Carbonaceous materials with modulated physical and chemical properties and methods of making and using same

Abstract

Disclosed herein is a carbonaceous material that exhibits properties and characteristics that facilitate its use in forming a composite material. In particular aspects, the carbonaceous material has a carbon content greater than or equal to 85% by weight, a surface area in the range of 150 m2 / g to 500 m2 / g, and an oil absorption value in the range of 50 g / 100 g to 100 g / 100 g. Methods for making and using the carbonaceous material, including forming a composite polymer composition, are also disclosed.

Description

[0001] Cross-reference to related applications

[0002] This application claims the interests and priorities of U.S. Provisional Application No. 63 / 455,522, filed March 29, 2023, and U.S. Provisional Application No. 63 / 525,306, filed July 6, 2023; the full text of each of these earlier applications is incorporated herein by reference. Technical Field

[0003] This disclosure relates to carbonaceous materials, composite polymer compositions containing carbonaceous materials, rubber-containing products containing carbonaceous materials, compositions containing carbonaceous materials, and methods for producing carbonaceous materials. Background Technology

[0004] Carbon black can be produced through the thermal decomposition of hydrocarbons (e.g., incomplete combustion) and is typically derived from fuels / synthetic feedstocks. Carbon black is a versatile material. Carbon black particles have a complex structure that can form aggregates and clusters; however, such particles can also have small diameters (e.g., in the nanometer range), which allows carbon black to absorb and scatter light, resulting in its eponymous "black" color. The color and intensity of carbon black enable it to produce dark, deep shades when used as a pigment in inks, paints, and other matrices.

[0005] Carbon black can also be used as a reinforcing filler in polymer products such as rubber tires, belts, and hoses. The aspect ratio and particulate structure of carbon black result in a reinforcing network of particles within the polymer matrix. This produces more durable materials and can also increase the stiffness, dimensional stability, and load-bearing capacity of the polymer matrix.

[0006] Conventional carbon black (including the methods used to prepare it) is associated with environmental and health considerations. In some cases, carbon black is produced through the incomplete combustion of fossil fuels such as petroleum products, coal tar, or natural gas. This can lead to greenhouse gas emissions and resource depletion. Fossil-based carbon black can also include polycyclic aromatic hydrocarbons (PAHs), which are known carcinogens. Therefore, improved methods for preparing and using materials that avoid these drawbacks are needed. Summary of the Invention

[0007] This disclosure advantageously provides carbonaceous materials produced from biomass feedstocks. In some aspects of this disclosure, the carbonaceous materials produced from biomass feedstocks contain a carbon content of 85% or more by weight. In some aspects, the carbonaceous materials also have a carbon content of 150 m... 2 / g to 500m 2 Surface area in the range of / g and / or oil absorption value in the range of 50g / 100g to 100g / 100g.

[0008] Some aspects of the disclosure relate to methods for producing the carbonaceous materials of this disclosure. In some aspects, the method includes obtaining a parent carbonaceous material from a biomass feedstock and post-treating the parent carbonaceous material, which may comprise a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, or combinations thereof. In some aspects, the post-treatment of the parent carbonaceous material at least partially deoxygenates the parent carbonaceous material to provide the carbonaceous material according to this disclosure. In a separate aspect, the post-treatment of the parent carbonaceous material does not include treating the parent carbonaceous material with an activator.

[0009] The foregoing and other objects, features and advantages of this disclosure will become more apparent from the following detailed description with reference to the accompanying drawings. Attached Figure Description

[0010] Figures 1A to 1F This is a SEM micrograph of the parent carbonaceous material produced from 100% Southern Pine raw materials.

[0011] Figures 2A to 2I It is a parent carbonaceous material and a carbonaceous material according to aspects of this disclosure ( Figures 2A to 2G ) and comparative materials ( Figure 2H and Figure 2I SEM micrographs of examples of ) Figure 2A and Figure 2C The product shown is made from lignin-free raw materials containing 100% corn starch. Figure 2A ) and lignin-containing raw materials containing 100% southern pine ( Figure 2C SEM micrograph of the parent carbonaceous material produced; Figure 2B and Figures 2D to 2G SEM micrographs of carbonaceous materials obtained from a specific parent material are shown; and Figure 2H and Figure 2I Images of comparative materials that lack the structural features exhibited by the materials of this disclosure are shown.

[0012] Figure 3 Several different properties of carbon black are illustrated schematically, including surface functionality, porosity and surface area, primary particle size, aggregate particle size and aggregate structure.

[0013] Figure 4 This is a schematic diagram illustrating a disclosed example, which includes a system for converting biomass feedstock into a parent carbonaceous material, which can be converted into the carbonaceous material of this disclosure.

[0014] Figure 5 This is a schematic diagram illustrating a disclosed example, which includes a system for converting biomass feedstock into a parent carbonaceous material containing lignin and / or humin.

[0015] Figure 6 Examples of 1-D CP MAS solid-state carbonaceous materials obtained from post-processed parent carbonaceous materials, particularly parent materials that have been heat-treated at different temperatures, are shown. 13 C NMR spectrum.

[0016] Figure 7 The results obtained from post-treatment (e.g., heat treatment at different temperatures under an inert gas) are shown. Figure 6 Raman spectra of carbonaceous materials (obtained using a 785 nm wavelength laser).

[0017] Figures 8A to 8C Raman BET, STSA, and microporous surface area as a function of temperature are shown for examples of carbonaceous materials disclosed herein.

[0018] Figure 9 Nitrogen physisorption isotherms of examples of carbonaceous materials disclosed herein are shown, compared to parent carbonaceous materials and commercially available carbon black N660, where solid circles represent adsorption and hollow circles represent desorption.

[0019] Figure 10A and Figure 10B It shows from Figure 9 The pore size distribution obtained from nitrogen physical adsorption data ( Figure 10A ) and cumulative pore volume (QSDFT, slit pore model, adsorption branch; Figure 10B ).

[0020] Figure 11 It shows the content of rich 13 1-D quantitative direct polarization (DP) MAS solid-state on a parent carbonaceous material generated from lignin-free C-glucose raw materials. 13 C NMR spectra were obtained and annotated with the proposed molecular structure of humin, which is present in a parent carbonaceous material derived from a lignin-free raw material.

[0021] Figure 12 It shows Figure 11 The NMR spectrum, which covers a region containing rich in 13 1-D quantitative DP MAS solid-state matrix material generated from lignin-containing raw materials of lignocellulose biomass 13 C NMR spectra, where the spectral intensities are normalized so that each spectrum has a similar total integral for easy comparison; NMR spectra are annotated with chemical portions corresponding to the structures present in the parent carbonaceous material.

[0022] Figure 13 It shows the result of Figure 11 2-D parent carbonaceous material generated from lignin-free raw materials 13 C-13 C. CPINADEQUATE solid-state NMR spectrum in the aromatic region, and it illustrates the NMR characteristics of humulin in the aromatic region of 2D NMR spectrum (e.g., in the 100-165 ppm SQ). 13 C chemical shift and 210-310 ppm DQ 13 (between C chemical shifts).

[0023] Figure 14 It shows the result of Figure 12 2-D of parent carbonaceous materials generated from lignin-containing raw materials 13 C- 13 The C CPINADEQUATE solid-state NMR spectrum in the aromatic region illustrates the characteristic NMR relationship corresponding to lignin.

[0024] Figure 15 Examples of MDR rheology of SBR curing packages with different levels of TBBS accelerators are shown, wherein the curing package also contains a carbonaceous material derived from a parent carbonaceous material produced from 100% Southern Pine and then heat-treated at 850°C for 2 hours (followed by dry media milling).

[0025] Figure 16 Tensile stress / strain of two instances of carbonaceous material obtained from a parent carbonaceous material that was heat-treated and dry-medium-milled for different durations are shown.

[0026] Figures 17A to 17B These are SEM micrographs of additional examples of carbonaceous materials, in which Figure 17A SEM micrographs of carbonaceous material obtained from a heat-treated parent carbonaceous material that has undergone dry media milling for four minutes are shown. Figure 17B SEM micrographs of the heat-treated carbonaceous matrix material after 40 minutes of dry media grinding are shown.

[0027] Figure 18 The dynamic modulus data of the carbonaceous material obtained from the heat-treated parent carbonaceous material subjected to media grinding are shown, compared with the pure rubber sample and the N660 sample.

[0028] Figure 19 Tensile stress / strain data are shown for examples of carbonaceous materials obtained from parent carbonaceous materials that were jet-milled using different classifier speeds, and samples of carbonaceous materials derived from (i) N660 carbon black and (ii) parent carbonaceous materials exposed to media milling for 40 minutes are also shown for comparison.

[0029] Figure 20Tensile stress / strain data are shown for examples of carbonaceous materials obtained from parent carbonaceous materials subjected to jet milling under different conditions and extracted from cyclone separators or bag filter chambers of jet milling equipment, with samples of carbonaceous materials derived from (i) N660 carbon black and (ii) parent carbonaceous materials exposed to 40 minutes of media milling also shown for comparison.

[0030] Figure 21 Tensile stress / strain data are shown for examples of carbonaceous materials for bag filters blended with N660 carbon black at loading ratios of 5%, 10%, 20%, 30%, and 40%, with average values ​​derived from N660 carbon black shown for comparison.

[0031] Figure 22 Tensile stress / strain data for additional examples of cyclone separator carbonaceous materials based on parent carbonaceous materials derived from blends derived from CS / HW are shown, where the carbonaceous materials are blended with N660 carbon black at loading ratios of 5%, 10%, and 20%; average values ​​of the data derived from N660 carbon black are shown for comparison.

[0032] Figure 23 Comparison of tensile stress / strain data for examples of polymeric materials containing the following different types of filler materials is shown: (i) N660 carbon black, (ii) carbonaceous material obtained from a parent carbonaceous material post-treated from 100% wood raw material (represented as "100% SP"), (iii) carbonaceous material obtained from a parent carbonaceous material post-treated from CS / wood blend (represented as "65 / 35CS / HW"), and (iv) carbonaceous material obtained from a parent carbonaceous material post-treated from 100% corn starch (represented as 100% CS).

[0033] Figure 24 A comparison of tensile stress / strain data for examples of polymeric materials containing the following different types of filler materials is shown: (i) N660 carbon black, (ii) N990 carbon black, and (ii) carbonaceous materials obtained from a parent carbonaceous material post-processed from corn starch, wherein the carbonaceous material is included in amounts of 5%, 10%, 20%, and 100%.

[0034] Figure 25 This is a graph showing the tanδ values ​​measured for various blends of N660 with different levels of jet-milled carbonaceous materials.

[0035] Figure 26 This is a graph showing the tensile storage modulus measured for various blends of N660 with different levels of jet-milled carbonaceous materials.

[0036] Figure 27This is a graph showing the tensile loss modulus of various blends of N660 with different levels of jet-milled carbonaceous materials. Detailed Implementation

[0037] I. Abbreviations

[0038] 1D: One-dimensional.

[0039] 2D: Two-dimensional.

[0040] AFEX: Ammonia fiber explosion.

[0041] atm: 1 atmosphere.

[0042] avg: average value.

[0043] barg: gauge pressure (in bar).

[0044] BH: Bag filter chamber.

[0045] BR: Bound rubber.

[0046] C6: A molecule containing six carbon atoms.

[0047] CP-INADEQUATE: Incredible Natural Abundance Double Quantum Transfer Experiment (IPD).

[0048] CS: Corn starch.

[0049] CY: Cyclone separator.

[0050] D50 value: In particle size distribution, the D50 value represents the 50% smallest and 50% largest particle size in terms of cumulative mass.

[0051] D90 value: In particle size distribution, the D90 value represents the particle size at which 90% of the cumulative mass is smaller and 10% is larger.

[0052] DOE: Design of Experiments.

[0053] DP: Direct polarization.

[0054] HW: Hardwood.

[0055] MAS: Magic Angle Rotation.

[0056] nm: nanometer.

[0057] OAN: Oil Absorption Count (also known as "Oil Absorption Value").

[0058] OCC: Used corrugated cardboard boxes / cardboard.

[0059] ONP: Old newspaper.

[0060] P: Reaction pressure.

[0061] Pa: Pascal pressure.

[0062] PAH: Polycyclic aromatic hydrocarbons.

[0063] ppm: Parts per million.

[0064] psi: pounds per square inch.

[0065] SA: Surface area.

[0066] SBR: Styrene-butadiene rubber.

[0067] SEM: Scanning Electron Microscope.

[0068] SP: Southern Pine.

[0069] ssNMR: Solid-state nuclear magnetic resonance.

[0070] TBBS: N-tert-butyl-benzothiazole sulfonamide.

[0071] UV: Ultraviolet radiation.

[0072] wt.%: weight percentage.

[0073] II. Overview of Terms, Scope, and Definitions

[0074] The foregoing general description and the following detailed description are exemplary and illustrative only, and are not intended to limit the scope of this disclosure.

[0075] As used herein, the singular includes the plural unless otherwise specified. For example, the singular forms “a,” “an,” and “the” used in the specification also include the plural aspect unless the context otherwise requires. Similarly, any singular term used in the specification also means plural or vice versa unless the context otherwise requires.

[0076] Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. While similar or equivalent methods and materials to those described herein may be used in the practice or testing of this disclosure, suitable methods and materials are described below. Materials, methods, and examples are illustrative only and are not intended to be limiting unless otherwise indicated. Further features of this disclosure will be apparent from the following detailed description and claims.

[0077] The disclosure of numerical ranges should be understood to refer to every discrete point within that range, including the endpoints, unless otherwise indicated. Unless otherwise indicated, all figures representing the amount or properties of components, such as molecular weight, percentage, etc., as used in the specification or claims, should be understood to be modified by the term "about". Therefore, unless otherwise implied or expressly indicated, or unless the context is properly understood by one of ordinary skill in the art (benefiting from this disclosure) to have a more explicit construction, non-numerical properties such as amorphous, continuous, crystalline, homogeneous, etc., as used in the specification or claims, should be understood to be modified by the term "substantially," meaning a large range or extent. Therefore, unless otherwise implied or expressly indicated, the proposed numerical parameters and / or non-numerical properties are approximate values, which may depend on the desired properties sought, the detection limits under standard test conditions / methods, limitations of the processing method, and / or the nature of the parameter or property. The disclosed figures are not approximate values ​​when examples are directly and explicitly distinguished from the prior art discussed, unless the word "about" is used.

[0078] As used herein, the term "or combinations thereof" refers to all permutations and combinations of the items listed preceding the term. For example, "A, B, C, or combinations 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 if the order is significant in the particular context. Continuing with this example, combinations containing repetitions of one or more items or terms are explicitly included, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, etc.

[0079] The term "activator" refers to an agent used to form a surface area with a high surface area (e.g., over 500 m²). 2 Impregnating materials, such as impregnating carbon materials, with a surface area of ​​(g / g) are used to form chemically reactive products. In all aspects of this disclosure, an activator is a chemical that is definitively added to a parent carbonaceous material to impregnate the material and thereby form activated carbon. Activators may include bases, acids, metal halides, urea, or combinations thereof, which are definitively added to promote impregnation of the parent carbonaceous material. The aspects of the products and methods disclosed herein do not include the use of activators. Any acids, bases, metal halides, and / or urea disclosed for use in preparing the parent carbonaceous material according to this disclosure are not activators and are not added to promote impregnation to form activated carbon.

[0080] The term "biomass feedstock" generally refers to any plant or plant-derived material composed of organic compounds (such as carbohydrates) with relatively high oxygen content, which can be used as a starting material for the production of the carbonaceous materials disclosed herein. In some aspects of this disclosure, biomass feedstock comprises lignin-free materials, as described in more detail below. In some more specific aspects, biomass feedstock comprises plant-based lignin-free materials. In other aspects of this disclosure, biomass feedstock comprises lignin-containing materials, as described in more detail below.

[0081] The term "carbonaceous material" generally refers to a material containing carbon that has been obtained from a parent carbonaceous material through post-processing and has a lower oxygen content than the parent carbonaceous material. In some instances, carbon is the main component (e.g., carbon is greater than 80% by weight of the carbonaceous material). In some aspects of this disclosure, the carbonaceous material has a carbon content of greater than or equal to 85% by weight, and at 150m 2 / g to 500m 2 Surface area in the range of / g and oil absorption value in the range of 50g / 100g to 100g / 100g.

[0082] The term "carbon black" generally refers to carbon materials produced by the incomplete combustion of coal tar or petroleum products, and does not include carbonaceous materials according to this disclosure.

[0083] 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 according to DIN 51732.

[0084] The term "cellulose" generally refers to a naturally occurring polysaccharide having approximately 70 to over 10,000 β(1→4) linked D-glucose units in a straight chain. Cellulose has the general formula (C6H2O). 10 O5) n :

[0085]

[0086] Cellulose is a structural component of plant cell walls. Approximately one-third of plant matter is cellulose. Wood contains about 50% by weight of cellulose. Cellulose polymers can be characterized by their degree of polymerization, which is the number of monomer units, specifically glucose units. Cellulose polymers can contain hundreds to thousands of glucose units. For example, the degree of polymerization can range from about 1000 in wood pulp to about 3500 in cotton fiber. Cellulose can be broken down into glucose through hydrolysis or by the enzyme cellulase.

[0087] The term "composite polymer composition" generally refers to a solid material composed of two or more constituent materials with different physical and / or chemical properties, which, when combined, produce a material in which each substance retains its identity while contributing the desired properties to the whole. "Retaining its identity" means that the individual materials remain separate and distinct within the composite structure. A composite material is not a solid solution or a simple physical mixture of its constituent materials. In other words, each particle of a composite material comprises regions or domains of two or more constituent materials.

[0088] The term "curing" generally refers to a chemical process that results in the formation of polymer chains. Curing processes may include linking monomeric units, dimeric units, oligomeric units, or combinations thereof together. Curing processes may additionally or alternatively include crosslinking between polymer chains or portions of polymer chains.

[0089] The term "deoxygenation" generally refers to a chemical process that results in the removal of oxygen atoms or molecules from a composition of substances.

[0090] The term "derivative" generally refers to a compound derived from a similar compound or a compound that can be imagined to be produced by another compound, for example, if one atom is replaced by another atom or group of atoms.

[0091] 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 in another solid component. A molecular dispersion is a system in which at least one component is dispersed uniformly or substantially uniformly in another component at the molecular level.

[0092] The term "elastomer" generally refers to a polymeric material that returns to its original shape after being stretched. Examples of elastomers include, but are not limited to, natural rubber (such as pure rubber), synthetic rubber (such as chloroprene rubber, isoprene rubber, silicone rubber, and butyl rubber), and thermoplastic elastomers (TPEs).

[0093] The term "filler material" generally refers to a substance added to a polymer to modify its properties. In some aspects of this disclosure, filler materials include particulate materials dispersed within a continuous phase of varying compositions. In some more specific aspects of this disclosure, filler materials include carbonaceous materials, carbon black, or combinations thereof.

[0094] The term "furan" generally refers to heterocyclic organic compounds that contain a five-membered aromatic ring with four carbon atoms and one oxygen atom.

[0095] The term "hardening" generally refers to the process of forming a solid material by cooling it. An example of hardening is the process of curing a thermoplastic polymer by cooling it below its melting point or glass transition temperature.

[0096] The term "heat treatment" generally refers to exposing a material to temperatures above its ambient temperature to alter the material's physical and / or chemical properties. In some aspects of this disclosure, heat treatment includes heating a carbonaceous material at 300°C or higher, such as 300°C to 1000°C or higher.

[0097] The term "humin" generally refers to a polymeric material that is insoluble in water and contains high molecular weight furan derivatives. Humin is typically a dark solid formed through a series of complex chemical reactions, such as ring-opening, dehydration, and condensation, and can be produced by the decomposition of carbohydrates and other organic compounds present in biomass.

[0098] 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 contains a multiphase and irregular polymer network of aromatic alcohols called lignin monomers, such as coniferyl alcohol, sinigrin, and p-coumaryl alcohol.

[0099] The term "lignin-containing material" generally refers to materials that contain lignin. Examples of lignin-containing materials include wood, grass, and paper products.

[0100] The term "lignin-free material" generally refers to a material that is essentially free of lignin. Examples of lignin-free materials include plant-derived carbohydrates such as glucose and cellulose.

[0101] The term "macromolecule" generally refers to a polymer molecule that has a relatively large molecular weight or structure relative to its monomer units.

[0102] The term "matrix" generally refers to a polymeric material in which filler materials are mixed or dispersed.

[0103] The term "grinding" generally refers to a physical process in which the size of solid material is reduced. Grinding can involve crushing, grinding, or cutting solid material to produce smaller fragments or particles. Examples of grinding processes include jet milling, ball milling, media milling, grinding, classifying milling, or combinations thereof.

[0104] The term "part" usually refers to a fragment of a molecule or a portion of a conjugate.

[0105] The term "oil absorption value" generally refers to a measure of a material's ability to absorb oil or other non-polar liquids. The oil absorption value can be determined according to ASTM D2414-15, "Standard Test Method for Carbon Black – Oil Absorption Count (OAN)".

[0106] The term "matrix carbonaceous material" generally refers to carbonaceous material produced from a process in which biomass feedstock is exposed to acid but prior to any post-processing steps according to the methods described herein.

[0107] The term "particulate material" generally refers to material having one or more discrete masses. The term "particle" is generally understood to mean material with very small or extremely small masses.

[0108] The term "polycyclic aromatic hydrocarbon" or "PAH" generally refers to a hydrocarbon molecule that contains multiple aromatic rings.

[0109] The term "polymer" generally refers to molecules of repeating structural units (e.g., monomers) formed through a chemical reaction, namely polymerization.

[0110] The term "post-processing" generally refers to the chemical or physical processes performed on the parent carbonaceous material after it has been manufactured to provide carbonaceous materials according to various aspects of this disclosure. In a separate aspect, post-processing does not include exposing the parent carbonaceous product to an activator.

[0111] The term "prepolymer material" generally refers to a chemical composition and / or chemical compound containing reactive functional groups capable of polymerization. Examples of prepolymer materials include partially polymerizable resins containing reactive functional groups, such as epoxy resins, polyesters, isocyanates, or polyurethanes. Other examples of prepolymer materials include partially polymerizable organosilicon 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 are used as a starting point for further polymerization reactions, typically with the addition of crosslinking agents, catalysts, or other additives to form a polymer product with desired properties.

[0112] The term "primary particle" generally refers to the smallest unit of material that forms larger aggregates or clusters. In some respects, primary particles are non-discrete and fused together at the neck of the particle.

[0113] The term "rubber" generally refers to a type of elastomeric material. In some instances, rubber exists naturally, for example, in the form of latex. Rubber can be synthesized additionally or alternatively through the polymerization of various monomers such as styrene, butadiene, and isoprene.

[0114] The term "rubber-containing product" generally refers to an apparatus / equipment or composition of substances that contains rubber. Some examples of rubber-containing products include automobile tires, industrial belts and hoses, seals, and gaskets.

[0115] The term "tensile strength" is generally a measure of the maximum amount of tensile (tension) stress a material can withstand before it breaks or fractures. It represents the resistance a material can withstand when 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).

[0116] The term "thermoplastic polymer" generally refers to a material that can be heated and softened repeatedly. Examples of thermoplastic polymers include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, and polycarbonate. In some aspects of this disclosure, the thermoplastic polymer comprises a thermoplastic elastomer. Examples of thermoplastic elastomers include styrene block copolymers (e.g., styrene-butadiene-styrene and styrene-ethylene-butene-styrene), thermoplastic polyurethanes, thermoplastic olefins (e.g., ethylene propylene diene monomer rubber, polyethylene, and polypropylene), and thermoplastic vulcanized rubbers.

[0117] The term "random-layered carbon" generally refers to a material in which carbon atoms are arranged in layers. In random-layered carbon, the layers of carbon atoms are not aligned with each other. The carbon layers can be randomly oriented or otherwise lack long-range order. This disordered structure produces properties different from more ordered structures, such as in graphite.

[0118] III. Introduction

[0119] As described above, carbon black is a common material; however, its production is associated with environmental and health considerations. To address these problems and other drawbacks associated with conventional carbon black materials, this disclosure provides carbonaceous materials produced from biomass feedstocks that can be used as an alternative to conventional carbon black materials. In some aspects of this disclosure, the carbonaceous material contains a carbon content of 85% or more by weight. In yet another aspect, the carbonaceous material has a carbon content of 150 μm. 2 / g to 500m 2 Surface area in the range of / g. In another aspect, the carbonaceous material exhibits an oil absorption value in the range of 50g / 100g to 100g / 100g. Additional characteristics of the carbonaceous material disclosed herein are described. Advantageously, the production of the carbonaceous material disclosed herein results in less carbon emissions than conventional fossil-based carbon black. In addition, the carbonaceous material does not have detectable levels of PAH or has PAH levels below the detectable limit, thereby reducing the negative health effects associated with conventional carbon black materials.

[0120] IV. Carbonaceous materials

[0121] Compared to carbonaceous materials, the parent carbonaceous material used to prepare the carbonaceous material according to this disclosure has a highly functionalized and relatively hydrophilic chemical structure. Some composite polymer materials require hydrophobic fillers and / or fillers with relatively fewer oxygen-containing groups than the parent carbonaceous material. Therefore, the parent carbonaceous material can be post-treated to at least partially deoxygenate it to form the carbonaceous material according to this disclosure. Not limited to a single theory, post-treatment is currently considered beneficial for forming a more hydrophobic, disordered layer surface.

[0122] In some respects, the chemical structure of carbonaceous materials may include a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based compounds, or any combination thereof. Examples of macromolecular furan derivatives include humulins. Huminins are macromolecules with a polymeric furan-type structure. Without wishing to be bound by any theory, in one possible mechanism, humulins may be formed as a result of ring-opening hydrolysis and cross-linking and / or branching of furans. As described in more detail below, humulins may be insoluble and remain in the solid phase along with the unreacted biomass during the production of the carbonaceous material. In some respects, carbonaceous materials derived from lignin-containing biomass are predominantly lignin-based, indicating the presence of unreacted lignin, partially decomposed lignin, lignin derivatives, or combinations thereof.

[0123] In some aspects of this disclosure, the carbonaceous material is in the form of particulate matter. The particles of the parent carbonaceous material (before post-processing) can have textures / features of various length scales. For example, parent carbonaceous materials derived from wood can have particles with a size of 0.1 to 10 mm and a shape generally similar to that of wood raw materials, such as… Figure 1A and Figure 1B As shown. However, the parent carbonaceous material also contains particles with an average size of 30 nm to 100 nm (or 3 x 10⁻⁶). -5 mm to 1x10 -4 Primary particles within the range of mm. Figure 1C and Figure 1D They are shown respectively Figure 1A and Figure 1B An enlarged image of the parent carbonaceous material, which reveals the primary particles in more detail. Figure 1E and Figure 1F They are shown respectively Figure 1A and Figure 1B An additional view of the parent carbonaceous material shows the layered, hierarchical nature of its structure. This hierarchical structure can be retained in carbonaceous materials obtained from the parent material. Materials obtained using certain methods known in the art do not form such a hierarchical structure. For example, exposing biomass feedstocks (such as corn starch) according to this disclosure to processing conditions including concentrated HCl, as described by methods known in the art, produces materials lacking discrete particles and any hierarchical structure, such as... Figure 2H and Figure 2I As can be seen in the text.

[0124] In some aspects, primary particles present in the parent carbonaceous material used to prepare carbonaceous materials may have a D50 value of 100 nm or larger, but typically less than 1 micrometer. In some such aspects, primary particles present in the parent carbonaceous material have a D50 value of 200 nm or larger, but typically less than 1 micrometer. Figure 2A An example of a parent carbonaceous material derived from a raw material containing corn starch is shown. Figure 2A The parent carbonaceous material has primary particles D50 of 236 nm. Figure 2B It shows from Figure 2A Examples of carbonaceous materials obtained from a parent material are obtained by heat treatment of the parent material followed by media grinding.

[0125] In contrast, the primary particles present in carbonaceous materials obtained from lignin-containing raw materials can be smaller than those obtained from lignin-free raw materials. Figure 2C The parent carbonaceous material derived from raw materials containing southern pine is shown. Figure 2D This shows the process from before media grinding. Figure 2C Carbonaceous materials obtained from the parent material. Figure 2E The carbonaceous material after media grinding is shown. Figure 2C The parent carbonaceous material has primary particles (D50) of 45 nm. Some products formed from lignin-containing raw materials may contain primary particles with diameters ranging from 10 nm to 100 nm, such as... Figures 1A to 1F As illustrated, this difference in primary particle size also affects the surface area (SA) of the material. In some cases, SA ranges from 10 to 100 m². 2 Within the range of / g, lignin-free feedstocks produce materials with lower surface areas, while lignin-containing feedstocks produce materials with higher SA (superoxide dismutase). For example, Figure 2A The parent carbonaceous material has 10m 2 / g to 20m 2 / g, such as 12-16m 2 / g of SA. Figure 2B Carbonaceous materials have approximately 50-90 μm 2 / g of SA.

[0126] The ability to adjust the morphology of carbonaceous materials according to this disclosure 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 typically comprises relatively small particles with dimensions ranging from about 20 to 100 nm. Reinforcing carbon black is characterized by its ability to increase the tensile strength, tear resistance, and abrasion resistance of polymers such as rubber materials. Unreinforcing carbon black contains larger particles, typically larger than 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 electrical conductivity or UV protection. Semi-reinforcing carbon black falls between the reinforcing and unreinforcing types, where the particle size is typically in the range of about 100 to 200 nm. Compared to reinforcing and unreinforcing carbon black, it provides moderate reinforcing properties but offers a balance between strength and flexibility. By adjusting the particle size, carbonaceous materials can be used to replace and / or complement grades of all three types of carbon black.

[0127] In some aspects, carbonaceous materials have properties at 150m 2 / g to 600m 2 / g such as 150m 2 / g to 550m 2 / g, or 150m 2 / g to 500m 2 / g, or 150m 2 / g to 450m 2 / g, or 150m 2 / g to 400m 2 / g, or 150m 2 / g to 350m 2 Surface area in the range of / g. In some aspects, carbonaceous materials have a surface area in the range of 150m. 2 / g to 330m 2 Surface area in the range of / g. Carbonaceous materials possess porosity levels achievable through heat treatment of the parent carbonaceous material. This porosity increases the surface area (SA) of the carbonaceous material relative to the parent material. For example, the SA of SP-derived parent carbonaceous materials ranges from 57 to 89 μm. 2 Within the range of / g, after heat treatment and media grinding of the parent material and without the application of an activator, the SA in carbonaceous materials increases to 270-295m. 2 / g. Without grinding, the SA of this example is 140m. 2 / g to 200m 2 / g. In this particular example, the heat treatment was carried out at 1000°C. In some other respects, lower temperatures (e.g., 850°C) can provide 380m prior to any grinding. 2 / g to 430m 2 SA value per g, and then up to 500 m after grinding (e.g., media grinding). 2 SA value per g. The SA of CS-derived parent carbonaceous materials is 12-16 m. 2 Within the range of / g, after heat treatment and media grinding of the parent material, the SA increased to 315m in carbonaceous materials. 2 / g. For this example, 259m was obtained prior to milling. 2 The SA value of the parent carbonaceous material derived from CS / HW is 45-64m. 2 Within the range of / g, after heat treatment and grinding (e.g., jet milling) of the parent material, the SA increases to 170-185m in carbonaceous materials. 2 / g. Figure 2F and Figure 2G Images of carbonaceous materials obtained from a CS / HW-derived parent carbonaceous material through heat treatment and jet milling are shown, in which... Figure 2F A cyclone separator section made of carbonaceous material is shown, and Figure 2G The bag filter chamber section is shown.

[0128] In some aspects of this disclosure, the oil absorption value of the carbonaceous material is in the range of 50 g / 100 g to 100 g / 100 g, such as 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. Oil absorbance value, or oil absorbance number (OAN), measures the amount of oil added to a material that still contributes to the percolation network. For example, the oil absorbance 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, structure refers to the degree of branching of the aggregate particles). For comparison, N660 has an OAN of 91.4 g / 100 g, 100% SP heat-treated carbonaceous material has an OAN in the range of 71.9–74.4 g / 100 g, and CS / HW parent carbonaceous material has an OAN of 7.9 g / 100 g.

[0129] Compared to carbon black, the disclosed carbonaceous material is more carbon negative in its production. Furthermore, the source material used to prepare the carbonaceous material has a carbon strength (CI) of -1.7 kg CO2 / kg carbonaceous material (dry basis), while fossil fuel-derived furnace black has a historical average CI of +2.4 kg CO2 / kg produced. Fossil-based ASTM-grade carbon black also has high levels of PAHs, known carcinogens. PAHs were not detected in the disclosed carbonaceous material (i.e., PAH content was 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 not expected to be present due to the high temperatures of the heat treatment process. The disclosed carbonaceous material also exhibits better performance than other bio-based solutions and performs better than existing carbon blacks in terms of sustainability.

[0130] In some aspects of this disclosure, the carbonaceous material has a carbon content of 85% or more, such as 85% to 100% by weight, or 90% to 100% by weight, or 95% to 100% by weight. In some aspects, the carbonaceous material has a carbon content of 90% or more, such as 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 aspects, these carbon content values ​​can be obtained by heat-treating the parent carbonaceous material as described herein at a temperature of 850°C or higher (e.g., 850°C to 1000°C). For example, in some aspects, carbonaceous materials derived from Southern Yellow Pine (SP) heat-treated at 1000°C have a carbon content in the range of 93-95%. In another exemplary aspect, carbonaceous materials derived from CS / HW have a carbon content in the range of 91-96%. Carbon content can be used as a proxy value for deoxidation level and hydrophobicity, which can be adjusted by changing the conditions of the heat treatment steps.

[0131] In some representative aspects, the carbonaceous material is obtained from a parent carbonaceous material that has been heat-treated at 850°C (or higher), and the carbonaceous material has a carbon content of greater than or equal to 85% by weight; at 150m 2 / g to 500m 2 Surface area in the range of / g; and oil absorption value in the range of 50g / 100g to 100g / 100g. In another representative aspect, the carbonaceous material is obtained from a parent carbonaceous material that has been heat-treated at 850°C (or higher), and the carbonaceous material has a carbon content greater than or equal to 90% by weight; in 150m 2 / g to 330m 2 Surface area in the range of / g; and oil absorption value in the range of 50g / 100g to 80g / 100g.

[0132] V. Applications of carbonaceous materials

[0133] The carbonaceous materials disclosed herein can be used as feedstocks for a variety of applications. In some respects, the suitability of an application may depend on the properties of the carbonaceous materials, such as primary particle size, aggregate particle size, surface area / porosity, surface functionality / hydrophobicity, and / or aggregate structure.

[0134] Carbonaceous materials can serve as a platform for various carbon products, including carbon black substitutes and / or supplements. The morphology of carbonaceous materials plays a role in their ability to be used in some products and / or functions, such as fillers for composite materials. The morphology of carbonaceous materials can be influenced by many factors, including but not limited to: feedstock, reaction time, temperature, acid concentration, brine concentration, organic phase to water ratio, reactor geometry, impeller design, impeller stirring speed, feed loading, and other factors.

[0135] The tunable morphology (including tunable primary particle size) of carbonaceous materials allows them to be engineered to behave similarly to various carbon black grades (e.g., N660 carbon black, N990 carbon black, carcass black, tread black, etc.) and other specialty carbon blacks including varying degrees of hydrophilicity or oxygen content. Therefore, the carbonaceous materials disclosed herein can be used as carbon black substitutes (for reinforcing and non-reinforcing applications and colorant applications) and / or supplements (e.g., they can be used in conjunction with carbon black). In some independent embodiments, carbonaceous materials can be used as activated carbon and / or fuels. The hydrophobicity of the carbonaceous materials can also be tuned, which can improve compatibility with different solvents.

[0136] In a particular aspect of this disclosure, carbonaceous materials according to this disclosure are used as fillers in composite polymer materials, such as reinforcing fillers in elastomers. Carbonaceous materials can exhibit the desired properties exhibited by carbon black. Some of these properties are... Figure 3 As shown in the figure, and may include, but not be limited to, surface functionality, porosity, primary particle size, aggregate particle size and / or aggregate structure.

[0137] Using the carbonaceous materials disclosed herein and the methods described herein, non-particulate materials in quantities of approximately 20 grams can be blended with SBR. The composite material is reinforced relative to unfilled materials (e.g., pure rubber). It has been demonstrated herein that blending carbonaceous materials with N660 can achieve similar, if not superior, properties. In certain aspects, 100% replacement of N660 with carbonaceous materials in SBR rubber exhibits reinforcement relative to unfilled pure rubber.

[0138] VI. Preparation of carbonaceous materials

[0139] Figure 4 A block diagram of an example system and method for converting biomass feedstocks into carbonaceous materials according to this disclosure is shown. Figure 4 In one example, biomass 102 is added to reactor 100 and contacted with organic solvent 104 and 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 furans and furan derivatives.

[0140] After the reaction is complete, in step 120, the reaction mixture is separated into an organic phase 112 and an aqueous phase 114 at a separation temperature. The parent carbonaceous material 122 (which may contain unreacted biomass, insoluble humin, and other materials) may remain with the aqueous phase 114. As described in more detail below, when biomass 102 includes lignin, the parent carbonaceous material may additionally include a lignin fraction, such as... Figure 5 exemplified.

[0141] A. Raw materials

[0142] Raw materials used to produce the parent carbonaceous material generally refer to starting materials used to produce the parent carbonaceous material, which is then converted into the carbonaceous material disclosed herein. Suitable raw materials may include any material containing sugar. In a particular aspect, the raw material comprises cellulosic biomass, such as lignocellulose and other cellulosic materials. Non-limiting examples of raw materials may include glucose, dextran, cellulose, lignocellulose, hemicellulose, starch, sucrose, or any mixture thereof.

[0143] In some aspects, the raw materials include six-carbon (C6) sugars and / or five-carbon (C5) monosaccharides. The terms "hexose sugar" or "C6 sugar" generally refer to a sugar in which the monomer unit has six carbons. The terms "pentose sugar" or "C5 sugar" generally refer to a sugar in which the monomer unit has five carbons. The raw materials may include monosaccharides, disaccharides, polysaccharides, or any mixture thereof. In one aspect of this disclosure, the raw materials include one or more C6 monosaccharides. In another aspect of this disclosure, the raw materials include disaccharides or polysaccharides comprising monomer units having six carbon atoms. It should be understood that the monomer units may be the same or different.

[0144] In one aspect, the raw material comprises a monosaccharide. Examples of suitable monosaccharides include glucose, fructose, and any other isomers thereof. In another aspect, the raw material comprises a disaccharide. Examples of suitable disaccharides include sucrose. In yet another aspect, the raw material comprises a polysaccharide. Examples of polysaccharides include cellulose, hemicellulose, cellulose acetate, and chitin. In other aspects, the raw material comprises a mixture of monosaccharides, disaccharides, and polysaccharides. For example, in one aspect of this disclosure, the raw material may include glucose, sucrose, cellulose, or any combination thereof. In another aspect of this disclosure, the raw material comprises dextran, starch (e.g., corn starch), cellulose, hemicellulose, another dehydrated sugar, or any combination thereof.

[0145] In some aspects, the raw material includes a C6 sugar selected from glucose, fructose (e.g., high-fructose corn syrup), cellobiose, sucrose, lactose, and maltose, or their isomers (including any stereoisomers), or any mixture thereof. In one aspect, the raw material includes glucose, or its dimer or polymer, or its isomer. In another aspect, the raw material includes fructose, or its dimer or polymer, or its isomer. In another aspect of this disclosure, the raw material is a sugar composition. For example, the sugar composition may include monosaccharides or mixtures of sugars, such as fructose, glucose, sucrose, lactose, and maltose.

[0146] Raw materials suitable for producing parent carbonaceous materials may also include derivatives of the aforementioned sugars. In some aspects, the raw materials may contain aldoses, ketoses, or any mixture thereof. In some aspects, the raw materials include C6 and / or C5 aldoses, C6 and / or C5 ketoses, or any mixture thereof.

[0147] In some aspects, the raw materials include aldoses or any polymers thereof. In one aspect of this disclosure, the raw materials include C6 aldoses or any polymers thereof. Examples of suitable aldoses include glucose. In another aspect of this disclosure, the raw materials include polyaldehydes.

[0148] In other respects, the raw materials include ketoses or any polymers thereof. In another respect, the raw materials include C6 ketoses or any polymers thereof. Examples of suitable ketoses include fructose. In another aspect of this disclosure, the raw materials include polyketoses.

[0149] In another aspect, the raw materials include a mixture of C6 aldoses and C6 ketooses. For example, in one aspect of this disclosure, the raw materials may include glucose and fructose.

[0150] In some respects, when the starting materials include sugar, the sugar may be present in open-chain form, cyclic form, or a mixture thereof. Those skilled in the art will recognize that when the starting materials include glucose, the open-chain form of glucose used may exist in equilibrium with several cyclic isomers in the reaction.

[0151] In other respects, when the raw material includes sugar, the sugar may be present as any stereoisomer or as a mixture of stereoisomers. For example, in some respects, the raw material may include D-glucose, L-glucose, or a mixture thereof. In other respects, the raw material may include D-fructose, L-fructose, or a mixture thereof.

[0152] In one aspect of this disclosure, the raw materials include hexoses. Hexoses are monosaccharides having six carbon atoms and the chemical formula C4H2O. 12 O6. Hexoses may include aldoses or ketoses or mixtures thereof. Hexoses may be in open-chain form, cyclic form or mixtures thereof. Hexoses may contain any stereoisomers or mixtures of stereoisomers. Suitable hexoses may include, for example, glucose, fructose, galactose, mannose, allose, arbutin, gulose, idole, taloose, allulose, sorbitol and tagatose or any mixture thereof.

[0153] Raw materials used to produce the parent carbonaceous material can be obtained from any commercially available source. For example, those skilled in the art will recognize that cellulose and hemicellulose can be present in biomass (e.g., cellulose biomass or lignocellulose biomass). Thus, in some aspects, the raw material comprises biomass, which can be any plant or plant-derived material composed of organic compounds with relatively high oxygen content, such as carbohydrates, and also contains a variety of other organic compounds. As described above, some of these raw materials (such as wood, grass, corrugated cardboard, etc.) also contain lignin. Biomass may also contain other materials, such as inorganic salts and clay.

[0154] Biomass can be pretreated to help make sugars in the biomass more readily available by disrupting the crystal structure of cellulose and hemicellulose and breaking down the lignin structure (if present). Pretreatment can include, for example, mechanical processing (e.g., chopping, crushing, milling), concentrated acid, dilute acid, SO2, alkali, hydrogen peroxide, wet oxidation, steam explosion, ammonia cellulose explosion (AFEX), supercritical CO2 explosion, liquid hot water, and organic solvent treatment.

[0155] Biomass can be derived from a variety of sources. For example, biomass can be derived from agricultural materials (e.g., corn kernels, corn cobs, corn stalks, rice husks, peanut shells, and waste grains), processing waste (e.g., paper sludge), and recycled cellulosic materials (e.g., cardboard, old corrugated cardboard / paperboard (OCC), old newspapers (ONP), and blended paper). Other suitable examples of biomass may include wheat straw, paper mill effluent, newsprint, municipal solid waste, wood chips, sawdust, forest thinnings, felled timber, miscanthus, switchgrass, sorghum, bagasse, manure, wastewater biosolids, green waste, and food / feed processing residues.

[0156] Any combination of the raw materials described herein may also be used. For example, in one aspect of this disclosure, the raw materials may include glucose, corn kernels, and sawdust. In another aspect of this disclosure, the raw materials may include sawdust and cardboard. In yet another aspect of this disclosure, the raw materials may include bagasse and cardboard. In yet another aspect of this disclosure, the raw materials may include empty fruit bunches. In yet another aspect of this disclosure, the raw materials may include corn starch and sawdust. In yet another aspect of this disclosure, the raw materials are substantially composed of or consist of corn starch. In the aspect where the raw materials are substantially composed of corn starch, the raw materials do not contain or do not contain another type of biomass from which the parent carbonaceous material may be derived.

[0157] B. Acid

[0158] In some respects, the acids used to produce the parent carbonaceous material are halogenated acids. Such acids have the formula HX, where X is a halogen. However, it should also be understood that any other suitable acid may be used. Other examples of suitable acids include halogenated inorganic acids or halogenated 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 fluoroboric acid. Combinations of any of the acids described herein may also be used.

[0159] Therefore, the acids used in this paper can be obtained from any commercially available source or generated in situ by providing suitable reagents to the reaction mixture. For example, hydrochloric acid can be generated in situ in the reaction mixture by providing sulfuric acid and sodium chloride to the reaction mixture.

[0160] In other respects, the acid fed into the reactor or reaction mixture is a gaseous acid. For example, at least a portion of this gaseous acid may dissolve or partially dissolve in the reaction mixture to produce an aqueous acid.

[0161] The concentration of acids used herein may vary depending on several factors, including the type of raw materials used. In some respects, concentrated acids are used. For example, those skilled in the art will recognize that concentrated hydrochloric acid is 12M. In other respects, the concentration of acids used to produce the materials disclosed herein is less than 12M, less than or equal to 11.5M, less than or equal to 11M, less than or equal to 10.5M, less than or equal to 10M, less than or equal to 9.5M, less than or equal to 9M, less than or equal to 8.5M, less than or equal to 8M, less than or equal to 7.5M, less than or equal to 7M, less than or equal to 6.5M, less than or equal to 6M, less than or equal to 5.5M, less than or equal to 5M, less than or equal to 4.5M, less than or equal to 4M, less than or equal to 3.5M, less than or equal to 3M, less than or equal to 2.5M, less than or equal to 2M, less than or equal to 1.5M, or less than or equal to 1M; or intermediate. Between 0.25M and 10M, between 0.25M and 9M, between 0.25M and 8M, between 0.25M and 7M, between 0.25M and 6M, between 0.25M and 5M, between 0.5M and 10M, between 0.5M and 9M, between 0.5M and 8M, between 0.5M and 7M, between 0.5M and 6M, between 0.5M and 5M, between 1M and 10M, between 1M and 9M, between 1M and 8M, between 1M and 7M, between 1M and 6M, between 1M and 5M, between 1M and 4M, or between 2M and 4M.

[0162] C. Salt

[0163] Salts are optionally used in the production of a parent carbonaceous material for obtaining the disclosed carbonaceous material. The salt may comprise one or more inorganic salts and / or one or more organic salts. "Inorganic salt" generally refers to a complex of a positively charged substance and a negatively charged substance, wherein neither substance includes elemental carbon. "Organic salt" generally refers to a complex of a positively charged substance and a negatively charged substance, wherein at least one substance includes elemental carbon.

[0164] The choice of salt can vary depending on the reaction conditions and the acid and solvent used. In some cases, the salt is an inorganic salt. In others, the salt is a halogenated acid. Examples of salts that can be used in certain applications include lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium salts. Combinations of any of the salts described herein may also be used.

[0165] The salt concentration can vary. In some respects, the salt concentration 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, between 5M and 15M, between 5.5M and 10M, between 7M and 10M, or between 7.5M and 9M; or about 10M, about 11M, about 12M, about 13M, about 14M, or about 15M. In other respects, the salt exists in the aqueous phase at about 0.1% to 50% (w / w).

[0166] The salts used in this article can be obtained from any commercially available source or generated in situ by providing suitable reagents to the reaction mixture. For example, some reagents can undergo ion exchange in the presence of hydrochloric acid to produce chloride salts for the production of parent carbonaceous materials.

[0167] D. Solvent

[0168] In some aspects, solvents are used in methods for producing parent carbonaceous materials. Solvents can be obtained from any source, including any commercially available source.

[0169] Any suitable solvent that can form a liquid / liquid biphase in the reaction mixture can be used, such that one phase is predominantly an organic phase and the individual phase is predominantly an aqueous phase.

[0170] Solvents can also be selected based on their dipole moments, which are measures of the solvent's polarity. The dipole moment of a liquid can be measured using a dipole meter. In some respects, the solvents used in this paper have dipole moments of less than 20.1D, less than or equal to 20D, less than or equal to 18D, or less than or equal to 15D.

[0171] Solvents can also be selected based on their boiling points. In some cases, solvents have boiling points of at least 110°C, at least 150°C, or at least 240°C.

[0172] Solvents may include a single solvent or a mixture of solvents. For example, in some aspects, solvents include one or more alkylphenyl solvents, one or more alkyl solvents (e.g., heavy alkyl solvents), one or more ester solvents, one or more aromatic solvents, one or more silicone oils, or any combination or mixture thereof. In other aspects, solvents include one or more hydrocarbons, one or more haloalkanes, one or more ethers, one or more haloethers, one or more cyclic ethers, one or more amides, one or more silicone oils, or any combination or mixture thereof.

[0173] In some respects, solvents include p-xylene, mesitylene, naphthalene, anthracene, toluene, dodecylbenzene, pentylbenzene, hexylbenzene, and other alkylbenzenes (e.g., A, B. AB F,

[0174] R, Cepsa 550-Q, Cepsa 900-Q 5. 7. Synnaph AB 3, Synnaph AB 4), sulfolane, hexadecane, heptadecane, octadecane, eicosane, dodecane, tridecane, tetradecane or any combination or mixture thereof.

[0175] It should be understood that solvents may fall into one or more of the categories listed herein. For example, solvents may include p-xylene, which is an alkylphenyl solvent and an aromatic solvent.

[0176] In some cases, the solvent includes water.

[0177] Combinations or mixtures of solvents may also be used. In some respects, ether solvents may be combined with one or more other types of solvents listed above.

[0178] The solvent used can vary depending on the type and amount of raw material used. For example, in some cases, the mass-to-volume ratio of raw material to solvent is between 1 g of raw material per 100 mL of solvent and 30 g of raw material per 100 mL of solvent.

[0179] It should also be understood that any description of the solvent used to produce carbonaceous materials can be combined with any description of the acid and salt as if each combination were listed separately. For example, in some aspects, the acid is hydrochloric acid, the salt is lithium chloride or calcium chloride or a combination thereof, and the solvent is an alkylphenyl solvent.

[0180] E. Reaction conditions

[0181] As used in this article, "reaction temperature" and "reaction pressure" refer to the temperature and pressure at which the reaction occurs to produce the parent carbonaceous material, respectively.

[0182] In some aspects of the steps for producing carbonaceous materials, 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 aspects, the reaction temperature is between 110°C and 300°C, between 110°C and 250°C, between 150°C and 300°C, or between 110°C and 250°C.

[0183] In some cases, the reaction pressure is between 0.1 atm and 10 atm. In others, the reaction pressure is atmospheric pressure.

[0184] 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 can also be expressed as gauge pressure (barg), which refers to pressure in bar, which is higher than ambient pressure or atmospheric pressure. Pressure can also be expressed in bar, atmosphere (atm), pascal (Pa), or pound-force per square inch (psi). Those skilled in the art will be able to convert the pressures described herein from one unit to another.

[0185] The reaction temperature and reaction pressure in the steps of 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。

[0186] Residence time will also vary with reaction conditions and desired yield. Residence time refers to the average amount of time spent producing the parent carbonaceous material from the reaction mixture. In some aspects of the step of producing the parent carbonaceous 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.

[0187] F. Separation

[0188] In some aspects, methods are provided for producing carbonaceous materials by: combining raw materials, an acid, and optionally a salt to form a reaction mixture; producing a parent carbonaceous material from at least a portion of the reaction mixture; and separating the parent carbonaceous material. As discussed above, the parent carbonaceous material may include unreacted raw material materials and may also include humin, carbohydrate moieties, and / or lignin moieties.

[0189] Refer again Figure 4 In step 122, the produced parent carbonaceous material is separated. Any suitable technique known in the art can be used to separate the parent carbonaceous material, such as filtration and centrifugation. For example, solid-liquid separation techniques such as filtration and centrifugation can be used to separate the produced carbonaceous material.

[0190] G. Post-processing

[0191] In some respects, Figure 4The parent carbonaceous material 122 is post-treated to at least partially deoxidize the parent carbonaceous material and provide carbonaceous material. In some instances, post-treatment of the parent carbonaceous material includes heat treatment of the parent carbonaceous material at a suitable temperature to convert at least a portion of the parent carbonaceous material into carbonaceous material.

[0192] In some respects, heat treatment of the parent carbonaceous material involves heating the parent carbonaceous material at a temperature ranging from 300°C to 1000°C. It should also be understood that the carbonaceous material can be heat treated at any other suitable temperature. Other examples of suitable temperatures may be less than 300°C or greater than 1000°C. Heat treatment of the parent carbonaceous material at temperatures within this range (e.g., at least 350°C to 500°C) can cause at least a portion of the parent carbonaceous material to transform into a disordered carbon-like structure.

[0193] In some cases, the parent carbonaceous material is heat-treated in an inert atmosphere, such as with argon or nitrogen. However, it should be understood that in some cases, the argon or nitrogen atmosphere may contain trace amounts of oxygen.

[0194] There are also specialty carbon black applications requiring more hydrophilic materials and / or materials with higher oxygen content. The carbonaceous materials described herein are well-suited to meet these specifications. In some respects, due to the parent carbonaceous materials produced (e.g., Figure 4 The parent carbonaceous material 122 contains a high oxygen content, and the carbonaceous material can be used to produce fillers with different desired (e.g., intermediate) levels of oxygen-containing groups. This can be achieved by modifying the heat treatment of the parent carbonaceous material. In some aspects, the heat treatment is modified to be carried out at a relatively lower temperature than the temperature used to deoxidize the parent carbonaceous material and / or for a shorter time than the time used to deoxidize the parent carbonaceous material, as described in more detail below.

[0195] In some aspects of this disclosure, the carbonaceous material has a carbon content of 85% or more, such as 85% to 100% by weight, or 90% to 100% by weight, or 95% to 100% by weight. In some aspects, the carbonaceous material has a carbon content of 90% or more, such as 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 aspects, 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 aspects, carbonaceous materials derived from Southern Yellow Pine (SP) heat-treated at 1000°C have a carbon content in the range of 93-95%. In another exemplary aspect, carbonaceous materials derived from CS / HW have a carbon content in the range of 91-96%. Carbon content can be used as a proxy value for deoxidation level and hydrophobicity, which can be adjusted by changing the conditions of the heat treatment steps.

[0196] Figure 6 Cross-polarized / magic-angle-rotated (CP / MAS) solid-state effects of carbonaceous materials heat-treated at different temperatures under nitrogen atmosphere are shown. 13 C NMR. The abundant functional groups in the initially produced parent carbonaceous material (before heat treatment) have a strong influence on the chemical environment of the carbon atoms within the parent carbonaceous material, resulting in heterogeneous spectra up to at least 550 °C.

[0197] In some respects, at least partial deoxidation of the parent carbonaceous material to the carbonaceous material occurs between 350°C and 550°C, where a disordered layered structure can be obtained. The formation of the disordered layered structure can be evaluated using Raman spectroscopy, for example... Figure 7 The data in the example are illustrated. Observation of Raman spectroscopy and 13 Both CNMR and other methods can produce carbonaceous materials with increased carbon structure / content that are closer to the level of N660 carbon black at temperatures of 850°C or near.

[0198] Figures 8A to 8C The formation and subsequent partial collapse of the microporous structure as a function of temperature are shown. This discovery reveals that carbonaceous materials themselves are naturally activated (up to 500 μm) at relatively mild temperatures (around 550 °C) and without the application of activators. 2 / g). Nitrogen physical adsorption isotherm at Figure 9 The figure shows that pore size distribution and cumulative pore volume are in Figures 10A to 10BThe carbonaceous material samples obtained from the heat-treated parent material (i.e., at 550 °C and 850 °C) show high adsorption and low relative pressure, indicating a high abundance of micropores, and 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 carbon black primarily contributes to its surface area. The pore size distribution indicates that the diameter of the formed micropores is less than 1 nm. The cumulative pore volume indicates the presence of mesopores, but these do not appear to be ordered, as evidenced by the lack of substantial peaks in the pore size distribution data between 2 and 30 nm.

[0199] H. Additional processing steps

[0200] As described herein, the carbonaceous material according to this disclosure is prepared by post-processing a parent carbonaceous material obtained from biomass feedstock. The method for preparing the parent carbonaceous material and the characteristics of the parent material are described in more detail below. In addition to the post-processing described herein, the produced parent carbonaceous material may undergo one or more additional processing steps to provide the carbonaceous material of this disclosure. For example, in some aspects, the produced carbonaceous material may be washed after heat treatment of the parent carbonaceous material. In one aspect of this disclosure, the produced carbonaceous material may be washed with an acid wash or a water wash or a combination thereof. For example, in one aspect of this disclosure, the carbonaceous material may be washed with an acid. The acid used to wash the produced carbonaceous material may be referred to as a "washing acid" or an acid wash. In some aspects, the washing acid is an aqueous acid. Suitable acids may include, for example, hydrochloric acid. The washing acid is not an activator and is not used to impregnate the carbonaceous material.

[0201] In other respects, carbonaceous materials can be washed with organic detergents, aqueous detergents, brine or alkaline detergents.

[0202] In other respects, the produced carbonaceous material can be dried with or without washing, as described above. For example, in one aspect of this disclosure, the produced carbonaceous material can be washed after heat treatment and then subjected to a drying step.

[0203] In some aspects of this disclosure, the particle size of aggregates of carbonaceous materials can be reduced by one or more physical processes, such as grinding, sieving, shearing, cavitation, etc. Examples of suitable grinding methods include jet milling, ball milling, media milling, deburring milling, hammer milling, or combinations thereof. Additional details regarding the grinding and application of the ground carbonaceous materials are described in more detail below.

[0204] Furthermore, in some aspects, carbonaceous materials are combined with prepolymer materials that are cured and / or hardened in the presence of the carbonaceous materials to form composite polymer compositions. In some aspects, 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 hardening. 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.

[0205] As described above, composite polymer materials can also be produced using blends of two or more chemically different filler materials. For example, carbonaceous materials can be blended with carbon black obtained from non-biomass sources to form a composite filler for composite polymers. In some aspects, the amount of carbonaceous material present as the first filler material is in the range of greater than 0 to 100% by weight, such as greater than 0 to 95% by weight, greater than 0 to 90% by weight, greater than 0 to 85% by weight, greater than 0 to 80% by weight, greater than 0 to 75% by weight, greater than 0 to 70% by weight, greater than 0 to 65% by weight, greater than 0 to 60% by weight, greater than 0 to 55% by weight, greater than 0 to 50% by weight, greater than 0 to 45% by weight, or greater than 0 to 40% by weight. For example, as described in more detail below, a blend of carbonaceous material and N660 carbon black in a 40:60 weight ratio in a styrene-butadiene rubber (SBR) matrix produces a composite polymer material with a tensile strength greater than or equal to 2500 psi (e.g., 2500 psi to 3500 psi, such as 2500 psi to 3000 psi), which is greater than or equal to a composite material filled only with N660 carbon black. In some aspects, the tensile strength is measured using ASTM D 412. In other aspects, the carbonaceous material of this disclosure may have an elongation in the range of 200% to 600%, such as 300% to 600%, 400% to 600%, or 500% to 600%. In some aspects, the elongation is in the range of 400% to 500%.

[0206] VII. Overview of Several Aspects

[0207] This article discloses various aspects of carbonaceous materials produced from biomass feedstocks, which contain: a carbon content of ≥85% by weight; and a carbon content of ≥150m. 2 / g to 500m 2 Surface area in the range of / g; and oil absorption value in the range of 50g / 100g to 100g / 100g.

[0208] In any or all of the foregoing, biomass feedstocks include lignin-free materials, lignin-containing materials, or combinations thereof.

[0209] In any or all of the foregoing, biomass feedstocks include corn starch, wood materials, or combinations thereof.

[0210] In any or all of the above, the biomass feedstock is corn starch.

[0211] In any or all of the foregoing, carbonaceous materials also include a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based and / or lignin-derived compounds, or combinations thereof.

[0212] In any or all of the above, the macromolecular furan derivative is humic acid.

[0213] In any or all of the above aspects, the oil absorption value is in the range of 65g / 100g to 80g / 100g.

[0214] In any or all of the foregoing, the carbonaceous material is in the form of a particulate material comprising primary particles having a D50 value of (i) 200 nm or greater, or (ii) a D50 value of 30 nm to 100 nm.

[0215] In any or all of the foregoing, carbonaceous materials are obtained by heat-treating a parent carbonaceous material at a temperature of 800°C to 1000°C.

[0216] In any or all of the foregoing, carbonaceous materials are obtained by heat-treating the parent carbonaceous material at a temperature of 850°C.

[0217] In any or all of the foregoing, the carbonaceous material contains less than 0.5 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

[0218] In any or all of the foregoing, the carbonaceous material contains less than 0.2 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

[0219] This document also discloses aspects of a composite polymer composition 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, the first filler component being any or all of the carbonaceous materials described above.

[0220] In any or all of the foregoing, the filler material also includes a second filler component that is chemically different from the first filler component.

[0221] In any or all of the foregoing, the second filler component comprises carbon black obtained from a non-biomass-based feedstock.

[0222] In any or all of the foregoing, the first filler component is present in an amount ranging from 0 to 60% by weight.

[0223] In any or all of the foregoing aspects, the composite polymer composition has a tensile strength greater than or equal to 2500 psi.

[0224] In any or all of the foregoing, the polymer matrix comprises a thermoplastic polymer or an elastomer.

[0225] In any or all of the foregoing aspects, the polymer matrix comprises one or more of styrene-butadiene rubber or natural rubber.

[0226] In any or all of the foregoing, the first filler component is a carbonaceous material according to any or all of the foregoing.

[0227] This document also discloses aspects of rubber-containing products that comprise any or all of the composite polymer compositions described above.

[0228] In any or all of the foregoing, the product containing rubber is the tire.

[0229] This document also discloses aspects 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, the first filler component being any or all of the carbonaceous materials described above.

[0230] In any or all of the foregoing, the prepolymer material comprises (i) a mixture of styrene and butadiene; or (ii) isoprene.

[0231] This article also discloses aspects of a method for producing carbonaceous materials, the method comprising: obtaining a parent carbonaceous material from a biomass feedstock, the parent carbonaceous material comprising a portion of unreacted biomass feedstock, a macromolecular furan derivative, a cellulose compound, a lignin-based compound, or a combination thereof; and post-treating the parent carbonaceous material to at least partially deoxygenate the parent carbonaceous material to provide carbonaceous material, wherein the post-treating of the parent carbonaceous material does not include treating the parent carbonaceous material with an activator.

[0232] In any or all of the foregoing aspects, post-treatment of the parent carbonaceous material includes heat treatment of the carbonaceous material.

[0233] In any or all of the foregoing, heat treatment of the parent carbonaceous material involves heating the parent carbonaceous material at a temperature in the range of 300°C to 1000°C.

[0234] In any or all of the foregoing aspects, post-processing of the parent carbonaceous material includes converting at least a portion of the parent carbonaceous material into disordered carbon.

[0235] In any or all of the foregoing, the carbonaceous material is a particulate material, and the method also includes reducing the aggregate particle size of the carbonaceous material.

[0236] In any or all of the foregoing, reducing the aggregate particle size of carbonaceous materials includes grinding carbonaceous materials.

[0237] In any or all of the foregoing, grinding includes jet milling, ball milling, media milling, or combinations thereof.

[0238] In any or all of the foregoing aspects, the method further includes combining a carbonaceous material with a prepolymer material; and curing and / or hardening the prepolymer material in the presence of the carbonaceous material to form a composite polymer composition.

[0239] In any or all of the foregoing aspects, forming a composite polymer composition includes forming a rubber-containing product.

[0240] In any or all of the foregoing aspects, the carbonaceous material contains 85% or more carbon by weight; at 150m 2 / g to 500m 2 Surface area in the range of / g; and oil absorption value in the range of 50g / 100g to 100g / 100g.

[0241] VIII. Examples

[0242] Various aspects of this teaching can be further understood from the following embodiments. While these embodiments are for experimental demonstration purposes, those skilled in the art will recognize that the embodiments are not limited to these small molecules or molecular weight ranges, and that the teachings herein enable those skilled in the art to prepare and use a wide variety of carbonaceous materials.

[0243] Synthesis of wet parent carbonaceous materials. The reaction of biomass with carbonaceous materials occurs in an 80-gallon pilot-scale reactor, with a target reaction temperature range of 135–145 °C and a reaction time of 10–24 minutes. The target concentration of the aqueous phase is typically 2 M HCl, 5.5% CaCl2, and 13 M total Cl. The feedstock mass fraction in the aqueous phase is typically in the range of 10–23% by weight and consists of a single feedstock (corn starch or wood only) or a blend of feedstocks (combined corn starch and wood). The “aqueous phase” is defined as the total water, CaCl2, and HCl in the reactor. The organic matter to water content ratio is in the range of 1.6 to 2.2. Note that various types of hardwood and softwood have been tested. The process steps are similar, but the specific amounts of raw materials added vary.

[0244] Drying and Carbonization. 56 kg of wet carbonaceous material with an 80% wet basis (%wb) moisture content was placed in the furnace system. The system underwent a nitrogen purging cycle to inert the furnace environment. Nitrogen was then introduced into the system at a set flow rate (50 standard liters per minute (slpm)) and maintained at a slight positive pressure (760-860 Torr). The system was heated to 175°C at 2.5°C / min, followed by a 12-hour isothermal cycle for the drying step. The system was then heated to 200°C at 0.2°C / min, followed by a 2-hour isothermal cycle to confirm material drying. The system was then heated to 530°C at 2.75°C / min, followed by an isothermal hold for 2 hours. The system was then heated to 1000°C at 7°C / min and held isothermally for 4 hours to ensure complete carbonization. The system was shut down and the equipment allowed to cool to ambient temperature, which took approximately 12 hours.

[0245] Jet milling. In the embodiments described herein, 200 to 1200 g of carbonaceous material is fed into an Alpine jet mill at a rate of 1 to 5 kg / hr. A milling gas pressure of 70 to 110 psi and a classifier speed of 12,000 to 22,000 rpm are used. A two-stage particle collection system consisting of a cyclone separator and a bag filter is employed. The cyclone separator and bag filter fractions are collected and tested separately. It should be recognized that these conditions may vary depending on the mill used. For example, a mill with a larger classifier can be used at a larger feed rate under different milling gas pressures and / or lower speeds.

[0246] Rubber compounding. Compounding was performed using the following ASTM standards: ASTM D 3182: Weighing and mixing (TPE / rubber and plastic blends); ASTM D 5289: Vulcanization using a rotorless curing apparatus (MDR)-rheometer; ASTM D412: Original physical properties of rubber - tensile stress and strength; ASTM D 3182: Molding and curing standard sheets or plates 6" x 6"; and ASTM D5992: DMA-Metravib-Strain scan at room temperature. Curing packages were used according to Table 1A.

[0247]

[0248] NMR: Rich 13 C D-glucose was purchased from Cambridge Isotope Laboratory, Inc. (CAS: 110187-42-3). 13The C-type hybrid poplar (Populus alba × Grandidentata) was obtained as a gift from Professor Jenny Mortimer of the Joint BioEnergy Institute, USA. Rooted poplar shoots (4 weeks old) were transferred to 12L plastic containers containing 11L of Hoagland's solution at pH 6.0. Poplar biomass... 13 C enrichment is in the presence of 13 C atmosphere and controlled growth conditions (28℃, 70% humidity, 155 μmol m) -2 s -1 The growth was carried out in a self-built growth chamber (with 18 hours of light). Poplars in 13 They are grown in a growth chamber for 68 days before being harvested.

[0249] The reaction was carried out using GC headspace vials with flap caps. Two separate vials were loaded with enriched... 13 C glucose (269mg) and rich 13 C lignocellulose biomass (245 mg) and the same stir bar were used. A brine / acid solution (1.25 mL) and toluene (2.00 mL) were added. The vial was capped and placed behind a blast-proof baffle in a heating block set to 130 °C. The stirring rate was set to 1000 rpm, and the vial was heated for 22.5 min. The reaction was quenched in an ice-water bath for rapid cooling. No weight loss was measured (<0.005 g), indicating no material leakage during the reaction. The reaction slurry was filtered through a funnel using 10 μm polyethylene glass frit (Chemglass), and the solid product was recovered and 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 tray covered with aluminum foil and dried in a 90 °C oven for approximately 48 h. Subsequently, the solid product was directly loaded into a solid-state NMR rotor for molecular structure studies.

[0250] exist Figure 11 and Figure 12 In the embodiments, make rich 13 C glucose and rich 13 Poplar biomass reacts in parallel to generate parent carbonaceous material for parallel comparison. According to Figure 11 An example of quantitative one-dimensional (1D) 13 C direct polarization (DP) ss NMR spectrum, rich in 13 C-glucose-derived parent carbonaceous materials ( 13C-Glu-HTC showed major characteristic chemical shifts at 151.1 ppm, 144.7 ppm, 121.3 ppm, and 111.5 ppm, representing the two α-carbons, linked β-carbons, and β-carbons of the furan subunit. Carbonyl and carboxylate groups were also detected in the chemical shift region, at 210–190 ppm and 183–167 ppm, respectively. Aliphatic carbon bonds of the furan subunit were detected in the chemical shift region of 53–10 ppm.

[0251] on the other hand, Figure 12 It shows rich 13 C. Poplar biomass-derived parent carbonaceous materials ( 13 Quantitative 1D of C-Bio-HTC) 13 C DP ss NMR spectrum, the parent carbonaceous material and 13 C-Glu-HTC has different major chemical shifts compared to it. 13 The spectrum of C-Bio-HTC is dominated by the aromatic region, with characteristic chemical shifts representing the aromatic rings of the lignin subunits, such as S3 / 5, G3, G1, G2, S2 / 6, and methoxy carbon 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 significant peaks in the carboxylate carbon chemical shift region, but the main chemical shifts are related to those from... 13 The carboxylate carbon in C-Glu-HTC is slightly different. Additionally, it differs from... 13 Compared to C-Glu-HTC 13 The not strong recording of C-Bio-HTC in the carbonyl carbon region suggests that... 13 C-Bio-HTC contains very little or no humin.

[0252] In addition, 13 C-Glu-HTC and 13 Both C-Bio and HTC conducted 2D 13C-13C related CP-INADEQUATE NMR experiments (respectively). Figure 13 and Figure 14 To achieve better resolution on the severely overlapping peaks in the aromatic regions. These [measures]... 13 C-Glu-HTC and 13 Different details of the molecular structure of C-Bio-HTC provide additional evidence. 13 The CP-INADEQUATE spectrum of C-Glu-HTC revealed five major types of furan structural environments, with no significant evidence of aromatic ring structures. However, 13The molecular structure of C-Bio-HTC is dominated by seven identified lignin-derived aromatic ring structures (three types of G units, two types of S units, and two types of oxidized S units), with no furan structures observed. This is consistent with... Figures 5 to 6 The results are consistent with those indicated by the 1D spectrum.

[0253] Figure 6 Examples of 1-D CP MAS solid-state carbonaceous materials obtained from post-processed parent carbonaceous materials, particularly parent materials that have been heat-treated at different temperatures, are shown. 13 C NMR spectroscopy. The spectrum provides a broad indicator of the relative abundance of heteroatoms (e.g., oxygen) in carbonaceous materials. Heat-treating carbonaceous materials at higher temperatures for the same time results in greater deoxidation compared to heat-treating at lower temperatures for the same duration. Deoxidation is indicated by the relative smoothing of the NMR spectrum, as the chemical diversity of the carbonaceous material decreases and the remaining carbonaceous material transforms into disordered carbon. In representative embodiments, the oxygen content is modified to the values ​​indicated in Table 1B.

[0254]

[0255] The molecular structures of the parent carbonaceous materials generated from lignin-free raw materials and lignocellulose biomass raw materials were obtained through magic angle rotation (MAS). 13 We used solid-state nuclear magnetic resonance (ssNMR) to study it. We employed a high-carbon enriched... 13 C-type lignocellulose biomass is used to produce parent carbonaceous materials whose molecular structures can be directly detected by ssNMR. Parent carbonaceous materials derived from lignin-containing raw materials have different molecular structures than those derived from lignin-free raw materials such as glucose and corn starch. The molecular structure of parent carbonaceous materials derived from lignin-free raw materials is mainly composed of humin, which is dominated by furan subunits with aliphatic bonds, carbonyl groups, and carboxylate groups, such as... Figure 11 As illustrated. In contrast, the molecular structure of parent carbonaceous materials derived from lignin-containing biomass is dominated by the lignin-based portion, such as... Figure 12 The aromatic cyclic subunits are illustrated in the examples. These lignin-based moieties can indicate the presence of unreacted lignin, lignin degradation products, lignin-based moieties with modified inter-unit bonds, or combinations thereof.

[0256] The inherent surface activity of the carbonaceous materials disclosed herein is beneficial in various specialized applications, such as coatings and inks. Certain functional surface activities can impart improved reinforcing effects compared to furnace black. This may be beneficial in overcoming the lower structural complexity of the carbonaceous materials disclosed herein (since the structure of carbon black provides reinforcement of rubber chain entanglement within the free volume of carbon black aggregates). Furthermore, rCB (recycled carbon black) has certain limitations compared to the disclosed carbonaceous materials due to its high ash content. High ash content may contain more silica and zinc, thereby reducing the tear strength of the reinforced rubber.

[0257] Figure 7 The results obtained from post-treatment (e.g., heat treatment at different temperatures under an inert gas) are shown. Figure 6 The Raman spectra of carbonaceous materials were obtained. The Raman spectroscopy showed that the carbonaceous materials transformed from resin to a disordered carbon structure between 350 and 550 °C.

[0258] In one instance, the carbonaceous material was dry-medium 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 embodiments of this disclosure. In some respects, a traveling modulus was observed, which could indicate that the accelerator loading may be too low. The accelerator used was N-tert-butyl-benzothiazole sulfonamide (TBBS). Not limited to a single-operation theory, it is assumed that the traveling modulus may be due to the microporosity of the heat-treated material (leading to the physical adsorption of TBBS) or to the abundance of oxygen-containing functional groups (leading to the neutralization and / or chemisorption of TBBS). Figure 15 The MDR rheology of SBRs cured with different levels of TBBS is shown. It was found that 1.9 phr TBBS gave a T90 curing time similar to N660, which has a “typical” curing profile. Therefore, 1.9 phr TBBS is recommended when compounding carbonaceous materials.

[0259]

[0260] Once the curing package is determined, routine testing of the carbonaceous material used as a filler can begin. Figure 16Tensile stress / strain curves for N660, pure rubber, and two carbonaceous material samples after dry media grinding for different durations are shown. It was found that the two carbonaceous material samples withstood significantly higher stresses than the pure rubber, indicating that these samples reinforced the rubber. Table 2 shows the data comparing the carbonaceous materials and N660 blends ground for 4 minutes and 40 minutes. At low strain (≤200%), the sample ground for 4 minutes withstood higher stresses than the sample ground for 40 minutes. However, in some aspects, the 4-minute sample failed at relatively low strains. Throughout the test, the sample ground for 40 minutes resulted in lower stresses than N660, but had comparable elongation at break in some aspects. The performance differences between the two carbonaceous material samples are likely due to aggregate size and structure, not limited to a single theory. Figure 17A As shown, the maximum size of the carbonaceous material milled for 4 minutes was approximately 26 micrometers. In the sample milled for 40 minutes, Figure 17B The largest visible particle size is 8 micrometers. In contrast, N660 carbon black has aggregated particles (D90) of approximately 0.4 micrometers. Surprisingly, 8-micrometer particles will have tensile strength comparable to N660. In some instances, particles larger than 1 micrometer can cause point defects in the rubber matrix, resulting in poor elongation at break (as observed in some aspects of samples ground for 4 minutes). Without being bound by theory, it is possible that samples ground for 40 minutes were ground thoroughly enough that the remaining tubular structures from the woody raw material were transformed into fragments (e.g., the walls of the tubes) and, due to their plate-like morphology, were sheared apart during the rubber / carbonaceous material mixing process.

[0261]

[0262] Table 2 shows that the OAN structure of the 4-minute-milled sample is close to that of the N660 OAN structure (compared to 97 and 90 g oil / 100 g carbon, respectively). The 40-minute-milled sample has an OAN of 57 g oil / 100 g carbon. The larger structure in the 4-minute-milled sample may be the reason for its good reinforcement (stress) at lower strain, and the reason for the lower reinforcement in the 40-minute-milled sample across the entire stress / strain range. Figure 18 The dynamic modulus data for these samples are shown. The relatively high storage modulus of the sample milled for 4 minutes indicates strong filler-filler interactions, likely due to the higher particle structure.

[0263] Other methods for reducing particle size were explored. In particular, contrasting air-jet mills (e.g., alpine mills) were used to grind heat-treated carbonaceous materials. Figure 19The figure shows tensile stress-strain data for an attempt to blend SBR with carbonaceous material produced by alpine jet milling. RPM speed indicates classifier speed. Some samples exhibited relatively poor tensile strength and elongation at break. These samples were taken only from the cyclone separator of the milling equipment and likely had an overly concentrated particle size distribution (approximately 8 micrometers).

[0264] Different alpine mill systems were tested, and materials from the cyclone separator and bag filter chambers were collected. Bag filter chamber materials can be used because they can be finer than cyclone separator materials (and may contain a higher fraction of primary particles). A design of experiments (DOE) was performed by varying the chamber pressure and air classifier speed. The resulting bag filter chamber and cyclone separator particle sizes and fractions are shown in Table 3. The bag filter chamber particle size did not appear to be significantly affected by the grinding conditions. However, the size of the material in the cyclone separator and the total fraction ultimately entering the bag filter chamber were both affected by the grinding conditions. At higher air classification speeds, the D90 in the cyclone separator was smaller, and the fraction of bag filter chamber material was larger. This is because the classifier speed largely determines the degree to which the particles are ground (higher classifier speeds result in finer grinding). Cyclone separators can only capture particles in the air to a certain size. Therefore, generally, the more the material is ground, the smaller the large end (D90) of the classifier's particle size distribution becomes, and the higher the fraction of material that is too small for the cyclone separator to separate (and thus collected in the bag filter chamber). Since the cyclone separator's D90 is controlled by the geometry of the cyclone separator itself, the particle size of the bag filter chamber's D90 remains relatively constant as a function of the classifier's speed.

[0265]

[0266] Several samples shown in Table 3 were compounded with SBR using the curing kits shown in Table 1C. The resulting tensile stress / strain curves were obtained in... Figure 20 The data are shown in Table 1, and other compounding data are shown in Table 4. The cyclone separator material exhibits high low-strain enhancement compared to those used in the first embodiment of the alpine jet mill. All samples showed relatively high low-strain enhancement and relatively low tensile strength. They also all showed relatively high hardness, suggesting that the optimal loading may be less than 50 phr used in these experiments. These data appear to confirm that grinding conditions may not affect the properties of the bag filter chamber material. Elongation and tensile strength showed no trend relative to classifier speed or chamber pressure. The observed variations are likely due to experimental error. The cyclone separator material does exhibit distinct properties, as it has the lowest elongation at break, the lowest tensile strength, and bends downwards upon failure.

[0267]

[0268] For example, bag filter chamber and cyclone separator materials from Table 3 were taken and blended with N660 carbon black obtained from non-biomass-based feedstocks (e.g., fossil fuel feedstocks) at 2.5, 5, and 10 phr (5, 10, and 20% by weight substitutes for N660) during blending. These batches were blended using curing packages shown in Table 1C (e.g., with 1.0 phr TBBS accelerator). The results of these experiments are shown in Figures 22 to 24 And as shown in Table 5. When the bag filter material is used to replace up to 20% by weight of N660, it exhibits almost identical properties to pure N660 in terms of stress / strain, tensile strength, elongation at break, hardness, bonded rubber, hysteresis loss, dynamic loss, and storage modulus. See also Figures 25 to 27 This indicates that this carbonaceous material family can be developed as a partial direct substitute for N660. For 10 wt% and 20 wt% substitution values, the tensile strength values ​​of the cyclone separator material are slightly lower than those of N660. This is a surprising result, as the tensile strength of samples using the cyclone separator material is expected to be poor.

[0269]

[0270] Figure 21 , Figure 22 Table 5 shows that heat-treated and jet-milled carbonaceous materials for bag filters (in this case, from corn starch / hardwood (CS / HW, 65% / 35%), heat-treated at 1000°C) can match the performance of N660 when blended with and replacing up to 40% of N660. These were all produced using the same curing package, i.e., the same amount of TBBS [1 part per hundred parts rubber (phr)], the same amount of filler (50 phr), etc. N660, 20%, and 40% samples include replicates, expressed as their average (“avg”).

[0271] Figure 23 Table 6 shows the mechanical test results of the media-milled carbonaceous materials. Media milling is more readily available than jet milling, can be performed in smaller facilities, and uses fewer resources. Figure 23 The samples in Table 6 were heat-treated at 1000°C and milled in a planetary ball mill for 40 minutes using 3mm media. The cured packages differed from the pure carbon black (CB) controls (i.e., N660, N990, etc.) and blends. The difference lay in the use of a higher amount of accelerator (1.9 phr TBBS), which was found to be necessary to avoid loss of traveling modulus when replacing 100% carbon black. Figure 23An unexpected finding illustrated in Table 6 is that the 100% corn starch (CS)-derived carbonaceous material performed almost as well as N660 (and this was a consistent repetition on two different dates). This was unexpected because, as described above, the primary particle size of the CS-derived carbonaceous material had a D50 value of 200 nm or greater (e.g., 236 nm, compared to approximately 45 nm for SP-derived carbonaceous material, approximately 49 to 60 nm for N660, and approximately 200 to 500 nm for N990). Based on particle size, the reinforcing properties of the CS-derived carbonaceous material were expected to be poor, but in fact, the opposite was observed. This can be explained in part by combining the rubber (BR) and oil absorption (OAN) values, which for N990 were 3.64% BR and 40.3 g / 100 g OAN, respectively, while the CS-derived carbonaceous material had 50% BR and 65.4 g / 100 g OAN. The significantly higher BR of CS-derived carbonaceous materials indicates a high degree of polymer / filler interaction, while a higher OAN indicates a higher structure (in this case, structure means the degree of branching of the aggregate particles). For comparison, N660 has an OAN of 91.4 g / 100 g, 100% SP heat-treated carbonaceous materials have an OAN of 57 g / 100 g to 75 g / 100 g (specific examples are in the range of 71 g / 100 g to 75 g / 100 g), and CS / HW parent carbonaceous materials have an OAN of 7.9 g / 100 g. Additional results comparing the performance of N660 and N990 are shown in... Figure 24 middle.

[0272]

[0273] Advantageously, the carbonaceous materials disclosed herein also possess polycyclic aromatic hydrocarbons (PAHs) at levels so low as to be undetectable. Table 7 shows the PAHs measured for the N660 sample compared to the parent and heat-treated carbonaceous materials. This is likely due to (i) the absence of PAHs in the feedstock used to produce the carbonaceous materials; and (ii) the high temperature (T ≥ 850 °C) used to produce the carbonaceous materials (which causes such molecules to desorb from the carbon surface).

[0274]

[0275] Given the many possible applications of the principles of this disclosure, it should be understood that the illustrated aspects are merely preferred examples of this disclosure and should not be considered as limiting its scope. Rather, the scope of this disclosure is defined by the following claims. Therefore, we claim that all content falling within the scope and spirit of these claims is part of our invention.

Claims

1. A carbonaceous material produced from biomass raw materials, said carbonaceous material comprising: Carbon content greater than or equal to 85% by weight; in the range of 150 m 2 / g to 500 m 2 / g; and Oil absorption value in the range of 50g / 100g to 100g / 100g.

2. The carbonaceous material of claim 1, wherein the biomass raw material comprises lignin-free materials, lignin-containing materials, or combinations thereof.

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

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

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

6. The carbonaceous material as described in claim 5, wherein the macromolecular furan derivative is 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 65g / 100g to 80g / 100g.

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, the particulate material comprising primary particles having a D50 value of (i) 200 nm or greater, or (ii) a D50 value of 30 nm to 100 nm.

9. The carbonaceous material according to any one of claims 1 to 8, wherein the carbonaceous material is obtained by heat-treating a parent carbonaceous material at a temperature of 800°C to 1000°C.

10. The carbonaceous material according to any one of claims 1 to 8, wherein the carbonaceous material is obtained by heat-treating a parent carbonaceous material at a temperature of 850°C.

11. The carbonaceous material as claimed in claim 9 or claim 10, comprising less than 0.5 mg / kg of polycyclic aromatic hydrocarbons (PAHs).

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

13. A composite polymer composition comprising: 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, the first filler component being a carbonaceous material as described in any one of claims 1 to 12.

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

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

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

17. The composite polymer composition according to any one of claims 13 to 16, having a tensile strength greater than or equal to 2500 psi.

18. The composite polymer composition of 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 according to claim 4.

21. A rubber-containing product comprising a composite polymer composition as described in any one of claims 13 to 20.

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

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

24. The composition of 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 carbonaceous materials, the method comprising: A parent carbonaceous material is obtained from biomass feedstock, the parent carbonaceous material comprising a portion of unreacted biomass feedstock, macromolecular furan derivatives, cellulose compounds, lignin-based and / or lignin-derived compounds, or combinations thereof; as well as The parent carbonaceous material is post-treated to at least partially deoxidize the parent carbonaceous material to provide the carbonaceous material, wherein the post-treatment of the parent carbonaceous material does not include treating the parent carbonaceous material with an activator.

26. The method of claim 25, wherein post-processing of the parent carbonaceous material includes heat treatment of the carbonaceous material.

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

28. The method of claim 25, wherein post-processing the parent carbonaceous material comprises converting at least a portion of the parent carbonaceous material into disordered carbon.

29. The method of 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 of claim 29, wherein reducing the aggregate particle size of the carbonaceous material comprises grinding the carbonaceous material.

31. The method of claim 30, wherein the grinding comprises jet grinding, ball milling, media grinding, or a combination thereof.

32. The method of claim 25, further comprising: The carbonaceous material is combined with the prepolymer material; as well as The prepolymer material is cured and / or hardened in the presence of the carbonaceous material to form a composite polymer composition.

33. The method of claim 32, wherein forming the composite polymer composition comprises forming a rubber-containing product.

34. The method of claim 25, wherein the carbonaceous material comprises: Carbon content greater than or equal to 85% by weight; in the range of 150 m 2 / g to 500 m 2 / g to 500 m 2 / g to 500 m 2 / g to 500 m 2 Oil absorption value in the range of 50g / 100g to 100g / 100g.

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