The present disclosure generally relates to the technical field of synthesis of graphene, synthetic graphite, and other carbon allotropes.
The synthesis of carbon allotropes including graphene, is highly dependent of carbon sources such as high purity gases, graphite or other organic sources of carbon. Likewise, the purity of metals or metal mix involved in the synthesis of carbon nanomaterials plays an important role into reaction yield and crystallinity of the nanomaterials.
Graphene which was initially isolated as a single layer of graphite and was obtained by its mechanical exfoliation. Further, graphene oxide (GO) was isolated as a product of the oxidation of graphite. Whereas the reduced graphene oxide (RGO) is obtained by the reacting of reductive agents with GO. Currently, graphene rather refers to a class of nanomaterials that includes: nanoplatelets (GNP), few-layer graphene (FLG), single-layer graphene (SLG), multi-layer graphene (MLG), graphene oxide (GO), reduced graphene oxide (RGO), etc.
Many techniques have been developed for the synthesis of graphene, including chemical exfoliation, chemical vapor deposition (CVD), thermal plasma, flash growth, electrochemical exfoliation, micromechanical exfoliation, laser ablation, ignition chamber, pyrolysis, etc. These techniques may accommodate different sources of carbon and may or may not require metals as catalyst. Techniques such as CVD, thermal plasma, laser ablation, ignition chamber, and flash growth may produce highly crystalline graphene with a single or few layers. Nonetheless, each of these techniques require a controlled atmosphere, and high purity gases including hydrogen and/or oxygen, plus high voltage discharge that need highly controlled conditions.
Likewise, synthetic graphite is majorly obtained by the Hazor technique that describes the chemical decomposition of methane catalyzed by iron-ore. Furthermore, other petroleum derivates are used to produce synthetic graphite.
Albeit, the current methods of synthesis of both carbon nanostructures or synthetic graphite rely on conventional sources of carbon and catalysts, a demand of unrecyclable carbon precursor materials and metals remains to be addressed.
One embodiment under the present disclosure comprises a method for manufacturing carbon material. The method includes mixing a carbon precursor with a catalyst in a controlled oxygen free environment, where the reaction is carried-out at a range from about 600° C. to 1400° C.
Another embodiment possible method embodiment under the present disclosure is a method of synthesizing carbon. The method comprises mixing a feed stock with molten aluminum; injecting the molten aluminum and feed stock mixture into a reaction vessel containing further molten aluminum, wherein the injection occurs below the surface of the molten aluminum in the reaction vessel; and reacting the feed stock with the molten aluminum, such that one or more carbon-containing products are formed.
Another embodiment under the present disclosure is a reaction vessel for reacting a carbon precursor with molten metal. The reaction vessel comprises: a reaction vessel wall; a refractory material lining an inside of the reaction vessel wall; and a cooling plate attached to an outside of the reaction vessel wall, wherein the cooling plate forms a channel for a cooling fluid between the cooling plate and the reaction vessel wall. It further comprises an aluminum feed line passing through to the reaction vessel wall; an injection line passing through the reaction vessel wall and having an outlet in the reaction vessel, and configured to carry the carbon precursor into the reaction vessel; and one or more collection lines passing through the reaction vessel wall and configured to collect one or more output products.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an indication of the scope of the claimed subject matter.
For a more complete understanding of the present disclosure, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
Before describing various embodiments of the present disclosure in detail, it is to be understood that this disclosure is not limited to the parameters of the particularly exemplified systems, methods, apparatus, products, processes, and/or kits, which may, of course, vary. Thus, while certain embodiments of the present disclosure will be described in detail, with reference to specific configurations, parameters, components, elements, etc., the descriptions are illustrative and are not to be construed as limiting the scope of the claimed embodiments. In addition, the terminology used herein is for the purpose of describing the embodiments and is not necessarily intended to limit the scope of the claimed embodiments.
There currently exist certain challenges in the field of graphene, graphite and carbon allotrope synthesis, as identified above. There continues to be a need for the development of alternative processes for producing carbon nanostructures (e.g., graphene, carbon nanotubes, etc.), and synthetic graphene under conditions applicable to an industrial scale using unrecyclable carbon and metals.
Certain aspects of the disclosure and their embodiments may provide solutions to these or other challenges. The present disclosure provides various processes and systems to recycle plastics, electronics, munitions, coal, coke or propellants and/or produce graphene, graphite and other carbon allotropes. Various embodiments may utilize a molten aluminum or molten aluminum alloy bath. Certain embodiments utilize a molten aluminum bath as the reactant. The ground feedstock may be introduced below the surface of the molten aluminum bath and react with the aluminum to decompose the feed stock. In the process, elemental carbon, sulfur, copper, iron, and rare earth and heavy metals and molecular hydrogen, nitrogen, methane, and other hydrocarbons can be removed from the molten bath. The products can be sold and the nitrogen is either vented to the atmosphere or captured.
Certain embodiments may provide one or more of the following technical advantages. Advantages can include (re)capture of a variety of materials, all of which can be reused and/or sold. This can make the described embodiments a truly “green” and zero waste solution.
Some of the embodiments contemplated herein will now be described more fully with reference to the accompanying drawings. Embodiments are provided by way of example to convey the scope of the subject matter to those skilled in the art.
Certain embodiments utilize a molten metal as the primary reactant, such as aluminum or an aluminum alloy bath. The aluminum can also be alloyed with other elements including, but not limited to, zinc, iron, copper, silicon and calcium. Other metals and metal alloys such as calcium and silicon are also envisioned. The flue gas stream, which contains oxygen containing greenhouse gases produced by combustion processes, is passed through the aluminum alloy bath to remove the oxygen-containing gases from the flue gas stream.
In the process, excess heat can be generated and can be used to facilitate other processes such as cogeneration of power. The excess heat generated by the process is a function of the makeup of the carbon precursor feedstock or gases in the feed.
When the feed stock contains other compounds, those compounds can also be decomposed or captured. For example, if the feed stock contains inorganic compounds, such as chlorine, the process will produce an aluminum salt, in this case aluminum chloride. The present disclosure also provides methods and systems for capturing heavy metals, such as, but not limited to mercury or rare earth metals, which are often found in consumer electronics or munitions. In the process, the molten metal bath breaks down the metal compounds as they are introduced into the molten metal bath. As additional aluminum is added to the bath, the heavy metals settle to the bottom of the reaction vessels and are removed from the reaction vessel. While some aluminum may be entrained in the heavy metals that are removed from the bottom of the reaction vessel, the aluminum can be removed and refined and the heavy metals can be captured.
Reaction vessel 220 also includes an aluminum feed line 221, which is used to supply additional aluminum compound to replace that consumed by the reaction with the ground feed stock. Additional heat may be required during start-up, for example. Heater 227 is provided for this purpose. Heater 227 can be any type of heater, including radiative, inductive, and convective. For example, heater 227 would be a microwave heater or a radio frequency heater wherein the frequency is tuned for the metal alloy used.
The heat generated by the process is preferably removed. Section A, which is shown in more detail in
Turning back to
Also, as described above, the reaction can also produce elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen, or other materials. These can be removed from the reaction vessel using blower 250. Blower 250 can e.g., pull high temperature elemental carbon, elemental sulfur, molecular nitrogen and molecular hydrogen from the reaction vessel 220 through heat exchanger feed line 241 into heat exchanger 240. Heat exchanger 240 will then cool this material to enable further processing. Any hydrocarbons that are produced may also be condensed in heat exchanger 240. These liquid hydrocarbons can be collected for further use or sale. Heat exchanger 240 can be any heat exchanger, however in the preferred embodiment, heat exchanger 240 is a forced air heat exchanger, however other heat exchangers, are also envisioned. The process stream then leaves the heat exchanger through line 242 and passes through blower 250 and blower discharge line 252 into two cyclone separators. The first separator 260 separates out carbon from process stream. The carbon is collected though separation line 263. The remaining process stream proceeds to the second separator 270, which separates out sulfur from the process stream. The sulfur may be removed using a cold finger as the stream is cooled to less than 444 degrees Celsius. The sulfur is collected through separation line 273. The remaining process stream, which may include gaseous nitrogen and hydrogen, is then separated in cryo unit 280. In this unit, the gas stream is cooled further and to allow the components to be separated.
Below is a limited list of possible ground feed stock that may be recycled, and the resulting elemental outputs produced by the reactions within the molten metal bath.
The vortex entry illustrated in
As described above, once the feed stock enters the aluminum bath or the vortex, then reactions of the ground feed stock material with the aluminum or aluminum alloy bath will begin. The denser materials will begin to settle while the lighter materials will rise. The lightest materials, such as gas will bubble to the surface, to be recovered there.
Other embodiments under the present disclosure can focus on the production of graphene, such as carbon nanostructures and synthetic graphite. One synthesis method to manufacture graphene can be defined by mixing between an unrecyclable carbon precursor with a catalyst in a controlled oxygen free environment. The reaction is carried-out at a range from about 600° C. to 1400° C. The apparatus or system used can be similar to those illustrated in
To assess various approaches to graphene synthesis, and to increase the graphitization levels, some growths were carried-out applying various reaction times, and temperatures. Thus, the system may be designed to vary the residence time of the carbon precursor to allow for the synthesis of various graphite or graphene structures. Various different metal catalysts (e.g., Mg, Fe, Co) can be added to the catalyst to aid in the synthesis of the different carbon allotropes. Embodiments of the reactor (e.g., of
Other methods might be used to functionalize the produced carbon. A combination of waste metals (e.g., Mg, Fe, Co, etc.) may be applied as secondary catalysts in some embodiments. The synthesis of carbon nanostructures and synthetic graphite may occur while recycling other metals. In certain embodiments, the synthesis of carbon nanostructures and synthetic graphite may occur in presence of chalcogenides (e.g., oxygen, sulfur, selenium, tellurium).
Several experiments were conducted to assess the graphene producing capabilities of certain embodiments. Several samples were prepared according with Table 1, below.
For Example 1, a mix of unrecyclable grinded plastic waste was inserted into the reactor with an aluminum alloy. An inert gas (e.g., nitrogen) was used as carrier to transport the graphene from the reaction chamber to the collecting container. The temperature range at the reaction chamber was kept between 600° C. to 950° C. The sample ER-01 included unrecyclable plastics (e.g., HDPE, PET, PP, Styrene, PVC) and tires (waste plastics). These served as a carbon precursor and aluminum alloys were used as catalyst.
For Example 2, natural gas was inserted into the reactor with aluminum alloy. An inert gas (e.g., nitrogen) was used as carrier to transport the graphene functionalized with sulfur from the reaction chamber to the collecting container. The temperature range at the reaction chamber was kept between 900° C. to 1100° C. The total reaction time was 120 min. Variations of the synthesis regarding the temperature/reaction time are as it follows, initial 60 minutes at temperature range of 900° C. to 950° C., followed by a ramp up to ˜1100° C. The material was kept at temperature plateau of ˜990° C. to 1100° C. for 30 minutes. After that the temperature was kept between 900° C. to 920° C. for 30 minutes.
For Example 3, high density polyethylene (HDPE) was inserted into the reactor with aluminum alloy. An inert gas (e.g., nitrogen) was used as carrier to transport the highly oriented pyrolytic graphite (HOPG) like from the reaction chamber to the collecting container. The temperature range at the reaction chamber was kept between 900° C. to 950° C.
Another possible method embodiment under the present disclosure is shown in
Another embodiment possible method embodiment under the present disclosure is shown in
To assist in understanding the scope and content of this written description and the appended claims, a select few terms are defined directly below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure pertains.
The terms “approximately,” “about,” and “substantially,” as used herein, represent an amount or condition close to the specific stated amount or condition that still performs a desired function or achieves a desired result. For example, the terms “approximately,” “about,” and “substantially” may refer to an amount or condition that deviates by less than 10%, or by less than 5%, or by less than 1%, or by less than 0.1%, or by less than 0.01% from a specifically stated amount or condition.
Various aspects of the present disclosure, including devices, systems, and methods may be illustrated with reference to one or more embodiments or implementations, which are exemplary in nature. As used herein, the term “exemplary” means “serving as an example, instance, or illustration,” and should not necessarily be construed as preferred or advantageous over other embodiments disclosed herein. In addition, reference to an “implementation” of the present disclosure or embodiments includes a specific reference to one or more embodiments thereof, and vice versa, and is intended to provide illustrative examples without limiting the scope of the present disclosure, which is indicated by the appended claims rather than by the present description.
As used in the specification, a word appearing in the singular encompasses its plural counterpart, and a word appearing in the plural encompasses its singular counterpart, unless implicitly or explicitly understood or stated otherwise. Thus, it will be noted that, as used in this specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. For example, reference to a singular referent (e.g., “a widget”) includes one, two, or more referents unless implicitly or explicitly understood or stated otherwise. Similarly, reference to a plurality of referents should be interpreted as comprising a single referent and/or a plurality of referents unless the content and/or context clearly dictate otherwise. For example, reference to referents in the plural form (e.g., “widgets”) does not necessarily require a plurality of such referents. Instead, it will be appreciated that independent of the inferred number of referents, one or more referents are contemplated herein unless stated otherwise.
References in the specification to “one embodiment,” “an embodiment,” “an example embodiment,” and the like indicate that the embodiment described may include a particular feature, structure, or characteristic, but it is not necessary that every embodiment includes the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
It shall be understood that although the terms “first” and “second” etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element could be termed a second element, and similarly, a second element could be termed a first element, without departing from the scope of example embodiments. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed terms.
It will be further understood that the terms “comprises”, “comprising”, “has”, “having”, “includes” and/or “including”, when used herein, specify the presence of stated features, elements, and/or components etc., but do not preclude the presence or addition of one or more other features, elements, components and/or combinations thereof.
The present disclosure includes any novel feature or combination of features disclosed herein either explicitly or any generalization thereof. Various modifications and adaptations to the foregoing exemplary embodiments of this disclosure may become apparent to those skilled in the relevant arts in view of the foregoing description, when read in conjunction with the accompanying drawings. However, any and all modifications will still fall within the scope of the non-limiting and exemplary embodiments of this disclosure.
It is understood that for any given component or embodiment described herein, any of the possible candidates or alternatives listed for that component may generally be used individually or in combination with one another, unless implicitly or explicitly understood or stated otherwise. Additionally, it will be understood that any list of such candidates or alternatives is merely illustrative, not limiting, unless implicitly or explicitly understood or stated otherwise.
In addition, unless otherwise indicated, numbers expressing quantities, constituents, distances, or other measurements used in the specification and claims are to be understood as being modified by the term “about,” as that term is defined herein. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the subject matter presented herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the subject matter presented herein are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Any headings and subheadings used herein are for organizational purposes only and are not meant to be used to limit the scope of the description or the claims. The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the present disclosure. Thus, it should be understood that although the present disclosure has been specifically disclosed in part by certain embodiments, and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and such modifications and variations are considered to be within the scope of this present description.
It will also be appreciated that systems, devices, products, kits, methods, and/or processes, according to certain embodiments of the present disclosure may include, incorporate, or otherwise comprise properties or features (e.g., components, members, elements, parts, and/or portions) described in other embodiments disclosed and/or described herein. Accordingly, the various features of certain embodiments can be compatible with, combined with, included in, and/or incorporated into other embodiments of the present disclosure. Thus, disclosure of certain features relative to a specific embodiment of the present disclosure should not be construed as limiting application or inclusion of said features to the specific embodiment. Rather, it will be appreciated that other embodiments can also include said features, members, elements, parts, and/or portions without necessarily departing from the scope of the present disclosure.
Moreover, unless a feature is described as requiring another feature in combination therewith, any feature herein may be combined with any other feature of a same or different embodiment disclosed herein. Furthermore, various well-known aspects of illustrative systems, methods, apparatus, and the like are not described herein in particular detail in order to avoid obscuring aspects of the example embodiments. Such aspects are, however, also contemplated herein.
It will be apparent to one of ordinary skill in the art that methods, devices, device elements, materials, procedures, and techniques other than those specifically described herein can be applied to the practice of the described embodiments as broadly disclosed herein without resort to undue experimentation. All art-known functional equivalents of methods, devices, device elements, materials, procedures, and techniques specifically described herein are intended to be encompassed by this present disclosure.
When a group of materials, compositions, components, or compounds is disclosed herein, it is understood that all individual members of those groups and all subgroups thereof are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and sub-combinations possible of the group are intended to be individually included in the disclosure.
The above-described embodiments are examples only. Alterations. modifications, and variations may be effected to the particular embodiments by those of skill in the art without departing from the scope of the description, which is defined solely by the appended claims.
This application claims the benefit of U.S. of America priority application No. 63/439,463 filed on Jan. 17, 2023, titled “Process for Producing Graphene, Other Carbon Allotropes and Materials,” the contents of which are hereby incorporated herein in its entirety. This application is a continuation-in-part of U.S. patent application Ser. No. 17/750,613, titled, “Gasification or Liquefaction of Coal Using a Metal Reactant Alloy Composition”, filed May 23, 2022; which is a continuation of U.S. patent application Ser. No. 16/434,771, now U.S. patent Ser. No. 11/359,253, titled, “Gasification or Liquefaction of Coal Using a Metal Reactant Alloy Composition”, filed Jun. 7, 2019; which is a continuation of U.S. patent application Ser. No. 14/973,243, now U.S. Pat. No. 10,316,375, titled, “Gasification or Liquefaction of Coal Using a Metal Reactant Alloy Composition”, filed Dec. 17, 2015; which is a continuation of U.S. patent application Ser. No. 13/487,430, now U.S. Pat. No. 9,216,905, titled, “Gasification or Liquefaction of Coal Using a Metal Reactant Alloy Composition”, filed Jun. 4, 2012; which claims the benefit of U.S. Provisional Patent Application No. 61/493,247, filed Jun. 3, 2011, titled, “Gasification or Liquefaction of Coal Using a Metal Reactant Alloy Composition”, the contents of which are hereby incorporated herein in its entirety.
Number | Date | Country | |
---|---|---|---|
63439463 | Jan 2023 | US | |
61493247 | Jun 2011 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 16434771 | Jun 2019 | US |
Child | 17750613 | US | |
Parent | 14973243 | Dec 2015 | US |
Child | 16434771 | US | |
Parent | 13487430 | Jun 2012 | US |
Child | 14973243 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 17750613 | May 2022 | US |
Child | 18415066 | US |