be separated by the cyclone increases (and is therefore collected in the baghouse). Since the cyclone D90 is controlled by the shape of the cyclone itself, the particle size of the baghouse D90 does not change relatively much with respect to the classifier speed. [Table 5]

[0181] Some of the samples shown in Table 3 were compounded with SBR using the hardened package shown in Table 1C. The resulting tensile stress / strain curves are shown in Figure 20, and other compounding data are shown in Table 4. The cyclone material showed higher low-strain reinforcement compared to that used in the first example of Alpine Jet Milling. All samples showed relatively high low-strain reinforcement and relatively low tensile strength. They also all showed relatively high hardness, which suggests that the optimal load may be lower than 50 phr used in these experiments. These data seem to confirm that milling conditions may not affect the properties of the baghouse material. No trends were observed in terms of elongation and tensile strength with respect to classifier speed or chamber pressure. The observed variations may be due to experimental error. The cyclone material appears to exhibit different properties, as it has the lowest elongation at fracture, the lowest tensile strength, and curves as it fractures. [Table 6]

[0182] For example, the baghouse and cyclone materials from Table 3 were taken and blended with N660 carbon black derived from non-biomass feedstocks (e.g., fossil fuel feedstocks) at concentrations of 2.5, 5, and 10 phr (replacing 5, 10, and 20 wt% of N660) during compounding. These batches were compounded using the curing packages shown in Table 1C (e.g., with 1.0 phr of TBBS accelerator). The results from these experiments are shown in Figures 22-24 and Table 5. When baghouse materials were used to replace up to 20 wt% of N660, they exhibited nearly identical performance to pure N660 in terms of stress / strain, tensile strength, elongation at break, hardness, binding rubber, hysteresis loss, and dynamic loss and storage modulus. See Figures 25-27. This indicates that this lineage of carbonaceous materials can be developed as a partial temporary substitute for N660. The cyclone material exhibited slightly lower tensile strength values ​​than N660 at 10% and 20% weight substitution values. This was a surprisingly unexpected result, as the tensile strength of samples using the cyclone material was expected to be lower. [Table 7]

[0183] Figures 21, 22, and Table 5 show that baghouse (BH) heat-treated and jet-milled carbonaceous material (in this case, derived from corn starch / hardwood (CS / HW, 65% / 35%), heat-treated at 1000°C) performs comparably to N660 when blended with N660 and replacing up to 40% of the N660. All were prepared using the same curing package, i.e., the same amount of TBBS [1 part per 100 rubber (phr)], the same amount of filler (50 phr), etc. Repeated measurements are included for N660, 20%, and 40% samples, and these are expressed as their average ("avg").

[0184] Figure 23 and Table 6 show the results of mechanical testing of media-milled carbonaceous materials. Media milling is more readily available than jet milling and can be performed in smaller facilities with fewer resources. The samples in Figure 23 and Table 6 were heat-treated at 1000°C and milled for 40 minutes using 3 mm media in a planetary ball mill. The cured packages differ from the pure carbon black (CB) control (i.e., N660, N990, etc.) and the blended materials. The difference was the use of a larger amount of accelerator (1.9 phr TBBS), which proved necessary to avoid marching modules when replacing 100% carbon black. An unexpected finding shown in Figure 23 and Table 6 is that the carbonaceous material derived from 100% corn starch (CS) performs almost identically to N660 (this is due to two consistent replicate experiments on different days). This was unexpected. This is because, as mentioned above, the primary particle size of carbonaceous materials derived from CS has a D50 value of 200 nm or more (e.g., 236 nm, approximately 45 nm for carbonaceous materials derived from SP, approximately 49-60 nm for N660, and 200-500 nm for N990). Based on the particle size, it would be expected that the reinforcing performance from carbonaceous materials derived from CS would be insufficient, but in reality, the opposite is observed. This can be partially explained by the binding rubber (BR) and oil absorption (OAN) values. For N990, the BR is 3.64% and the OAN is 40.3 g / 100 g, respectively, while carbonaceous materials derived from CS have 50% BR and 65.4 g / 100 g OAN. The much higher BR of carbonaceous materials derived from CS indicates a higher degree of polymer / filler interaction, while a higher OAN indicates a higher structure (in this case, structure refers to the branching state of aggregate particles). For comparison, the OAN of N660 is 91.4 g / 100 g, the OAN of 100% SP heat-treated carbonaceous materials ranges from 57 g / 100 g to 75 g / 100 g (particle examples range from 71 g / 100 g to 75 g / 100 g), and the OAN of CS / HW carbonophilic materials is 7.9 g / 100 g. Additional results comparing the performance of both N660 and N990 are shown in Figure 24. [Table 8]

[0185] Conveniently, the carbonaceous materials disclosed herein also contain low to undetectable levels of polycyclic aromatic hydrocarbons (PAHs). Table 7 shows the PAH levels measured for N660 samples compared to those of the carbohydrate and heat-treated carbohydrate materials. This may be due to (i) the absence of PAHs in the feedstock used to prepare the carbohydrate materials, and (ii) the high temperatures (T≧850°C) used to prepare the carbohydrate materials (which cause the desorption of such molecules from the carbon surface). [Table 9]

[0186] In view of the many possible embodiments to which the principles of this disclosure may be applied, it should be recognized that the exemplary embodiments are merely preferred examples of this disclosure and should not be construed as limiting the scope of this disclosure. Rather, the scope of this disclosure is defined by the following claims. Accordingly, the inventors claim all things that fall within the scope and spirit of these claims as their inventions.

Claims

1. A carbonaceous material produced from biomass raw materials, wherein the carbonaceous material is Carbon content of 85% by weight or more, 150m ２ / g to 500m ２ Surface area in the range of / g, and The carbonaceous material includes oil absorption values ​​in the range of 50 g / 100 g to 100 g / 100 g.

2. The carbonaceous material according to claim 1, wherein the biomass supply raw material includes a lignin-free material, a lignin-containing material, or a combination thereof.

3. The carbonaceous material according to any one of claims 1 to 2, wherein the biomass supply raw material includes corn starch, wood material, or a combination thereof.

4. The carbonaceous material according to any one of claims 1 to 3, wherein the biomass supply raw material is corn starch.

5. A carbonaceous material according to any one of claims 1 to 4, further comprising a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, and / or lignin-derived compounds, or a combination thereof.

6. The carbonaceous material according to claim 5, wherein the macromolecule furan derivative is a humic acid.

7. The carbonaceous material according to any one of claims 1 to 6, wherein the oil absorption value is in the range of 65 g / 100 g to 80 g / 100 g.

8. The carbonaceous material according to any one of claims 1 to 7, wherein the carbonaceous material is in the form of a particulate material, comprising (i) primary particles having a D50 value of 200 nm or more, or (ii) primary particles having a D50 value of 30 nm to 100 nm.

9. The carbonaceous material is obtained by heat-treating a carbonophilic material at a temperature of 800°C to 1000°C, as described in any one of claims 1 to 8.

10. The carbonaceous material is obtained by heat-treating a carbonophilic material at a temperature of 850°C, as described in any one of claims 1 to 8.

11. A carbonaceous material according to claim 9 or claim 10, comprising less than 0.5 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

12. A carbonaceous material according to any one of claims 9 to 11, comprising less than 0.2 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

13. polymer matrix and A composite polymer composition comprising a filler material dispersed in the polymer matrix, wherein at least a portion of the filler material comprises a first filler component which is a carbonaceous material according to any one of claims 1 to 12.

14. The composite polymer composition according to claim 13, wherein the filler material further comprises a second filler component which is chemically different from the first filler component.

15. The composite polymer composition according to claim 14, wherein the second filler component includes carbon black obtained from a non-biomass raw material.

16. The composite polymer composition according to any one of claims 13 to 15, wherein the first filler component is present in an amount ranging from more than 0 to 60% by weight.

17. A composite polymer composition according to any one of claims 13 to 16, having a tensile strength of 2500 psi or more.

18. The composite polymer composition according to any one of claims 13 to 17, wherein the polymer matrix comprises a thermoplastic polymer or an elastomer.

19. The composite polymer composition according to any one of claims 13 to 18, wherein the polymer matrix comprises one or more of styrene-butadiene rubber, butadiene rubber, ethylene propylene diene monomer rubber, isoprene rubber, butyl rubber, and natural rubber.

20. The composite polymer composition according to any one of claims 13 to 19, wherein the first filler component is the carbonaceous material described in claim 4.

21. A rubber-containing product comprising the composite polymer composition according to any one of claims 13 to 20.

22. The rubber-containing product according to claim 21, wherein the rubber-containing product is a tire.

23. Prepolymer materials and A composition comprising a filler material dispersed in the prepolymer material, wherein at least a portion of the filler material comprises a first filler component which is a carbonaceous material as described in any one of claims 1 to 12.

24. The composition according to claim 23, wherein the prepolymer material comprises styrene-butadiene rubber, butadiene rubber, ethylene propylene diene monomer rubber, isoprene rubber, butyl rubber, and natural rubber.

25. A method for producing a carbonaceous material, wherein the method is The method involves obtaining a carbonophilic material from biomass raw materials, wherein the carbonophilic material includes a portion of the unreacted biomass raw materials, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, or a combination thereof. The method comprising providing the carbonaceous material by post-treating the carbonophilic material to at least partially deoxygenate the carbonophilic material, wherein the post-treatment of the carbonophilic material does not include treating the carbonophilic material with an activator.

26. The method according to claim 25, wherein post-treatment of the carbonophilic material includes heat treatment of the carbonaceous material.

27. The method according to claim 25 or claim 26, wherein the heat treatment of the carbonophilic material includes heating the carbonophilic material at a temperature in the range of 300°C to 1000°C.

28. The method according to claim 25, wherein the post-treatment of the carbonophilic material includes converting at least a portion of the carbonophilic material into randomly structured carbon.

29. The method according to any one of claims 25 to 28, wherein the carbonaceous material is a particulate material, and the method further comprises reducing the aggregate particle size of the carbonaceous material.

30. The method according to claim 29, wherein reducing the aggregate particle size of the carbonaceous material includes milling the carbonaceous material.

31. The method according to claim 30, wherein the milling includes jet milling, ball milling, media milling, or a combination thereof.

32. The carbonaceous material is combined with a prepolymer material, The method according to claim 25, further comprising curing and / or solidifying the prepolymer material in the presence of the carbonaceous material to form a composite polymer composition.

33. The method according to claim 32, wherein forming the composite polymer includes forming a rubber-containing product.

34. The carbonaceous material mentioned above is Carbon content of 85% by weight or more, 150m ２ / g to 500m ２ Surface area in the range of / g, and The method according to claim 25, comprising oil absorption values ​​in the range of 50 g / 100 g to 100 g / 100 g.

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