Feedstock for graphitization and process for producing feedstock for graphitization

Abstract

A process for producing a feedstock for graphitization includes washing a potassium hydroxide heat treated petcoke with an acid to remove metal contaminants. A process for producing graphite includes cleaning a potassium hydroxide heat treated petcoke to remove contaminants and yield a feedstock graphitizing the feedstock to yield graphite.

Description

FEEDSTOCK FOR GRAPHITIZATION AND PROCESS FOR PRODUCING FEEDSTOCK FOR GRAPHITIZATIONCROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority to United States Provisional Patent Application No. 63 / 602,400 filed on November 23, 2023, which is incorporated herein by reference in its entirety.FIELD

[0002] This document relates to graphite, such as battery-grade graphite. More specifically, this document relates to feedstocks for graphitization, processes for producing feedstocks for graphitization, graphite produced from said feedstocks, and batteries including said graphite.SUMMARY

[0003] The following summary is intended to introduce the reader to various aspects of the detailed description, but not to define or delimit any invention.

[0004] Processes for producing a feedstock for graphitization are disclosed.

[0005] According to some aspects, a process for producing a feedstock for graphitization includes: a. washing a potassium hydroxide heat treated petcoke with an acid to remove metal contaminants.

[0006] In some examples, step a. includes washing the potassium hydroxide heat treated petcoke with hydrochloric acid. In some examples, step a. includes washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

[0007] In some examples, the process further includes: prior to step a., grinding the potassium hydroxide heat treated petcoke.

[0008] In some examples, the process further includes: after grinding the potassium hydroxide heat treated petcoke and prior to step a., washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash. In some examples, washing the potassium hydroxide heat treated petcoke with water includes washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

[0009] In some examples, the process further includes: after step a., heating the potassium hydroxide heat treated petcoke to remove oxygen. In some examples, heating the potassium hydroxide heat treated petcoke includes heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

[0010] In some examples, the process further includes: after heating the potassium hydroxide heat treated petcoke to remove the oxygen, washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

[0011] In some examples, the process further includes: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke. In some examples, the potassium hydroxide heat treated petcoke includes a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

[0012] In some examples, the feedstock for graphitization includes at least 90 wt% carbon, or at least 95 wt% carbon.

[0013] Processes for producing graphite are also disclosed.

[0014] According to some aspects, a process for producing graphite includes: a. cleaning a potassium hydroxide heat treated petcoke to remove contaminants and yield a feedstock; and b. graphitizing the feedstock to yield graphite.

[0015] In some examples, the process further includes: prior to step a., grinding the potassium hydroxide heat treated petcoke.

[0016] In some examples, step a. includes: i. washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash. In some examples, step i. includes washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees for between 5 minutes and 60 minutes.

[0017] In some examples, step a. further includes: ii. after step i., washing the potassium hydroxide heat treated petcoke with an acid to remove metal contaminants. In some examples, step ii. includes: washing the potassium hydroxide heat treated petcoke hydrochloric acid. In some examples, step ii. includes: washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 80 degrees for between 5 minutes and 60 minutes.

[0018] In some examples, step a. further includes: iii. after step ii., heating the potassium hydroxide heat treated petcoke to remove oxygen. In some examples, step iii. includes heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

[0019] In some examples, step a. further includes: iv. after step iii., washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

[0020] In some examples, the process further includes: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke.

[0021] In some examples, the potassium hydroxide heat treated petcoke includes a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

[0022] In some examples, the feedstock includes at least 90 wt% carbon or at least 95 wt% carbon.

[0023] In some examples the graphite includes at least 95 wt% carbon or at least 99 wt% carbon.

[0024] Also disclosed are feedstocks for graphitization made by the processes described herein, graphites made from the feedstock for graphitization disclosed herein, and batteries including the graphites disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The drawings included herewith are for illustrating various examples of articles, methods, and apparatuses of the present specification and are not intended to limit the scope of what is taught in any way. In the drawings:

[0026] Figure 1 is a flowchart of an example process for producing potassium hydroxide heat treated petcoke;

[0027] Figure 2 is a flowchart of an example process for cleaning potassium hydroxide heat treated petcoke to yield a feedstock for graphitization;

[0028] Figure 3 is an XPS scan of potassium hydroxide heat treated petcoke, prior to being subjected to a cleaning process;

[0029] Figure 4 is an XPS scan of potassium hydroxide heat treated petcoke, after being subjected to an acid wash step;

[0030] Figure 5 is an XPS scan of potassium hydroxide heat treated petcoke, after being subjected to an acid wash step and a heat treatment;

[0031] Figure 6 is an XPS scan of potassium hydroxide heat treated petcoke, after being subjected to a water wash step;

[0032] Figure 7 is an XPS scan of potassium hydroxide heat treated petcoke, after being subjected to a water wash step and an acid wash step; and

[0033] Figure 8 is an XPS scan of potassium hydroxide heat treated petcoke, after being subjected to a water wash step, an acid wash step, and a heating step.DETAILED DESCRIPTION

[0034] Various apparatuses or processes or compositions will be described below to provide an example of an embodiment of the claimed subject matter. No embodiment described below limits any claim and any claim may cover processes or apparatuses or compositions that differ from those described below. The claims are not limited to apparatuses or processes or compositions having all of the features of any one apparatus or process or composition described below or to features common to multiple or all of the apparatuses or processes or compositions described below. It is possible that an apparatus or process or composition described below is not an embodiment of any exclusive right granted by issuance of this patent application. Any subject matter described below and for which an exclusive right is not granted by issuance of this patent application may be the subject matter of another protective instrument, for example, a continuing patent application, and the applicants, inventors or owners do not intend to abandon, disclaim or dedicate to the public any such subject matter by its disclosure in this document.

[0035] As used herein, the term “potassium hydroxide product” refers to potassium hydroxide and / or a direct or indirect reaction product thereof. For example, the term “potassium hydroxide product” may refer to (but is not limited to) potassium hydroxide, the potassium oxide that is formed when potassium hydroxide is decomposed in the processes disclosed herein, the pure potassium that is formed when potassium oxide reacts with carbon in the processes disclosed herein, the potassium carbonate that is formed when potassium oxide reacts with carbon dioxide in the processes disclosed herein, the pure potassium that is formed when potassium carbonate reacts with carbon in the processes disclosed herein, and / or combinations thereof.

[0036] As used herein, the terms “non-aqueous” refers to a product that is not in aqueous solution. For example, the term “non-aqueous potassium hydroxide” may refer to potassium hydroxide that is in solid form (e.g. pellets, crushed pellets, powder, or rods) or in a melt state. For greater clarity, the term “non-aqueous potassium hydroxide” includes potassium hydroxide that has adsorbed or absorbed water due to hygroscopicity. For example, potassium hydroxide pellets, which are considered to be a non-aqueous potassium hydroxide, may often contain about 10% water. In this document, the term“potassium hydroxide in a non-aqueous state” is interchangeable with term “non-aqueous potassium hydroxide.”

[0037] As used herein, the term “micropore” (and related terms such as “microporous” and “microporosity”) refers to pores that have a diameter of less than about 2 nm. The term “mesopore” (and related terms such as “mesoporous” and “mesoporosity”) refers to pores that have a diameter of between about 2 to about 50 nm. The terms “microporosity percentage” or “percent microporosity” refer to the number of a pores in a sample that are microporous, as percentage of the total number of pores in the sample. The terms “mesoporosity percentage” or “percent mesoporosity” refer to the number of pores in a sample that are mesoporous, as percentage of the total number of pores in the sample.

[0038] As used herein, the term “about” indicates that a referenced value may vary by plus or minus 5%. For example, a reference to a temperature of “about 800 degrees Celsius” indicates that the temperature may be between 760 degrees Celsius and 840 degrees Celsius.

[0039] As used herein, the term “feedstock for graphitization” refers to a material that is suitable for use as an input to a graphitization process. In particular, the term “feedstock for graphitization” refers to a carbonaceous material (e.g. amorphous carbon) from which graphite may be synthetically produced.

[0040] As used herein, the term “potassium hydroxide heat treated petcoke” refers to a petcoke (e.g. crushed fluid coke and / or crushed delayed coke) that has been subjected to a potassium hydroxide heat treatment - i.e. a treatment in which the petcoke is combined with potassium hydroxide and heated - to create pores therein.

[0041] In this document, unless specified otherwise, all ranges are inclusive of the bounds of the range. For example, the statement that a temperature may be “between 750 degrees Celsius and 900 degrees Celsius” indicates that the temperature may be 750 degrees Celsius, or 900 degrees Celsius, or any number therebetween.

[0042] In any instance in which the disclosure refers to a single instance of an element, examples may include a multiple of such elements. The term “at least one” in referenceto any element is not intended to force an interpretation on any other reference elsewhere in the disclosure to a single instance of an element to mean only one such instance of the element.

[0043] In this document, for clarity, process steps may be described in a particular sequence, and terms such as “then” or “next” may be used. However, the processes described herein are no limited to any particular order of steps unless expressly indicated as such in the claims.

[0044] Generally disclosed herein are feedstocks for graphitization (also referred to herein simply as “feedstocks”), and related processes for producing said feedstocks. Further disclosed herein are graphites produced from said feedstocks, and processes for producing said graphites. Further disclosed herein are batteries including said graphites.

[0045] The feedstocks disclosed herein may be of relatively high purity, and thus may be particularly useful in producing battery grade graphite, which requires or may benefit from a high purity graphite.

[0046] The feedstocks disclosed herein may generally be produced using potassium hydroxide heat treated petcoke (KOH-Q-PetCoke) as a starting product. The KOH-Q- PetCoke may generally be obtained by subjecting a crushed petcoke (e.g. crushed fluid coke and / or crushed delayed coke) to a potassium hydroxide heat treatment process. An example potassium hydroxide heat treatment process is described in further detail below; however, in some examples, the potassium hydroxide heat treatment may be the treatment described in International Patent Application Publication No. WO 2023 / 004502 (to Pede et al.), which is incorporated herein by reference in its entirety.

[0047] The feedstocks disclosed herein may generally be produced by subjecting the KOH-Q-PetCoke to a cleaning process, in order to remove contaminants. It has been determined that contaminants in the KOH-Q-Petcoke, in particular metal contaminants, may be readily removable by the cleaning process disclosed herein. The cleaning process may generally include a step of washing the KOH-Q-PetCoke with an acid (e.g. hydrochloric acid) to remove metal contaminants, and thereby yield a feedstock that is ofrelatively high purity. For example, the feedstocks disclosed herein may in some examples have a carbon content of greater than 90 wt% (e.g. about 92 wt%), with the remainder being oxygen as carbonates (e.g. about 8 wt% oxygen) and trace amounts of silicates (e.g. about 0.5 wt% silicates). The carbon content may be further increased by following the acid wash step with a heating step. This may remove the oxygen by burning off the oxygen to yield ash. The ash may then be removed in a subsequent water wash step.

[0048] The feedstocks may then be graphitized according to any suitable process, in order to yield graphite.Potassium Hydroxide Heat Treated Petcoke (KOH-Q-PetCoke)

[0049] As mentioned above, the feedstocks disclosed herein may generally be produced using potassium hydroxide heat treated petcoke (KOH-Q-PetCoke) as a starting product. The KOH-Q-PetCoke may be obtained by subjecting a crushed petcoke (e.g. crushed fluid coke and / or crushed delayed coke) to a potassium hydroxide heat treatment process. Referring to Figure 1 , an example potassium hydroxide heat treatment process 100 shown.

[0050] The raw feed to the process 100 may include a non-aqueous potassium hydroxide, as well as crushed petcoke.

[0051] Preferably, the non-aqueous potassium hydroxide is in the form of potassium hydroxide pellets.

[0052] The crushed petcoke may have a particle size of, for example, at most about 8 mesh, and may generally include a mixture of larger particles (i.e. particles that may be described as granules, which may have a particle diameter of up to about 2380 microns) and smaller particles (i.e. particles that may be described as a fines, which may have a particle diameter of about 44 microns). The crushed petcoke may optionally be obtained in crushed form and fed to the process 100; however, in the example shown, the process includes a step of crushing the petcoke (step 102). Crushing the petcoke may beachieved by using a cone crusher or similar device. The crushing may be done in a single pass or through a staged process.

[0053] Optionally, the crushed petcoke may be pre-treated by heating it at about 400 degrees Celsius under air for about 1 hour, in order to remove water and any volatile compounds (step 104).

[0054] At step 106, the crushed petcoke and potassium hydroxide pellets are combined, for example in a rotary calciner. Because the process as shown uses non-aqueous potassium hydroxide, a relatively small amount of potassium hydroxide may be used, as the contact area of the potassium hydroxide and the carbon source is relatively high. For example, the potassium hydroxide and crushed petcoke may be combined in a mass ratio of between about 0.1 :1 and about 3:1 , KOH: petcoke, or more specifically between about 0.125:1 and about 0.5:1 (e.g. about 0.25:1 , or about 0.5:1 , or about 0.75:1 , or about 1 :1 , or about 2:1 , or about 3:1 KOH:petcoke).

[0055] At step 108, the crushed petcoke and potassium hydroxide pellets are heated to a first temperature that is at or above a melting point of the potassium hydroxide, but below the temperature at which the carbon of the crushed petcoke reacts with the potassium hydroxide (or a product thereof) to form pores in the crushed petcoke. The first temperature may be, for example, between about 360 degrees Celsius and about 750 degrees Celsius (e.g. about 400 degrees Celsius). If the first temperature is below the combustion temperature of the petcoke (e.g. below about 550 degrees Celsius), then step 108 may optionally be carried out under air. If the first temperature is above the combustion temperature of the petcoke, then step 108 may be carried out in an inert environment (e.g. under nitrogen or another inert gas).

[0056] Optionally, the crushed petcoke and potassium hydroxide pellets may be mixed during step 108.

[0057] At the first temperature, the potassium hydroxide pellets melt to coat the crushed petcoke and form an agglomerate with the crushed petcoke; however, reaction of the carbon of the crushed petcoke with the potassium hydroxide (or a product thereof) to formpores in the carbon generally does not occur. That is, pores are not created, or are created in a negligible or non-substantial amount. It is believed that at the first temperature, at least some of the potassium hydroxide is converted to potassium oxide according to the following reaction:(Reaction I)

[0058] It is further believed that at least some of the potassium oxide reacts with organic sulfur in the petcoke, to yield inorganic sulfur. There are a variety of sulphur species that may exist in the petcoke. An example of a reaction of the organic sulphur with the potassium oxide is as follows:C2S(s) + 2K2O(I) 2K2S(S) + 2CO(g) (Reaction II)

[0059] The first temperature may be maintained for a retention time of, for example, at least about 15 minutes (e.g. about 30 minutes).

[0060] The product of step 108 may generally include an agglomerate of non-aqueous potassium hydroxide products (e.g. melted potassium hydroxide and potassium oxide), and the crushed petcoke.

[0061] At step 110, the product of step 108 is heated to a second temperature, under substantially inert conditions, to yield the KOH-Q-PetCoke. The second temperature is at least the temperature at which the carbon of the crushed petcoke reacts with the potassium hydroxide (or a product thereof) to form pores in the crushed petcoke (this temperature may in some instances be referred to as the activation temperature of the crushed petcoke). For example, the product of step 108 may be heated to between about 750 degrees Celsius and about 900 degrees Celsius (e.g. about 800 degrees Celsius). This temperature may be maintained for a retention time of between about 2 minutes and about 60 minutes, or between about 7 minutes and about 60 minutes, or between about 7 minutes and about 30 minutes, or about 15 minutes. Optionally, step 110 may be carried out with mixing, for example in a rotary calciner.

[0062] At the second temperature, it is believed that the following reactions occur, resulting in the creation of pores in the petcoke:(Reaction III)(Reaction IV)K2CO3 + 2 C (S) T> 2 K + 3 CO(g) (Reaction V)

[0063] In Reaction IV, it is believed that carbon dioxide is present due to thermal decomposition of surface oxidation sites on the petcoke.

[0064] It further is believed that the following additional reactions may occur with any water that remains in the system: (Reaction VI)(Reaction VII)

[0065] As mentioned above, step 110 is carried out under substantially inert conditions. The term “substantially inert conditions” indicates that conditions are maintained such that extensive combustion does not occur. For example, step 110 may be carried out under an inert gas such as nitrogen. However, it is possible that a small amount of oxygen (e.g. so that the reaction environment is between about 0.1 % and about 0.3% oxygen, by mass) may be bled into the system, to promote a small and controlled amount of combustion. This small and controlled amount of combustion may supply heat to step 110, so that step 110 is effectively self heated.

[0066] The product of step 110 - i.e. the KOH-Q-PetCoke - may generally include porous carbon, potassium hydroxide products, other reaction by-products, and contaminants (e.g. inorganic sulfur, carbonates, silicates, metals, and / or ash).

[0067] It has been found that the product of step 110 has a microporosity percentage (also referred to herein as a “first microporosity percentage”) of between about 45% and about 80% (e.g. about 75%), with the remaining pores being mesoporous.

[0068] In some examples, process 100 may end after step 110, and the KOH-Q-PetCoke may then be cooled and sent to the cleaning process described below. In other examples, prior to the cleaning process, the KOH-Q-Petcoke may be serially cooled and reheated. For example, the KOH-Q-PetCoke may be cooled and step 110 may be repeated to decrease the microporosity of the KOH-Q-PetCoke (e.g. to decrease the microporosity percentage to between about 65% and about 35%, for example about 60%, with the remaining pores being mesoporous). Optionally, the KOH-Q-PetCoke may further be cooled and reheated a second time to further decrease the microporosity thereof (e.g. to decrease the microporosity percentage to between about 20% and about 40%, for example about 35%, with the remaining pores being mesoporous). Such serial cooling and reheating is described in International Patent Application Publication No. WO 2023 / 004502 (to Pede et al.), which is incorporated herein by reference in its entirety.Cleaning Process

[0069] As mentioned above, the feedstocks disclosed herein may generally be produced by subjecting the KOH-Q-PetCoke to a cleaning process, which may generally include washing the KOH-Q-PetCoke with an acid to remove contaminants (e.g. metal contaminants).

[0070] Referring now to Figure 2, an example cleaning process 200 is shown.

[0071] In the example shown, at step 202, the KOH-Q-PetCoke is ground to reduce the particle size thereof and break up the agglomerates. For example, the KOH-Q-PetCoke may be ground until the particles thereof pass through a mesh screen of 0.260 mm.

[0072] At step 204, the KOH-Q-PetCoke is washed with water. This may remove water soluble contaminants, such as inorganic sulfur, potassium products, and / or ash, which in turn renders the pores of the KOH-Q-Petcoke accessible to the acid in the subsequent acid wash step, and prevents reactions between water soluble contaminants and the acid in the subsequent wash step. For example, washing the KOH-Q-PetCoke with water may remove potassium products, and thereby prevent or minimize the risk of the potassium products reacting with the acid in the subsequent wash step to yield potassium carbonate,which may block the pores. Step 204 may include, for example, washing the KOH-Q- PetCoke with water at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes. In some particular examples, the KOH-Q-PetCoke may be washed with water at 80 degrees Celsius for 1 hour, at a ratio of 1 g KOH-Q-PetCoke to 10 mL water. The KOH-Q-PetCoke may then be vacuum filtered. Optionally, step 204 may be repeated one or more times.

[0073] Optionally, potassium hydroxide may be recovered from the wash water, and reused. Further optionally, calcium hydroxide may be added to the wash water, to react with potassium carbonate and form potassium hydroxide and precipitate calcium carbonate as a by-product. The calcium carbonate may be sold, used, or may be stockpiled as sequestered carbon dioxide.

[0074] At step 206, after washing the KOH-Q-PetCoke with water, the KOH-Q-PetCoke is washed with an acid. This may remove metal contaminants from the KOH-Q-PetCoke, such as vanadium, titanium and aluminum, which may be within the pores of the KOH-Q- PetCoke. In particular, metal contaminants may be present as metal oxides and / or metal hydroxides, which may not be soluble in water or alkaline solutions. However, in acid, the metal oxides may be protonated and / or the hydroxide ligand may be stripped from the metal hydroxides, to yield soluble metal species, which are then washed from the KOH- Q-PetCoke.

[0075] Step 206 may include, for example, washing the KOH-Q-Petcoke hydrochloric acid, such as between 0.01 M and 0.1 M hydrochloric acid. The KOH-Q-PetCoke may, for example, be washed with the hydrochloric acid for between about 5 minutes and about 60minutes at between 60 and 90 degrees Celsius (e.g. about 80 degrees Celsius) and at a ratio of 1 g KOH-Q-PetCoke to 10 mL acid.

[0076] The hydrochloric acid may optionally be reused in subsequent washings, for example to concentrate the metal contaminants for recover. Optionally, step 206 may be repeated one or more times, with fresh acid. The acid may then optionally be rinsed from the KOH-Q-Petcoke with water.

[0077] It has been determined that after washing the KOH-Q-Petcoke with acid, the KOH- Q-Petcoke may be relatively pure. For example, after washing the KOH-Q-Petcoke with acid, the KOH-Q-Petcoke may have a carbon content of greater than 90 % (e.g. about 92 %), with the remainder being oxygen as carbonates (e.g. about 8 % oxygen) and trace amounts of silicates (e.g. about 0.5 % silicates).

[0078] At step 208, after washing the KOH-Q-Petcoke with acid, the KOH-Q-Petcoke may be heated. The heating step may remove at least some of the remaining oxygen from the KOH-Q-Petcoke. In particular, the oxygen may be present as carbonate species. The heating step may decompose the carbonates to oxides (which can be removed in a subsequent wash), thus releasing carbon dioxide. The heating step may include, for example heating the KOH-Q-Petcoke to between 250 degrees Celsius and 900 degrees Celsius for between 5 and 30 minutes.

[0079] At step 210, after heating the KOH-Q-Petcoke, the KOH-Q-Petcoke may again be washed with water, to remove ash. For example, the KOH-Q-PetCoke may be washed with water at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes. In some particular examples, the KOH-Q-PetCoke may be washed with water at 80 degrees Celsius for 1 hour, at a ratio of 1 g KOH-Q-PetCoke to 10 mL water. The KOH- Q-PetCoke may then be vacuum filtered. Optionally, the wash step may be repeated one or more times.Graphitization

[0080] The product of process 200 may then be used as a feedstock for graphitization. That is, the feedstock may be graphitized, to yield graphite. The graphitization process may be any suitable process in which graphite is synthetically produced from the feedstock, such as a thermal process.

[0081] Due to the relatively high purity of the feedstock (e.g. at least 90 wt% carbon, or at least 95 wt% carbon), the resulting graphite may be relatively pure (e.g. at least 95 wt% carbon, or at least 99 wt% carbon), and thus may be suitable for use in batteries.

[0082] While the above description provides examples of one or more processes or apparatuses or compositions, it will be appreciated that other processes or apparatuses or compositions may be within the scope of the accompanying claims.

[0083] To the extent any amendments, characterizations, or other assertions previously made (in this or in any related patent applications or patents, including any parent, sibling, or child) with respect to any art, prior or otherwise, could be construed as a disclaimer of any subject matter supported by the present disclosure of this application, Applicant hereby rescinds and retracts such disclaimer. Applicant also respectfully submits that any prior art previously considered in any related patent applications or patents, including any parent, sibling, or child, may need to be re-visited.

[0084] The present disclosure describes what are considered to be practical example embodiments. It is recognized, however, that departures may be made within the scope of the invention according to a person skilled in the art. Further, the subject matter of the present disclosure supports and provides sufficient basis for any element, feature, structure, function, and / or step of any aspect, and / or example embodiment described in the present disclosure including the figures, clauses and / or claims herein to be claimed alone in an independent claim and be fully supported herein, or be combined with any other one or more elements, features, structures, functions, and / or steps of any aspect and / or example embodiment described in the present disclosure including the figures, clauses and / or claims herein, as basis for an independent or dependent claim herein.EXAMPLESExample 1

[0085] Petroleum coke (8 g) was mixed with potassium hydroxide pellets (8 g), then heated in an oven to 400 degrees C at a rate of 40 degrees C / min, and held at 400 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to yield potassium hydroxideheat treated petcoke (KOH-Q-Petcoke), and washed with water at 80 degrees C. Figure 3 is an XPS scan of the KOH-Q-Petcoke after washing with water.

[0086] After washing with water, the KOH-Q-Petcoke was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water. Figure 4 is an XPS scan of the KOH-Q-Petcoke after washing with acid, and shows that the acid wash results in a reduction in sulphur content, metal oxide content and silicate content in the KOH-Q-Petcoke.

[0087] After washing with acid, KOH-Q-Petcoke was then heated under a blanket of N2 flow for 30 minutes at 500 degrees, by heating to 500 degrees C at a rate of 40 degrees C per minute. Figure 5 is an XPS scan of the KOH-Q-Petcoke after heating, and shows that the heating step results in a reduction in sulphur and oxygen content.Example 2

[0088] Petroleum coke was mixed with potassium hydroxide pellets at a mass ratio of 1 :1 KOH: Petcoke, then heated in an oven to 400 degrees C at a rate of 40 degrees C / min, and held at 400 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to yield KOH- Q-Petcoke, and washed with water at 80 degrees C. Figure 6 is an XPS scan of the KOH- Q-Petcoke after washing with water. After washing with water, the KOH-Q-Petcoke was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water. Table 1 summarizes the XPS data for the KOH-Q-Petcoke after washing with water versus the KOH-Q-Petcoke after washing with water and acid. Table 1 shows that the acid washing reduces sulfur and potassium from the product.Table 1Example 3

[0089] Petroleum coke was mixed with potassium hydroxide pellets at a mass ratios of 0.25:1 KOH: Petcoke; 0.5:1 KOH: Petcoke; 0.75:1 KOH: Petcoke; and 1 :1 KOH: Petcoke. Samples were heated in an oven to 400 degrees C at a rate of 40 degrees C / min, and held at 400 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to yield KOH-Q- Petcoke, and washed with water at 80 degrees C. After washing with water, the KOH-Q- Petcoke was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water. Figure 7 is an XPS scan of the KOH-Q-Petcoke (0.75:1 KOH:Petcoke) after washing with acid and rinsing. Table 2 summarizes the XPS data for the sulphur and silicon content of KOH-Q-Petcoke after washing with acid and rinsing, at all ratios.Table 2Example 4

[0090] Petroleum coke was mixed with potassium hydroxide pellets at a mass ratio of 1 :1 KOH: Petcoke. Samples were heated in an oven under nitrogen to 430 degrees C at a rate of 40 degrees C / min, and held at 430 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to yield KOH-Q-Petcoke, and washed with water at 80 degrees C. After washing with water, the KOH-Q-Petcoke was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water. After rinsing, the KOH-Q- Petcoke samples were then dried and heated in a furnace under nitrogen to various temperatures and for various times. Table 3 summarizes the XPS data for KOH-Q- Petcoke after heating at each temperature and time. Table 3 shows that increasing time of heating results in in carbon attrition and no decrease in oxygen content; however it is believed that this was due to the nature of the furnace, and that purging of oxygen from the furnace would result in decreased oxygen content. Figure 8 is an XPS scan of the KOH-Q-Petcoke after heat treatment at 1100 degrees C for 1 hour; the inset shows the sulfur signal at the noise level.Table 3Example 5

[0091] The purity of the following different samples was tested using glow discharge mass spectrometry (GDMS). Results are shown in Table 4.

[0092] Sample 1 : Petroleum coke was mixed with potassium hydroxide pellets (1 :1 mass ratio), then heated in an oven to 400 degrees C at a rate of 40 degrees C / min, and held at 400 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to yield potassium hydroxide heat treated petcoke (KOH-Q-Petcoke), and washed with water at 80 degrees C. After washing with water, the KOH-Q-Petcoke was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water, to yield Sample 1 .

[0093] Sample 2: Sample 1 was graphitized by heating in a high-temperature furnace under argon for 5 minutes at 2700 degrees C, to yield Sample 2.

[0094] Sample 3: For comparison, a commercially available carbon allotrope mixture was tested for purity. The commercially available carbon allotrope mixture was obtained via thermal catalytic decomposition of methane.

[0095] Sample 4: Sample 3 was mixed with potassium hydroxide pellets (1 :1 mass ratio), then heated in an oven to 400 degrees C at a rate of 40 degrees C / min, and held at 400 degrees C for 30 minutes. This was followed by a heating cycle where the temperature of the oven was increased at a rate of 90 degrees C / min to 900 degrees C, where it was held for 15 minutes. Samples were cooled to 25 degrees C to, and washed with water at 80 degrees C. After washing with water, the sample was then washed with 0.1 M hydrochloric acid at 80 degrees C for one hour, and then rinsed with water, to yield Sample 4. The purity of Sample 4 was not considered high enough to proceed with graphitization (a threshold of 95% purity was required for introduction into the high temperature furnace).Table 4

[0096] Table 4 shows that the processes described herein can yield a relatively high purity feedstock for graphitization, which may in turn yield a relatively high purity graphite.CLAUSES

[0097] Non-limiting examples are described in the following clauses:

[0098] 1 . A process for producing a feedstock for graphitization, comprising: a. washing a potassium hydroxide heat treated petcoke with an acid to remove metal contaminants.

[0099] 2. The process of any of the preceding or following clauses, wherein step a. comprises washing the potassium hydroxide heat treated petcoke with hydrochloric acid.

[0100] 3. The process of any of the preceding or following clauses, wherein step a. comprises washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

[0101] 4. The process of any of the preceding or following clauses further comprising: prior to step a., grinding the potassium hydroxide heat treated petcoke.

[0102] 5. The process of any of the preceding or following clauses, further comprising: after grinding the potassium hydroxide heat treated petcoke and prior to step a., washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash.

[0103] 6. The process of any of the preceding or following clauses, wherein washing the potassium hydroxide heat treated petcoke with water comprises washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

[0104] 7. The process of any of the preceding or following clauses, further comprising: after step a., heating the potassium hydroxide heat treated petcoke to remove oxygen.

[0105] 8. The process of any of the preceding or following clauses, wherein heating the potassium hydroxide heat treated petcoke comprises heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

[0106] 9. The process of any of the preceding or following clauses, further comprising: after heating the potassium hydroxide heat treated petcoke to remove the oxygen, washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

[0107] 10. The process of any of the preceding or following clauses, further comprising: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke.

[0108] 11. The process of any of the preceding or following clauses, wherein the potassium hydroxide heat treated petcoke comprises a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

[0109] 12. The process of any of the preceding or following clauses, wherein the feedstock for graphitization comprises at least 90 wt% carbon.

[0110] 13. The process of any of the preceding or following clauses, wherein the feedstock for graphitization comprises at least 95 wt% carbon.

[0111] 14. A feedstock for graphitization made by the process of any of the preceding or following clauses.

[0112] 15. A graphite made from the feedstock for graphitization of any of the preceding or following clauses.

[0113] 16. The graphite made from any of the preceding or following clauses, wherein the comprises at least 95 wt% carbon.

[0114] 17. The graphite made from any of the preceding or following clauses, wherein the comprises at least 99 wt% carbon.

[0115] 18. A battery comprising the graphite of any of the preceding or following clauses.

[0116] 19. A process for producing graphite, comprising: a. cleaning a potassium hydroxide heat treated petcoke to remove contaminants and yield a feedstock; and b. graphitizing the feedstock to yield graphite.

[0117] 20. The process of any of the preceding or following clauses, further comprising: prior to step a., grinding the potassium hydroxide heat treated petcoke.

[0118] 21. The process of any of the preceding or following clauses, wherein step a. comprises: i. washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash.

[0119] 22. The process of any of the preceding or following clauses, wherein step i. comprises washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees for between 5 minutes and 60 minutes.

[0120] 23. The process of any of the preceding or following clauses, wherein step a. further comprises: ii. after step i., washing the potassium hydroxide heat treated petcoke with an acid to remove metal contaminants.

[0121] 24. The process of any of the preceding or following clauses, wherein step ii. comprises washing the potassium hydroxide heat treated petcoke hydrochloric acid.

[0122] 25. The process of any of the preceding or following clauses, wherein step ii. comprises washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 80 degrees for between 5 minutes and 60 minutes.

[0123] 26. The process of any of the preceding or following clauses, wherein step a. further comprises: iii. after step ii., heating the potassium hydroxide heat treated petcoke to remove oxygen.

[0124] 27. The process of any of the preceding or following clauses, wherein step iii. comprises heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

[0125] 28. The process of any of the preceding or following clauses, wherein step a. further comprises: iv. after step iii., washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

[0126] 29. The process of any of the preceding or following clauses, further comprising: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke.

[0127] 30. The process of any of the preceding or following clauses, wherein the potassium hydroxide heat treated petcoke comprises a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

[0128] 31 . The process of any of the preceding or following clauses, wherein the feedstock comprises at least 90 wt% carbon.

[0129] 32. The process of any of the preceding or following clauses, wherein the feedstock comprises at least 95 wt% carbon.

[0130] 33. The process of any of the preceding or following clauses, wherein the graphite comprises at least 95 wt% carbon.

[0131] 34. The process of any of the preceding or following clauses, wherein the graphite comprises at least 99 wt% carbon.

[0132] 35. A graphite made by any of the preceding or following clauses.

[0133] 36. A battery comprising the graphite of any of the preceding clauses.

Claims

WE CLAIM:1 . A process for producing a feedstock for graphitization, comprising: a. washing a potassium hydroxide heat treated petcoke with an acid to remove metal contaminants.

2. The process of claim 1 , wherein step a. comprises washing the potassium hydroxide heat treated petcoke with hydrochloric acid.

3. The process of claim 1 or claim 2, wherein step a. comprises washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

4. The process of any one of claims 1 to 3 further comprising: prior to step a. , grinding the potassium hydroxide heat treated petcoke.

5. The process of claim 4, further comprising: after grinding the potassium hydroxide heat treated petcoke and prior to step a., washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash.

6. The process of claim 5, wherein washing the potassium hydroxide heat treated petcoke with water comprises washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees Celsius for between 5 minutes and 60 minutes.

7. The process of any one of claims 1 to 6, further comprising: after step a., heating the potassium hydroxide heat treated petcoke to remove oxygen.

8. The process of claim 7, wherein heating the potassium hydroxide heat treated petcoke comprises heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

9. The process of claim 7 or claim 8, further comprising: after heating the potassium hydroxide heat treated petcoke to remove the oxygen, washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

10. The process of any one of claims 1 to 9, further comprising: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke.

11. The process of any one of claims 1 to 10, wherein the potassium hydroxide heat treated petcoke comprises a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

12. The process of any one of claims 1 to 11 , wherein the feedstock for graphitization comprises at least 90 wt% carbon.

13. The process of any one of claims 1 to 11 , wherein the feedstock for graphitization comprises at least 95 wt% carbon.

14. A feedstock for graphitization made by the process of any one of claims 1 to 13.

15. A graphite made from the feedstock for graphitization of claim 13 or claim 14.

16. The graphite of claim 15, wherein the graphite comprises at least 95 wt% carbon.

17. The graphite of claim 15 or 16, wherein the graphite comprises at least 99 wt% carbon.

18. A battery comprising the graphite of claim 16 or 17.

19. A process for producing graphite, comprising: a. cleaning a potassium hydroxide heat treated petcoke to remove contaminants and yield a feedstock; and b. graphitizing the feedstock to yield graphite.

20. The process of claim 19, further comprising: prior to step a. , grinding the potassium hydroxide heat treated petcoke.

21. The process of claim 19 or claim 20, wherein step a. comprises: i. washing the potassium hydroxide heat treated petcoke with water to remove sulfur, remove potassium, and / or remove ash.

22. The process of claim 21 , wherein step i. comprises washing the potassium hydroxide heat treated petcoke with water at between 60 and 90 degrees for between 5 minutes and 60 minutes.

23. The process of any one of claims 21 or 22, wherein step a. further comprises: ii. after step i., washing the potassium hydroxide heat treated petcoke with an acid to remove metal contaminants.

24. The process of claim 23, wherein step ii. comprises washing the potassium hydroxide heat treated petcoke hydrochloric acid.

25. The process of claim 23 or 24, wherein step ii. comprises washing the potassium hydroxide heat treated petcoke with between 0.01 M and 0.1 M hydrochloric acid at between 60 and 80 degrees for between 5 minutes and 60 minutes.

26. The process of any one of claims 23 to 25, wherein step a. further comprises: iii. after step ii., heating the potassium hydroxide heat treated petcoke to remove oxygen.

27. The process of claim 26, wherein step iii. comprises heating the potassium hydroxide heat treated petcoke to between 250 degrees and 900 degrees for between 5 and 30 minutes.

28. The process of claim 26 or 27, wherein step a. further comprises: iv. after step iii., washing the potassium hydroxide heat treated petcoke with water to remove ash and yield the feedstock.

29. The process of any one of claims 19 to 28, further comprising: prior to step a., subjecting a crushed petcoke to a potassium hydroxide heat treatment to yield the potassium hydroxide heat treated petcoke.

30. The process of any one of claims 19 to 29, wherein the potassium hydroxide heat treated petcoke comprises a potassium hydroxide heat treated fluid coke and / or a potassium hydroxide heat treated delayed coke.

31. The process of any one of claims 19 to 30, wherein the feedstock comprises at least 90 wt% carbon.

32. The process of ay one of claims 19 to 31 , wherein the feedstock comprises at least 95 wt% carbon.

33. The process of any one of claims 19 to 32, wherein the graphite comprises at least 95 wt% carbon.

34. The process of any one of claims 19 to 33, wherein the graphite comprises at least 99 wt% carbon.

35. A graphite made by the process of any one of claims 16 to 34.

36. A battery comprising the graphite of claim 35.

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