Method of making carbon-coated particles from recovered carbon and other particles

Abstract

Methods of forming carbon-coated particles are described. A method of forming a coated particle involves subjecting the particle to an energy source that is at least one of a hot gas, microwave energy, inductive energy, direct current through the particle, electromagnetic radiation, or solar radiation to form a heated particle, and feeding a hydrocarbon source in the form of a gas or vapor into a chamber, the hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, and thereby the heated matrix particles are coated with the carbon deposit and carbon-coated particles are formed. A coated particle produced by one of the methods of the invention is further described. Advantages achieved with the method are further described.

Description

[0001] This invention relates to methods for coating various particles with carbon coating materials, such as recycled carbon and other carbon particles, as well as carbon coating materials for other types of particles. The invention further relates to carbon-coated carbon particles and other carbon-coated particles, and articles containing them.

[0002] There is a growing need and effort to recycle materials in order to prevent them from ending up in waste fills and to avoid further depletion of natural resources.

[0003] Therefore, using recycled carbon (rC) from used tires (or other sources) as a substitute for carbon black (CB) in rubber-reinforced applications may be a promising strategy. However, compared to CB with the same surface area and structure as measured by OAN, recycled carbon exhibits lower rubber-reinforcing properties, such as lower tensile modulus, lower tear strength, and / or lower fatigue life. One hypothesis is that the primary reason for rC's low rubber-reinforcing properties is its low surface activity. Other possible reasons for low rubber-reinforcing properties include a high percentage of large and difficult-to-disperse aggregates of recycled particles present in the rubber as defects in the form of large undispersed particles, which significantly reduces the rubber's tensile strength, tear strength, and fatigue life. However, another possible reason for the low reinforcing properties of recycled carbon is its compact structure, which is very different from the more extensive fractal structure of carbon black, which enables high rubber-reinforcing properties. Other materials from recycling or other sources besides recycled carbon may have the same or similar problems as recycled carbon.

[0004] Therefore, there is an industrial need to develop processes for using rC and other similar particles that are unsuitable for use as fillers in rubber reinforcement and other applications, making them suitable alternatives or partial alternatives to virgin carbon black. For example, coating regenerated carbon particles with fresh, carbon-black-like carbon is expected to enhance their surface activity. While some technologies may have been explored for carbon-coating particles, there is an industrial need for alternative methods for coating particles such as rC that do not rely on carbon black reactors or similar technologies.

[0005] All patents and publications mentioned in this article are incorporated herein by reference in their entirety. Summary of the Invention

[0006] One feature of the present invention is to provide a method for coating regenerated carbon with a carbon layer.

[0007] Another feature of the present invention is to provide a method for coating particles other than recycled carbon (e.g., particles as non-ASTM reinforced grade particles) with a carbon layer.

[0008] Another feature of the present invention is to provide a method for making recycled carbon a more viable material for use as a reinforcing material in applications such as rubber.

[0009] Another feature of the invention is to provide a method for altering one or more properties of recycled carbon or other particles to make them more suitable as materials for use as reinforcing grade fillers.

[0010] Furthermore, a feature of the present invention is to provide a method for processing recycled carbon and / or other carbon particles and / or other non-ASTM reinforced particles and carbon-free particles, such that the particles can be endowed with rubber-reinforcing properties comparable to virgin carbon black, such as, but not limited to, acceptable tensile modulus, hysteresis (measured by tanδ), tear strength and / or fatigue life.

[0011] Another feature of the present invention is to provide a method for processing recycled carbon and / or other carbon particles and / or other non-ASTM reinforced particles and carbon-free particles, such that the particles can impart superior rubber-reinforcing properties, such as, but not limited to, acceptable tensile modulus, hysteresis (measured by tanδ), tear strength and / or fatigue life, compared to unprocessed starting materials.

[0012] Another feature of the invention is to provide carbon-coated regenerated carbon and / or carbon-coated particles that have one or more different properties compared to non-carbon-coated regenerated carbon (e.g., regenerated carbon or milled regenerated carbon).

[0013] Another feature of the present invention is to provide a method for manufacturing carbon-coated recycled carbon and / or carbon-coated particles that reduces or does not produce carbon dioxide emissions.

[0014] Another feature of the present invention is to provide a method for preparing carbon-coated recycled carbon and / or carbon-coated particles having low greenhouse gas intensity and / or high recycling content.

[0015] To achieve these and other advantages, and in accordance with the purposes of the invention, as embodied and broadly described herein, the invention relates in part to a method for forming carbon-coated matrix particles (e.g., carbon-coated carbon particles). More specifically, one method relates to forming carbon-coated matrix particles, wherein the method includes introducing matrix particles into a chamber and subjecting the matrix particles to an energy source, the energy source being at least one of hot gas, microwave energy, inductive energy, direct current passing through the matrix particles, electromagnetic radiation, or solar radiation, to form heated matrix particles. The method includes feeding a hydrocarbon source comprising or as a gas or vapor into the chamber. The hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated matrix particles with the carbon deposit and forming carbon-coated matrix particles. Exemplary matrix particles used in this method may be or include regenerated carbon particles or other carbon particles as non-ASTM reinforced grade particles.

[0016] The present invention also relates to using the above process on particles, for example, particles having a lower amount of carbon in the particles compared to recycled carbon.

[0017] Furthermore, this invention relates in part to a method for forming carbon-coated precipitated silica particles. The method may include introducing precipitated silica particles into a chamber and subjecting the precipitated silica particles to microwave energy or other forms of energy as detailed herein to form heated precipitated silica particles. The method further includes feeding a hydrocarbon source, comprising or presenting as a gas or vapor, into the chamber. The hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated precipitated silica particles with the carbon deposit and forming carbon-coated precipitated silica particles.

[0018] Furthermore, the present invention relates in part to carbon-coated particles and carbon-coated particles formed by the method of the present invention.

[0019] The present invention further relates to products and / or articles formed at least in part from the coated particles of the present invention, such as, but not limited to, tires, tire components and / or elastomer compounds.

[0020] It should be understood that the foregoing general description and the following detailed description are merely exemplary and explanatory, and are intended to provide further explanation of the claimed invention.

[0021] Various features of the invention are illustrated in conjunction with the accompanying drawings, which are incorporated in and constitute a part of this application, and together with the description, serve to explain the principles of the invention. Attached Figure Description

[0022] Figure 1 This is a simplified cross-sectional view of an example system having a chamber suitable for the methods of the present invention.

[0023] Figure 2 This is a simplified cross-sectional view of a further example of a two-chamber system applicable to the methods of the present invention.

[0024] The figures are not drawn to scale and are provided as simplified views, and need not show all possible implementations or components (components) that may exist. Detailed Implementation

[0025] This invention relates to a method for carbon-coating various types of particles, thereby obtaining carbon-coated particles, and the accompanying generation of hydrogen gas. The coated particles can be carbon particles. The coated particles can be particles with a carbon content. The coated particles can be non-ASTM reinforced particles. The carbon particles that can be coated include recycled carbon. The coated particles can also be carbon-free particles, such as silica particles, preferably precipitated silica particles.

[0026] The method of the present invention relates to forming carbon-coated matrix particles. The method includes, comprises, substantially consists of, or consists of the following steps: introducing matrix particles into a chamber and subjecting the matrix particles to an energy source, said energy source being at least one of microwave energy, inductive energy, direct current passing through said matrix particles, electromagnetic radiation, or solar radiation, thereby forming heated matrix particles. The method includes feeding a hydrocarbon source into said chamber, said hydrocarbon source comprising, containing, substantially consisting of, or consisting of a gas or vapor. The hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated matrix particles with the carbon deposit to form carbon-coated matrix particles. The matrix particles may comprise, substantially consist of, consist of, include, or consist of: a) regenerated carbon particles and / or b) other carbon particles as non-ASTM reinforced grade particles. The temperature of the heated matrix particles can be at least 800°C, at least 900°C, at least 1000°C, at least 1100°C, at least 1200°C, at least 1300°C, at least 1400°C, or at least 1500°C, for example, 900 to 1200°C or 1300 to 1600°C.

[0027] The matrix particles introduced into the chamber can be various types of carbon particles. Furthermore, as described later, instead of carbon particles, the particles can be particles that contain or do not contain carbon. For the purposes of this invention, carbon particles are particles primarily composed of carbon. Carbon particles typically have carbon as a primary component (e.g., based on the total weight of the particles, carbon is present at at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 98 wt%, at least 99 wt%, for example, 75 wt% to 95 wt% or 75 wt% to 100 wt%)). Examples of carbon particles include, but are not limited to, regenerated carbon particles (rC). rC may optionally be depolymerized (i.e., depolymerized regenerated carbon or depolymerized rC depolymerized from regenerated carbon aggregates (i.e., recovered aggregates)).

[0028] rC, such as rC aggregates, is commercially available. Typically, rC aggregates are produced by the pyrolysis of tires and / or other rubber or plastic materials containing filler or reinforcing materials such as carbon black. rC is primarily made from carbon black used to reinforce rubber or plastics. The source tires and other rubber or other source materials contain pyrolyzable components, such as rubber components, and at least a portion of these components are pyrolyzed to produce pyrolytic carbon due to the high temperatures used in the methods of the present invention described herein. The pyrolytic carbon is treated to remove at least one macroscopic contaminant, such as fabric or yarn, and to produce recycled carbon (rC). The average particle size can optionally be reduced by jet milling or grinding as described in WO2023122582, the entire contents of which are incorporated herein by reference.

[0029] Carbon particles that are not ASTM-reinforced grade particles are carbon particles that do not meet one of the ASTM 100, 200, or 300 series carbon black fillers, or one of the ASTM 500, 600, or 700 series carbon black fillers. Examples of such carbon particles can be carbon black, but also include, but are not limited to, solid hydrothermal carbon (HTC), silicon-treated carbon black, silica-coated carbon black, graphene, reduced graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, and biochar. Furthermore, the aforementioned regenerated carbon particles also do not meet this ASTM standard.

[0030] Instead of carbon particles, other types of particles with some carbon content can be used (e.g., 10% to 75% by weight, or 10% to 60% by weight, or 10% to 50% by weight, or 10% to 40% by weight of carbon based on the total weight of the particles). For example, the particles can be graphene oxide, lignin, or nanocrystalline cellulose. Other examples of carbon-containing particles include bio-based particles. Specific examples of bio-based particles include, but are not limited to, polysaccharides or engineered polysaccharides.

[0031] Instead of carbon particles, the particles have little or no carbon content (e.g., less than 10% by weight of carbon). For example, the particles can be precipitated silica, rice husk silica, clay, nano-clay, diatomaceous earth, metal oxides, or metal carbonates.

[0032] Alternatively, and in order to facilitate more efficient heating of the matrix particles and further result in potentially more uniform or more effective coating of the matrix particles, the matrix particles may have one or more of the following particle size parameters:

[0033] A: Volume-weighted average aggregate size is less than 2 micrometers (e.g., less than 1.75 micrometers, less than 1.5 micrometers, less than 1 micrometer, less than 0.9 micrometers, less than 0.8 micrometers, less than 0.7 micrometers, less than 0.6 micrometers, e.g., 0.5 micrometers to 1.9 micrometers, 0.5 micrometers to 1.7 micrometers, 0.5 micrometers to 1.5 micrometers, 0.5 micrometers to 1.25 micrometers, 0.5 micrometers to 1 micrometer, 0.5 micrometers to 0.8 micrometers, 0.6 micrometers to 1.9 micrometers, 0.7 micrometers to 1.9 micrometers, 0.8 micrometers to 1.9 micrometers, 0.9 micrometers to 1.9 micrometers, 1 micrometer to 1.9 micrometers);

[0034] B: D10 aggregate size is below 400nm (e.g., below 375nm, below 350nm, below 325nm, below 300nm, below 275nm, below 250nm, below 225nm, below 200nm, below 175nm, below 150nm, such as 140nm to 390nm, 150nm to 390nm, 160nm to 390nm, 170nm to 390nm, 180nm to 390nm, 190nm to 390nm, 200nm to 390nm, 140nm to 380nm, 140nm to 350nm, 140nm to 300nm, 140nm to 250nm, 140nm to 200nm);

[0035] C: D25 aggregate size is less than 1 micrometer (e.g., less than 0.9 micrometers, less than 0.8 micrometers, less than 0.7 micrometers, less than 0.6 micrometers, less than 0.5 micrometers, less than 0.4 micrometers, less than 0.3 micrometers, less than 0.25 micrometers, less than 0.2 micrometers, e.g., 0.2 to 0.9 micrometers, 0.3 to 0.9 micrometers, 0.4 to 0.9 micrometers, 0.5 to 0.9 micrometers, 0.2 to 0.8 micrometers, 0.2 to 0.5 micrometers, 0.2 to 0.4 micrometers);

[0036] D: D50 aggregate size is less than 4 micrometers (e.g., less than 3.5 micrometers, less than 3 micrometers, less than 2.5 micrometers, less than 2 micrometers, less than 1.5 micrometers, less than 1 micrometer, less than 0.75 micrometers, less than 0.5 micrometers, less than 0.4 micrometers, less than 0.35 micrometers, e.g., 0.35 micrometers to 3.9 micrometers, 0.4 micrometers to 3.9 micrometers, 0.5 micrometers to 3.9 micrometers, 0.6 micrometers to 3.9 micrometers, 0.7 micrometers to 3.9 micrometers, 0.8 micrometers to 3.9 micrometers, 0.35 micrometers to 3.5 micrometers, 0.35 micrometers to 3 micrometers, 0.35 micrometers to 2.5 micrometers, 0.35 micrometers to 2 micrometers, 0.35 micrometers to 1.5 micrometers, 0.35 micrometers to 1 micrometer, 0.35 to 0.9 micrometers);

[0037] E: D75 aggregate size is less than 4.5 micrometers (e.g., less than 4 micrometers, less than 3.5 micrometers, less than 3 micrometers, less than 2.75 micrometers, less than 2.5 micrometers, less than 2.25 micrometers, less than 2 micrometers, less than 1.75 micrometers, less than 1.5 micrometers, less than 1.25 micrometers, less than 1 micrometer, e.g., 1 micrometer to 4 micrometers, 1 micrometer to 3.5 micrometers, 1 micrometer to 3 micrometers, 1 micrometer to 2.5 micrometers, 1 micrometer to 2 micrometers, 1 micrometer to 1.5 micrometers, 1.1 micrometer to 4 micrometers, 1.2 micrometer to 3.5 micrometers, 1.3 micrometer to 3 micrometers);

[0038] F: D90 aggregate size is less than 5 micrometers (e.g., less than 4.5 micrometers, less than 4 micrometers, less than 3.5 micrometers, less than 3 micrometers, less than 2.75 micrometers, less than 2.5 micrometers, less than 2.25 micrometers, less than 2 micrometers, e.g., 2 micrometers to 4.5 micrometers, 2 micrometers to 4.25 micrometers, 2 micrometers to 4 micrometers, 2 micrometers to 3.5 micrometers, 2 micrometers to 3 micrometers, 2.25 micrometers to 4 micrometers, 2.5 micrometers to 4 micrometers, 2.75 micrometers to 4 micrometers);

[0039] G: Heterogeneity index (HI) (defined as the ratio of volume-weighted average aggregate size to number-weighted average aggregate size) is less than 20 (e.g., less than 15, less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, e.g., 4 to 15, 4 to 10, 4 to 9, 4 to 7, 4 to 6, 5 to 15, 6 to 15, 7 to 15, 8 to 12);

[0040] H: >1 micrometer mass percentage less than 60% (e.g., less than 55%, less than 50%, less than 45%, less than 40%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, e.g., 10% to 55%, 10% to 50%, 10% to 45%, 10% to 40%, 10% to 35%, 10% to 30%, 10% to 25%, 15% to 45%, 20% to 45%, 25% to 45%, 30% to 45%).

[0041] The matrix particles may have one or all of the above aggregate size parameters. Any combination of A to H is possible (e.g., one or more of AH, two or more of AH, three or more of AH, four or more of AH, five or more of AH, six or more of AH, seven or all of AH).

[0042] Compared to rC aggregates, depolymerized rC can have any one or more of the following reduced mass percentages: average aggregate size, D10 aggregate size, D25 aggregate size, D50 aggregate size, D75 aggregate size, D90 aggregate size, HI and / or >1 micrometer, by 10%, 20%, 50%, 75% or more.

[0043] rC may contain a certain amount of non-carbon materials. For example, rC may contain 1% to 20% or more (by total weight of rC) of non-carbon materials or components, such as, but not limited to, silica particles and / or ZnO.

[0044] Regarding the chamber, the chamber can have any suitable shape and size, and is made of a material that allows energy from the energy source to contact the matrix particles to produce heated matrix particles and pyrolyze the hydrocarbon source. For example, the chamber can be a fluidized bed reactor, an ablation pyrolysis reactor, a vacuum pyrolysis reactor, a fixed bed drop-type reactor, or a solar pyrolyzer.

[0045] Regarding the energy sources that the matrix particles undergo to produce heated matrix particles, these energy sources include, but are not limited to, exposure to hot gases, resistance heating, microwave energy, induction energy, direct current passing through the matrix particles, electromagnetic radiation, or solar radiation. Heating of the particles can be achieved through dielectric heating or induction heating. For methods relying on passing an electric current through the matrix particles, it is preferable that the matrix particles exhibit electrical conductivity.

[0046] Microwave energy can be obtained from any type of microwave generator. For example, a microwave generator can be a magnetron, which includes a vacuum-sealed chamber with a heated filament and a magnetic field. When the filament is heated, it emits electrons accelerated by the magnetic field, generating an electron stream moving towards the anode. As the electrons pass through the resonant cavity, they oscillate and generate a high-frequency electromagnetic field, which is then guided out of the cavity by an antenna. Other types of microwave generators include klystrons, traveling wave tubes, solid-state devices, etc. The microwave generator can be located within or adjacent to the chamber. Commercial examples include, but are not limited to, MUEGGE microwave generators, CEM microwaves such as the CEM LABWAVE and AIRWAVE models, THERMEX THERMATRON microwave generators, etc.

[0047] Microwave generators can produce electromagnetic radiation with frequencies of at least 0.5 GHz, for example, from 0.5 GHz to 300 GHz or higher.

[0048] Microwave generators can operate at power levels of 300 watts to 4 MW or higher, such as 1 kW to 1 MW, 10 kW to 500 kW, 100 kW to 400 kW, or 200 kW to 300 kW.

[0049] Induction energy can be provided by induction heaters. Induction heating is a non-contact method of heating materials by using a strong magnetic field that induces alternating current within the material, exciting and heating the atoms in the material. Induction heaters incorporate coils that are directly powered by a power source. These coils, also known as inductors, are used to transfer energy from the power source to the material. Inductors range in complexity from simple wound solenoids (including multiple turns of copper tubing wound around a mandrel) to precision items made of solid copper that are machined, brazed, and soldered together. Commercial examples of such induction heaters include, but are not limited to, AMBRELL's EASYHEAT and EKOHEAT induction heating systems, INDUCTOHEAT's INDUCTOFORGE induction heating system, and ENRX's HEATLINE induction heater.

[0050] For example, the induction heater can operate at a frequency of at least 5 kHz, such as 5 kHz to 500 kHz or higher. The induction heater can operate at an induction heater energy level of at least 50 MJ / kg, such as 50 MJ / kg to 250 MJ / kg or higher (where kg is the amount of particles being processed in the chamber).

[0051] The matrix particles can be heated by passing direct current through a DC power source. The DC power source can be a battery, power supply, electrochemical cell, renewable power system, etc.

[0052] For example, a DC power supply can have a voltage of at least 1V to 400V or higher. For example, the voltage of a DC power supply can be 10V to 300V, 50V to 200V, or 100V to 150V.

[0053] Electromagnetic radiation includes waves of electromagnetic fields, such as radio waves, infrared radiation, microwaves, visible light, ultraviolet radiation, X-rays, induction heating, and... Electromagnetic radiation. Examples of microwave generators and induction heating generators have been provided above. Other devices that generate electromagnetic radiation include infrared heaters, lasers, and radio frequency heaters.

[0054] The frequency and power required for an electromagnetic radiation generator depend on the type of electromagnetic radiation being generated. For example, infrared heaters can have a frequency range between 1 μm and 100 μm and a power level ranging from 1 W to 100 kW. Radio frequency heaters can have a frequency range between 1 kHz and 100 MHz and a power level ranging from 1 W to 100 kW. Laser systems can have frequencies from 1 tHz to 100 tHz and power levels ranging from 1 mW to 100 kW.

[0055] Solar radiation can be used to heat particles such as matrix particles. This invention utilizes solar radiation concentrators to increase the intensity of solar radiation to heat matrix particles. Solar radiation concentrators may include solar collectors, solar furnaces, solar ovens, solar kilns, etc. These devices utilize parabolic troughs, dish collectors, tower collectors, mirrors, lenses, reflectors, etc., to amplify and concentrate the heat from solar radiation onto the matrix particles.

[0056] The energy source used can optionally be generated from renewable energy sources, such as renewable electricity (e.g., generated by solar power, wind power, etc.).

[0057] Regarding the hydrocarbon source, as indicated, the hydrocarbon source includes, comprises, substantially consists of, consists of, or is a gas or vapor fed into the chamber. The hydrocarbon source can be considered a carbon source that can be pyrolyzed to form carbon deposits.

[0058] The hydrocarbon source may include natural gas, or contain natural gas, or be natural gas.

[0059] Other examples of hydrocarbon sources include, but are not limited to, propane. Hydrocarbon sources may include, or include, the following: bio-oils, recycled oils, vapors of sustainable oils; byproducts of biofuel or biochemical production; or oils derived from tires (e.g., from tire pyrolysis), oils derived from plastic pyrolysis or recycling, or oils from hydrothermal liquefaction or paper processing.

[0060] Other specific examples of hydrocarbon sources include the following:

[0061] Glycerin produced from biodiesel.

[0062] Other hydrocarbon byproducts of biofuel production, such as distilled corn oil.

[0063] Vaporizable fractions of hydrocarbons derived from hydrothermal liquefaction

[0064] Crude tall oil, tall oil pitch, turpentine, resin or tall oil fat vaporizable components.

[0065] Waste cooking oil.

[0066] Biomethane or renewable natural gas produced from the decomposition of sludge, sewage, agricultural waste, or landfill materials.

[0067] Oil derived from lignin.

[0068] Edible or inedible vegetable oils (e.g., jatropha oil).

[0069] Tire pyrolysis oil is derived from the pyrolysis of tires or rubber products made from natural rubber.

[0070] Hydrocarbons derived from seaweed, algae, or other non-crop plants.

[0071] Hydrocarbons derived from or produced by cyanobacteria.

[0072] Hydrocarbons derived from black liquor produced during the papermaking process.

[0073] Vaporizable oils derived from animal waxes or fats, such as lanolin, lard, or beef tallow.

[0074] Oils refined from animal processing byproducts (such as turkey carcasses) through pyrolysis, thermal decomposition, or rendering.

[0075] Recycled oil or gasifiable hydrocarbons can be:

[0076] Vaporizable components of used engine oil.

[0077] Oil or hydrocarbon gases derived from the pyrolysis of plastic waste.

[0078] Oil or hydrocarbon gases derived from the pyrolysis of municipal solid waste.

[0079] Oil or hydrocarbon gases derived from the pyrolysis of scrap or discarded tires.

[0080] The hydrocarbon source can be from one source or a mixture of two or more sources.

[0081] The hydrocarbon source can be fed into the chamber as one feed or multiple feeds. For example, the hydrocarbon source can be fed (e.g., injected) into the chamber via one or more injectors or feed lines. Multiple feed lines can be located or distributed around the chamber, so that the hydrocarbon source is uniformly distributed in the chamber, which can result in better distribution of carbon deposits from the pyrolysis of the hydrocarbon on the matrix particles.

[0082] The amount of hydrocarbon source can be based on the amount of particles being coated and / or the desired coating thickness, and can depend on the carbon content and pyrolysis behavior of the hydrocarbon source. For example, the amount of hydrocarbon source can be 0.01 kg or more per 1 kg of particles, or 0.1 kg or more per 1 kg of particles, or at least 0.15 kg per 1 kg of particles. Other amounts below or above these ranges can also be used. The hydrocarbon source or hydrocarbon source containing gas or vapor can be gas or vapor. The amount of hydrocarbon source containing gas or vapor can be any amount. The amount of hydrocarbon source in gas or vapor can be, for example, at least 25% by volume, or at least 50% by volume, or at least 75% by volume, or at least 80% by volume, or at least 90% by volume, or at least 95% by volume, or at least 99% by volume.

[0083] The amount of pyrolyzed hydrocarbon source is preferably 100% by volume or about 100% by volume. Amounts less than 100% by volume are possible (e.g., 50% to 99% by volume, or 75% to 99% by volume, or 85% to 99% by volume, or other volume amounts, based on the total volume of hydrocarbon source present). If a certain amount of hydrocarbon source is not pyrolyzed, this unused amount can optionally be recycled and used in subsequent batches to form carbon-coated particles.

[0084] Alternatively, hydrocarbons can be heated in addition to or as an alternative to heating matrix particles. Hydrocarbons can be heated to temperatures of at least 800°C, at least 900°C, at least 1000°C, at least 1100°C, at least 1200°C, at least 1300°C, at least 1400°C, or at least 1500°C, for example, 900-1200°C or 1300-1600°C.

[0085] Alternatively, an oxidizing atmosphere may be present in the chamber for at least a portion of the residence time of the matrix particles within the chamber. The oxidizing atmosphere can be achieved, at least by introducing water into the chamber. Preferably, the oxidizing atmosphere is present in the early or initial phase of the residence time of the matrix particles in the chamber (e.g., during the first half, first third, or first quarter of the residence time). Preferably, oxygen is not introduced into the chamber during the pyrolysis of the hydrocarbon source, thereby delaying or preventing the generation of carbon dioxide and carbon monoxide. More preferably, carbon dioxide and carbon monoxide are not introduced into the chamber during pyrolysis, thus reducing or eliminating carbon dioxide and / or carbon monoxide in the gas stream discharged from the chamber after pyrolysis.

[0086] Alternatively, the method of the present invention may include vapor oxidation of the matrix particles in a chamber. Vapor oxidation can occur at any point during the residence time in the chamber. Preferably, this selection occurs in the early or initial phase of the residence time of the matrix particles in the chamber (e.g., during the first half, first third, or first quarter of the residence time).

[0087] Alternatively, the method of the present invention may further include, in a second step (subsequent step), heating the carbon-coated particles in the same or a different chamber under a neutral or reducing atmosphere. Thus, this further step can be performed once the matrix particles have been carbon-coated by the method of the present invention. The further heating can be achieved using the same or a different energy source as used in the coating step, or it can be a completely different energy source, such as, but not limited to, a rotary kiln, furnace, carbon black reactor (e.g., a multi-stage carbon black reactor or a furnace-type carbon black reactor), or a modified carbon black reactor (e.g., a carbon black reactor excluding any inlet for carbon black forming feedstock). The heating chamber may be an adiabatic chamber. The rotary kiln may be a direct-fired rotary kiln or an indirect-fired rotary kiln. The rotary kiln may be a Feeco rotary kiln.

[0088] The heating in this optional second step can be at a temperature of at least 300°C, at least 500°C, or at least 800°C. If heating is used, the temperature may depend on its function. If heating is used to promote or further promote pyrolysis, a higher heating temperature (at least 500°C or at least 800°C) may be more desirable. If heating is used to promote or further promote the removal of volatiles, a lower heating temperature (e.g., at least 300°C) may be sufficient. This optional heating may benefit from the vaporization (evaporation) or other removal of non-carbonaceous substances or at least a portion of these types of substances. The residence time in this optional second step can be at least 10 seconds, at least 10 minutes, or at least 1 to 2 hours.

[0089] Alternatively, the non-reactive carrier gas may be present as a mixture with the hydrocarbon source or introduced into the chamber together, or introduced before and / or after the hydrocarbon source. Examples of such gases include, but are not limited to, nitrogen, argon, helium, or any combination thereof. The amount of this optional gas can be up to 20:80 (hydrocarbon:non-reactive gas volume ratio). Amounts below or above this ratio are possible.

[0090] As noted, hydrocarbon gases can be introduced into the chamber at two or more locations within the chamber. Furthermore, alternatively, an optional non-reactive carrier gas can be introduced into the chamber, either alone or together with the hydrocarbon gas, at two or more locations within the chamber.

[0091] Regarding the introduction or feeding of matrix particles into the chamber, the matrix particles can be fed into the chamber in batches, continuously, or semi-continuously. For example, the matrix particles can be placed on a tray and then introduced into the chamber. Alternatively, as an alternative, a conveyor or other mechanical device that moves or supplies particles from one location to another can be used to feed the matrix particles into the chamber.

[0092] The feed rate of the matrix particles into the chamber can be any feed rate and can depend on the energy source and the size of the chamber. Examples of suitable feed rates may be at least 100 kg / h or at least 250 kg / h, or at least 500 kg / h, or at least 750 kg / h, or at least 1000 kg / h, or at least 2,000 kg / h, or at least 3,000 kg / h, or at least 4,000 kg / h, or at least 5,000 kg / h particles. The matrix particles can be positioned or located on a fixed bed within the chamber, or they can be placed on a pallet, a moving platform, or a conveyor to be introduced into the chamber.

[0093] Alternatively, the matrix particles can be placed on a moving bed that passes through the chamber.

[0094] In the method of the present invention, when the hydrocarbon source is pyrolyzed and forms a carbon deposit, the carbon deposit can completely coat the matrix particles. Alternatively, the carbon can be deposited almost completely on the matrix particles, such that at least 75%, or at least 80%, or at least 90%, or at least 95%, or at least 98%, or at least 99% of the external exposed surface area of ​​the matrix particles is coated with the carbon deposit.

[0095] The ratio of the Raman D-band area to the Raman G-band area (ID / I / G) of the resulting carbon-coated matrix particles can be from 0.5 to 2.45, for example, from 1 to 2.45 or from 1.5 to 2.45. Raman measurements are based on Gruber et al., “Raman Studies of Heat-Treated Carbon Blacks,” Carbon, Vol. 32 (7), pp. 1377-1382, 1994, which is incorporated herein by reference. The Raman spectrum of carbon includes approximately 1340 cm⁻¹. -1 and 1580cm -1 The two main "resonance" bands at this point are designated as "D" and "G" bands, respectively. The D band is generally considered to be attributed to disordered spp. 2 Carbon and G-bands are attributed to the graphite or "ordered" sp. 2 Carbon. Therefore, the D / G band ratio (also known as I) D / I G The decrease in ) corresponds to a more ordered crystal structure.

[0096] Regarding the coating on the matrix particles, the coating may have a uniform or substantially uniform thickness around the outer surface of the matrix particles. For example, the thickness (average) around the outer surface of the matrix particles may vary by less than 20%, less than 15%, less than 10%, or less than 5%. This determination may be based on, for example, analysis of 5% by weight, 2% by weight, or 1% by weight of the coated matrix particles in a batch.

[0097] The carbon deposit coating can have an average thickness of about 0.5 nanometers (nm) to about 500 nm or greater, or about 0.75 nm to 500 nm or greater, or about 1 nm to 500 nm or greater, for example, 0.5 nm to 450 nm, 0.5 nm to 400 nm, 0.5 nm to 350 nm, 0.5 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 125 nm, 1 nm to 100 nm, 1 nm to 75 nm, 1 nm to 50 nm, 1 nm to 25 nm, 1 nm to 20 nm, 1 The thickness can be from nm to 15 nm, 1 nm to 10 nm, 1 nm to 7.5 nm, 1 nm to 5 nm, 1 nm to 2.5 nm, 0.5 nm to 1 nm, 0.5 nm to 5 nm, 10 nm to 500 nm, 50 nm to 500 nm, 100 nm to 500 nm, 250 nm to 500 nm, 1 nm to 500 nm, 7.5 nm to 50 nm, 10 nm to 50 nm, 1.25 nm to 5 nm, 1.5 nm to 5 nm, 2 nm to 5 nm, 2.5 nm to 5 nm, 3 nm to 5 nm, or any range based on any two values ​​described herein. The average thickness can be based, for example, on an analysis of 5 wt%, 2 wt%, or 1 wt% of the carbon-coated particles in the batch.

[0098] Alternatively, the method of the present invention can result in carbon deposits at least partially coating the matrix particles rather than coating 100% of the matrix particles. For partial coating, for example, 25% to 75% or 50% to 95% of the outer surface of the matrix particles (on average) are coated with carbon deposits.

[0099] The residence time of matrix particles in the chamber is typically sufficient for carbon deposits to form and coat the matrix particles. The residence time can depend on the amount of matrix particles being heated, the type of energy source, the power or frequency of the energy source, the hydrocarbon source, and the heating temperature. For example, the residence time of matrix particles in the chamber can range from 1 second to 3 hours or longer. The permitted stay durations are 1 second to 2.75 hours, 1 second to 2.5 hours, 1 second to 2.25 hours, 1 second to 2 hours, 1 second to 1.75 hours, 1 second to 1.5 hours, 1 second to 1.25 hours, 1 second to 1 hour, 1 second to 45 minutes, 1 second to 30 minutes, 1 second to 15 minutes, 1 second to 10 minutes, 1 second to 5 minutes, 1 second to 60 seconds, 1 second to 30 seconds, 5 seconds to 2 hours, 5 seconds to 1 hour, 5 seconds to 30 minutes, 5 seconds to 15 minutes, 5 seconds to 3 hours, 30 seconds to 3 hours, 1 minute to 3 hours, 5 minutes to 3 hours, 30 minutes to 3 hours, etc.

[0100] Alternatively, the method of the present invention can be carried out in the absence of any catalyst.

[0101] Alternatively, the method of the present invention can be carried out in the absence of any introduced oxygen or oxygen-containing gas (e.g., gas in which oxygen accounts for more than 10% or more than 15% or more than 20% of the total volume of the gas).

[0102] Alternatively, the method of the present invention may produce no or substantially no carbon dioxide or carbon monoxide (e.g., the amount of carbon dioxide and / or carbon monoxide produced is less than 0.5 kg of CO2 and CO per kilogram of carbon-coated particles). Furthermore, the decomposition of hydrocarbons results in the production of hydrogen. Therefore, the produced hydrogen contains no or substantially no carbon dioxide, wherein the carbon from the hydrocarbons is deposited as a solid on the matrix particles. For example, the gas exiting the chamber may contain at most 0.5 kg of a combination of carbon dioxide and carbon monoxide relative to 1 kg of carbon-coated particles, for example, at most 0.2 kg of carbon dioxide and carbon monoxide relative to 1 kg of carbon-coated particles or at most 0.1 kg of carbon dioxide and carbon monoxide relative to 1 kg of carbon-coated particles. The resulting hydrogen can be separated from other gases exiting the chamber by any technique known to those skilled in the art (e.g., pressure swing adsorption, hydrogen-permeable ceramic membranes, etc.).

[0103] The gas discharged from the chamber may be at least 50% by volume hydrogen. In embodiments where no oxygen-containing gas, vapor, or other carrier gas is introduced into the chamber, or only a limited amount is introduced, the gas discharged from the chamber may be at least 60% by volume, at least 70% by volume, at least 80% by volume, or at least 90% by volume hydrogen, for example, 60% to 90% by volume, 70% to 95% by volume, or 80% to 99% by volume. The resulting hydrogen can be used as a fuel source. In some embodiments, the gas discharged from the chamber can be used as a fuel source without further purification processes.

[0104] The matrix particles, heated by an energy source within a chamber, are heated to temperatures of, for example, at least 800°C, or at least 900°C, or at least 1200°C, or at least 1500°C, such as 800°C to 1600°C, or 800°C to 1400°C, or 800°C to 1300°C, or 800°C to 1200°C, or 800°C to 1100°C, or 800°C to 1000°C, or 800°C to 900°C, or 900°C to 1500°C, or 1000°C to 1500°C, or 1100°C to 1500°C. Temperatures of 1200°C to 1400°C, or 1200°C to 1500°C, or 850°C to 1500°C, or 875°C to 1500°C, or 950°C to 1500°C, or 1050°C to 1500°C, or 1150°C to 1500°C, or 1250°C to 1500°C, or 1350°C to 1500°C, or 800°C to 1450°C, or 850°C to 1450°C, or temperatures above 1500°C, or any temperature range from any endpoint of any combination of ranges.

[0105] The temperatures relating to the heated particles mentioned herein and throughout the text (for any other steps) are based on thermodynamic calculations of the material input into the reactor (excluding any heat loss through the chamber or reactor walls). Alternatively, the chamber may have more than one heating zone. When there is more than one heating zone in the heating chamber, one or more of the other zones may be used as additional heat treatment zones (i.e., zones with temperatures of at least 300°C, 500°C, or 800°C) or as quenching zones and / or for other purposes. If more than one zone is used to achieve zone temperatures of at least 300°C, 500°C, or 800°C, each of these zones may have the same, similar, or different heating temperatures. If used, the residence times of each of these zones may be the same, similar, or different. If used, the temperature and / or residence time of each of these zones may deviate from each other by no more than 1%, 5%, 10%, 20%, 30%, 40%, 50%, or 75%, or may differ by at least any of the percentages provided herein.

[0106] If the chamber has more than one heating zone, the energy source used in each zone can be the same or different.

[0107] Alternatively, the chamber may comprise at least a first chamber and a second chamber. In such a configuration, in the first chamber, the matrix particles are subjected to at least one energy source (e.g., microwave energy or inductive energy) such that the matrix particles reach an average surface temperature of at least 800°C, at least 900°C, at least 1000°C, at least 1100°C, at least 1200°C, at least 1300°C, at least 1400°C, at least 1500°C, or at least 1600°C (e.g., 800°C to 1600°C, 800°C to 1500°C, or 1000°C to 1300°C) in the absence of any hydrocarbon source, to obtain heated matrix particles. The heated matrix particles are then conveyed to the second chamber, in which the hydrocarbon source (and any other optional characteristics of the hydrocarbon source) is fed.

[0108] In the second chamber, further heating of the matrix particles may or may not occur. The particles can be heated to an elevated temperature sufficient to eliminate the need for further heating in the second chamber, and this temperature induces pyrolysis of the hydrocarbon source within the second chamber. While not mandatory, but optional, the matrix particles in the second chamber may be further heated using a different energy source, or the same energy source as in the first chamber. The type of energy source may be the same as or different from the energy source used in the first chamber.

[0109] When a further heat source is used in the second chamber, the heat source can maintain the heated matrix particles at an average surface temperature of at least 800°C, at least 900°C, at least 1000°C, at least 1100°C, at least 1200°C, at least 1300°C, at least 1400°C, at least 1500°C, or at least 1750°C, or at least 2000°C (e.g., 800°C to 2200°C, or 800°C to 2000°C, or 1000°C to 1800°C). Alternatively, the heated matrix particles are located on a moving bed in the second chamber.

[0110] Alternatively, at least one catalyst may be used during the method of the invention. For example, the catalyst may be a metallic catalyst or an inorganic catalyst. As a further alternative, recycled iron or limestone may be used and applied to at least a portion of the surface of the matrix particles before exposure to an energy source. In the method of the invention, the catalyst is preferably covered by a carbon deposit coating the matrix particles and is therefore not exposed or visible on the surface of the coated matrix particles. The amount of catalyst may be consistent with that used in conventional or general waste contamination processes. The catalyst may be, but is not limited to, a catalyst-based material having one or more of these metals, such as potassium, sodium, magnesium, calcium, aluminum, nickel, iron, or any combination thereof. Intentionally adding a known pyrolysis catalyst, such as iron, may be advantageous, for example, at a maximum of 10% by weight (other amounts may be used).

[0111] When using two or more chambers, alternatively, the matrix particles may be at least partially depolymerized in the first chamber if they have not yet depolymerized.

[0112] When two or more chambers are used, the chambers (e.g., the first chamber compared to the second chamber) can have different dimensions in terms of volume. As an example, the volume of the first chamber can be at least 25% or at least 50% smaller than the volume of the second chamber (e.g., 25% to 75% smaller than the volume of the second chamber).

[0113] By applying some key aspects of the method of the present invention to particles other than carbon particles, the present invention can provide a method for coating non-carbon particles (e.g., silicon dioxide, preferably precipitated silicon dioxide particles) with carbon.

[0114] For example, the present invention further relates to a method for forming carbon-coated precipitated silica particles. The method includes introducing precipitated silica particles into a chamber and subjecting the precipitated silica particles to one of the energy sources described herein, such as microwave energy or inductive energy, to form heated precipitated silica particles. The method further includes feeding a hydrocarbon source, comprising or presenting as a gas or vapor, into the chamber. The hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated precipitated silica particles with the carbon deposit and forming carbon-coated precipitated silica particles.

[0115] The various details and examples of the methods described above regarding the carbonaceous matrix particles being coated, as well as the operating parameters and other aspects, also apply here to this part of the invention.

[0116] This invention reveals that the size of the matrix particles can affect the ability to obtain carbon-coated particles. While the coated particles are in particulate form, they can be in the form of larger aggregates (particularly from commercial sources supplying the particles). Therefore, one aspect of the invention may involve taking steps to reduce the size of the particles to be coated, such that their size results in carbon-coated particles.

[0117] Alternatively, depolymerization can occur in the same chamber and by the same heating of the particles that cause the hydrocarbon source to pyrolyze.

[0118] Regarding the method steps for depolymerizing particles (e.g., rC aggregates), prior to the step of coating the particles, the method described herein may be used in U.S. Patent Application No. 63 / 493,812, filed April 3, 2023 (the entire contents of which are incorporated herein by reference). In summary, a method for at least partially depolymerizing particles (e.g., carbon particles, such as rC aggregates) comprises, substantially consists of, comprises, or includes the following steps: introducing the particles (e.g., rC aggregates) (e.g., initial rC aggregates) into a heated chamber having one or more regions. As part of the method, the heated chamber has at least one region having a region temperature of at least 800°C or at least 900°C. The initial particles (e.g., rC aggregates) are located in at least one region, said region having a residence time sufficient to cause at least a portion of the particles (e.g., rC aggregates) to depolymerize. Thus, the method results in obtaining depolymerized particles, such as depolymerized rC aggregates (i.e., aggregates with small aggregate sizes or aggregates with smaller aggregate sizes compared to the initial aggregate size of the initial rC aggregates). Other steps can be performed before and / or after depolymerization.

[0119] Aggregate size distribution can be measured using TEM images of the particles according to ASTM D3849 method. Approximately 20 mg of particles were added to 13 mL of chloroform in a beaker, and then sonicated for 10 minutes at 50% amplitude in an ice bath using a Misonix XL2020 ultrasonic probe with a half-inch tip. The sonicated dispersion was further diluted with additional chloroform to approximately 100-120 ppm, and then sonicated again for another three minutes. A drop of this dispersion was placed on a 200-mesh carbon-coated TEM grid and allowed to dry in a desiccator. Image resolution of 1.6 nm / pixel and a minimum particle size of 5 μm were measured using a JEOL JEM-1200 transmission electron microscope (TEM) with an electron accelerating voltage of 80 kV. TEM images were obtained with a field of view of 5 μm. The images were then analyzed using an automated program based on the NIH ImageJ macro language and Microsoft Excel Visual Basic for Applications (VBA) according to ASTM D3849 method. The projected area equivalent diameter D of the regenerated carbon aggregates was determined. circle Used as a measure of aggregate size. Analyze at least 2000 aggregates to obtain both number-weighted and volume-weighted aggregate size distributions of the regenerated carbon sample.

[0120] When used as a partial or complete substitute for virgin carbon black, the presence of rC aggregates larger than 1 micrometer is considered a major cause of its low rubber-reinforcing properties. Aggregates larger than 1 micrometer can account for a significant portion of the total rC aggregates by mass. Therefore, it is believed that, if used "as is," a substantial percentage of the initial rC aggregates or other aggregates of similar size do not provide positive rubber-reinforcing properties or are actually detrimental to achieving positive rubber-reinforcing properties.

[0121] Furthermore, when used in compositions such as elastomeric products, starting aggregates with aggregate sizes greater than 1 micrometer (e.g., 1.1 micrometers to 10 micrometers or higher) are considered to significantly reduce fatigue life and abrasion resistance. For example, elastomeric products prepared using starting rC aggregates can have 5 to 10 times larger numbers of undispersed particles compared to typical carbon black-containing elastomeric composites containing virgin carbon black instead of starting rC aggregates.

[0122] Compared to sidewall formulations containing virgin carbon black, undispersed large rC particles or other particles may be a significant factor leading to reduced fatigue life in tire sidewall formulations containing rC (e.g., fatigue life reduction of up to 60% by DeMattia fatigue testing).

[0123] The accompanying drawings are provided to illustrate aspects of the invention in a simplified schematic manner.

[0124] Figure 1 A general cross-sectional view of the apparatus used in embodiments of the present invention is provided. The entire system or apparatus 10 may have at least one chamber 14 in which the heating of particles (e.g., carbon particles 18) occurs. The particles are introduced via an inlet or port or door 20, and once the process is complete, the carbon-coated particles may exit through the inlet 20 in the same manner, or may exit via an outlet or door 22. The particles may be on a bed or other support surface 24. This may be a fixed bed or a moving bed. Hydrocarbon gas or vapor may be introduced into the chamber 14 via a tube or syringe or feed 12. If desired, more than one feed may be present, and it may be uniformly distributed throughout the chamber. An energy source 16 is located in or adjacent to the chamber 14. The location of the energy source (or a portion thereof) may be below, above, or around the particles 18.

[0125] Once carbon-coated particles are formed, they exit through the chamber outlet, allowing for recovery. The carbon-coated particles can be cooled for use in the recovery step, for example, through one or more quenching steps in one or more quenching zones. The carbon-coated particles can be recovered in the same or similar manner as the recovery of virgin carbon black from the carbon black reactor.

[0126] Figure 2A simplified cross-sectional view of a further embodiment of the entire system or apparatus 30 of the present invention is provided, wherein two chambers are used. A first chamber 42 may initially receive particles 48 (e.g., carbon particles or other particles), and heating may occur in the absence of a hydrocarbon source. Heating may be performed in an oxygen atmosphere, an inert atmosphere, or a vacuum. Heating the particles in the first chamber provides sufficiently hot heated particles such that, upon contact with a hydrocarbon source (in the second chamber 34, the hydrocarbon source introduced through a pipe or inlet 32 ​​is pyrolyzed and coats the particles 37), and / or heating may be used to depolymerize the particles 48. Heating of the first chamber may be achieved using any energy source 44 described herein or other types of energy sources (e.g., ovens, kilns, etc.). The energy source (or a portion thereof) may be located below, above, or around the particles 48. Once heating is achieved in the first chamber 42, the heated particles 46 can be transferred 46 to an inlet or port 38 toward the second or main chamber 34 by any conventional means (e.g., tray, conveyor, container, inlet). The heated particles 37 can be subjected to hydrocarbon-containing gases or vapors that can be introduced into the chamber 34 via a tube or syringe or inlet 32. After the particles are coated, they can exit through inlet 38 in the same manner, or via outlet or port 50. The particles can be on a bed or other support surface 35. This can be a fixed bed or a moving bed. If desired, more than one feed can be present, and it can be uniformly distributed throughout the chamber. An energy source 36 can optionally be located in or adjacent to chamber 34. A further energy source 36 can be used to maintain the particles at a desired temperature and / or to remove volatiles from the particles. The location of the energy source (or a portion thereof) can be below, above, or around the particles 37.

[0127] Alternatively, the matrix particles can be coated in a two-step process. For example, particles 18 exiting chamber 14 can be guided to a further chamber similar to chamber 14 or chamber 34 to be coated with additional carbon. This further chamber can be maintained at a higher or lower temperature than chamber 14. Alternatively or additionally, particles 38 exiting chamber 34 can be guided to a further chamber similar to chamber 14 or chamber 34 to be coated with additional carbon. This further chamber can be maintained at a higher or lower temperature than chamber 34. Using higher or lower temperatures can affect one or more of the kinetics of carbon deposition and the ratio of disordered carbon to graphitic carbon, such as I D / I G The above is not bound by any particular theory; it is believed that higher temperatures are associated with lower ratios of I. D / I G This is related to, and therefore to, a higher proportion of graphitic carbon and / or a larger graphite grain size La.

[0128] Alternatively, the starting matrix particles may be subjected to one or more size reduction processes, such as mechanical grinding, before being introduced into the chamber. Mechanical grinding can reduce the size of any agglomerates to form starting carbon particles or other particles. However, mechanical grinding does not reduce the aggregate size of particles such as rC. Typically, mills can be configured to crush, grind, and / or refine the starting carbon particles or other particles into smaller agglomerates. Mills may include hammer mills, bead mills, jet mills, steam mills, and / or any other grinding, crushing, or milling machines. The grinding steps and / or techniques, as well as the parameters of the starting particles and the ground particles, as described in International (PCT) Publication No. WO2023122582 filed December 20, 2022, are applicable to the purposes of this invention, the entire contents of which are incorporated herein by reference.

[0129] The mill can be directly connected to the inlet of the chamber. For example, rC or other particles can be fed into the mill, and the mill will feed the ground rC or other particles directly into the chamber. Alternatively, the mill can be separate from the chamber, where the particles (e.g., rC) are first ground and then conveyed to the inlet of the chamber.

[0130] After carbon-coated particles are formed, the method of the present invention may include a quenching step.

[0131] Alternatively, the chamber outlet may lead to the inlet of a quenching chamber or quenching zone. The quenching chamber may spray a quenching fluid, such as water, onto the carbon-coated particles. Typically, quenching is used to cool the initial matrix particles. Optionally, quenching may be staged or performed at several points within the quenching chamber. Pressure spraying, gas atomization spraying, or other quenching techniques may be used. For the complete quenching of carbon-coated particles or other particles, any conventional means may be used to quench the carbon-coated particles or other particles downstream of the chamber, and such means are known to those skilled in the art. For example, a quenching fluid, which may be water or other suitable fluid, may be injected to cool the carbon-coated particles or other particles.

[0132] After quenching, the cooled carbon-coated particles or other particles are fed downstream into any conventional cooling and separation process to recover the carbon-coated particles. Any conventional means for recovering the coated particles can be used, and these means may include, but are not limited to, settlers, cyclone separators, bag filters, or other means known to those skilled in the art. After recovering the carbon-coated particles, they may optionally be subjected to a granulation step, similar to that of virgin carbon black.

[0133] To granulate the carbon-coated particles in the mixer, the spray nozzles can be wetted with a binder (e.g., water, toluene, mineral oil, etc.) onto the carbon-coated particles or other particles. The mixer mixes the binder and the carbon-coated particles into a substantially homogeneous mixture that agglomerates (or clumps) into granules of carbon-coated particles. The granules can then be dried to a specific moisture content, for example, less than 1% by weight. By reducing the moisture content of the granules, the method of the present invention prevents the introduction of unwanted moisture into the rubber mixture, which can help control off-gassing emissions when the granules are heated in the rubber mixer and / or the masterbatch batch mixer. These off-gassing emissions can carry toxic components such as polycyclic aromatic hydrocarbons into the air of the manufacturing facility as residual moisture in the agglomerates evaporates under heating.

[0134] The carbon-coated particles of this invention can be used as a substitute or in combination with carbon black or other reinforcing agents as a component in elastomers or rubber products. The carbon-coated particles can be used as a reinforcing agent or filler in materials such as rubber products, like tire components.

[0135] The carbon-coated particles of the present invention can be incorporated into rubber products, for example, for tire treads, particularly for passenger car, light vehicle, truck and bus tires, off-road (“OTR”) tires, aircraft tires, etc.; sub-treads; liner wraps; sidewalls; cushioning rubber for retreading tires; and other tire applications.

[0136] In other applications, the carbon-coated particles of the present invention can be used in industrial rubber products, such as engine mounts, hydraulic supports, bridge bearings and shock absorbers, tank tracks or treads, mining conveyors, hoses, gaskets, seals, blades, weatherstripping products, bumpers, vibration damping components, etc.

[0137] The carbon-coated particles of this invention can be added as a substitute or supplement to a first reinforcing agent for tire components and / or other industrial rubber end uses. The carbon-coated particles of this invention can be combined with natural and / or synthetic rubber in suitable dry or wet mixing processes based on internal batch mixers, continuous mixers, or roller mills.

[0138] The performance of the carbon-coated particles of the present invention as a reinforcing agent in rubber blends can be evaluated, for example, by determining the performance of a rubber composition utilizing the carbon-coated particles of the present invention relative to the performance of a comparable rubber composition that is similar in all respects except for using the carbon-coated particles of the present invention. Alternatively, the values ​​obtained from compositions prepared according to the present invention can be compared with values ​​known in the art related to desired parameters in a given application.

[0139] Carbon-coated rC or other particles, produced using the process described herein, can improve the properties of rubber compounds prepared from carbon-coated materials compared to uncoated matrix particles. For example, carbon-coated rC can improve reinforcing properties such as tensile modulus, hysteresis (measured by tanδ), tear strength, and / or fatigue life. The properties of rubber compounds prepared with coated rC can be comparable to those prepared with virgin carbon black. Alternatively or additionally, the properties of rubber compounds prepared with coated rC can be comparable to those prepared with uncoated rC. In any of these embodiments, properties can be determined by one or more of the following: tensile modulus at 100% strain, tensile modulus at 300% strain, elongation at break, tanδ (60°C), tear strength (ASTM D624, Die B), and / or fatigue life (ASTM D4482). For any of these properties, the performance may be improved by at least 5%, at least 10%, at least 15%, or at least 20%, for example, 5-25%, 10-20%, 5-15%, or 15-30%. Tensile modulus and elongation at break are measured according to ASTM D412 (Test Method A, Type C) at 23°C, 50% relative humidity, and a crosshead speed of 500 mm / min. The Tanδ was determined using a dynamic strain sweep between 0.01% and 60% at 10 Hz and 60 °C. 最大 (Sometimes written as tanδ) is taken as the maximum value of tanδ within this strain range. Fatigue life is measured according to ASTM D4482.

[0140] Unless otherwise stated, all material percentages described in this document are by weight.

[0141] This invention includes the following aspects / implementations / features in any order and / or in any combination:

[0142] 1. The present invention includes a method for forming carbon-coated matrix particles (e.g., carbon-coated carbon particles), the method comprising:

[0143] A matrix particle is introduced into a chamber and subjected to an energy source, at least one of hot gas, microwave energy, inductive energy, direct current passing through the matrix particle, electromagnetic radiation, or solar radiation, to form a heated matrix particle. A hydrocarbon source comprising gas or vapor is fed into the chamber, wherein the hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated matrix particle with the carbon deposit and forming the carbon-coated matrix particle, wherein the matrix particle optionally contains recycled carbon particles.

[0144] 2. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles comprise carbon particles or particles having a carbon content of at least 10% or at least 75%.

[0145] 3. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles comprise solid hydrothermal carbon (HTC) carbon particles, said carbon particles being non-ASTM reinforced particles, silicon-treated carbon black, silica-coated carbon black, graphene, reduced graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, biochar, and any combination thereof.

[0146] 4. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles comprise graphene oxide, lignin, nanocrystalline cellulose, bio-based particles, polysaccharides, engineered polysaccharides, or any combination thereof.

[0147] 5. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the recovered carbon particles comprise depolymerized and / or ground recovered carbon particles.

[0148] 6. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles comprise precipitated silica, rice husk silica, clay, nano-clay, diatomaceous earth, metal oxides, metal carbonates, or any combination thereof.

[0149] 7. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are subjected to the microwave energy.

[0150] 8. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the microwave energy is at least 0.5 GHz, for example, 0.5 GHz to 10 GHz.

[0151] 9. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are subjected to induced energy.

[0152] 10. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the induced energy is provided by an induction heater operating at a frequency of at least 5 kHz.

[0153] 11. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the induced energy is provided by an induction heater operating at a frequency of 5 kHz to 500 kHz.

[0154] 12. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the induction heater operates at an induction heater power of at least 50 MJ / kg.

[0155] 13. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the induction heater operates at an induction heater power of 50 MJ / kg to 250 MJ / kg.

[0156] 14. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the chamber comprises a fluidized bed reactor, an ablation pyrolysis reactor, a vacuum pyrolysis reactor, a fixed bed feed reactor, or a solar pyrolyzer.

[0157] 15. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the microwave energy or induced energy is generated by regenerable electricity.

[0158] 16. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are bio-based particles.

[0159] 17. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the hydrocarbon source comprises natural gas.

[0160] 18. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the hydrocarbon source is composed of natural gas.

[0161] 19. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the method is carried out in the absence of a catalyst.

[0162] 20. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the method is performed in the absence of introduced oxygen.

[0163] 21. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the method produces at most 0.5 kg of carbon dioxide and carbon monoxide relative to 1 kg of carbon-coated particles, for example, without carbon dioxide and carbon monoxide.

[0164] 22. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are heated to a temperature of at least 800°C.

[0165] 23. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are heated to a temperature of at least 900°C.

[0166] 24. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are heated to a temperature of at least 1000°C.

[0167] 25. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are heated to a temperature of at least 1500°C.

[0168] 26. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the hydrocarbon source comprises: bio-oil, recycled oil, vapor of sustainable oil; byproduct of biofuel or biochemical production, or oil derived from tires (e.g., from tire pyrolysis), oil derived from plastic pyrolysis or recycling, or oil from hydrothermal liquefaction or paper processing.

[0169] 27. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are on a fixed bed within the cavity.

[0170] 28. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are on a moving bed passing through the chamber.

[0171] 29. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the carbon deposit uniformly coats the matrix particles.

[0172] 30. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the carbon deposit at least partially coats the matrix particles.

[0173] 31. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the carbon-coated matrix particles of the product have a coating with an average thickness of 0.5 to 500 nanometers.

[0174] 32. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles have a residence time of 1 second to 3 hours in the chamber.

[0175] 33. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles have a residence time of 5 seconds to 2 hours in the chamber.

[0176] 34. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the chamber comprises at least a first chamber and a second chamber, wherein in the first chamber, the matrix particles are subjected to microwave energy or induced energy such that the matrix particles reach an average surface temperature of at least 800°C in the absence of any hydrocarbon source to obtain heated matrix particles, and then the heated matrix particles are conveyed to the second chamber, in which the hydrocarbon source is fed.

[0177] 35. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein in the second chamber, the second chamber has a heat source that maintains the heated matrix particles at a surface temperature of at least 800°C.

[0178] 36. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the heated matrix particles are on a moving bed in the second chamber.

[0179] 37. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein recycled iron or limestone is applied to at least a portion of the surface of the matrix particles before being subjected to the energy source.

[0180] 38. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the matrix particles are at least partially depolymerized in the first chamber.

[0181] 39. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein for at least a portion of the method, an oxidizing atmosphere is present in the chamber.

[0182] 40. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein for at least a portion of the method, an oxidizing atmosphere is present in the chamber, the oxidizing atmosphere being achieved at least by introducing water into the chamber.

[0183] 41. The method of any of the foregoing or subsequent embodiments / features / aspects further includes performing vapor oxidation of the matrix particles in the chamber.

[0184] 42. The method of any of the foregoing or subsequent embodiments / features / aspects further includes, in a second step, heating the carbon-coated particles in the same or different chambers in a neutral or reducing atmosphere.

[0185] 43. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the non-reactive carrier gas is present together with the hydrocarbon source.

[0186] 44. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the hydrocarbon gas is introduced into the chamber at two or more locations within the chamber.

[0187] 45. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the non-reactive carrier gas is introduced into the chamber individually or together with the hydrocarbon gas at two or more locations in the chamber.

[0188] 46. ​​The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the volume of the first chamber is at least 25% smaller than the volume of the second chamber.

[0189] 47. The method of any of the foregoing or subsequent embodiments / features / aspects, wherein the volume of the first chamber is at least 50% smaller than the volume of the second chamber.

[0190] 48. The method of any of the foregoing or subsequent embodiments / features / aspects further includes introducing the carbon-coated matrix particles into an additional chamber and subjecting the matrix particles to an energy source, the energy source being at least one of hot gas, microwave energy, inductive energy, direct current passing through the matrix particles, electromagnetic radiation, or solar radiation, to form heated carbon-coated matrix particles, and feeding a hydrocarbon source comprising gas or vapor into the additional chamber, wherein the hydrocarbon source is at least partially pyrolyzed in the additional chamber to form a carbon deposit, thereby coating the heated carbon-coated matrix particles with the additional carbon deposit.

[0191] 49. The present invention further relates to a method for forming carbon-coated precipitated silica particles, the method comprising:

[0192] Precipitated silica particles are introduced into a chamber and subjected to microwave or induced energy to form heated precipitated silica particles. A hydrocarbon source containing gas or vapor is fed into the chamber, wherein the hydrocarbon source is at least partially pyrolyzed in the chamber to form a carbon deposit, thereby coating the heated precipitated silica particles with the carbon deposit and forming carbon-coated precipitated silica particles.

[0193] 50. The present invention further relates to coated carbon particles or other particles formed by any method of any of the foregoing or the following embodiments / features / aspects.

[0194] 51. The present invention further relates to a method for producing hydrogen, comprising the method of performing any of the foregoing embodiments / features / aspects, wherein the pyrolysis of the hydrocarbon source results in the production of a gas stream containing hydrogen.

[0195] 52. Any of the foregoing or following embodiments / features / aspects of the method further includes separating hydrogen from the remainder of the gas stream to obtain a purified hydrogen stream.

[0196] 53. Any of the foregoing or following embodiments / features / aspects of the method further includes the remainder of the gas stream to the hydrocarbon source.

[0197] 54. Any method of the foregoing or the following embodiments / features / aspects, wherein the gas stream comprises at least 60% by volume of hydrogen, for example, 80-99% by volume of hydrogen.

[0198] 55. The present invention further relates to carbon-coated particles, each of said carbon-coated particles comprising a matrix particle and a carbon deposit disposed around the outer surface of said matrix particle, the carbon-coated particles exhibiting a Raman D band (1340 cm⁻¹). -1 ) and Raman G band (1590cm)-1 The area ratio is 0.5 to 2.45, for example, 1 to 2.45 or 1.5 to 2.45.

[0199] 56. Any carbon-coated particles of the foregoing or the following embodiments / features / aspects, wherein the matrix particles comprise carbon particles or particles having a carbon content of at least 10% by weight or at least 75% by weight.

[0200] 57. Any carbon-coated particles of the foregoing or following embodiments / features / aspects, wherein the matrix particles comprise recycled carbon particles.

[0201] 58. Any carbon-coated particles of the foregoing or the following embodiments / features / aspects, wherein the matrix particles comprise carbon particles, said carbon particles being non-ASTM reinforced grade particles, solid hydrothermal carbon (HTC), silicon-treated carbon black, silica-coated carbon black, graphene, reduced graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, biochar, and any combination thereof.

[0202] 59. Any carbon-coated particles of the foregoing or the following embodiments / features / aspects, wherein the matrix particles comprise graphene oxide, lignin, nanocrystalline cellulose, bio-based particles, polysaccharides, engineered polysaccharides, or any combination thereof.

[0203] 60. Any carbon-coated particles of the foregoing or following embodiments / features / aspects, wherein the recovered carbon particles comprise depolymerized and / or milled recovered carbon particles.

[0204] 61. Any carbon-coated particles of the foregoing or the following embodiments / features / aspects, wherein the matrix particles comprise precipitated silica, rice husk silica, clay, nano-clay, diatomaceous earth, metal oxides, metal carbonates, or any combination thereof.

[0205] 62. Any carbon-coated particles of the foregoing or following embodiments / features / aspects, wherein the coating of the carbon deposit has an average thickness of 0.5 nm to 500 nm.

[0206] 63. A rubber article which incorporates carbon-coated particles of any of the foregoing or following embodiments / features / aspects.

[0207] 64. Any rubber article of the foregoing or the following embodiments / features / aspects, wherein the rubber article is: a tire assembly selected from tire tread, sub-tread, liner pad, sidewall and cushioning rubber, engine mount, hydraulic mount, axle support, shock absorber, tank track, tank tread, mining conveyor belt, hose, gasket, seal, blade, weatherstripping, bumper or vibration damping component.

[0208] 65. The present invention further relates to an elastomeric composite comprising carbon-coated particles of any of the foregoing or following embodiments / features / aspects, wherein the matrix particles are recycled carbon, and the elastomeric composite having at least one mechanical property selected from tensile modulus at 100% strain, tensile modulus at 300% strain, elongation at break, tanδ at 60°C, tear strength, and fatigue life in a value at least 5% greater than that of an elastomeric composite having the same composition but using recycled carbon instead of carbon-coated particles.

[0209] Example

[0210] Example 1 - Regenerated carbon (CBP Cyprus Ltd) was fed into a tube furnace at a rate of 360 g / h and treated at the temperature specified in Table 1 below for a residence time of approximately 1 hour. The tube had a diameter of 6 inches (15 cm) and a heating section of 60 inches (152 cm) in length, and rotated at a rate of 1.8 rpm. Gas was fed into the tube at a rate of 25 scfh (708 L / h) (nitrogen) or 21 scfh (595 L / h) (methane), with an additional 6 scfh (170 L / h) of nitrogen always used to purge the system inlet and outlet. Samples were collected after one hour of steady-state operation, meaning that the flow rates of rC into and out of the furnace were stable, the temperature was stable, and the desired gas (nitrogen or methane) had flowed through the tube for at least 90 minutes.

[0211] Table 1

[0212]

[0213] The percentage increase in carbon calculated based on constant silicon.

[0214] Elemental analysis was performed by first determining the mass percentage of carbon using the ashing method specified in ASTM D1506, assuming that all non-ash content was carbon. Inorganic elements were quantified by scanning electron microscopy / energy-dispersive X-ray spectroscopy (SEM / EDS) of the thick ash layer printed with carbon ribbons on a SEM stub. Measurements were taken at 560 micrometers using an EDS detector. The region was 420 micrometers in size until a total of 50,000,000 X-ray counts were recorded.

[0215] The results showed that carbon was deposited on the surface of the rC particles. The reduction in ash content also indicated that the ZnO in the rC was reduced and then the metallic zinc (boiling point 907 °C) was evaporated. Assuming little or no silicon loss during deposition, the increase in Si concentration in the ash indicates the amount of ash reduction, while the decrease in the proportion of Si in the rC indicates that the amount of new carbon added to the rC increases with processing temperature. Furthermore, I D / I G The decrease indicates that the crystallinity of the deposited carbon increases with processing temperature.

[0216] Example 2 - In a manner substantially similar to that of US10087330 Figure 2 The pilot-scale fluidized bed reactor discussed uses carbon-coated regenerated carbon (e.g., from CBP Cyprus Ltd), the entire contents of which are incorporated herein by reference. In a laboratory-scale fluidized bed apparatus, the ideal fluidization rate of the regenerated carbon was evaluated with air at room temperature. An initial charge of the regenerated carbon starting material was loaded into the fluidized bed, positioned on top of the bottom plate. The bed was then sealed, and a nitrogen flow was introduced through the regenerated carbon, passing through the bottom plenum, through the bottom plate, and then through the regenerated carbon, and finally exiting through the top of the fluidized bed reactor. The electric heater was started to bring the bed temperature to 1000°C. The nitrogen flow was then stopped, and a natural gas flow with an apparent velocity approximately equal to the ideal fluidization rate was introduced to begin operation. Samples were periodically pulled from the bed using impregnation tubes and measured to track the progress of carbon black deposition. At the end of the desired run time, the natural gas flow was shut off along with the electric heater, and nitrogen was reintroduced into the fluidized bed while it cooled to room temperature. The final bed product was then collected from the bottom of the fluidized bed reactor. Compared to the starting product, this product is expected to have carbon deposited on the surface and a reduced amount of zinc.

[0217] Example 3 - In having with respect to US10087330 Figure 2In a pilot-scale fluidized bed reactor system with a similar configuration discussed, carbon-coated granular silica (e.g., precipitated silica) is used, the entire contents of which are incorporated herein by reference. In a laboratory-scale fluidized bed apparatus, the ideal fluidization rate for granular silica was evaluated using air at room temperature. An initial charge of granular silica starting material was loaded into the fluidized bed, positioned on top of the bottom plate. The bed was then sealed, and a nitrogen flow was introduced through the granular silica, entering through the bottom pressure chamber, passing through the bottom plate and then through the granular silica, and finally exiting through the top of the fluidized bed reactor. The electric heater was started to bring the bed temperature to 1250°C. The nitrogen flow was then stopped, and a natural gas flow with an apparent velocity approximately equal to the ideal fluidization rate was introduced to begin operation. Samples were periodically pulled from the bed using impregnation tubes and measured to track the progress of carbon black deposition. At the end of the desired run time, the natural gas flow was shut off along with the electric heater, and nitrogen was reintroduced into the fluidized bed while it cooled to room temperature. The final bed product was then collected from the bottom of the fluidized bed reactor. The product is expected to have carbon deposited on the surface.

[0218] Example 4. An elastomer composite with a granular loading of 50 phr was prepared using each of the five granules from Example 1, the amounts of smalls and curing agent given in Table 2, and Kralex SBR 1502 styrene-butadiene rubber. All compositions were mixed in two stages in a 439 mL Brabender premixer with two cam rotors, as described in Table 3. The mixture was sheeted on a two-roll mill operating at 50°C and approximately 22 rpm, and then passed through six times with a roll gap of approximately 5 mm, with a settling time of at least 3 hours before the next stage of mixing (or curing, after the last stage). Curing was carried out for 30 minutes in a heated press (150°C, 2500 psi). Compared with formulations prepared with uncoated rC, formulations prepared with carbon-coated rC are expected to exhibit superior mechanical properties (e.g., at least 5% improvement in one or more of the following: tensile modulus at 100% strain, tensile modulus at 300% strain, elongation at break, tanδ (60°C), tear strength, and fatigue life).

[0219] Table 2

[0220]

[0221] a) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6PPD (Western Reserve Chemical)

[0222] b) Poly(1,2-dihydro-2,2,4-trimethylquinoline), antioxidant DQ granules (Akrochem Corporation)

[0223] c) From Akrochem Corporation

[0224] d) AKROWAX TM 5031 (Akrochem Corporation)

[0225] e) N-tert-butyl-2-benzothiazole sulfinamide (Akrochem Corporation)

[0226] Table 3

[0227]

[0228] This invention may include any combination of the various features or embodiments described above and / or below as set forth in any sentence and / or paragraph herein. Any combination of the features disclosed herein is considered part of the invention and is not intended to limit the composable features.

[0229] The applicant specifically incorporates the entire contents of all cited references into this disclosure. Furthermore, when quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value and any lower or preferred value, regardless of whether the range is disclosed individually. In the case of numerical ranges enumerated herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. When defining ranges, it is not intended to limit the scope of the invention to the specific values ​​enumerated.

[0230] Other embodiments of the invention will become apparent to those skilled in the art upon consideration of this specification and the practice of the invention disclosed herein. This specification and the embodiments are intended to be considered exemplary only, wherein the true scope and spirit of the invention are indicated by the appended claims and their equivalents.

Claims

1. A method for forming carbon-coated substrate particles, the method comprising: introducing substrate particles into a chamber and subjecting the substrate particles to an energy source, the energy source being at least one of a hot gas, microwave energy, inductive energy, direct current through the substrate particles, electromagnetic radiation, or solar radiation, to form heated substrate particles, and feeding a hydrocarbon source comprising a gas or vapor into the chamber, wherein the hydrocarbon source at least partially pyrolyzes in the chamber to form a carbon deposit, and thereby coat the heated substrate particles with the carbon deposit and form the carbon-coated substrate particles, wherein the substrate particles optionally comprise recycled carbon particles.

2. The method of claim 1, wherein the substrate particles comprise carbon particles or particles having at least 10% or at least 75% carbon content.

3. The method of claim 1 or 2, wherein the substrate particles comprise carbon particles that are non-ASTM reinforcing grade particles, solid hydrothermal carbon (HTC), silicon-treated carbon black, silica-coated carbon black, graphene, reduced graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, biochar, and any combination of these.

4. The method of any one of claims 1-3, wherein the substrate particles comprise graphene oxide, lignin, nanocrystalline cellulose, biobased particles, polysaccharides, engineered polysaccharides, or any combination of these.

5. The method of any one of claims 1-4, wherein the recycled carbon particles comprise depolymerized and / or milled recycled carbon particles.

6. The method of any one of claims 1-5, wherein the substrate particles comprise precipitated silica, rice hull silica, clay, nanoclay, diatomite, metal oxides, metal carbonates, or any combination of these.

7. The method of any one of claims 1-6, wherein the substrate particles are subjected to the microwave energy.

8. The method of claim 7, wherein the microwave energy is at least 0.5 GHz, for example 0.5 GHz to 10 GHz.

9. The method of any one of claims 1-6, wherein the substrate particles are subjected to inductive energy.

10. The method of claim 9, wherein the inductive energy is provided by an induction heater operating at a frequency of at least 5 kHz.

11. The method of claim 9 or 10, wherein the inductive energy is provided by an induction heater operating at a frequency of 5 kHz to 500 kHz.

12. The method of any one of claims 9-11, wherein the induction heater operates at an induction heater power of at least 50 MJ / kg.

13. The method of any one of claims 9-12, wherein the induction heater operates at an induction heater power of 50 MJ / kg to 250 MJ / kg.

14. The method of any one of claims 1-13, wherein the chamber comprises a fluidized bed reactor, an ablative pyrolysis reactor, a vacuum pyrolysis reactor, a fixed bed falling material reactor, or a solar pyrolyzer.

15. The method of any one of claims 1-14, wherein the microwave energy or inductive energy is generated from renewable electricity.

16. The method of any one of claims 1-15, wherein the base particles are biobased particles.

17. The method of any one of claims 1-16, wherein the hydrocarbon source comprises natural gas.

18. The method of any one of claims 1-17, wherein the hydrocarbon source consists of natural gas.

19. The method of any one of claims 1-18, wherein the method is performed in the absence of a catalyst.

20. The method of any one of claims 1-19, wherein the method is performed in the absence of introduced oxygen.

21. The method of any one of claims 1-20, wherein the method produces at most 0.5 kg of carbon dioxide and carbon monoxide per 1 kg of carbon-coated particles.

22. The method of any one of claims 1-21, wherein the base particles are heated to a temperature of at least 800 °C.

23. The method of any one of claims 1-22, wherein the base particles are heated to a temperature of at least 900 °C.

24. The method of any one of claims 1-23, wherein the base particles are heated to a temperature of at least 1000 °C.

25. The method of any one of claims 1-24, wherein the base particles are heated to a temperature of at least 1500 °C.

26. The method of any one of claims 1-25, wherein the hydrocarbon source comprises: a bio-oil, a recycled oil, a vapor of a sustainable oil; a biofuel or a byproduct of a bio-chemical production, or an oil derived from tires, tire pyrolysis oil, an oil derived from plastic pyrolysis or recycling, or from hydrothermal liquefaction or paper processing.

27. The method of any one of claims 1-26, wherein the base particles are on a fixed bed within the chamber.

28. The method of any one of claims 1-27, wherein the base particles are on a moving bed through the chamber.

29. The method of any one of claims 1-28, wherein the carbon deposit uniformly coats the base particles.

30. The method of any one of claims 1-29, wherein the carbon deposit at least partially coats the base particles.

31. The method of any one of claims 1-30, wherein the product carbon-coated particles have a coating of an average thickness of 0.5 to 500 nanometers.

32. The method of any one of claims 1-31, wherein the base particles have a residence time in the chamber of 1 second to 3 hours.

33. The method of any one of claims 1-32, wherein the substrate particles have a residence time in the chamber of from 5 seconds to 2 hours.

34. The method of any one of claims 1-33, wherein the chamber comprises at least a first chamber and a second chamber, wherein in the first chamber the substrate particles are subjected to microwave energy or induction energy such that the substrate particles reach an average surface temperature of at least 800°C in the absence of any hydrocarbon source to obtain heated substrate particles, and then the heated substrate particles are transported to the second chamber where the feeding of the hydrocarbon source takes place.

35. The method of claim 34, wherein in the second chamber the second chamber has a heat source that maintains the heated substrate particles at a surface temperature of at least 800°C.

36. The method of claim 34 or 35, wherein the heated substrate particles are on a moving bed in the second chamber.

37. The method of any one of claims 34-36, wherein the substrate particles are at least partially deagglomerated in the first chamber.

38. The method of any one of claims 34-37, wherein the volume of the first chamber is at least 25% smaller than the volume of the second chamber.

39. The method of any one of claims 34-38, wherein the volume of the first chamber is at least 50% smaller than the volume of the second chamber.

40. The method of any one of claims 1-39, wherein recycled iron or limestone is applied to at least a portion of the surface of the substrate particles prior to being subjected to the energy source.

41. The method of any one of claims 1-40, wherein for at least a portion of the method an oxidizing atmosphere is present in the chamber.

42. The method of any one of claims 1-41, wherein for at least a portion of the method an oxidizing atmosphere is present in the chamber, the oxidizing atmosphere being achieved at least by introducing water into the chamber.

43. The method of any one of claims 1-42, further comprising performing steam oxidation of the substrate particles in the chamber.

44. The method of any one of claims 1-43, further comprising heating the carbon-coated particles in a neutral or reducing atmosphere in a second step, in the same chamber or in a different chamber.

45. The method of any one of claims 1-44, wherein a non-reactive carrier gas is present with the hydrocarbon source.

46. The method of claim 45, wherein the non-reactive carrier gas is introduced into the chamber separately or with the hydrocarbon gas at two or more locations in the chamber.

47. The method of any one of claims 1-46, wherein the hydrocarbon gas is introduced into the chamber at two or more locations in the chamber.

48. The method of any one of claims 1-47, further comprising introducing the carbon- coated base particles into a further chamber and subjecting the base particles to an energy source that is at least one of a hot gas, microwave energy, inductive energy, direct current through the base particles, electromagnetic radiation, or solar radiation to form heated carbon-coated base particles, and feeding a hydrocarbon source comprising a gas or vapor into the further chamber, wherein the hydrocarbon source at least partially pyrolyzes in the further chamber to form a carbon deposit and thereby coat the heated carbon-coated base particles with additional carbon deposit.

49. A method for forming carbon-coated precipitated silica particles, the method comprising: introducing precipitated silica particles into a chamber and subjecting the precipitated silica particles to microwave energy or inductive energy to form heated precipitated silica particles, and feeding a hydrocarbon source comprising a gas or vapor into the chamber, wherein the hydrocarbon source at least partially pyrolyzes in the chamber to form a carbon deposit and thereby coat the heated precipitated silica particles with the carbon deposit and form the carbon-coated precipitated silica particles.

50. A method of producing hydrogen gas, comprising carrying out the method of any one of the preceding claims, wherein pyrolysis of the hydrocarbon source results in the production of a gas stream comprising hydrogen.

51. The method of claim 50, further comprising separating hydrogen gas from the remainder of the gas stream to obtain a purified hydrogen gas stream.

52. The method of claim 51, further comprising directing the remainder of the gas stream to the hydrocarbon source.

53. The method of any one of claims 50-52, wherein the gas stream comprises at least 60 vol% hydrogen gas, for example, 80-99 vol% hydrogen gas.

54. Carbon-coated particles, each of the carbon-coated particles comprising a base particle and a carbon deposit disposed around an outer surface of the base particle, the carbon-coated particles having an area ratio of Raman D band (1340 cm"1) to Raman G band (1590 cm"1) of 0.5 to 2.45, for example 1 to 2.45 or 1.5 to 2.

45. -1 ) with a Raman G band (1590 cm -1 ).

55. The carbon-coated particles of claim 54, wherein the base particles comprise carbon particles or particles having a carbon content of at least 10 wt% or at least 75 wt%.

56. The carbon-coated particles of claim 54 or 55, wherein the base particles comprise recycled carbon particles.

57. The carbon-coated particles of any one of claims 54-56, wherein the base particles comprise carbon particles that are non-ASTM reinforcing grade particles, solid hydrothermal carbon (HTC), silicon-treated carbon black, silica-coated carbon black, graphene, reduced graphene oxide, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanostructures, carbon black-coated particles, biochar, and any combination of these.

58. The carbon-coated particles of any one of claims 54-57, wherein the base particles comprise graphene oxide, lignin, nanocrystalline cellulose, biobased particles, polysaccharides, engineered polysaccharides, or any combination of these.

59. The carbon-coated particles of any one of claims 54-58, wherein the recycled carbon particles comprise depolymerized and / or milled recycled carbon particles.

60. The carbon-coated particles of any one of claims 54-59, wherein the base particles comprise precipitated silica, rice hull silica, clay, nanoclay, diatomite, metal oxide, metal carbonate, or any combination of these.

61. The carbon-coated particles of any one of claims 54-60, wherein the coating of the carbon deposit has an average thickness of 0.5 nm to 500 nm.

62. A rubber article incorporating the carbon-coated particles of any one of claims 54-61.

63. The rubber article of claim 62, wherein the rubber article is a tire component selected from a tire tread, a secondary tread, a cord coating, a sidewall, and a cushion gum, an engine mount, a hydraulic mount, a bridge bearing, a shock absorber, a tank track, a tank tread, a mining conveyor belt, a hose, a gasket, a seal, a blade, a weather stripping article, a bumper, or a vibration isolation component.

64. An elastomeric composite comprising the carbon-coated particles of any one of claims 54-61, wherein the base particles are recycled carbon, and the elastomeric composite has at least a 5% greater magnitude of at least one mechanical property selected from tensile modulus at 100% strain, tensile modulus at 300% strain, elongation at break, tan delta at 60°C, tear strength, and fatigue life than an elastomeric composite having the same composition but with recycled carbon instead of the carbon-coated particles.

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