CHARCOAL PRODUCTS MADE WITH PHENOLIC RESIN BINDERS AND METHOD FOR MAKING SAME - Patent application

Abstract

The present disclosure describes compositions (biocarbon materials) and methods of making the compositions that include a binder (such as a phenolic binder that may include cardanol) and charcoal, preferably in powder form. The compositions may also include accelerators / catalysts. The binder, charcoal powder, and accelerator may be mixed together, formed (pressed, rolled, or extruded), and then cured. The resulting compositions may be used as metallurgical reducing agents, processed into anodes for use in the metallurgical industry, used in the construction industry, for example, as a component of concrete, or used as a cooking fuel.

Description

[Technical field]

[0001] The present disclosure generally relates to agglomerates, carbon-based materials, charcoal compositions, charcoal products, and methods for making charcoal products, particularly high-performance carbon products, by using charcoal and binders. More specifically, the present disclosure relates to materials formed from "recovered" carbon, such as materials formed from charcoal and binders, and corresponding processes for making such materials. Products made from these compositions can be used to create carbon dioxide neutral products for many potential uses, including as fuels, as reducing agents in the metallurgical industry, to replace the use of currently used fossil fuels, and / or as fillers in concrete, asphalt, and other construction materials, and as anodes for the aluminum industry. [Background technology]

[0002] Climate change is a growing concern for governments and individuals, and more efforts and proposals are being made to use less fossil fuel-based carbon sources and more "CO2-neutral" carbon sources. The simplest form of "carbon capture" is the use of biomass-based carbon sources, such as wood or processed wood, e.g., charcoal. Carbon dioxide-neutral carbon sources rely on carbon that has previously been captured from the atmosphere, so that it does not contribute to atmospheric carbon if that carbon is subsequently released. In "carbon capture," atmospheric carbon is captured and stored away from the atmosphere for an extended period of time to obtain a net reduction in atmospheric carbon. Similarly, the process of generating CO2 can be "offset" if the resulting product also serves to sequester carbon from the atmosphere for an extended period of time. Products produced using biomass-derived charcoal have the potential to store atmospheric carbon and thus provide a carbon-neutral replacement for past fossil fuel-based carbon sources. Furthermore, if these materials can be used to store that carbon for an extended period of time, they can be used to offset the carbon dioxide generated in the making of certain materials, e.g., cement.

[0003] Products made from carbon and binder materials have been known for a long time. Many improvements in the field of bound charcoal materials, many of which are patentable and many of which are eco-friendly, have been made since 1939. U.S. Patent No. 5,298,040 discloses the use of a water-soluble oxidizer for waterproofing fuel briquettes. U.S. Patent No. 5,221,290 discloses the use of clay and organic binders. Hundreds of patents have been granted in this field. However, each of these has deficiencies and there remains a need for high performance biocarbon-based materials that can replace fossil carbon products (e.g., coke and fossil carbon fuels) and / or can be used to sequester biocarbon from the atmosphere. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there is a need in the art for compositions and methods of making compositions that provide eco-friendly and / or high performance bio-carbon materials that can be used for many purposes: within the metallurgical industry as a reducing agent to make bio-carbon anodes, in the construction industry as "bio-carbon stones" to reduce the carbon footprint of building materials, and / or in the BBQ industry to provide significant performance improvements over current BBQ briquette fuels. [Means for solving the problem]

[0005] To minimize limitations in the cited references, and others that may become apparent upon reading and understanding this specification, this specification discloses bio-carbon-based materials comprising charcoal and at least one binder material, and methods for producing these materials.

[0006] Thus, in a first aspect, the present disclosure provides a biocarbon-based material comprising charcoal and at least one binder comprising a phenolic resin. The binder component can comprise at least 50% (e.g., 50-100%) phenolic resin, such as at least 75% or at least 90% phenolic resin (all by weight %).

[0007] In one embodiment, the phenolic resin may be formed or formable from at least one phenol of formula I:

[0008] [ka]

[0009] where X is H or OH and R is H or an optionally substituted, saturated or unsaturated, hydrocarbon moiety having 1 to 24 carbon atoms, which may be linear or branched. There may be one or two independent R groups, which may be independently ortho, meta or para to the depicted -OH group. One meta R group is preferred. In one embodiment, the at least one phenol of formula I includes at least one phenol where R is not hydrogen.

[0010] The at least one phenol of formula I can comprise, consist essentially of, or consist of a phenol of formula I in which at least one non-hydrogen R group is preferably present in the meta position relative to the -OH moiety.

[0011] In one embodiment, the at least one phenol of formula I may comprise a phenol of formula I in which at least one non-hydrogen R group is preferably present in a meta position relative to the -OH moiety and which comprises in part a phenol and / or a resorcinol.

[0012] In one embodiment, the phenolic resin may be a polymer of at least one phenol of formula I, optionally with other components (e.g., as described herein, e.g., a formyl carbon source, e.g., hexamine).

[0013] In one embodiment, the phenolic resin may be formed or formable from at least one phenol of formula I, where the at least one phenol comprises cardol and / or cardanol.

[0014] In one embodiment, the phenolic resin may be formed or formable from at least one phenol of formula I by reaction with at least one aldehyde, urea or formyl carbon source, such as hexamine.

[0015] In one embodiment, the biocarbon-based material may contain up to 30% by weight (eg, 1-30% by weight) of inorganic filler, such as sand or rock dust.

[0016] In a second aspect, the present disclosure provides a biocarbon-based material comprising charcoal and at least one binder, the biocarbon-based material having a compressive strength of at least 5 MPa (e.g., 5-150 MPa, preferably at least 20 MPa, e.g., at least 30 MPa or at least 40 MPa) when tested according to the method described below (as described herein with reference to the Examples below). In one particular embodiment, the biocarbon-based material has a compressive strength of at least 40 MPa (e.g., 40-120 MPa), preferably at least 50 MPa, more preferably at least 60 MPa (e.g., 60-100 MPa). One suitable test for measuring the compressive strength of the biocarbon material is the American Society for Testing Materials ASTM C39 / C39M method, which provides a standard test method for the compressive strength of cylindrical concrete specimens. This method for testing compressive strength is covered herein unless otherwise indicated.

[0017] In a further aspect, the present disclosure provides a method for forming a biocarbon-based material, comprising mixing charcoal, at least one binder material, and optionally an accelerator or catalyst, and forming the mixture into any desired shape (e.g., block, rod, or briquette).The resulting product can be used in any manner, including but not limited to: as a highly uniform biocarbon-based reductant in the metallurgical industry; creating a biocarbon-based anode for the aluminum industry; in the construction industry, especially as a total or preferably partial replacement for rock or gravel in concrete, asphalt, or other composites; and / or as a cooking fuel in the BBQ industry.

[0018] One embodiment can produce a heat or energy rich solid fuel material, e.g., briquettes. This material can be produced from charcoal, preferably charcoal powder, using a phenolic resin as a binder. A very suitable binder for this embodiment is cardol and / or cardanol.

[0019] In various embodiments, the biocarbon material of the present disclosure can have a fixed carbon (i.e. weight percentage of non-volatile carbon) ranging from 2 to 99%. Preferably, the fixed carbon is at least 60% or at least 75% by weight. This varies depending on the nature of the charcoal and binder, the conditions under which the charcoal is made and / or processed, and the curing and optional second heat treatment of the biocarbon material. Charcoal having a fixed carbon content of at least 70% (e.g. 75 to 98%) can be used. In one embodiment, the charcoal used in the biocarbon material has a fixed carbon content of at least 80%. Such charcoal can be produced, for example, by heat treatment to 300 to 900°C in the absence of oxygen. In further embodiments, the charcoal used can be at least 80%, at least 90% or at least 95% fixed carbon. Such charcoal can be produced, for example, by heat treatment to at least 700°C (e.g. 800 to 1200°C) in an inert atmosphere.

[0020] The compositions may include catalysts and / or accelerators to improve cure times, reduce cure temperatures, and / or control binder properties.

[0021] In one embodiment, the accelerator or catalyst may be hexamine, which when mixed with other binder components (e.g., the phenol of formula I) and charcoal powder, can initiate the polymerization process. Aldehydes, such as formaldehyde and their precursors, such as polymethylene glycol, are also suitable accelerators or catalysts. Additional accelerators and catalysts are discussed below and can be used in any suitable embodiment of the invention.

[0022] In one embodiment, the bio-carbon material (e.g., briquettes) can be cured at a temperature in the range of 150 to 400 degrees Celsius ("°C"). Preferably, the temperature is 180 to 250°C, e.g., 190 to 220°C. The curing period depends on the binder, optional accelerators / catalysts, and processing temperature. However, typical curing periods are from 5 minutes to 12 hours, preferably from 20 minutes to 3 hours, e.g., from 30 minutes to 2 hours.

[0023] In one embodiment, the pressure used to form the bio-carbon material into pieces (e.g., briquettes, blocks, rods, or any suitable shape including those discussed herein) is at least 5 kN / cm 2 (i.e. at least 50MPa) For example, 5 to 500 kN / cm 2 (50 to 5000 MPa). A suitable compression force may be, for example, at least 8 kN / cm 2 , e.g., 10 kN / cm 2 However, a larger compression, e.g. at least 20 N / cm 2 (200MPa) or at least 50N / cm 2 Vibration may also be used as an alternative or in addition to compress and / or compact the products of the present disclosure prior to curing. In one embodiment, vibration is used in combination with the compressive forces noted above.

[0024] Typically, higher compression forces (preferably in combination with vibration) are associated with a final material with greater density, smaller surface area, lower water absorption and / or stronger compressive strength. Repeated compression can also be used, optionally in combination with vibration. Compression can be performed once, twice, three times or more (e.g., 1-10 times). Vibration may or may not be used independently during each compression step.

[0025] When the bio-carbon materials of the present invention are in the form of briquettes, they can be used for any suitable purpose, including, for example, as cooking fuel in the BBQ industry. The bio-carbon briquettes can also be used as a reducing agent in metallurgical processes.

[0026] In one embodiment, the charcoal and binder mixture can be pressed in a hydraulic press, a mechanical press, an extruder, and / or a roller press, and can have a pillow-like, prismatic (e.g., cubic or cylindrical), or other uniform shape. Forming by extrusion is the preferred method.

[0027] In one embodiment of the present invention, the bio-carbon material has a compressive strength of more than 50 MPa (505 kg / cm 2 The biocarbon material can have a compressive strength of more than 10 ...

[0028] Thus, in a further aspect, the present disclosure provides a concrete comprising cement (e.g., Portland cement) and at least one biocarbon material as described herein. Such concrete can comprise the biocarbon material of the present disclosure formed, molded, cut, or broken (e.g., crushed) into pieces. Such pieces are referred to herein as "charcoal stones."

[0029] Preferably, these "charcoal stones" may have a size similar to that of standard crushed stone for use in concrete. This may be, for example, an average diameter of around 4-40 mm (e.g., 8-40 mm) for coarse crushed stone (e.g., between 15-30 mm diameter by weight average). Alternative crushed stone with a weight average diameter of around 40 mm (e.g., average 35-45 mm) may also be suitable. Fine crushed stone with a weight average diameter of 10 mm or less (e.g., maximum diameter around 9.55 mm) may also be suitable.

[0030] The concrete of the present disclosure may contain any suitable amount of carbon stone (biocarbon material of the present invention), but the amount is advantageously at least around 100 kg (e.g., 80-300 kg or 100-300 kg, e.g., 100-200 kg) per cubic meter of concrete. This makes the concrete almost "carbon neutral" as discussed herein. Amounts greater than 100 kg per cubic meter can be used to effectively sequester carbon from the atmosphere, trapping it away from the atmosphere and in a long-term storage medium. Alternatively, the atmospheric carbon impact of a material such as concrete can be reduced without the need to fully offset the carbon dioxide released in its production. Amounts of carbon stone of at least 20 kg per cubic meter, preferably at least 50 kg (e.g., 50-120 kg per cubic meter), can partially or fully offset the carbon dioxide released in the manufacture of building materials such as concrete. Thus, concretes with these levels of carbon stone form further embodiments.

[0031] The concretes of the present disclosure can be used as standard industrial concretes (e.g., for use in sidewalks, industrial, residential or office buildings, bridges, siding, large diameter pipes, roads, tunnels and / or road surfaces, among many other applications).

[0032] There are many standards for concrete compressive strength. The biocarbon material of the present disclosure can be used in any suitable concrete. Standard concrete strengths range from around 7.5 MPa to 50 MPa for curb bases and sewer construction, and even higher for agricultural and industrial reinforced concrete. In one embodiment, the concrete of the present disclosure includes charcoal stone that has a strength at least as high as the nominal 28-day strength of standard concrete in which charcoal stone is used.

[0033] By adding the disclosed charcoal rock to a concrete mix, the carbon footprint of the concrete can be controlled, shrinking the carbon footprint and even making it carbon neutral or negative, depending on the amount of charcoal rock included in the concrete mix. By adding the disclosed charcoal rock to concrete, the carbon dioxide captured from the atmosphere and contained as carbon with the stone is bound in a ratio of approximately 1:3 (12 kg of elemental carbon is equivalent to 44 kg of CO2). This means that for every kg of charcoal rock added, approximately 3 kg of carbon dioxide is prevented from entering the atmosphere (up to 3.6 kg for pure carbon materials). The production of one cubic meter of cement releases around 300 kg of carbon dioxide, so the production of around 100 kg of charcoal rock (e.g., 80-150 kg / m3) 3 Incorporation of charcoal in the form of charcoal stone (e.g. 10-99 or 10-120 kg / m) can sequester a similar amount of carbon from the atmosphere for a longer period of time, thus making the cement "carbon neutral". Such a period may be decades or hundreds of years (e.g. 100-500 years). This is because even if the concrete reaches the end of its useful life, it can be embedded or crushed and used as hard core or filler in future materials (e.g. future concretes), thus continuing to capture carbon from the atmosphere. Less charcoal stone (e.g. 10-99 or 10-120 kg / m) can be used if a reduction or partial offset of carbon emissions is desired, or if less Portland cement is needed for offsetting, or if less standard crushed stone is needed for the mix. 3Similarly, in manufacturing mixes having higher levels of carbon emissions (e.g., having more Portland cement) or where total removal of carbon from the atmosphere is desired, more charcoal rock (e.g., 150-250 kg / m) may be included in the concrete. 3 ) can be used to offset the released carbon dioxide.

[0034] Thus, in one embodiment, the present disclosure provides a "carbon neutral" concrete in which the carbon dioxide released in the formation of the concrete (particularly in the formation of the cement binder in the concrete, e.g., Portland cement) is at least offset by the recovered carbon contained in the charcoal rock captured in the concrete. Preferably, a carbon neutral cement is a cement in which 100±20% (e.g., 100±10%) of the amount of carbon released to the atmosphere during the formation of the concrete is captured in the concrete in the form of recovered carbon in the charcoal rock. Thus, in a further embodiment, the present disclosure provides a "carbon negative" concrete in which the carbon dioxide released in the formation of the concrete (particularly in the formation of the cement binder in the concrete, e.g., Portland cement) is even more offset by the recovered carbon contained in the charcoal rock captured in the concrete. Preferably, a carbon negative cement is a cement in which at least 100% (e.g., 100-500%) of the amount of carbon released to the atmosphere during the formation of the concrete is captured in the concrete in the form of recovered carbon in the charcoal rock. Such carbon neutral and / or carbon negative concrete could form a valuable tool in reducing carbon emitted by the construction / building industry and / or sequestering carbon from the atmosphere for decades to come.

[0035] In one embodiment, the binder may be approximately 2-50% by weight of the final mixture (and thus the final bio-carbon material). This is preferably 5-30% by weight. The amount of binder may vary depending on the application, but higher compressive strength generally requires a larger amount of binder. For briquettes for use as a reducing agent in metallurgical processes or as a fuel, the amount of binder may typically be 2-15% or 5-10% by weight of the bio-carbon material. Where strength is more important, for example when forming "charcoal stones" for use in construction materials or when forming anodes for aluminum production, higher levels of binder are used, for example 15-25% or 20-30% by weight.

[0036] The "binder" referred to herein can include at least one phenolic component (e.g., those described herein, particularly those of formula I), but can also include at least one reaction promoter and / or catalyst. The reaction promoter, e.g., hexamine (as well as others described herein and known in the art), can preferably be present at approximately 4-10% (e.g., 6-8%) by weight of the binder component. In one embodiment, the reaction promoter is a source of formyl carbon and is present in an amount equivalent to at least one mole of formyl carbon per mole of phenol present in the binder.

[0037] In addition to the optional accelerator / catalyst, the binder component may include at least one oil component. Such oils form an optional part of the binder and may therefore be absent or may be present up to 50% of the total weight of the binder (i.e. up to about the same content by weight as the phenolic component). Suitable oils include "drying oils". Drying oils typically include glycerol triesters of highly unsaturated fatty acids, particularly alpha-linolenic acid. The "iodine number" is a measure of the number of double bonds in an oil and therefore its tendency to be a drying oil. Oils having an iodine number greater than 130 are considered to be drying and are preferred as oil components in the present invention. Oil components having an iodine number between 115 and 130 are semi-drying and may preferably be used in combination with drying oils. One preferred drying oil is linseed oil. Such oils may be dried by oxidative crosslinking and, without being bound by theory, hardened by such a process with an unsaturated phenolic component. In one embodiment, the oil component is used in combination with at least one phenol of formula I having an unsaturated "R" group. Examples include cardanol and cardol.

[0038] One embodiment may be a composition comprising cardanol (and optionally cardol) and charcoal powder, where the cardanol and charcoal powder are mixed together to form a mixture and the mixture is cured to form a biocarbon material. The composition may further comprise a reaction promoter or catalyst, where the reaction promoter / catalyst is mixed with the cardanol and charcoal powder as part of the mixture. The mixture may be compressed and, when compressed, has a strength of approximately 5-500 kN / cm. 2 (50-5000MPa), e.g., 5-100kN / cm 2 Suitable pressures are described herein, for example, in the range of 10 to 50 kN / cm. 2The mixture may be cured preferably at less than 450° C. Suitable curing temperatures may range from about 150 to 300° C., for example, from 180° C. to 250° C. Curing times may vary, but may be as little as 1 minute, about 2 hours, or longer. Suitable curing times are described herein, but may be, for example, from 5 minutes to 2 hours, for example, from 15 minutes to 1 hour.

[0039] In any embodiment of the present disclosure, the mixture can be cured via a curing mechanism selected from the group of curing or heating mechanisms consisting of one or more of the following: indirect heating; direct heating; radiant heat; ultraviolet light; infrared; microwave; ultrasonic; inductive power; and combinations thereof. Direct heating, e.g., electrical heating, forms the preferred curing method.

[0040] The compacted mixture can be directly cured into its final shape (e.g., formed into briquettes, cylinders, rods, blocks, cubes, balls or prisms before curing). Alternatively, the mixture can be formed into its final shape after curing by any suitable means, such as cutting, grinding or crushing. Briquettes can be in a shape suitable for use as a metallurgical reductant or as a fuel. Alternatively, the bio-carbon material can be formed and / or further processed into any suitable form. Further processing can include, for example, shaping the bio-carbon material by cutting and / or crushing, or by subsequent processing, such as by further curing, coating or heat treatment of the kind commonly used for conventional carbon anodes for the production of aluminum (known as second heat treatment or SHT). For charcoal, the bio-carbon material can be first formed into small pieces (e.g., blocks of standard dimensions) and, after curing, crushed (e.g., by a jaw crusher) and sieved into the desired grade for use as crushed stone (e.g., crushed stone for concrete).

[0041] With regard to petroleum coke anodes for the aluminum industry and all other metallurgical companies that use anodes made from fossil resources, the entire metallurgical industry has been searching for ways to reduce their carbon dioxide footprint for many years. Typical anodes are made from petroleum coke and have coal pitch added as a binder. Coal pitch and petroleum coke use and release large amounts of carbon dioxide. Thus, there has been a long-standing need in the art for new raw materials and binders for use in the manufacture of metallurgical anodes that use and release less carbon dioxide.

[0042] The use of biocarbon materials may include use in anodes for use in the metallurgical industry, particularly in the production of metals, such as aluminum. The biocarbon materials of the present invention provide significant advantages over existing carbon anodes. Existing carbon anodes typically require curing temperatures of over 1000°C for long periods of time and are formed from fossil carbon. As a result of this and other factors, in the production of 1000 kg of aluminum, up to around several hundred kilograms of fossil carbon (including around 400 Kg of fossil carbon anodes) are released as carbon dioxide to the atmosphere. This means that in the production of every ton of aluminum, up to around 6 tons of carbon dioxide are released (at 2014 levels). Thus, there is a significant need to reduce the utilization of fossil carbon in aluminum production. In one embodiment, the biocarbon materials of the present disclosure are in the form of anodes. In certain embodiments, such anodes can be made without the need for very high temperature processing and / or long periods of heat processing. Current petroleum coke anodes are processed at temperatures above 450°C for periods of around 8 days. Therefore, it would be preferable if lower temperatures (e.g., less than 450°C) and / or shorter heating times (especially less than a day) were possible. In particular, if the charcoal is heated to high temperatures before mixing with the binder, and / or if the binder is made utilizing certain additives (e.g., ionic liquids, as described herein), high temperature treatment may not be required to form the anode. Thus, in one embodiment, the present disclosure provides a carbon anode formed from the bio-carbon material of the present disclosure without heat treatment above 450°C. In an alternative embodiment, the bio-carbon material of the present disclosure may be subjected to a second heat treatment (SHT). The SHT can be performed by known methods, but typically involves heating the bio-carbon material of the present disclosure to a temperature in the range of 800-1500°C, e.g., 1000-1200°C, in an inert atmosphere. The heating period is preferably shorter than the 300-400 hours typically required for conventional petroleum pitch / coke anodes. In one embodiment, the SHT is carried out for 72 hours or less (eg, 2 to 72 hours), preferably 48 hours or less or 24 hours or less.In one embodiment, SHT is performed on products (e.g., anodes, briquettes, or other products, e.g., as described herein) formed with the biocarbon material of the present disclosure until there are less than 3.5 wt. % (e.g., 3.5-0.1 wt. %) volatiles present in the product. Higher levels of volatiles may be acceptable for certain industries, e.g., steel production. A shorter SHT or no SHT may be possible in some cases, but volatiles should be low (e.g., less than 5% or less than 3.5%) depending on the combination of charcoal, binder, and heat used. Cardanol, cardol, and other long chain phenols (e.g., phenols of formula I with R containing at least 8 carbons) can have low amounts of volatiles, and in certain cases reduced heat treatment may be required (e.g., as described herein).

[0043] The biocarbon material of the present invention can also be used as a partial substitute for standard petroleum coke in anode production. In such an embodiment, at least 50% of the carbon in the anode is derived from recovered carbon (biocarbon), with the remainder derived from fossil sources. The binder in such an anode can be a conventional pitch binder or more preferably an organic binder (e.g., as described herein) and / or an inorganic binder. Such products of the present invention formed in part from biocarbon materials (e.g., at least 50% recovered carbon) can also be used as reducing agents and in various other embodiments described herein.

[0044] The metallurgical and construction industries as a whole have been searching for carbon neutral solutions for decades, so the products and methods of the present disclosure are not obvious in light of what has been done before: if it were obvious, the methods of the present disclosure would already have been done by others.

[0045] The hardened and pressed mixture (bio-carbon material) can be used as one of the ingredients to make concrete, as described herein. This can preferably be "carbon neutral concrete". In such use, the bio-carbon material can be formed or processed into suitable crushed stone, gravel or pebble sized pieces (see above). This formation can be by breaking the formed material into smaller pieces, for example by using a jaw crusher. In one embodiment, the bio-carbon material can be formed into high performance materials, for example anodes for the metallurgical (particularly aluminum) industry, and those items that do not reach the required resistance can be broken into suitable pieces for use as charcoal in concrete or similar materials (e.g. asphalt) or recycled into new anodes.

[0046] Typically for the bio-carbon materials of the present disclosure, the binder in the mixture (e.g., cardanol and / or cardol, optionally including promoters) may range from approximately 2% to 50% by weight of the final material / mixture. The binder in the mixture is typically 5% to 30% by weight, e.g., 8% to 24% by weight. For carbon anodes, this may be 10 to 30% by weight, e.g., 15 to 25% by weight.

[0047] The charcoal powder in a typical mixture may range from approximately 10% to 98% by weight of the mixture. More typically, at least 20%, preferably at least 40% and more preferably at least 50% of the material is made up of charcoal. For use in the anode and certain other uses, the level of volatiles in the charcoal powder can be maintained at a low level. Thus, in one embodiment, the level of volatiles in the charcoal may be less than 5% (e.g., 0.1 to 5%), preferably less than 3%.

[0048] The catalyst / accelerator in the mixture is preferably hexamine and may range from 0.1% to 15% by weight of the amount of binder, suitable amounts being described herein.

[0049] In one embodiment, the charcoal powder may be pure charcoal powder, and thus the biocarbon material consists or essentially consists of charcoal and a binder (optionally including an accelerator). Such charcoal may have reduced volatiles as described herein. In alternative embodiments, at least one inorganic filler may be present. Preferably, the biocarbon material contains (e.g. is formed from) no more than 30% by weight of inorganic filler. This may be 0-30% or 1-30% by weight, such as 10-25% or 15-25% by weight of filler. The inorganic filler may function to increase the compressive strength of the biocarbon material and / or may be used to control the density of the material. In particular, for certain applications, for example for use in concrete, it may be advantageous to increase the density of the biocarbon material. This may aid in its incorporation into mixtures, such as cement or asphalt. Suitable inorganic fillers include those disclosed herein below and can include materials such as rock dust (very fine rock particles, such as those produced by drilling into rock or crushing rock), such as granite dust, silicon powder or fine sand. The particle size of the preferred fillers may range from 50 nm to 500 μm in diameter, such as from 100 nm to 200 μm, such as from 3 to 100 μm. Very fine fillers, such as those having an average particle diameter of less than 100 μm (e.g. from 100 nm to 80 μm or from 1 to 50 μm), can also be used.

[0050] Another particular embodiment is a composition comprising cardanol (optionally containing up to 12% cardol), charcoal powder, and hexamine, wherein the cardanol, charcoal powder, and hexamine are mixed together to form a mixture, and the mixture is cured at a temperature in the range of approximately 180° C. to 250° C. for a period of 1 to 2 hours, and the mixture is cured at a temperature in the range of approximately 3 to 50 kN / cm 2in the range of approximately 8% to 35% by weight (e.g., 8 to 20% by weight) of the mixture, charcoal powder in the range of approximately 50% to 92% by weight of the mixture, and catalyst / accelerator (e.g., hexamine) in the range of 0.1% to 20% by weight (e.g., 0.1 to 15% by weight) of the cardanol / cardol component. All discussion herein pertaining to the various features of the present embodiment may be utilized and combined with the present embodiment where technically feasible.

[0051] Another embodiment may be a method of preparing a charcoal powder and cardanol product, comprising the steps of providing cardanol, providing charcoal powder, mixing the cardanol with the charcoal powder to create a cardanol and charcoal powder composition, pressing the cardanol and charcoal powder composition, and hardening the cardanol and charcoal powder composition. The method may include providing a catalyst, mixing the catalyst with the cardanol and charcoal powder, such that the cardanol and charcoal powder composition includes the catalyst. The cardanol may be in the range of approximately 2% to 50% by weight of the cardanol and charcoal powder composition, the charcoal powder may be in the range of approximately 10% to 98% by weight of the cardanol and charcoal powder composition, the accelerator / catalyst may be in the range of 0.1% to 15% by weight of the binder (cardanol) component, and the cardanol and charcoal powder composition has a compressive strength of approximately 3 to 100 kN / cm. 2 Pressure may be applied (optionally with vibration) in the range of 180° C. to 250° C., and the mixture may be cured at temperatures in the range of approximately 180° C. to 250° C. for 30 minutes to 2 hours.

[0052] Other features and advantages will become apparent to those skilled in the art from the following detailed description and its accompanying figures.

[0053] The figures show illustrative embodiments and do not represent all embodiments. Other embodiments may be used in addition to or instead of the illustrated embodiments. Details that may be obvious or unnecessary may be omitted for purposes of saving space or for a more effective illustration. Some embodiments may also be practiced with additional components or steps and / or without some or all of the components or steps provided in the illustrations. When different figures contain the same numerical values, the numerical values ​​refer to the same or similar components or steps. [Brief description of the drawings]

[0054] [Figure 1] FIG. 1 is a block flow diagram of one embodiment of a process for creating bio-carbon materials and products. [Diagram 2] FIG. 1 is a diagram of one embodiment of a process for producing charcoal dust and phenolic binder briquettes. [Diagram 3] FIG. 1 is a graph showing that when cardanol is used as the phenol forming the phenolic binder, the more binder is added in a particular formulation, the stronger the resulting product (within certain limits). [Figure 4] 1 is a photograph of a cylindrical bio-carbon material of the present disclosure after compressive strength testing. [Diagram 5] FIG. 1 is a photograph of the extrusion of a biocarbon material formed with a binder comprising a phenolic resin and a second binder of potato starch modified to be cold water soluble. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0055] In the following detailed description of various embodiments, numerous specific details are set forth in order to provide a thorough understanding of various aspects of the embodiments. However, the embodiments may be practiced without some or all of these specific details. In other instances, well-known procedures and / or components have not been described in detail in order not to unnecessarily obscure aspects of the embodiments.

[0056] While some embodiments are disclosed below, other embodiments will become apparent to those skilled in the art as a result of the following detailed description. These embodiments are susceptible to modifications in various obvious aspects, all without departing from the spirit and scope of protection. The figures and these detailed descriptions are to be considered as exemplary in nature and not restrictive. Furthermore, reference or non-reference to specific embodiments should not be interpreted as limiting the scope of protection.

[0057] In the following description, certain terms are used to describe certain features of one or more embodiments. For purposes of this specification, unless otherwise specified, the term "substantially" refers to the complete or near complete extent or degree of an action, feature, characteristic, state, structure, item, group of items, or result. For example, in one embodiment, an object located "substantially" within an enclosure would mean that the object is either completely within the enclosure or nearly completely within the enclosure. The extent of deviance from absolute completeness that is certainly acceptable may depend on the particular context in some cases. Generally speaking, however, near completeness would have the same overall result as if absolute and total completeness had been obtained. The use of "substantially" is also equally applicable, when used in a negative sense, to refer to a complete or near complete lack of an action, feature, characteristic, state, structure, item, group of items, or result. In another example, substantially all of a group of items may include all of the items in that group, or at least all of the items in that group that are generally within normal parameters for the items. To the extent that a group of items may contain members far beyond normal parameters, this abnormal item cannot be expected to be part of substantially all of the group of items.

[0058] As used herein, the terms "approximately" and "about" generally refer to deviations within 5% of a given number or range of numbers. Together, "substantially pure" or "consisting essentially of" suggest that something is practically pure, but allows for a certain degree of impurity, e.g., less than 12%, less than 10%, less than 5%, or less than 1% of other material(s). In one embodiment, the terms "approximately" and "about" can refer to deviations between 0.0001 and 39% from a given number or range of numbers.

[0059] As used herein, the term "charcoal" (sometimes referred to in the art as "biochar" and used equivalently herein so that "charcoal" herein may be interpreted as "biochar") can be produced from any organic material that is subjected to carbonization. Generally, charcoal / biochar is a solid, carbon-rich material obtained from the thermochemical conversion of biomass in an oxygen-limited environment. Preferably, charcoal can be derived from any biomass, including, but not limited to, sugarcane, bagasse, straw, bamboo, nut shells and other nut by-products (e.g., coconut or cashew nut shells and / or solid residues), rice husks, agricultural residues (e.g., agricultural waste), municipal solid waste, hardwoods and softwoods. Any such material, or any other organic matter, can be the base ingredient for charcoal. An advantageous aspect of the present invention is a facility that uses carbon captured from the atmosphere to reduce the net carbon emitted in the production of products and / or to sequester carbon from the atmosphere and incorporate it into long-life products such as concrete. Thus, in one embodiment, charcoal (biochar) is formed from recently living (growing) biomass. This may be biomass that has been growing (and thus harvesting carbon from the atmosphere) within the last 100 years (e.g., 1 week to 100 years prior to use) or within the last 50 years. For some forms of biomass (e.g., bamboo or harvest residues such as straw or rice husks, among others), the biomass may have been growing within the last 5 years (e.g., within the last 3 years or within the last year).

[0060] Preferably, the charcoal used in the compositions of the present disclosure is in the form of charcoal powder. "Charcoal powder" as used herein generally has a weight average particle size of 20 mm or less, e.g., 8 mm or less in its largest dimension (e.g., 1 nm to 20 mm, 1 nm to 8 mm, e.g., 100 nm to 8 mm or 1 μm to 8 mm). Preferably, the charcoal powder has a weight average particle size of 2 mm or less (e.g., 3 μm to 1 mm or 10 μm to 1 mm). The inventors have found that smaller charcoal particles generally result in stronger biocarbon materials, and thus the preferred charcoal powder size is 200 μm or less in its largest dimension (e.g., 10 to 200 μm), preferably 100 μm or less.

[0061] As used herein, the term "charcoal dust" refers to crushed or pulverized charcoal, preferably of the size indicated above. "Charcoal dust" is a waste product consisting of fine charcoal and small pieces that can be obtained during the processing of charcoal for barbecue, metallurgical industry, or any other application where charcoal is commonly used, and can be used as a starting material for charcoal dust. Charcoal dust can be found at the bottom of charcoal bales, or as a residue from charcoal, which is a powdery material of black soot that is usually found at charcoal manufacturing and / or packaging sites. Charcoal dust is generally small pieces of charcoal, usually less than 40 millimeters in diameter. These are then crushed and / or ground into charcoal dust. Preferably, the charcoal dust used can have a diameter of less than 2 millimeters (as described herein).

[0062] The charcoal powder in various embodiments of the present invention should be approximately 60%-100% or 70%-100% pure charcoal, with approximately 40% or 30% or less of carbon-based filler (by weight of the charcoal component). As used herein, the term "carbon-based filler" refers to, for example, coal, coke, anthracite, graphite, wood dust, sawdust, wood chips, wood flour, lignite, semi-coke, petroleum coke, metallurgical coke, carbon fiber, and the like. This is in contrast to the "inorganic filler" described herein, which is optional. In one embodiment, the charcoal component is pure charcoal or substantially solid charcoal.

[0063] Inorganic fillers can be used up to 40% of the biocarbon material, preferably up to 30% by weight (as discussed above). Such fillers can be used for any purpose, for example, to add strength to the material, reduce the surface area or water absorption of the material, and / or increase the density of the biocarbon material. Suitable fillers include rock flour (very fine rock particles, such as those produced by drilling into rock or crushing rock), silicon powder, or fine sand. In certain embodiments, granite flour is particularly suitable, as are carbonate minerals, such as calcium magnesium carbonate (dolomite). The particle size of the preferred inorganic fillers may be in the range of 1 nm to 100 μm, for example, in the range of 1 to 20 μm or 3 to 1 μm.

[0064] In the biocarbon material of the present disclosure, at least 10 wt% (e.g., 10-98 wt%) of the biocarbon material is composed of charcoal. This is preferably at least 40 wt% (e.g., 40-95 wt%), and more preferably 50-90 wt%. In an embodiment, for applications such as fuels and reductants where low levels of binder (e.g., 2-15 wt%) may be sufficient, the weight percent of charcoal may be 75 wt%-98 wt%, 75 wt%-95 wt%, or 80 wt%-90 wt%. In further embodiments, for higher strength applications such as "charcoal rock" (as discussed herein) and anodes for aluminum production, the binder content may be higher (e.g., 20-30 wt%) and thus the charcoal content may be lower (e.g., 70-80 wt%). If inorganic filler is also included, the charcoal content may be 40-70 wt% or 45-60 wt%.

[0065] As used herein, "recovered carbon" refers to carbon that has been removed from the atmosphere within the last 100 years or within the last 50 years. This is usually by plant growth, e.g., trees, bamboo, or agricultural crops, but may be done by other means, e.g., chemical methods. Recovered carbon can be contrasted with "fossil carbon" from fossil fuels. If the captured carbon is utilized in a manner that releases carbon into the atmosphere as CO2, the net effect is simply to replace carbon that was previously in the atmosphere (e.g., carbon previously removed from the atmosphere by plant growth). The overall effect of this on the carbon content of the atmosphere is zero, known as "carbon neutral." In conjunction, if the captured carbon is sequestered from the atmosphere for a long period of time (e.g., 100 years or longer, e.g., 100-500 years), the overall effect is "carbon negative" in the sense that carbon has been taken from the atmosphere and not replaced.

[0066] As used herein, "carbon neutral" or "CO2 neutral" is the property of having zero net carbon dioxide emissions. A product can be carbon neutral by balancing the carbon dioxide emissions associated with the process by capturing a corresponding amount of carbon from the atmosphere. Since precise measurement can be difficult, an imbalance in the weight of carbon released and absorbed of ±20% or ±10% or less, preferably ±5% or less, is considered "carbon neutral" herein. In combination, a product is "carbon negative" if the carbon dioxide emissions associated with its production are less than the carbon dioxide absorbed from the atmosphere by the product itself. Generally, a product can be considered "carbon negative" herein if the weight of carbon captured from the atmosphere into the product is more than 10%, preferably more than 20%, greater than the amount of carbon released as carbon dioxide in the manufacture of the product.

[0067] As used herein, the term "biocarbon" is used to indicate recovered carbon that has been taken from the atmosphere within the last 100 years or within the last 50 years (preferably within the last 30 years) by biological processes, e.g., plant growth. Together, the "biocarbon material" referred to herein is a material that contains biocarbon. In particular, the carbon content of the biocarbon material should contain at least 50% biocarbon, preferably at least 80% biocarbon. In some embodiments, the carbon content of the biocarbon material consists essentially of or consists of biocarbon as described herein. The use of biocarbon is of great significance because it avoids the release or risk of release of fossil carbon (in the form of CO2) into the atmosphere. Biocarbon (also called "recovered carbon") is also at least moderately different from fossil carbon in its isotopic profile and can be distinguished from fossil carbon by radiocarbon methods. For example, the carbon content of the atmosphere is at least 50% biocarbon, preferably at least 80% biocarbon. 14 The ratio of C is 12 C atoms 10 12 in one piece 14 Approximately 1 C atom, similar to the terrestrial biosphere. Thus, the carbon captured is 14 C: 12C atomic ratio: about 1:10 12 , for example, 1:10 12 ~1:10 13 Between or 1:10 12 ~1:10 14 The ratio may be between about 1:10. 15 Less than 14 C: 12 Carbon having an atomic ratio of C likely contains high levels of carbon that has not been present in the atmosphere or biosphere for at least 50,000 years, and therefore is not considered "recovered carbon" or biocarbon herein.

[0068] In various embodiments of the present disclosure, at least one binder is utilized. A preferred binder comprises at least one phenolic resin. Phenolic resins are typically produced by polymerization of at least one phenol with or using at least one aldehyde or a formyl carbon source such as hexamine.

[0069] Suitable phenols for forming phenolic resins for use as binders include phenols of Formula I:

[0070] [ka]

[0071] In formula I, X is H or OH, and R is H or an optionally substituted, saturated or unsaturated, hydrocarbon moiety having 1 to 24 carbon atoms, which may be linear or branched. In one embodiment, the at least one phenol of formula I includes at least one phenol in which R is not hydrogen. R is typically in the meta position relative to the phenolic OH group. Generally, unsubstituted phenols do not form the only phenol for producing the phenolic resins described herein.

[0072] Thus, in general, a phenolic resin is formed from (i.e. is a polymer of) at least one phenol, at least a portion of which of the phenols of formula I have R as a moiety other than hydrogen. Preferably, no more than 60% by weight (e.g. 1-50% by weight) or no more than 30% by weight, preferably no more than 10%, more preferably no more than 1% have R=H. In one embodiment, the phenol(s) of formula I have no hydrogen as an R moiety. Typical examples of R include C1-C24 hydrocarbons, e.g., C6-C20 (e.g., C8-C18 or C10-C17) saturated or unsaturated hydrocarbons, having linear or branched chains. Such hydrocarbon moieties may be saturated or unsaturated. Such unsaturation may be in the form of at least one double bond and / or triple bond in the hydrocarbon moiety, e.g., 1, 2, 3, 4 or 5 double bonds. The double bonds, if present, may be cis or trans double bonds. Preferably, at least one cis double bond may be present in at least a portion of the phenols of formula I. In one embodiment, there may be 0, 1, 2 or 3 double bonds, or a mixture of 2 or more, in the phenol of formula I. When the R moiety is a substituted hydrocarbyl moiety, it may be substituted with any suitable group, for example, Cl, F, OH, NH2 epoxy or other substituents. Amine and hydroxyl substituted compounds of formula I are particularly suitable. Epoxy substitution may also be used. In one embodiment, R is C 15 H 31 -n, where n is 0, 2, 4 and / or 6.

[0073] In one embodiment, the phenolic binder can be (e.g., formed or formable from) a polymer of a phenol of formula I that comprises, consists essentially of, or consists of cardanol and / or cardol. In one embodiment, the phenolic binder is formed or formable from a phenol that comprises at least 50% (e.g., 50%-100%) cardol and / or cardanol (e.g., at least 70% or at least 80%, e.g., at least 90%).

[0074] As an alternative or partial replacement for pure phenolic resin binders, epoxy resins can also be utilized. In particular, the phenols of formula I can be epoxidized using known methods, for example, epichlorohydrin. For example, cardanol can be epoxidized as follows:

[0075] [ka]

[0076] Additionally, the phenols of formula I may be formed into novolac-type phenolic resins by use of a formyl carbon source, such as hexamine, as disclosed herein, which may then be epoxidized and then further crosslinked by reaction of the epoxidized prepolymer:

[0077] [ka]

[0078] In an alternative embodiment, the phenolic resin does not contain any epoxy groups and does not include any epoxidation step in the synthesis of the phenolic resin.

[0079] As used herein, the term "cashew nut shell liquid" or "CNSL" refers to a yellowish, shiny natural resin found in the honeycomb structure of cashew nut shells and a liquid by-product of cashew nut processing. Naturally occurring CNSL contains four main components: anacardic acid, cardanol, cardol, and 2-methylcardol. These four components are mono- or dihydric phenols or phenolic acids with a hydrocarbon side chain at the meta position. CNSL can be heat treated to decarboxylate the anacardic acid, producing cardanol-rich technical grade CNSL. Distillation of this material yields distilled, technical CNSL containing 78% cardanol and 8% cardol. In one embodiment, the phenol of formula I is around 78% cardanol and around 8% cardol (e.g., 75-85% cardanol and 5-15% cardol).

[0080] As used herein, the term "cardanol" or "cardanol oil" refers to C 21 H 30 O, C 21 H 32 O, C 21 H 34 O and / or C 21 H 36 O as well as the following structure:

[0081] [ka]

[0082] where n is 0, 2, 4, or 6. Usually, mixtures containing at least some n=6 are present.

[0083] Cardanol is a phenolic lipid obtained from anacardic acid, the main component of cashew nut shell liquid.

[0084] [ka]

[0085] Some anacardic acid (eg, 0-20% by weight, such as 1-15% by weight or 1-10% by weight) may be present in the binder.

[0086] Cardanol, as a mixture of long chain alkylphenols having C15 chains as shown above (corresponding to the group "R" in formula I and the structures herein), has the CAS number 37330-39-5. 15 H 25 Purified cardanol having the same CAS number is also available. Either grade may be used as all or part of the phenol of formula I in various aspects of the invention. In one embodiment, at least 50%, preferably at least 75%, of the phenol of formula I consists of cardanol CAS 37330-39-5, e.g., the cardanol mixture shown above.

[0087] In the biocarbon materials of the present disclosure, the amount of binder component is typically 5% to 30% by weight (as discussed herein). This may vary for different applications as discussed above. If the material is to form a "charcoal stone", the amount of binder is generally at least 15% by weight, (e.g., 12-30% by weight), preferably at least 15% by weight or at least 18% by weight. A maximum of around 25-30% binder is preferred, since if a higher amount is utilized, the material may lose binder when compressed. However, the particle size of the charcoal and / or filler may affect the maximum amount of binder, so an upper limit is easily determined for any particular charcoal powder and optional filler.

[0088] The binder component in various embodiments of the present invention can include or consist of a phenolic binder. Such binders can include or consist of a polymer of phenol, for example, a phenol of formula I described herein. The method of forming the biocarbon material of the present disclosure can include mixing charcoal powder with phenol(s) and other materials, for example, optional accelerators (as described herein), forming the material into a desired shape, optionally compressing the material (as described herein), and curing the material (as described herein). Alternatively, the binder component can be in the form of a prepolymer, for example, a "novolac" type resin (known in the art and described above). This prepolymer includes charcoal and can be mixed with additional phenol(s) and other components, optionally including optional components, for example, accelerator(s), drying oil and / or filler(s). These various components are described herein. The prepolymer mixture can then be cured by crosslinking, for example by reaction with an aldehyde or formyl carbon source, by epoxy modification and crosslinking (see above), and / or by oxidative crosslinking (as known for drying oils).

[0089] In one embodiment, at least 50% of the carbon present in the binder is recovered carbon. This may be 50-100% by weight, or 50-98% by weight, or 70-99% by weight. The use of binders that include materials derived from natural sources (e.g., cardanol with or without cardol) increases the amount of recovered carbon in the biocarbon material and improves carbon capture and sequestration properties. Binders that utilize fossil carbon can also be used as a total or partial replacement.

[0090] In one embodiment, the binder is free of lignin or contains lignin in an amount less than 1% by weight of the binder component.

[0091] As used herein, the term "pressed" or "compressed" refers to the act of subjecting a mixture or composition to pressure. The applied pressure can be via air press, mechanical press, electric press, extruder, roller press, etc. Compression can be done once or multiple times (e.g., 2, 3, 5 or 10 times). Once cured, multiple compressions can result in a stronger product. Whenever pressing or compression is referred to herein, this can optionally be accompanied by vibration, either sequentially or simultaneously.

[0092] CNSL and cardanol can be extracted and purified using many different methods, including mechanical extraction, thermal extraction, solvent extraction (static, Soxhlet, ultrasonic, carbon dioxide), and pyrolysis. Mechanical and thermal extraction are preferred and are the most commonly used and commercially practiced. In one embodiment, CNSL is typically treated at high temperatures to decarboxylate the anacardic acid and produce cardanol. Additional distillation of the CNSL removes at least some of the cardol, leaving cardanol in a pure or at least purer form.

[0093] As used herein, the term "hexamine", also known as urotropine, methenamine, and hexamethylenetetramine, refers to a heterocyclic organic compound having the formula (CH2)6N4. Hexamine is a white crystalline compound that is highly soluble in water and polar organic solvents. It is useful in the synthesis of other organic compounds, including additives for plastics, pharmaceuticals, and rubber. It can also be used as a promoter or catalyst. Other sources of formyl carbon, including those described herein, can also be used as promoters.

[0094] Other catalysts and accelerators that can be used are cationic agents, ionic agents, and oxidizing agents that, when heated, can promote the polymerization of cardanol. Other alkalis can also be used as catalysts.

[0095] Although hexamine is a useful source of formyl carbon, other formyl sources can be used. These include formaldehyde and oligomers of polymethylene glycol, such as formalin or paraformaldehyde. Other aldehydes can also be used.

[0096] Urea and / or urea derivatives (e.g., methylol urea) can also be used as promoters, either alone or in combination with a formyl carbon source. Metal oxides, such as magnesium oxide, can be of value as catalysts when urea or a urea derivative is included.

[0097] Phenolic resin binders (especially those formed at least in part from cardanol) form one preferred embodiment of the present disclosure. Such phenolic binders can be formed by reaction of phenols, for example, with the phenols of formula I herein by themselves (e.g., by oxidative crosslinking) or with accelerators, such as hexamine or other formyl carbon sources. These may be further epoxidized either as monomers or prepolymers, or cured with conventional epoxy curing agents, such as amines (e.g., phenalkamines). In one particular embodiment, epoxidized phenols and / or phenolic prepolymers, such as those shown herein, can be cured with or with the addition of ionic liquids. In particular, phosphonium-based ionic liquids can be used. In one embodiment, the phenolic resin is not an epoxy resin. For example, in one embodiment, the phenolic resin does not include any epoxy components (e.g., is not formed by epoxidation of phenol or any prepolymer). In one embodiment, the binder component comprises, consists essentially of (e.g., contains 90% to 100% by weight) or consists of at least one phenolic resin.

[0098] Other binders may be utilized as an alternative to the phenolic binder. In particular, in one aspect of the present disclosure, a biocarbon-based material is provided comprising charcoal and at least one binder, the biocarbon-based material having a compressive strength of at least 30 MPa, at least 50 MPa, or at least 60 MPa, as tested, for example, by ASTM C39 / C39M, as described herein (as described herein). Such materials are sufficiently hard to be used as at least a partial filler in construction materials, for example, concrete, and concrete comprising such materials forms a further aspect of the present disclosure. Any suitable binder may be utilized, in all proportions and embodiments described herein, as a total or partial alternative to the phenolic resin binders described herein, where technically feasible. Such alternative binders include other polymers, for example, melamine or epoxy resins, or inorganic binders. Suitable inorganic binders, for example, polysialates include water glass (e.g., sodium silicate) modified with nanoparticles of metal oxides. Such materials are described in EP3524372A1, which is incorporated herein by reference. Inorganic binders can be used in combination with organic binders, such as the phenolic resin binders described herein.

[0099] In addition to the primary (particularly phenolic) binder, the biocarbon material and all corresponding aspects of the present invention may also include an optional secondary binder. In one embodiment, the secondary binder serves to increase the "green strength" of the material, which is the strength after formation but before curing. The secondary binder may be any binder that serves to increase the "green strength" of the mix without compromising the strength of the cured product.

[0100] Exemplary "second binders" include those discussed herein above, including "drying oils", such as linseed oil, and polysaccharide binders, such as alginates, guar gums, or starch-based binders. Starch binders can include any form of starch, such as corn starch, wheat starch, potato starch, rice starch, and any combination thereof. "Starch" includes in all instances "modified starch", such as modified corn starch, modified wheat starch, modified potato starch, modified rice starch, and any combination thereof. "Modified starch" is a term well understood in the art and includes starch that has been physically, enzymatically, and / or chemically treated from any suitable source.

[0101] Particularly useful starch modifications include modifications that render the starch cold water soluble. These can include extrusion, drum drying, spray drying, or dextrinization (roasting with HCl). In one embodiment, the second binder comprises a cold water soluble modified starch (e.g., from potato).

[0102] The second binder may be present in an amount of up to 50% by weight (e.g., 1-50% by weight) of the binder component, or in an amount around 15% by weight of the total biocarbon material, preferably 5-40% or 10-35% (e.g., 15-30%) of the binder component.

[0103] Water may be used as a processing aid in the methods described herein. It may particularly act as a lubricant during forming (e.g., extrusion, briquetting, or pelleting) and may also aid in the incorporation of a second binder, e.g., a polysaccharide binder (e.g., starch or modified starch). If water is added to the mixture, this is usually done before shaping the product and is usually removed by drying before the binder hardens. In one embodiment, the shaped "green" product (i.e., before hardening) is dried at a temperature of 50-120°C (e.g., 80-105°C) for 10 minutes to 2 hours before the hardening step. This drying step may be to reduce the water content of the green product to less than 10% by weight, preferably less than 8% by weight or less than 5% by weight, before hardening. If high levels of water remain in the product during the hardening step, the binder may not be effectively hardened and the properties of the final product may be inferior. Water used as a processing aid is not taken into account in the calculation of the weight percentages of the components herein, since this water is generally not present in high levels in the final product.

[0104] Specific Example Embodiments One embodiment of the present disclosure comprises the steps of: Providing at least one phenol of formula I (e.g., cardanol), - preferably in the range of approximately 2 to 50% by weight, *If the mixture has more than approximately 50% by weight of binder (e.g., cardanol), the binder may seep or flow out of the mixture when pressure is applied (saturation of the binder (e.g., cardanol) occurs at or about 50%); *As detailed in Figure 2, the more binder in the mix, the harder the briquette or product will be resulting, more preferably, the binder (particularly cardanol) may be in the range of 5-30% by weight of the final mixture; Providing charcoal, preferably in the form of charcoal powder, - preferably in the range of 30 to 98% by weight, In some embodiments, the charcoal may be ground to provide a uniform charcoal powder; - in some embodiments, the charcoal powder can be thickened with a carbon filler up to approximately 30% by weight of the charcoal powder (as described herein); mixing a binder (e.g., cardanol) with charcoal powder to create a composition of cardanol and charcoal powder; In one embodiment, after approximately 10 minutes, the composition is thoroughly mixed; - in some embodiments, the charcoal can be diluted to approximately 30% with a carbon filler; - loading the mixture of binder and charcoal into a die or other suitable container for pressing; Alternatively, the mixture can be extruded or passed through a roller press, whereby pressure can be provided, subjecting the mixture of binder (e.g., cardanol) and charcoal powder to pressure, In one embodiment, a hydraulic press may be used, although other pressure mechanisms may be used, including a mechanical press, an extruder, or a roller press; - Preferably, the pressure is approximately 3 to 200 N / cm 2 and preferably about 10 N / cm 2 may be - the composition may be pressed multiple times to increase the compressive strength; hardening the pressed binder (e.g., cardanol) and charcoal powder composition, In one embodiment, the pressed binder (e.g., cardanol) and charcoal composition is heated in an oven for approximately 1 minute to 2 hours (or longer); In one embodiment, the pressed binder and charcoal composition is cured in an oven at a temperature below 450°C, preferably in the range of approximately 180°C to 250°C; - The curing may be via direct heat, indirect heat, radiant heat, ultraviolet light / rays (UV), infrared light (IR), microwave, ultrasonic, inductive power, etc. The method may include:

[0105] The composition of hardened binder and charcoal powder (bio-carbon material) can be used as industrial or BBQ briquettes.

[0106] The hardened binder and charcoal powder composition (biocarbon material) can be used as a total or partial replacement for rock, stone, or other fillers commonly used in concrete, if desired, without reducing the overall strength of the concrete. Such use can lower the carbon footprint of the concrete. With such use, concrete can be carbon neutral or even carbon negative with respect to the carbon released in its production.

[0107] The hardened binder and charcoal powder composition (biocarbon material) can be used as a metallurgical reducing agent and / or as an anode, for example for use in aluminum production; - Preparation of the anode usually requires heating to high heating temperatures, which is defined as temperatures above 1000°C.

[0108] The resulting compressive strength of the binder and charcoal products of the present disclosure (particularly the cardanol and charcoal products) was a pleasant surprise. In fact, even with as little as 18% binder, the resulting cardanol and charcoal products are as hard as certain grades of concrete and can therefore be used by themselves, including as a construction material or for use as a composite material. For such uses, binder levels around 18-30% are preferred. The binder percentage can be varied so that the hardness and strength of the resulting product can be customized.

[0109] One embodiment of the present disclosure comprises the steps of: Providing a phenolic binder (e.g., cardanol); Providing charcoal, preferably in the form of charcoal powder; Providing a catalyst in a binder, - the catalyst may be hexamine or another source of formyl carbon or an aldehyde; the catalyst may be any cationic agent, ionic agent, oxidizing agent or alkali that, when heated, promotes the polymerization of the binder (e.g., phenol, e.g., cardanol); - in one embodiment, hexamine is added at approximately 6-8% by weight of the phenol (e.g. cardanol) added; mixing phenol (cardanol), a catalyst, and charcoal to create a composition; pressurizing (and optionally simultaneously or sequentially vibrating) the composition; - curing the composition; Optionally, processing the hardened phenolic, catalyst, and charcoal composition to create briquettes that can be used as an ingredient in concrete, as a metallurgical reducing agent, as a cooking fuel in the BBQ industry, and / or as an anode for use in, for example, aluminum production; - Preparing the anode usually requires heating to high temperatures (defined as temperatures above 1000°C) Typical conditions for conventional petroleum coke and pitch anodes are 1100° C. for 200-300 hours.

[0110] The higher the cardanol and catalyst content, the stronger the resulting material (e.g., briquette). The higher the cardanol content, the more water resistant the material (e.g., briquette).

[0111] In one embodiment, the bio-carbon materials (e.g., briquettes) described herein can be waterproof or substantially weatherproof and can be stored outside in the elements. In one embodiment, the bio-carbon materials (e.g., briquettes) described herein can be waterproof to the extent that the material does not disintegrate or lose its structure after immersion in water for 24 hours, preferably 48 hours, and more preferably 7 days. Preferably, the bio-carbon materials (e.g., briquettes) described herein can take up 5-10% water by weight and be exposed without any structural weakness of the material.

[0112] In one embodiment, the bio-carbon materials (e.g., briquettes) described herein are strong enough that they may be carried, transported, unloaded, and stored without packaging, using equipment and practices similar to those currently commonly used in the handling and storage of coal, petroleum coke, metallurgical coke, and gravel.

[0113] Preferably, the briquettes of the present disclosure are not susceptible to self-ignition during transportation or storage.

[0114] Prior to the compositions and methods of the present disclosure, the volatile organic compounds and gases in the charcoal range in volume from approximately 0 to 30% by weight. Cardanol is a preferred binder for use in the various embodiments of the present invention. After purification and distillation of CNSL, cardanol has approximately less than 1% volatile organic compounds. Thus, cardanol is not only environmentally friendly, but also non-volatile and essentially non-toxic.

[0115] In one embodiment, the pressing (compression) can be performed at standard pressure (approximately 1 bar or approximately 0.1 MPa).

[0116] In one embodiment, the curing is carried out in an inert, standard atmosphere.

[0117] For SHT, an inert atmosphere is used and the temperature can be increased to the range of 700-1300°C. The optimum temperature (in an inert atmosphere) is approximately 1000-1100°C. Hardening and SHT may be performed in a single heating step or may be performed sequentially.

[0118] When cured in an oxygen-rich atmosphere without the application of pressure, the curing temperature can be reduced to approximately 400°C and below (as described herein), with less than 300°C or less than 200°C being preferred.

[0119] In one embodiment, the bio-carbon material has at least the compressive strength of a standard petroleum coke anode, which has a bending strength of approximately 8-10 MPa, a compressive strength of approximately 30-50 MPa, and a static modulus of elasticity of approximately 4-5.5 GPa (gigapascals). Thus, the product of the present disclosure has all of the same minimum technical requirements as a petroleum coke anode, but is formed from bio-carbon. Thus, the bio-carbon material is also carbon dioxide neutral.

[0120] The figures show illustrative embodiments of products made with the methods of the present disclosure and do not represent all embodiments. Other embodiments may be used in addition to or instead of the illustrated embodiments. Details that may be obvious or unnecessary may be omitted for purposes of saving space or for a more effective illustration. Some embodiments may be practiced with additional components or steps and / or without some or all of the components or steps provided in the illustrations. When different figures contain the same numerical values, the numerical values ​​refer to the same or similar components or steps.

[0121] FIG. 1 is a block flow diagram of one embodiment of a process for creating charcoal and cardanol products. As shown in FIG. 1, process 1 is used to create a composition and thus can have several different usable products 7. Cardanol is combined with charcoal, in this case charcoal powder, and mixed in a grinding and mixing step 2. If required, the charcoal can be ground to create a uniform charcoal powder. Preferably, the charcoal powder particles are sized, e.g., approximately 1 nm to 1 millimeter in diameter, as described herein, although larger pieces can also be used. The mixture can be transferred to a mold, die, container, or pressing device that provides pressing 4 or extrusion 5 to the mixture. The pressed / extruded mixture can then be subjected to hardening 6, which is typically an oven or other device that provides hardening to the mixture. The resulting hardened, pressed mixture can then be further shaped, processed, or hardened, if desired. In one embodiment, the resulting composition can be used as industrial or BBQ briquettes 8. In one embodiment, the product can be broken into smaller pieces or "carbon stones" (also referred to herein as "bio-carbon stones" or "charcoal stones") 12. These may be used as a raw material or in concrete, e.g., "carbon neutral" concrete 13. In one embodiment, the product may be used as a reducing agent 11 or processed into an anode 10, and may optionally be cured by a second heat treatment above 1000°C (in an inert atmosphere).

[0122] FIG. 2 is an illustration of one embodiment of a process for producing charcoal powder and cardanol briquettes. As shown in FIG. 2, the process 100 for making charcoal and cardanol briquettes can include preparing charcoal powder and cardanol and mixing them in a mixer 102. Alternatively, other compounds can be added, such as hexamine, or another type of catalyst. The mixture can then be transferred 104 to a processor 106. The processor 106 can apply pressure to the mixture to compact and / or form it into a particular shape. FIG. 2 shows how the mixture can be extruded through a roller press 107. The briquettes 110 can be screened 108 and the residual material 120 can be recycled back to the mixer 102. FIG. 2 shows that the briquettes 110 can be shaped into pillows. In a preferred embodiment, the briquettes 110 can be cured using heat or some other curing source, such as UV, IR, microwave, ultrasound, induction power, direct heat, indirect heat, radiant heat, etc.

[0123] FIG. 3 is a graph showing that the more cardanol is added, the stronger the resulting product. The graph shows the results of several compressive strength tests, where known pressures were applied to briquettes of different compositions to determine their strength. All briquettes made were pressed identically and subjected to the same hardening process. The briquettes relating to data point 300 on the graph were all pressed twice at approximately 100 MPa, turned over, and then pressed again. This additional pressing made the briquettes stronger. Generally, the other briquettes were pressed once at approximately 100 MPa. RK is a charcoal powder, cardanol, and hexamine based briquette made from the method of the present disclosure. RKHYD is the same briquette but with the addition of 5% slagged lime by weight of the composition. As shown, the strength of the briquettes is greater when additional pressure is applied.

[0124] As shown in Figure 3, cardanol, a "binder," was added at 16% to 28% by weight. Kilogram force per square centimeter (kgf / cm 2 ) is in the range of 220-400. Just below 18% cardanol, the pressure is approximately 240kgf / cm 2 This is higher than the 140 kg / cm3 of standard metallurgical coke. 2 The strength is sufficient. The briquette surface area is 8.04 cm 2 At just under 18% cardanol, it broke at a force of approximately 240 kg, which is equivalent to a pressure of 2.5 metric tons. Figure 3 shows that as the weight percentage of cardanol increases, the strength of the briquette also increases.

[0125] Figure 4 is a photograph of a cylinder of the bio-carbon material of the present disclosure after compressive strength testing. The "hour glass" failure pattern observed is a typical failure pattern for concrete and is not typically seen in other charcoal materials, demonstrating the high degree of compatibility between the bio-carbon material of the present disclosure and concrete.

[0126] FIG. 5 is a photograph of an extrusion of a biocarbon material formed by the method of Example 5. The extruded "rods" that can be seen in the photograph have a high "green strength" due at least in part to the inclusion of a second binder. In the example photograph, potato starch modified to be cold water soluble was used as the second binder. The rods can be seen to survive dropping from the extruder into a collection tray without any significant loss of morphology. Thus, such "green" materials are strong enough to withstand manual and automated handling, such as on conveyors, prior to curing.

[0127] Unless otherwise stated, all measurements, values, ratings, positions, dimensions, sizes, locations, and other specifications set forth in this specification, including the claims which follow, are approximate and not exact values, and are intended to have a reasonable range consistent with their pertinent functions and those customary in the art to which they pertain.

[0128] The foregoing description of preferred embodiments has been presented for the purpose of illustration and description. Although several embodiments have been disclosed, further other embodiments will be apparent to those skilled in the art from the above detailed description. These embodiments can be modified in various obvious aspects, all without departing from the spirit and scope of protection. The detailed description is therefore to be considered as being exemplary in nature and not restrictive. Also, although not explicitly listed, one or more embodiments can be implemented in combination or cooperation with each other. Furthermore, reference or non-reference to a particular embodiment should not be interpreted as limiting the scope of protection. It is intended that the scope of protection is not limited by this detailed description, but by the claims attached hereto and the equivalents of the claims.

[0129] Except as immediately above, nothing described or exemplified is intended to, or should be construed to, cause the public to benefit from any component, step, feature, object, benefit, advantage, or equivalent, whether or not recited in a claim.

[0130] The present invention will now be further illustrated with reference to the following non-limiting examples:

[0131] [Example 1] Formation of charcoal articles using phenolic binders. Charcoal was ground in a laboratory grinder to produce charcoal powder, which was passed through a sieve with a mesh size of 1 mm width and 2 mm length (the sieve holes were rectangular in shape) to obtain particles smaller than 100 μm.

[0132] The particle size of the charcoal powder was measured by laser using a Mastersizer3000E laser size analyzer, and the particles were found to have a distribution of 10 μm to 100 μm.

[0133] To make briquettes with strength >= 30MPa, 30g of technical grade cardanol was mixed with 2.4g hexamine and 100g of the charcoal powder. The mixture was stirred for about 5 minutes until it was moist but not wet. The total binder (cardanol + hexamine) was 24.4% of the total weight of the mixture.

[0134] 20.5 g of the wet mixture was transferred to a 32 mm inner diameter die and pressurized at 10 kN / cm using a laboratory hydraulic press. 2 The green tablet blocks / briquettes were formed by pressing with a force of 0.1 MPa. Repeated pressing was found to improve the strength of the final product.

[0135] The green tablet blocks / briquettes were cured in an oven at 200°C for 2 hours and then cooled in the open air.

[0136] [Example 2] Strength Test Charcoal blocks prepared as described in Example 1 were allowed to cool completely and tested for compressive strength according to the following method: Cylindrical tablet blocks / briquettes, 32 mm in diameter and 25-30 mm in length, were placed in a hydraulic instrument linked to a computer which measures the compressive strength.

[0137] The force applied to the block / briquette was increased in linear, equal steps at a rate of 100 N per minute until breakage. The maximum force at breakage was noted to be ≧30 MPa.

[0138] The typical "hourglass" failure pattern observed for the biocarbon cylinder is shown in Figure 4. This is a common pattern for concrete cylinders, but has not been previously observed for charcoal materials. This indicates that the biocarbon material exhibits a similar response to compressive stress as observed in concrete, indicating a potentially high compatibility between concrete and the biocarbon material.

[0139] [Example 3] Water resistance test. Ten briquettes of bio-carbon material were weighed and placed in a closed jar of water. The briquettes were soaked for 12, 24, 48 and 72 hours, respectively, before being removed and re-weighed. The mass of any briquette did not increase by more than 5% after soaking in water. Furthermore, no weakness was found in the briquettes when they were placed in a tumbler and tumbled for 30 minutes after soaking.

[0140] [Example 4] Phenolic prepolymer formation Phenol (8 kg), technical cardanol-technical grade (Rishabh Resins & Chemicals, Telangana, India, 2 kg), formaldehyde (37% solids, 10 kg), ammonia liquid (25% solids, 450 g) and 5-6 kg methanol are charged to the reactor. The reactor is heated to 60-70°C and maintained at a temperature of 70-100°C for 30 minutes. Water is refluxed back into the reactor and heating is maintained for 60-70 minutes until a gel time of 120-140 seconds of the prepolymer is achieved on the hot plate. The reaction is then maintained below 90°C to remove water by vacuum distillation. Once sufficient water has been removed, the mixture is cooled and diluted with methanol as required. The prepolymer can be used as a total or partial replacement for the cardanol in Example 1.

[0141] [Example 5] Use of phenolic binders and modified starch as a secondary binder Charcoal prepared from Norway birch by vacuum paralyzing at 650°C (94.3% fixed carbon, 1.9% ash, 3.8% volatile matter) was ground in a free-standing hammer mill to produce charcoal powder.

[0142] Charcoal powder 64.8% (all parts by weight), modified starch (Empre KST cold water soluble modified potato starch, Emsland, Germany) 5% and hexamine 1.6% were thoroughly mixed as dry powders in a high speed industrial mixer. Once the powders were mixed, cardanol 10.6% and water 18% were added and the mixture was introduced into the extruder.

[0143] 15 mm rods were extruded and cut to lengths of 200 mm circumference. The rods were immediately found to have sufficient "green" strength for manual and automated handling without loss of shape. The extrusion process is depicted in Figure 5.

[0144] The extruded rods were then dried by a two-step drying process with initial drying at 105°C until the trapped water was removed (approximately 2 h), followed by curing at 150-200°C for 1-2 h (e.g., 200°C for 2 h).

[0145] After hardening, the 200 mm rod with a diameter of 15 mm was so strong that it could not be broken by hand.

[0146] [Example 6] Use of Phenolic Binders and Secondary Binders - Alternative Mixes The manufacturing method of Example 5 was repeated, but rather than mixing the dry components first, an "all-in" mixing method was used: all ingredients (wet and dry) were added together and mixed thoroughly in a high speed industrial mixer.

[0147] The mixed material was then transferred to an extruder and extruded to form a 15 mm by approximately 200 mm rod.

[0148] After drying and curing as in Example 5, the "all-in" mixed material exhibited the same properties of strength and hardness as the two-step mix of Example 5.

[0149] Note that the ratios (by weight) of the ingredients, excluding water (which is used only as a processing aid), are as follows: charcoal powder 79%, cold water soluble modified potato starch 6%, hexamine 2%, cardanol 13%. [Explanation of symbols]

[0150] 1 Process 2. Grinding and mixing of binder 4 Pressurization (optionally vibration) 5 Extrusion 6 hardening 7 Products 8 Briquette Pellets 10 Biocarbon anode 11 Metallurgical reducing agents 12 Biocarbon Stone 13 Carbon Neutral Concrete 100 Processes 102 Mixer 104 Transfer process 106 processors 107 Roller Press 108 Screening 120 Residual substances 110 Briquette 300 data points

Claims

1. A biocarbon material comprising 10% by weight to 98% by weight of charcoal and at least one binder comprising a phenolic resin, The bio-carbon material, wherein the binder is present in an amount of 2% to 50% by weight.

2. The phenolic resin comprises at least one phenol of formula I: 【Chemistry 1】 2. The bio-carbon material of claim 1, wherein X is H or OH, and R is H or an optionally substituted, saturated or unsaturated, hydrocarbon moiety having 1 to 24 carbon atoms, which may be linear or branched, and optionally a polymer of a promoter.

3. 3. The bio-carbon material of claim 2, wherein the at least one phenol of formula I comprises at least one phenol where R is a C6 to C20 unsaturated hydrocarbyl moiety optionally substituted with at least one amine, hydroxyl and / or epoxy moiety.

4. 3. The bio-carbon material of claim 2, wherein the at least one phenol of formula I comprises, consists essentially of, or consists of cardol and / or cardanol.

5. 5. The bio-carbon material according to claim 2, wherein the phenolic resin is a polymer of at least one phenol of formula I and at least one promoter selected from at least one aldehyde and a formyl carbon source.

6. 5. The bio-carbon material according to claim 1, wherein the binder consists or consists essentially of at least one phenolic resin.

7. by combining the charcoal and the binder to form a mixture and curing the binder; The bio-carbon material according to any one of claims 1 to 4, wherein the mixture is repeatedly compressed between 1 and 10 times in the range of 3 to 50 MPa.

8. A bio-carbon material described in any one of claims 1 to 4, which is cured at a temperature in the range of 150°C to 250°C for 1 minute to 3 hours.

9. The bio-carbon material according to any one of claims 1 to 4, wherein the binder is present in the range of 5% to 30% by weight of the mixture.

10. 5. The bio-carbon material according to claim 1, comprising up to 30% by weight of an inorganic filler.

11. the binder further comprises 1-50 wt. % of a second binder binder component which increases the uncured (green) strength of the material; The bio-carbon material according to claim 1 , wherein the second binder is a drying oil and / or at least one polysaccharide.

12. A composition comprising cardanol, charcoal powder, and hexamine, the cardanol, the charcoal powder, and the hexamine are mixed together to form a mixture; The mixture is cured at a temperature ranging from 150° C. to 250° C. The mixture is pressurized in the range of 3 to 50 MPa, the cardanol is in the range of 8% to 35% by weight of the mixture; the charcoal powder is in the range of 50% to 92% by weight of the mixture; A composition wherein said hexamine is in the range of 0.1% to 15% by weight of said mixture.

13. A method for preparing a bio-carbon material, comprising the steps of: Providing at least one phenol; Providing charcoal powder; mixing at least one of said phenols with said charcoal powder to create a phenol and charcoal composition; compressing and optionally vibrating the phenolic and charcoal composition; curing the phenolic and charcoal composition; A method comprising:

14. Providing a catalyst and / or promoter, mixing said catalyst and / or accelerator with said phenol and said charcoal, so that said phenol and charcoal composition contains said catalyst and / or accelerator; The method of claim 13 further comprising:

15. the phenol is present in the range of 2% to 50% by weight of the phenol and charcoal composition; the charcoal powder is in the range of 10% to 98% by weight of the phenol and charcoal composition; the catalyst and / or promoter is in the range of 0.1% to 15% by weight of the phenol and charcoal composition; The phenol and charcoal composition is pressurized in the range of 3 to 50 MPa; The method of claim 14, wherein the mixture is cured in the range of 150°C to 250°C.

16. 5. Concrete comprising at least one biocarbon material according to any one of claims 1 to 4.

17. 17. The concrete of claim 16, wherein the bio-carbon material has a compressive strength at least as strong as a nominal 28 day strength of the concrete.

18. 17. The concrete of claim 16, wherein the bio-carbon material has a compressive strength of at least 50 MPa when tested according to ASTM C39 / C39M.

19. The bio-carbon material according to any one of claims 1 to 4, The anode is subjected to a second heat treatment at 1000-1200° C. for 2-72 hours.

20. The bio-carbon material according to any one of claims 1 to 4, Waterproof, briquettes.

Images