Modified hydrocarbon fluids for producing enhanced cokes and pitches

Abstract

A variety of methods and systems for producing battery grade carbonaceous precursors by modifying heavy hydrocarbon fluids using composition additives are disclosed. In embodiments, the modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes comprises a heavy hydrocarbon fluid in an amount of about 50 wt.% to about 99.9 wt.%, based on a total mass of the modified heavy hydrocarbon fluid, and a graphitization catalyst present in an amount of about 0.1 wt.% to about 50 wt.%, based on the total mass of the modified heavy hydrocarbon fluid.

Description

MODIFIED HYDROCARBON FLUIDS FOR PRODUCING ENHANCED COKES AND PITCHES FIELD

[0001] This application relates to methods and systems for producing battery grade carbonaceous precursors by modifying heavy hydrocarbon fluids using composition additives. BACKGROUND

[0002] Graphite is a carbon allotrope comprised of a large number of stacked sheets of sp2-hybridized carbons arranged in a highly ordered structure. Among the many beneficial attributes of graphite are its high thermal and electrical conductivity values, the latter of which makes graphite especially useful as a negative electrode material in lithium-ion batteries. In addition, the crystalline structure of graphite promotes an ability to store lithium ions through intercalation, which is useful for lithium-ion battery applications. Additional applications in which graphite finds extensive use include, for example, fiber production, composite manufacturing, lubrication, and as electrodes for electric arc furnaces.

[0003] Graphite may be obtained from natural sources or produced synthetically through pyrolysis of a carbonaceous precursor. The latter material is referred herein to “synthetic graphite.” Suitable carbonaceous precursors for producing synthetic graphite include raw coke or green coke, sponge coke, and pitches, each of which contain large aromatic molecules that may be converted to graphite under pyrolysis conditions. Green coke is a coke product that can alternatively be referred to as needle coke, green petcoke, or green needle coke. Green coke is the primary solid carbonization product from high boiling hydrocarbon fractions obtained at temperatures below 625 °C. It contains a fraction of matter that can be released as volatiles during subsequent heat treatment at temperatures up to approximately 1350 °C. This mass fraction, called volatile matter, is in the case of green coke between 4 and 15 wt.%, but it may depend upon the heating rate and time of cooking. More specifically, green coke may comprise from about 4 wt.% to about 6 wt.%, or from about 5 wt.% to about 6 wt.% volatiles as measured according to the ISO 9406 Test Method. Green coke may comprise from about 60 to about 100 HGI as measured according to the ISO 5074 Test Method. Green coke may comprise from about 5 to about 10 wt.% water as measured according to the ISO 11412 Test Method. Green coke may comprise from about 0 to about 0.4 wt.% sulfur as measured according to the ISO 12980 Test Method. Green coke may comprise from about 0 to about 0.1 wt.% ash as measured according to the ISO 8005 Test Method.Green coke may comprise from about 0 to about 0.4 wt.% nitrogen as measured according to the ASTM D5291 Test Method.

[0004] Large aromatic molecules in coke and pitches may first be converted to high carbon containing carbonized coke in a carbonization process taking place at a temperature of about 500 °C to about 1800 °C under inert conditions, followed by subsequent conversion to graphite in a graphitization process taking place at a higher temperature of about 2800 °C to about 3400 °C. Both conversion processes take place in the absence or substantial absence of oxygen. To achieve a high-percentage conversion of cokes to graphite (e.g., greater than 90 % conversion to graphite on a mass basis), temperatures up to and exceeding 3000 °C and extended reaction times up to about 20 hours are frequently needed. Because such extended, high-temperature conversion processes are exceedingly energy intensive, the production of synthetic graphite remains expensive, despite the low cost of coke and pitch as graphite precursors. Commercial graphitization processes may further employ a range of graphitization temperatures, which may impact the quality of the graphite produced therefrom.

[0005] Green coke and highly crystalline pitch materials may be used as carbonaceous precursors for producing battery grade or high-quality graphite (degree of graphitization > 90 %) suitable for various applications including negative electrode for lithium-ion battery and graphite electrodes used in electric arc furnaces (EAF). With the rise of electrification and the goal of reaching net-zero carbon emissions, producing high quality carbon precursors at lower energy usage is key to realizing both goals.

[0006] The production of cokes and mesophase pitches today in a batch or continuous process largely focuses on controlling the pressure, temperature, gas flow, recycle ratio, and residence time within the reactor. Green coke and delayed cokes can be produced in a delayed coker by using refinery residues such as vacuum resid, slurry oil, decant oil, ethylene tar, and thermal tar. With the recycle ratio and gas flow being limited by equipment and safety, the main knobs for improving the product quality are temperature, pressure, and residence time. Typical delayed coker or needle coker operates at temperatures of 450 °C to 550 °C, so called green petroleum coke. Two main disadvantages are realized when pursuing these routes: uneven quality distribution and low throughput. Regulating pressure and temperature results in creating a wide distribution in the conditions across the reactor, which in return translates to a variation in the quality between the bottom, middle, and top of the reactor. While increasing the residence time might help mitigate this phenomenon to some extent, the downside would be a lower total production of materials which is highly undesirable. Therefore, introducing a new method formaking high quality green cokes and pitches under the same or milder standard conditions may be desired.

[0007] Mesophase pitch may be produced via continuous reactor with isotropic pitch as feedstock. In the Acheson graphitization, catalyst, carbides, and oxides may be used to achieve high degree of graphitization. The catalysts include iron, nickel, titanium, silicon, and boron, for example. However, the catalysts are used in substantial quantities of catalyst (from about 3 wt % to about 30 wt.%). Further, the distribution of the catalyst is inhomogeneous. For example, a large quantity may be found on the surface of the coke particles, but not found deep into the coke particles. The objective of the present invention is to provide a graphite precursor (green coke, delayed coke, or mesophase pitch) with a homogenous distribution of the catalyst in the individual grains. SUMMARY

[0008] Further disclosed herein is an example of a modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes comprising a heavy hydrocarbon fluid and a graphitization catalyst. The heavy hydrocarbon fluid is present in an amount of about 50 wt.% to about 99.9 wt.%, based on a total mass of the modified heavy hydrocarbon fluid. The graphitization catalyst is present in an amount of about 0.1 wt.% to about 50 wt.%, based on the total mass of the modified heavy hydrocarbon fluid.

[0009] Further disclosed herein is an example of a method for producing modified heavy hydrocarbon fluid for producing graphitic particles for negative electrode for lithium-ion batteries comprising including at least one graphitization catalyst in a heavy hydrocarbon fluid to produce the modified heavy hydrocarbon fluid, wherein the at least one graphitization catalyst is included in an amount of about 0.1 wt.% to about 50 wt.%, based on a total mass of a carbonaceous precursor, and wherein the heavy hydrocarbon fluid has an initial boiling point of about 200 °C or greater.

[0010] Further disclosed herein is an example of a method for producing carbonaceous precursors for electrodes comprising including a graphitization catalyst in a carbonaceous precursor, wherein the graphitization catalyst is included in an amount of about 0.1 wt.% to about 50 wt.%, based on a total mass of the carbonaceous precursors.

[0011] Further disclosed herein is an example of a method for producing graphitic materials for electrodes comprising carbonizing at least one carbonaceous precursor to form at least carbonized particles by a process comprising heating the at least one carbonaceous precursor to a temperature of about 500 °C to about 1800 °C, and graphitizing at least a portion of the carbonized particles to form at least graphitic particles by a process comprising heating the at least one carbonaceousprecursor to a temperature up to about 3400 °C, wherein the graphitic particles comprise a carbon matrix and two or more additives dispersed in the carbon matrix in an amount up to about 50%, based on a total mass of the graphitic particle.

[0012] These and other features and attributes of the disclosed modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows. DETAILED DESCRIPTION

[0013] Disclosed herein are methods and systems for producing carbonaceous precursors from modified heavy hydrocarbon fluids that include at least one graphitization catalyst (or precursor thereof). Optional additives that may be included in the modified heavy hydrocarbon fluids include surfactants, dispersants, conductive carbons, application performance enhancers, or any combination thereof. The carbonaceous precursors include pitch and coke suitable for producing battery grade graphitic particles that can be used in various applications including negative electrode for lithium-ion battery and graphite electrodes. For example, the pitch and coke may be converted to battery-grade graphitic particles with a degree of graphitization equal to or above 90 %.

[0014] As discussed above, graphite is a highly versatile material with a number of important uses due to its high electrical and thermal conductivity values, as well as its crystalline structure that may promote intercalation of lithium ions. Although graphite may be produced synthetically from inexpensive precursors, such as coke and pitch, processes for producing synthetic graphite are usually very energy intensive and lead to high production costs as a result. Additionally, synthetic pitch-based graphite anodes are often limited in their ability to achieve high capacity, fast charging, and cycle life.

[0015] The present disclosure employs a new approach to incorporate various additives, including a graphitization catalyst (or a precursor thereof) to at least partially address the foregoing issue. Unless otherwise specified or evident from context in the present disclosure, the term “graphitization catalyst” is used herein to refer equivalently to a graphitization catalyst or a graphitization catalyst precursor. Suitable graphitization catalysts may lower the temperature and / or the time required to produce synthetic graphite under the pyrolysis conditions or raise the amount of synthetic graphite produced under a given set of pyrolysis conditions. In addition, graphitic particles produced using modified heavy hydrocarbon fluids with the graphitization catalyst may have a number of improved properties including higher conductivity, mechanical integrity, and stability, for example. Moreover, graphitization catalysts can reduce the severity ofthe conditions required to produce high quality graphite precursors such as pitch or coke during the process.

[0016] In some embodiments, a process for producing battery grade graphitic particles may include mixing at least one graphitization catalyst with a heavy hydrocarbon fluid to form a modified heavy hydrocarbon fluid. The heavy hydrocarbon fluid may include from 0.01 micrometer (µm) to 10,000 µm, from 0.1 µm to 1,000 µm, from 0.5 µm to 500 µm, from 1 µm to 250 µm, from 5 µm to 100 µm, from 10 µm to 75 µm, from 15 µm to 50 µm, or 20 µm to 30 µm, of coke fines, for example. The cokes fines may be any fines including pitch fines, petroleum coke fines, fluid coke fines, sponge coke fines, coal tar pitch coke fines, coke breeze fines, biochar fines, gas pyrolysis coke fines, or any combination thereof, for example. The coke fines may be green or calcined with volatiles content from 0.1 wt % to 50 wt % or any number in between. In embodiments, the at least one graphitization catalyst and / or coke fines may be added via spraying or bubbling through the oil.

[0017] The mixing may be performed by any high shear mixing device such as an extruder, bed mill mixer, high shear homogenizer, or any combination thereof, for example. The mixing and / or dispersing may be performed in any dispersing machine such as a high-speed shearing disperser, for example. The rotating speed of the mixing and dispersing machine may be from 25 rotation- per-minute (rpm) to 10,000 rpm, from 50 rpm to 5,000 rpm, from 100 rpm to 2,500 rpm, from 500 rpm to 1,500 rpm, from 800 rpm to 1,250 rpm, such as 1,000 rpm, for example. The mixing and / or dispersing time is from 5 seconds (s) to 100,000 s, from 10 s to 10,000 s, from 100 s to 5,000 s, from 500 s to 2,500 s, from 800 s to 1,500 s, from 1,000 s to 1,250 s, such as 1,200 s, for example. The solid content of the hydrocarbon fluid slurry before mixing may be from 0.001 % to 75 %, from 0.01 % to 50 %, from 0.1 % to 25 %, from 1 % to about 15 %, from about 5 % to about 12.5 %, or 10%, for example.

[0018] The mixing may be performed below, at, or above the softening point of the pitch and / or coke. For example, mixing the at least one graphitization catalyst with a heavy hydrocarbon fluid may be performed in a high shear mixing device above the softening point of the pitch and / or coke to produce a homogeneous dispersion of modified heavy hydrocarbon fluid. Mixing may be done above the softening point in a high shear extruder (twin screw or single screw) fed with the graphitization catalyst and fines by melting the hydrocarbon fluid with a screw rotating between 10 rpm and 2,000 rpm, for example. The graphitization catalyst may also be dispersed in the hydrocarbon fluid via powder blowing or bubbling the powder of catalyst and fines using an inert gas such as nitrogen or argon to uniformly disperse it in the fluid before coking.

[0019] Homogenous dispersion may be assessed via microscopy measurement of the produced carbon precursor from the coking of the modified hydrocarbon fluid. The graphitization catalyst and fines have particle size in the carbon precursor from about 0.01 µm to about 50,000 µm, from about 0.1 µm to about 10,000 µm, from about 0.5 µm to about 1,000 µm, from about 1 µm to about 100 µm, from about 2 µm to about 25 µm, from about 5 µm to about 10 µm, for example.

[0020] Additional additives may also be mixed with the heavy hydrocarbon fluid, including surfactants, dispersants, conductive carbons, application performance enhancers, or any combination thereof. The conductive carbons may be single wall carbon nanotubes or multiple walls carbon nanotubes, for example. The conductive carbon may be present from about 0.001 wt% to about 50 wt%, from about 0.01 wt% to about 25 wt%, from about 0.1 wt% to about 10 wt%, from about 1 wt% to about 5 wt%, for example.

[0021] At least a portion of the modified heavy hydrocarbon fluid may then be converted to a carbonaceous precursor, such as pitch or coke. Converting the modified heavy hydrocarbon fluids to the carbonaceous precursor may include, for example, heating the heavy hydrocarbon fluid to a temperature of 100 °C to 1000 °C in a vertical or horizontal reactor, drum, or tube, for example. The vertical reactor may optionally have a rotating mixing element inside. The horizontal reactor may also have rotating barrel in addition to rotating mixing element inside the tube. Examples of reactors include VCJ mixer, VJ mixer, Rotary Kiln system. Alternatively, the coking device may be a delayed coker or needle coker. Further, the coking device may have an inert gas atmosphere such as nitrogen, argon, for example, from atmospheric pressure to high pressures such as 10000 psi, or 1000 psi, for example. When the temperature is from about 150 °C to about 300 °C, the atmosphere in the coking device may be oxidative containing air or oxygen containing atmosphere, for example.

[0022] The carbonaceous precursor may then be converted to graphitic particles, for example, battery-grade graphitic particles. Converting the carbonaceous precursor to graphitic particles may include a number of steps, including carbonization at temperatures of 500 °C to 1800 °C or about 500 °C to about 1400 °C and then graphitization at temperatures up to 3400 °C. Example Heavy Hydrocarbon fluids

[0023] Non-limiting examples of suitable heavy hydrocarbon fluids include hydrocarbon pyrolysis tars, ethylene tars, atmospheric residues, vacuum residue, slurry oil, isotropic pitch, synthetic isotropic pitch, coal tar pitch, hydrogenated oil, and other heavy hydrocarbon streams with high aromatic content. As used herein, a heavy hydrocarbon fluid refers to a fluid that comprises aromatic hydrocarbons, wherein the fluid has an ASTM D8610% distillation point of > 60 °C and a 90% distillation point of < 425 °C. A higher boiling point of the feed may translateto a heavier feed which results in a higher coke and / or pitch yield. Example heavy hydrocarbon fluids may comprise 2-ring and / or 3-ring aromatic compounds in an amount of >25 wt.%, >40 wt.%, >50 wt.%, >55 wt.%, or >60 wt.%, based on the weight of the heavy hydrocarbon fluid. The heavy hydrocarbon fluid can have a true boiling point distribution, for example, having an initial boiling point of >177°C and a final boiling point of <430°C. True boiling point distributions (“TBP”, the distribution at atmospheric pressure) are determined in accordance with ASTM D7500. When the final boiling point is greater than that specified in the standard, the true boiling point distribution can be determined by extrapolation. Example heavy hydrocarbon fluids may have a Bureau of Mines Co-relation Index (BMCI) of about 90 to about 160. In some embodiments, two or more hydrocarbon fluids are processed to prepare the battery grade carbonaceous material.

[0024] Heavy hydrocarbon fluid is a high-boiling, viscous, hydrocarbon fluid that may be produced from pyrolysis processes, such as steam cracking, in the conversion of saturated hydrocarbons to higher-value products such as light olefins, e.g., ethylene and propylene. Heavy hydrocarbon fluid typically include complex, cyclic, and branched molecules as well as high molecular weight non-volatile components including paraffin insoluble compounds, such as pentane-insoluble compounds and heptane-insoluble compounds, including asphaltenes. In addition to these compounds, the heavy hydrocarbon fluid may also include a high sulfur content, for example, as high as 5 wt.%, leading to production of high-sulfur coke.

[0025] Hydro-processing may be used as a hydrocarbon conversion process of heavy hydrocarbon fluid referred to as a solvent assisted heavy hydrocarbon fluid conversion in which the heavy hydrocarbon fluid is processed in the presence of a utility fluid in at least one of the processing stages. The solvent assisted heavy hydrocarbon fluid conversion process is a processing technology that addresses fouling caused by feedstocks. Accordingly, example embodiments include processing the heavy hydrocarbon fluid in a solvent assisted heavy hydrocarbon fluid conversion process, for example, contacting the heavy hydrocarbon fluid with at least one graphitization catalysts and a battery performance enhancer in at least one processing stage to form a processed product, wherein the processing in at least one of the one processing stages is performed in the presence of a utility fluid. The solvent assisted heavy hydrocarbon fluid is a “milder” treating process (e.g., lower pressures and temperatures) than severe treating process (e.g., 20700 kPa) that can convert the heavy hydrocarbon fluid to a processed product with low sulfur while minimizing aromatic saturations; thus, preserving the aromatic rings content for coke formation. The processed product may include sulfur in an amount from about 0.01 wt.% to about 1.5 wt.%, or of ≤ 1.5 wt.%, ≤ 1 wt.%, ≤ 0.5 wt.%, ≤ 0.4 wt.%, or ≤ 0.1 wt.%, for example.

[0026] In some embodiments, a heavy hydrocarbon fluid is upgraded in a solvent assisted heavy hydrocarbon fluid process to provide a heavy hydrocarbon fluid with improved properties for delayed coking or pitch production. The heavy hydrocarbon fluid includes aromatic compounds. In some embodiments, the heavy hydrocarbon fluid includes aromatic compounds having ≥ 15 carbon atoms in an amount of ≥ 50 wt.%, ≥ 75 wt.%, or ≥ 90 wt.%, based on the weight of the heavy hydrocarbon fluid. Heavy hydrocarbon fluid generally has a metals content less than crude oil of the same viscosity, for example. Heavy hydrocarbon fluids may have a metals content of ≤ 1.0×103ppmw, based on the weight of the heavy hydrocarbon fluid, which is an amount of metals that is far less than that found in crude oil (or crude oil components) of the same average viscosity.

[0027] In some embodiments, the heavy hydrocarbon fluid has an insolubility number (“IN”) of ≥ 80. For example, the heavy hydrocarbon fluid can have an IN ≥ 85, IN ≥ 90, IN ≥ 100 IN ≥ 110, IN ≥ 120, IN ≥ 130, or IN ≥ 135. As used herein, the insolubility number or IN is determined in accordance with ASTM D7112.

[0028] Additionally, the solubility blending number (“SBN”) of the heavy hydrocarbon fluid can be as low as SBN ≥ 130, but is typically SBN ≥ 140, SBN ≥ 145, SBN ≥ 150, SBN ≥ 160, SBN ≥ 170, SBN ≥ 175 or even SBN ≥ 180. In some embodiments, the heavy hydrocarbon fluid can be one having SBN ≥ 200 or SBN ≥ 220. In further embodiments, the heavy hydrocarbon fluid has an SBN up to 240. As used herein, the solubility blending number or SBN is determined in accordance with ASTM D7112. With this test method, pentane has an SBN of 25, toluene has an SBN of 100, and quinoline has an SBN of 200.

[0029] Further, example embodiments of the heavy hydrocarbon fluid include C7 insolubles. In some embodiments, the heavy hydrocarbon fluid has a C7insoluble content of ≤ 50 wt.%, such as an amount of ≤ 15 wt.%, ≤ 25 wt.%, ≤ 30 wt.%, ≤ 45wt.%. Thus, the heavy hydrocarbon fluid has, for example, a C7insoluble content from about 15 wt.% to about 50 wt.% or from about 30 wt.% to about 50 wt.%.

[0030] In particular embodiments, a heavy hydrocarbon fluid has an IN of 110 to 135, an SBN of 180 to 240, and a C7 insoluble content from about 30 wt.% to about 50 wt.%.

[0031] In addition to sulfur, heavy hydrocarbon fluid may also include high molecular weight non-volatile components including paraffin insoluble compounds, such as pentane-insoluble compounds and heptane-insoluble compounds, including asphaltenes, that can lead to undesirable fouling during coking. In some embodiments, heavy hydrocarbon fluid contains > 0.5 wt.%, sometimes > 1 wt.% or even > 2 wt.% of toluene insoluble compounds. The high molecular weight compounds are typically multi-ring structures that are also referred to as tar heavies (“TH”). Asused herein, the term tar heavies refers to a product of hydrocarbon pyrolysis, having a boiling point at atmospheric pressure of ≥ 565 °C and comprising ≥ 5 wt.% of molecules having a plurality of aromatic cores, based on the weight of the product. The tar heavies are typically solid at 25 °C and generally include the fraction of hydrocarbon pyrolysis tar that is not soluble in a 5:1 (vol.:vol.) ratio of n-pentane:hydrocarbon pyrolysis tar at 25.0 °C. Example Composition Additives

[0032] In some embodiments, at least one graphitization catalyst may be added to the heavy hydrocarbon fluid to produce a modified heavy hydrocarbon fluid. In addition to the graphitization additive, one or more additional additives may also be added to the heavy hydrocarbon including a surfactant, a dispersant, conductive carbons, application performance enhancers, or any combination thereof. The added one or more additives may include a tin-containing additive, an aluminum-containing additive, a silicon-containing additive, titanium-containing additive, and combinations thereof.

[0033] The additives may be added simultaneously or sequentially to the heavy hydrocarbon fluid. In some embodiments, the additives may be combined then added to the heavy hydrocarbon fluid. As discussed herein, the modified heavy hydrocarbon fluid with the graphitization catalyst and optional additives may then be converted to carbonaceous precursors (e.g., pitch or coke), which may in turn be converted to graphitic particles.

[0034] A “graphitization catalyst” is a substance capable of promoting conversion of a carbonaceous precursor into graphite under suitable pyrolysis conditions. Suitable graphitization catalysts may promote conversion of carbonaceous precursors (e.g., pitch or coke) to graphite by one or more mechanisms including, but not limited to, diffusion and intercalation, carbon dissolution-precipitation, carbide formation-decomposition, or any combination thereof. Graphitization catalyst precursors may undergo a chemical reaction, including decomposition, to produce an active graphitization catalyst in the course of being heated up to a desired carbonization temperature and / or a desired graphitization temperature. Suitable graphitization catalysts may lower the temperature needed to convert carbon materials into graphite, decrease the amount of time needed to convert carbon materials into graphite, increase the amount of carbon converted into graphite, or any combination thereof, any or all of which may facilitate graphite production with a decreased energy consumption relative to conversion of pitch or coke into graphite under un-catalyzed conditions. Further, the homogenous distribution of the graphitization catalyst in the heavy hydrocarbon fluid translates into a homogenous dispersion inside the pitch and / or coke. Moreover, having a larger portion of the graphitization catalysts inside the pitch or coke matrix can further facilitate graphite production while minimizing energy consumption and resistancecompared to having the catalyst on the pitch or coke surface due to enhanced dispersion quality and limited nitride and carbide formation.

[0035] In some examples, suitable graphitization catalysts may promote graphitization by virtue of the diffusion constant of one or more elements therein. Without being bound by theory or mechanism, an element with a diffusion constant larger than carbon in both the transverse and longitudinal directions may enhance graphitization of the pitch and similar graphite precursors by becoming intercalated between aromatic rings in adjacent layers, thereby leaving large voids that carbon may exploit through self-diffusion to improve the graphitization rate. Suitable graphitization catalysts that may promote graphitization through intercalation and diffusion include those containing a Group 13 element. Group 13 elements include boron, aluminum, gallium, indium, and thallium. In some examples, suitable graphitization catalysts containing a Group 13 element may comprise boron. Suitable boron-containing graphitization catalysts may include, but are not limited to, boric acid, organic esters of boric acid, sodium tetraborate, tetrahydroxyborate salts, orthoborate salts, metaborate salts, triborate salts, tetraborate salts, pentaborate salts, octaborate salts, boronic acids, boronate esters, boron oxides, boron carbides, borane-pyyridine complexes, the like, or any combination thereof. An example of a suitable boron-containing graphitization catalyst includes the following borane pyridine complex:Structure 1.

[0036] Another example of a suitable boron-containing graphitization catalyst includes the following 2-methylpyridine borane complex:Structure 2.

[0037] Other examples of a suitable boron-containing graphitization catalyst include divinylbenzene-tri-(allyl)-borane and styrene-tri(allyl)-borane, for example.

[0038] Additional examples of graphitization catalyst containing a Group 13 element may include, but are not limited to, an aluminum-containing graphitization catalyst, such as alumina, organo-aluminum, or any combination thereof.

[0039] In some examples, suitable graphitization catalysts may promote graphitization by a dissolution-precipitation mechanism (i.e., a carbon dissolution-precipitation mechanism). Withoutbeing bound by theory or mechanism, graphitization catalysts promoting graphitization by dissolution-precipitation may dissolve carbon (e.g., amorphous carbon) and then re-precipitate the dissolved carbon in ordered graphitic layers. Suitable graphitization catalysts that may promote graphitization through dissolution and precipitation include those containing a Group 8-10 element. Group 8-10 elements include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. In preferred examples, suitable graphitization catalysts containing a Group 8-10 element may comprise iron, cobalt, or nickel. Suitable graphitization catalysts containing a Group 8-10 element may include, but are not limited to, Fe2O3, Fe3O4, Fe metal, Co metal, Ni metal, Fe-Ni alloys, Co-Ni alloys, Fe-Co alloys, Ni-Co alloys, iron carbides, the like, or any combination thereof.

[0040] Examples of suitable iron-containing graphitization catalysts include ferrocene and its derivatives:Structure 3.

[0041] An example of a suitable cobalt-containing graphitization catalyst includes {(Pentyl)4N]3CoBr3}Cl2.

[0042] In some examples, suitable graphitization catalysts may promote graphitization by a carbide formation-decomposition mechanism. Without being bound by theory or mechanism, graphitization catalysts promoting graphitization by carbide formation-decomposition may form an initial metal carbide reaction product that subsequently decomposes to produce graphite and free metal. Suitable graphitization catalysts that may promote graphitization through carbide formation include those containing a Group 4-7 element. Group 4-7 elements include titanium, vanadium, chromium, manganese, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, and rhenium. In preferred examples, suitable graphitization catalysts containing a Group 4-7 element may comprise titanium, vanadium, chromium, or manganese. Suitable graphitization catalysts containing a Group 4-7 element may include, but are not limited to, Ti metal, V metal, Cr metal, Mn metal, titanium oxide, vanadium oxide, chromium oxide, manganese dioxide, and the like.

[0043] Additional graphitization catalysts that may be suitable for use herein include, for example, organic derivatives of metallic compounds; Group 2 elements such as beryllium, calcium, magnesium, strontium, and barium; Group 11 elements such as copper, silver and gold;Group 12 elements such as zinc; and Group 14 elements such as silicon and tin. In some embodiments, the organic derivatives of metallic compounds may have an initial boiling point similar to the initial boiling point of the heavy hydrocarbon fluid itself. For example, the organic derivatives of metallic compounds may have an initial boing point without the heavy hydrocarbon fluid about 5% of the initial boiling point of the heavy hydrocarbon fluid. The organic derivatives of metallic compounds may have an initial boiling point of around 100 °C and a final boiling point of around 600 °C, for example.

[0044] Specific examples of silicon-containing graphitization catalysts may include, but are not limited, silicon, silicon derivatives such as organo-silicate (e.g., tetrapropyl orthosilicate), for example, or any combination thereof. In general, tin-containing graphitization catalysts may include any suitable tin derivatives that release tin atoms throughout the carbon matrix in a well dispersed manner. Specific examples of tin-containing graphitization catalysts may include, but are not limited to, tin, tin derivatives such as organo-tin (e.g., trimethyl tin chloride), tin aromatic complexes (e.g., tributylstannyl pyridine), or any combination thereof, for example. In general, tin-containing graphitization catalysts may include any suitable tin derivatives that release tin atoms throughout the carbon matrix in a well dispersed manner.

[0045] Accordingly, the graphitization catalyst or the precursor thereof may comprise a compound containing at least one of a Group 2 element, a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, a Group 8 element, a Group 9 element, a Group 10 element, a Group 13 element, such as copper or zinc. Suitable compounds containing an element from the foregoing groups of the Periodic Table include, but are not limited to, oxides, carbides, salts, coordination compounds, and any combination thereof.

[0046] Accordingly, the modified heavy hydrocarbon fluids may comprise a graphitization catalyst or a graphitization catalyst precursor blended with a heavy hydrocarbon fluid. In more specific examples, the modified heavy hydrocarbon fluids may comprise from about 0.1 wt.% to about 50 wt.% graphitization catalyst or a precursor thereof and a heavy hydrocarbon fluid in an amount of about 50 wt.% to about 99.9 wt.%, based on total mass of the modified heavy hydrocarbon fluid. In non-limiting examples, the modified heavy hydrocarbon fluids may contain the graphitization catalyst or a precursor thereof in an amount ranging from about 0.0001 wt.% to about 30 wt.%, from about 0.001 wt.% to about 15 wt.%, or about 0.01 wt.% to about 15 wt.%, or about 0.1 wt.% to about 5 wt.%, or about 1 wt.% to about 15 wt.%, or about 1 wt.% to about 10 wt.%, or about 1 wt.% to about 5 wt.%, or about 2 wt.% to about 50 wt.%, about 2 wt.% to about 30 wt.%, or about 3 wt.% to about 25 wt.%, or about 3 wt.% to about 20 wt.%, or about 4 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%, or about 10 wt.% to about 20 wt.%, orabout 3 wt.% to about 10 wt.%, based on a total mass of the modified heavy hydrocarbon fluids. In non-limiting examples, the modified heavy hydrocarbon fluids may contain the hydrocarbon fluid in an amount ranging from about 50 wt.% to about 99.9 wt.%, or about 30 wt.% to about 80 wt.%, or about 40 wt.% to about 75 wt.%, or about 30 wt.% to about 50 wt.%, or about 50 wt.% to about 70 wt.%, or about 70 wt.% to about 90 wt.%, or about 80 wt.% to about 98 wt.%, or about 85 wt.% to about 99 wt.%, or about 90 wt.% to about 99.9 wt.%, based on a total mass of the modified heavy hydrocarbon fluid.

[0047] One specific example of a graphitization catalyst may include two or more graphitization catalysts selected from the group of boron-containing graphitization catalysts, silicon-containing graphitization catalyst, tin-containing graphitization catalyst, or aluminum-containing graphitization catalyst, which may be added simultaneously and / or sequentially to the heavy hydrocarbon fluid. The boron-containing graphitization catalyst may be any suitable boron- containing graphitization catalyst. The loading of the boron-containing graphitization catalyst may range from about 0.1 wt % to about 10 wt %, or from about 0.1 wt % to about 5 wt %, or from about 1 wt % to about 5 wt %, based on a total mass of the modified heavy hydrocarbon fluids. The tin-containing graphitization catalyst may be a suitable graphitization catalyst, for example, due to the tin’s high theoretical specific capacity of about 1000 mAh / g. The loading of the tin- containing graphitization catalyst may range from about 0.1 wt % to about 20 wt %, or from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, based on a total mass of the modified heavy hydrocarbon fluids. The silicon-containing graphitization catalyst may be a suitable graphitization catalyst, for example, due to silicon’s high theoretical specific capacity of about 3600 mAh / g. The loading of the silicon-containing graphitization catalyst may range from about 0.1 wt % to about 20 wt %, or from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % based on a total mass of the modified heavy hydrocarbon fluids. The aluminum-containing graphitization catalyst may be a suitable graphitization catalyst, for example, due to aluminum’s high theoretical specific capacity of about 2235 mAh / g. The loading of the aluminum- containing graphitization catalyst may range from about 0.1 wt % to about 20 wt %, or from about 0.1 wt % to about 15 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt % based on a total mass of the modified heavy hydrocarbon fluid.

[0048] As noted above, additional additives may also be included in the heavy hydrocarbon fluid as desired for a particular application. These optional additives may include, for example, conductive carbons, surfactants, dispersants, or any combination thereof. Carbon black and carbon nanotube are examples of carbon additives that may be beneficial for various applications, as theycan be conductive additives for various applications including batteries. The good dispersion of these materials in the coke and pitch when prepared from the heavy hydrocarbon fluids makes the modified-heavy hydrocarbon fluids a suitable process for producing graphitic particles. The loading of the carbon black in the heavy hydrocarbon fluid may range from about 0.01 wt % to about 10 wt %, or from about 0.1 wt % to about 5 wt %, or from about 0.1 wt % to about 2 wt %, based on a total mass of the modified heavy hydrocarbon fluids. The loading of the carbon nanotubes in the heavy hydrocarbon fluid may range from about 0.01 wt % to about 10 wt %, or from about 0.1 wt % to about 5 wt %, or from about 0.1 wt % to about 1 wt %, based on a total mass of the modified heavy hydrocarbon fluid.

[0049] The surfactant may include any alcohol including short chain alcohols, polyvinyl alcohol, or any combination thereof. The loading of the surfactant in the heavy hydrocarbon fluid may range from about 0.1 wt % to about 20 wt %, or from about 0.1 wt % to about 5 wt %, or from about 0.1 wt % to about 2 wt %, based on a total mass of the modified heavy hydrocarbon fluid.

[0050] The dispersant may include any cellulose-based dispersant including carboxymethyl cellulose, tin cellulose, or any combination thereof and / or any polymeric surfactants including styrene-butadiene rubber (SBR), cellulose methyl cellulose, or any combination thereof. The loading of the dispersant in the heavy hydrocarbon fluid may range from about 0.1 wt % to about 20 wt %, or from about 0.1 wt % to about 5 wt %, or from about 0.1 wt % to about 2 wt %, based on a total mass of the modified heavy hydrocarbon fluid. Example Conversion to Carbonaceous Precursors

[0051] Example embodiments may include conversion of the modified heavy hydrocarbon fluid to a carbonaceous precursor, such as pitch or coke. As discussed previously, the modified heavy hydrocarbon fluid may include a heavy hydrocarbon fluid mixed with at least one graphitization catalyst and optional additives. As mentioned above, suitable heavy hydrocarbon fluids include, but are not limited to, hydrocarbon pyrolysis tar, an atmospheric residue, a vacuum residue, slurry oil, isotropic pitch, synthetic isotropic pitch, coal tar pitch, coal hydrogenated oil, and any combinations thereof, and other heavy hydrocarbon stream with high aromatic content. The conversion of the modified heavy hydrocarbon fluid to a carbonaceous precursor may include a number of process steps, including, for example, heating the modified heavy hydrocarbon fluid to a temperature of 350 °C to 500 °C. For example, the conversion may include coking at least a portion of the hydroprocessed product to form a coker effluent and coke. The method for producing carbonaceous precursor may include producing a modified hydrocarbon fluid in a high shear mixing device comprising the graphitization catalyst in the carbonaceous precursor and heating the modified hydrocarbon fluid in a coking or semi-coking device at a temperature of 400°C or above to produce an additive containing coke. The heating may be performed in a delayed coker, a needle coker, a horizontal mixer, a vertical mixer, or any combination thereof. There may be a rotating device inside these devices with heat chamber with center electrode or a horizontal kiln with rotors or baffles inside, for example.

[0052] Because the graphitization catalyst was included in the modified heavy hydrocarbon fluid, the carbonaceous precursor should also comprise the graphitization catalyst. Accordingly, the carbonaceous precursor (e.g., pitch or coke) may comprise a graphitization catalyst or a graphitization catalyst precursor blended in the pitch or coke. In more specific examples, the carbonaceous precursor may comprise from about 0.1 wt.% to about 50 wt.% graphitization catalyst or a precursor thereof and a pitch or coke in an amount of about 50 wt.% to about 99.9 wt.%, based on total mass of the carbonaceous precursor. In non-limiting examples, the carbonaceous precursor may contain the graphitization catalyst or a precursor thereof in an amount ranging from about 0.1 wt.% to about 30 wt.%, from about 0.1 wt.% to about 15 wt.%, or about 0.1 wt.% to about 15 wt.%, or about 0.1 wt.% to about 5 wt.%, or about 1 wt.% to about 15 wt.%, or about 1 wt.% to about 10 wt.%, or about 1 wt.% to about 5 wt.%, or about 2 wt.% to about 30 wt.%, or about 3 wt.% to about 25 wt.%, or about 3 wt.% to about 20 wt.%, or about 4 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%, or about 10 wt.% to about 20 wt.%, or about 30 wt.% to about 50 wt.%, or about 3 wt.% to about 10 wt.%, based on a total mass of the carbonaceous precursor. In non-limiting examples, the carbonaceous precursor may contain the pitch or coke in an amount ranging from about 50 wt.% to about 99.9 wt.%, or from about 50 wt.% to about 80 wt.%, or from about 40 wt.% to about 75 wt.%, or from about 30 wt.% to about 50 wt.%, or from about 50 wt.% to about 70 wt.%, or from about 70 wt.% to about 90 wt.%, or from about 80 wt.% to about 98 wt.%, or from about 85 wt.% to about 99 wt.%, or from about 90 wt.% to about 99.9 wt.%, based on a total mass of the carbonaceous precursor. Additionally, the carbonaceous precursor may include the optional additives (e.g., conductive carbons, surfactants, dispersants), for example, in an amount of from about 0.1 wt. % to about 20 wt. % based on total mass of the carbonaceous precursor. Example Pitch

[0053] Examples may include processing the modified heavy hydrocarbon oil mixed with the graphitization catalyst and optional additives to produce pitches before producing graphitic particles for battery applications. Pitch is a carbon source of the residue obtained from the heat treatment and distillation of petroleum fractions or coal tar, for example. It is solid at room temperature, comprising a complex mixture of numerous predominantly aromatic hydrocarbons and exhibiting a broad range of softening temperatures instead of a defined melting temperature.Pitch may have a temperature softening point between 200 °C and 500 °C depending upon its carbon content (e.g., from about 80 wt.% to about 90 wt.%) and its molecular weight. As used herein, the “softening point” or “softening temperature” of pitch refers to the point at which the pitch will flow under a given load on heating. The softening point depends upon a number of factors, including average molecular weight and intrinsic viscosity. The softening point is determined in accordance with ASTP D36 / D36M using a ring-and-ball apparatus.

[0054] Pitch is liquid at high temperatures and may easily be removed from the equipment as compared to coke. The raw materials in pitch may be petrochemical byproducts such as pyrolysis fuel oil, fluid catalytic cracking-decant oil, and vacuum residue, which are cost-effective, abundant, and high in carbon content with an aromatic structure. While the yield of pitch from most crude oils may be relatively low, the large crude oil runs in refineries can result in the production of large amounts of pitch. A pitch can be produced from petroleum, coal tar, biomass tar, or from an acid-catalyzed oligomerization of small molecules (e.g., naphthalene), for example.

[0055] The highly ordered crystalline structure of pitch makes it a suitable carbonaceous precursor for making graphitic particles with high electric and thermal conductivity. These pitch- derived graphitic particles may also have high strength through traditional heat treatment processes (e.g., carbonation and graphitization). prior to undergoing carbonization or graphitization, which may be unsuitable for producing objects having strict size or shape tolerances such as an anode for a lithium-ion battery.

[0056] The pitch may be isotropic pitch or mesotropic pitch. Pitch comprises a complex mixture of aromatic molecules that may be at least partially ordered and coalesced into a liquid crystalline phase. The liquid crystalline phase may be referred to as “mesophase pitch,” which may comprise a majority or all of a pitch in some cases. In some examples, the mesophase pitch may be formed, for example, by thermal conversion of isotropic pitch in an open or closed system. The pitch may have a mesophase content of from 0 wt % to 100 wt %. In some examples, at least a majority of the pitch may comprise a mesophase pitch. Once carbonized and converted to graphitic particles, the highly aligned structure of mesophase pitch may promote enhanced electrical conductivity of the graphite, about 50 wt.% or greater, or about 60 wt.% or greater, or about 70 wt.% or greater, or about 80 wt.% or greater, or about 90 wt.% or greater, or about 95 wt.% or greater, or about 99 wt.% or greater, or about 99.9 wt.% or greater, such as about 80 wt.% to about 99.9 wt.%, or about 90 wt.% to about 99.9 wt.%, or about 95 wt.% to about 99.9 wt.%, or even 100 wt.%, each based on a total mass of the pitch. However, pitch with less than a majority of mesophase pitch may also be used in accordance with example embodiments. For example, thepitch used herein may have a mesophase pitch content of less than 5 wt.%. The mesophase content may be measured using polarized light microscopy.

[0057] In embodiments, the compositions of isotropic pitch may comprise: at least two monomers linked with at least one methylene bridge between each one of the at least two monomers, wherein each one of the at least monomers comprises one or more aromatic classes comprising one or more 5-membered rings, 6-membered rings, and any combination thereof, and wherein the isotropic pitch composition has a weight average molecular weight (Mw) of about 300 g / mol to about 1,500 g / mol, a softening point (Tsp) of 90 °C. or greater, and a micro carbon residue (MCR) of about 18 wt % or greater, based on the total weight of the isotropic pitch composition. The isotropic pitch compositions of the present disclosure are methylene-bridged aromatic oligomers produced by reacting aromatic feedstocks with formaldehyde or paraformaldehyde in the presence of acetic acid and sulfuric acid. Herein, the aromatic classes may comprise: unsubstituted aromatics and / or substituted aromatics selected from the group consisting of 1-ring aromatics (ARC1), 2-ring aromatics (ARC2), 3-ring aromatics (ARC3), 4 or more-ring aromatics (ARC4), 5-ring aromatics (ARC5), 6-ring aromatics (ARC6), 7-ring aromatics (ARC7), 8-ring aromatics (ARC8), 9-ring aromatics (ARC9), 10 or more-ring aromatics (ARC10+), and any combination thereof.

[0058] The substituted aromatics can be selected from the group consisting of C1 to C20 hydrocarbyl monosubstituted aromatics, C1to C20hydrocarbyl disubstituted aromatics, C1to C20hydrocarbyl trisubstituted aromatics, and any combination thereof, such as the substituted aromatics can be selected from the group consisting of C1to C10hydrocarbyl monosubstituted aromatics, C1 to C10 hydrocarbyl disubstituted aromatics, C1 to C10 hydrocarbyl trisubstituted aromatics, and any combination thereof, such as the substituted aromatics can be selected from the group consisting of C1 to C5 hydrocarbyl monosubstituted aromatics, C1 to C5 hydrocarbyl disubstituted aromatics, C1to C5hydrocarbyl trisubstituted aromatics, and any combination thereof The isotropic pitch compositions may be produced from well-defined, highly pure, and cost-effective substituted and / or non-substituted single-ring aromatic feedstocks, substituted and / or non-substituted polycyclic aromatic hydrocarbon (PAH) feedstocks, and any combination thereof. PAH may include two-ring aromatic feedstocks or multi-ring aromatic feedstocks (e.g., three ring aromatic feedstocks or greater).

[0059] The reaction conditions of the methods of making isotropic pitch can impact the molecular weight distribution and the softening point of the isotropic pitch compositions. Advantageously, methods of the present disclosure enable to control both properties by tuning the molar ratio of sulfuric acid and formaldehyde (or paraformaldehyde). The softening points of theisotropic pitch compositions can increase particularly with reaction time, the amount of sulfuric acid and formaldehyde (or paraformaldehyde). Further, little to no water is present in the reaction mixture, and any residual acids can be easily removed by filtration after washing the residue comprising the isotropic pitch composition with basic solution, thus facilitating the isolation of the said isotropic pitch composition as a highly pure material (i.e., starting materials quantitatively consumed, confirmed by mass spectrometry,1H NMR, and13C NMR spectra).

[0060] The isotropic pitch may be produced by distilling or thermally processing a feedstock comprising the heavy feedstock described herein. The distillation or thermal processes may be carried out in various process units such as visbreaker units. Visbreaker units are generally of two types, soaker or coil. The soaker type unit uses a heater ahead of a heat soak drum, which is a tank-like vessel fitted with internals to reduce back mixing and improve plug flow, in which the heated feed is held for a time sufficient to enable the desired degree of thermally-induced cracking to proceed. The coil visbreaker normally has a two-zone fired heater with the reaction zone formed by furnace coils through which the feed passes in plug flow. The soaker visbreaker operates at lower temperatures with longer residence times than the coil type visbreaker and, as a result, tends to have a lower energy requirement. The coil visbreaker, however, enables better control of the reaction conditions with varying feeds and can, moreover, be more easily decoked by steam-air decoking. In both cases, however, the cracking reactions are terminated by quenching and no resort is made to recycle. A coil unit typically operates at an outlet temperature of from about 700 °F to about 1100 °F (from about 371 °C to about 593 °C), outlet pressure from about 150 psig to about 750 psig, and a residence time in the coil from about 1 minute to about 20 minutes. A soaker unit typically operates at less harsh conditions with a furnace outlet temperature of from about 700 °F to about 900 °F (from about 371 °C to about 482 °C), an outlet pressure from about 45 psig to about 150 psig, and a residence time from about 5 minutes to about 10 minutes.

[0061] The resultant isotropic pitch may be characterized by its coking value and softening point. The isotropic pitches of the present disclosure may have a higher coking value for a similar softening point as compared to isotropic pitches produced with a traditional feedstock. The softening point may be determined by a ring and ball methods as described in ASTM D36 / D36M- 14e. The coking value may be determined by ASTM D4715-98.

[0062] In embodiments, the isotropic pitch may be blended with the modified heavy hydrocarbon oil mixed with the graphitization catalyst and optional additives to regulate the viscosity of the mixture and keep the graphitization catalysts suspended and avoid settling. A stable dispersion of the isotropic pitch blended with the modified heavy hydrocarbon oil mixed with the graphitization catalyst and optional additives may have a Zeta potential from about 30mV to about 1000 mV, from about 40 mV to about 500 mV, or from about 50 mV to about 100 mV, for example. The Zeta potential characterizes the dispersion of graphitization catalyst in the hydrocarbon oil or blend of hydrocarbon oil and isotropic pitch. The modified heavy hydrocarbon oil may be produced by the dispersion of the organometallic compound or isotropic pitch or coal tar pitch (or a mixture of these three) with optional organotin compounds, for example.

[0063] In some embodiments, the pitch may have a softening point of about 500 °C or below, or about 450 °C or below, or about 400 °C or below, or about 350 °C or below, or about 300 °C or below. In non-limiting examples, the softening point of the pitch may reside within a range of about 180 °C to about 500 °C, or about 250 °C to about 500 °C, about 250 °C to about 400 °C, or about 280 °C to about 400 °C, or about 180 °C to about 400 °C, or about 250 °C to about 330 °C, or about 300 °C to about 340 °C. As used herein, “glass transition temperature” (Tg) refers to a temperature or a range of temperature at which a material (e.g., a polymer substrate) changes from a rigid glassy material to a soft material. The Tg and the change in the heat capacity can be measured using the differential scanning calorimeter (DSC) technique. Tgrefers to a mid-point of the temperature at which a change in heat capacity is recorded on the second heating scan of a differential scanning calorimeter experiment at about 10 °C. / min heating and cooling rate. For purposes of the disclosure herein, Tg may be measured using, for example, thermal analysis TA INSTRUMENTS DISCOVERY DSC or TA INSTRUMENTS Q2000™, as indicated.

[0064] In some embodiments, the corresponding coking value may be the result of using a heavy feedstock. A first example of a resultant isotropic pitch may be characterized as having a coking value of about 55 wt.% to about 65 wt.% and a softening point of about 50 °C to about 125 °C. A second example of a resultant isotropic pitch may be characterized as having a coking value of about 65 wt.% to about 75 wt.% and a softening point of about 125 °C to about 175 °C. A third example of a resultant isotropic pitch may be characterized as having a coking value of from about 70 wt.% to about 80 wt.% and a softening point from about 175°C to about 200°C.

[0065] Any suitable technique may be used to process the modified heavy hydrocarbon fluids to produce pitch. Example techniques may include thermal or catalytic conversion of the modified heavy hydrocarbon fluids to pitch. For example, pitch production may include thermal and / or catalytic conversion of the modified heavy hydrocarbon fluid at elevated temperatures under vigorous stirring and long residence times to produce a pitch. High temperatures and vacuum may be required to effectively separate components of the crude pitch product to produce a finished pitch. In some embodiments, the elevated temperatures may range from about 250 °C to about 500 °C. High pressures and long residence times may also be necessary to produce a finishedpitch. In some embodiments, the pressures may range from about 1 psi to about 1000 psi with residence times ranging from about 1 second to about 10 hours. Example Coke

[0066] Examples may include processing the modified heavy hydrocarbon oil mixed with the graphitization catalyst and optional additives to produce coke before producing graphitic particles for battery applications. Coke may be produced by the coking of the modified heavy hydrocarbon fluids (or a derivative thereof) in any reactor including horizontal cokers, vertical coker, delayed coker, or any combination thereof. The coking reactor may comprise a vessel with a mixing attachment from the top that rotates in some embodiments. The vessel temperature may be increased from room temperature to 400 °C then 600 °C and finally to 900 °C using a temperature ramp rate of 2 to 5 °C / min, for example. The soaking time at each temperature may range from 1 hour to 30 hours or any value in between. The soaking time at each temperature may be from 0.5 hour to 30 hours, from 1 hour to 20 hours, from 1.5 hours to 10 hours, from 2 hour to 7 hours, for example. The loading of the vessel may range from 100 kg to 300 kg of material. The feed may be prepared using a high shear mixing device with a rotating element by adding at least one graphitization catalyst in a heavy hydrocarbon fluid to produce graphite. The mixture may comprise boron-containing additive, boric acid (around 1 μm) at 7 wt%, and calcined coke fines (around 1 μm) at 30 wt% to a pitch material (500-1000 μm), for example. The two materials may be mixed at a temperature starting at 300 °C and going up to 350 °C with the rotational element setting at 300 RPM, for example. The total mixing time may be around 30 seconds, for example.

[0067] For example, the coke product produced in the coking may comprise coke in an amount of about 20 wt. %, 25 wt. %, 35 wt. %, 40 wt. %, 50 wt. %, 60 wt. %, or more. In some embodiments, the coke comprises coke in an amount from about 25 wt. % to about 60 wt. %. Coke can be converted to graphite for use in electrodes by a graphitization process that includes heating to high temperatures above 2800 °C. Electrodes produced from coke are used in negative electrodes in lithium-ion batteries and in arc furnaces to melt steel.

[0068] The particular composition of the coke depends on a number of factors, including the particular coking conditions, such as the delayed coking conditions and feed composition. In some embodiments, the coke includes carbon in an amount from about 80 wt.% to about 98 wt.% based on a total weight of the coke.

[0069] The coking of the modified heavy hydrocarbon fluid to produce coke may include any suitable coking process. Coking is a refining process that includes thermal cracking of longer chain molecules into shorter chain molecules with excess carbon left behind in the form of coke, which can include pitch fines, petroleum coke, fluid coke, sponge coke, coal tar pitch coke, cokebreeze, biochar, gas pyrolysis coke, needle coke, for example. The coke have any dimensions including coke fines from 0.01 µm to 10,000 µm, from 0.1 µm to 1,000 µm, from 0.5 µm to 500 µm, from 1 µm to 250 µm, from 5 µm to 100 µm, from 10 µm to 75 µm, from 15 µm to 50 µm, or 20 µm to 30 µm, for example. Coking processes in modern refinery settings can typically be categorized as delayed coking or fluidized bed coking. In both processes, the feedstock is cracked to produce gas and liquid products, leaving behind coke. In delayed coking, the feedstock is heated and fed to a coking reactor (commonly referred to as a “coke drum”) where the cracking takes place. To remove the coke, alternating drums can be used. In fluidized coking, the feedstock is heating in the coking reactor where cracking takes place with coke transferred from the coking reactor to a heater as a fluidized solid.

[0070] The coking products produced from coking include a cracking effluent, which may include a gas, a liquid, or a mixture thereof. The cracking effluent can be fractionated or otherwise separated to form desirable product streams, such as coker gas (e.g., C4 and lighter hydrocarbons), coker naphtha, and coker gas oil. The coking products further include coke. Coke produced in a coking process is typically a carbonaceous solid material of which a majority is carbon. The particular composition of the coke depends on a number of factors, including the particular coking process, such as a delayed coker or fluidized coker. Additional components in the coke include hydrogen, nitrogen, sulfur, and heavy metals, such as aluminum, boron, calcium, chromium cobalt, iron, manganese, magnesium, molybdenum, nickel, potassium, phosphorous, silicon, sodium, titanium, and / or vanadium. Example Graphitic Particle Production

[0071] Example embodiments may process the carbonaceous precursor to form graphitic particles. As discussed above, the carbonaceous precursor may include, for example, coke and / or pitch. The graphitic particles may have a degree of graphitization of at least 90 % or above. The d002interlayer spacing and graphitization degree were evaluated using X-ray diffraction (XRD) patterns (based on the position of the graphite 002 peak). This high degree of graphitization may be achieved using graphitization temperature as low as 2500 °C instead of a conventional temperature of 3000 °C or above to achieve similar degree of graphitization without graphitization catalyst and battery performance enhancer, which saves energy and time.

[0072] The example process for forming battery grade graphitic particles from the carbonaceous particles may include carbonization followed by graphitization. For example, the large aromatic molecules in the coke and / or pitch may first be carbonized at a temperature of about 500 °C to about 1800 °C, or about 500 °C to about 1400 °C followed by subsequent conversion of the carbonized carbon to graphite in a graphitization process taking place at a highertemperature of about 2800 °C to about 3400 °C. Additional steps may include one or more of grinding, stabilizing, agglomeration, and / or deagglomeration.

[0073] In some embodiments, the carbonaceous precursors may be subjected to grinding and / or stabilization before carbonization and / or graphitization. The grinding may be performed in a grinding apparatus to produce a plurality of carbonaceous precursor particles. To facilitate the production of pitch particles, the pitch may be maintained at a temperature below the softening temperature in the grinding apparatus. Grinding may be utilized to facilitate preparation of the pitch particles herein. Any suitable grinding apparatus or technique may be used to facilitate production of pitch particles through pulverization of a pitch sample. The terms “grinding” and “pulverizing,” as well as grammatical variants thereof, are to be considered equivalent herein. Suitable grinding processes may employ a grinding apparatus that may be operated in a batchwise manner or a continuous manner. Batchwise grinding apparatuses may employ, for example, ball milling and like techniques. Continuous grinding apparatuses may employ, for example, jet milling, Wiley milling, extrusion, and related techniques. In particular examples, grinding in the disclosure herein may be performed by jet milling. Jet milling may be especially desirable since it typically produces narrow particle size distributions. Moreover, because jet milling equipment lacks blades and other direct contact grinding structures, there is a lower likelihood of introducing contaminants from the mill (e.g., due to micro abrasion of the milling equipment) compared to other types of grinding processes. In some embodiments, two or more grinding apparatuses may be used in combination with one another in implementing the embodiments of the present disclosure. For example, two or more jet mills or extruders in series may be utilized to achieve a desired particle size and / or two or more jet mills or extruders in parallel may be utilized to increase throughput.

[0074] After grinding, the carbonaceous precursor particles may be subjected to stabilization. Stabilization may be performed, for example, where in the carbonaceous precursor particles comprise pitch particles. For example, the pitch particle may be stabilized by a heat treatment to promote at least partial crosslinking in accordance with example embodiments. The pitch particles may be stabilized at any suitable temperatures. For example, the pitch particles may be heated in a low oxygen environment (e.g., 1 mol% oxygen to about 20 mol% oxygen). In some embodiments, the pitch particles may be heated to a temperature below the softening temperature of the pitch. In other embodiments, the pitch particles may be heated to a temperature above the softening temperature of the pitch. In some embodiments, the pitch particles may be heated to a to a temperature of 180 °C to 500 °C, for example, 200 °C to 450 °C, 200 °C to 300 °C, 200 °C to 250 °C, 250 °C to 300 °C, or 300 °C to 450 °C. When heated, the pitch particles may undergoat least some crosslinking with a concurrent increase in the softening temperature may occur upon crosslinking of the pitch.

[0075] The carbonaceous precursor particles formed from the grinding, which may also be stabilized and / or agglomerated, may further undergo carbonization in accordance with example embodiments. In carbonization, the carbonaceous particles may be pyrolyzed (e.g., carbonized) to form a carbon matrix comprising disordered carbon. In some embodiments, disordered carbon may be formed upon heating the pitch particles at a carbonization temperature under nitrogen, argon, or helium flow. In some embodiments, the carbonization may occur in a no-oxygen or very low-oxygen environment, for example, comprising 0.1 mol% oxygen or below, preferably in the presence of an inert gas environment. The carbonization temperature may range, for example, from 500 °C to 1800 °C, or 700 °C to 1800 °C, or 900 °C to 1500 °C, or 1000 °C to 1500 °C, or 900 °C to 1400 °C. Upon carbonization, the stickiness of the carbonaceous particles should dissipate, and the pitch particles solidify after cooling down to ambient temperature.

[0076] A small amount of mass loss may occur upon carbonization as the pitch particles form disordered carbon. Without being limited by theory or mechanism, the mass loss is believed to result from various reactions of the pitch that form gaseous products. Such reactions may include, for instance, dehydrogenation, polymerization with side chain loss and / or hydrogen production, condensation of aromatic rings, and decomposition of oxygen-containing groups. Gaseous products may include, for example, carbon monoxide, carbon dioxide, water vapor, hydrocarbon vapor, methane, and the like. Up to 20 wt % mass loss may occur during carbonization due to such reactions. Preferably, the amount of mass loss is 10 wt % or less, or 5 wt % or less, or 2 wt % or less.

[0077] After converting the carbonaceous precursor particles to carbonized particles, example embodiments may further include a de-agglomeration step, which may optionally be performed prior to graphitization. In deagglomeration, the carbonized particles may be broken into particles with a d50 ranging, for example, from 1 µm to 50 µm, from 5 µm to 35 µm, from 10 µm to 20 µm, from 12 µm to 18 µm, from 13 µm to 15 µm, or from 14 µm to 16 µm, for example. This may be accomplished by jet milling or crushing, for example. In some embodiments, jet milling may be especially desirable since it typically produces narrow particle size distributions. Other suitable grinding process may be used for deagglomeration, including impact mills and hammer mills. In accordance with some embodiments, the deagglomeration may be performed at ambient temperature and pressure but under a constant flow of nitrogen or air. However, other embodiments may perform deagglomeration at elevated temperatures and / or pressures.

[0078] Example embodiments may further include graphitization of the carbonized particles, which be performed after deagglomeration. Graphitization of the c carbonized particles may form graphitic particles in accordance with example embodiments. Graphitization occurs when the carbonized particles are heated to elevated temperatures, for example, above 2000 °C. This extreme heat triggers a rearrangement of carbon atoms, transforming the carbonized particles into graphite. The graphitization process imparts enhanced conductivity and other desirable properties to the particles.

[0079] In the absence of the graphitization catalyst, graphite may be formed from the carbonized particles carbon by heating to a higher temperature ranging from about 2800 °C to about 3400 °C, or about 2800 °C to about 3000 °C in a no-oxygen or very low-oxygen environment, preferably in the presence of an inert gas environment, over a time that may range up to about 24 hours, or up to about 48 hours, or even up to about 72 hours. By using a graphitization catalyst according to the disclosure herein, increased graphite yields may be realized at lower heating temperatures and / or over a shorter heating time.

[0080] In non-limiting examples, graphitization of the carbonized particles disclosed herein may take place at a graphitization temperature up to about 3400 °C, such as a graphitization temperature ranging from about 2000 °C to about 3400 °C, or about 2000 °C to about 2500 °C, or about 2500 °C to about 3000 °C, or about 2800 °C to about 3200 °C, or about 2200 °C to about 2800 °C, or even at a graphitization temperature lower than about 2000 °C but above the carbonization temperature. When utilizing a graphitization catalyst according to the disclosure herein, about 80 wt.% or more, or about 85 wt.% or more, or about 90 wt.% or more, or about 90 wt.% or more of the carbonaceous particles may undergo conversion into graphite. Under the foregoing conditions, the time period over which graphitization is conducted may be about 18 hours or less, or about 15 hours or less, or about 12 hours or less, or about 10 hours or less, or about 9 hours or less, or about 8 hours or less, or about 7 hours or less, or about 6 hours or less, or about 5 hours or less, or about 4 hours or less, or about 3 hours or less, or about 2 hours or less, or about 1 hour or less. In some examples, graphitization may take place at a graphitization temperature of about 3000 °C to about 3400 °C but over a short graphitization time of about 1 hour or less, or about 50 minutes or less, or about 40 minutes or less, or about 30 minutes or less, or about 20 minutes or less, or about 10 minutes or less.

[0081] The graphitic particles may include a graphitization catalyst. For example, at least one graphitization catalyst may be dispersed in the carbon matrix. In some embodiments, two or more graphitization catalysts may be dispersed in the carbon matrix. In addition, additional compositions additives including the conductive carbons may also be dispersed in the carbonmatrix. One specific example may include up to about 50 wt.% of a graphitization catalyst dispersed in a carbon matrix, wherein the graphitization catalyst may include a boron-containing graphitization catalyst and at least one of a silicon-containing and / or tin-containing and / or aluminum-containing additives. The loading of the boron-containing graphitization catalyst may range from 0.1 wt % to 10 wt %, or from 0.1 wt % to 5 wt %, or from 1 wt % to 5 wt %, based on a total mass of the graphitic particles. The loading of the tin-containing additives may range from 0.1 wt % to 50 wt %, or from 0.1 wt % to 25 wt %, or from 0.1 wt % to 10 wt %, based on a total mass of the graphitic particles. The loading of the silicon-containing additives may range from 0.1 wt % to 30 wt %, or from 0.1 wt % to 20 wt %, or from 0.1 wt % to 10 wt %, or from 1 wt % to 5 wt % based on a total mass of the graphitic particles. The loading of the aluminum- containing additive may range from 0.1 wt % to about 30 wt %, or from 0.1 wt % to 20 wt %, or from 0.1 wt % to 15 wt %, or from 1 wt % to 10 wt % based on a total mass of the graphitic particles. Additional Embodiments

[0001] Accordingly, the present disclosure may provide modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes. The methods and compositions may include any of the various features disclosed herein, including one or more of the following statements.

[0082] Embodiment 1. A modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes comprising a heavy hydrocarbon fluid in an amount of about 50 wt.% to about 99.9 wt.%, based on a total mass of the modified heavy hydrocarbon fluid, and a graphitization catalyst in an amount of about 0.1 wt.% to about 50 wt.%, based on a total mass of the modified heavy hydrocarbon fluid.

[0083] Embodiment 2. The modified heavy hydrocarbon fluid of embodiment 1, wherein the heavy hydrocarbon fluid comprises from 0.1 µm to 1000 µm of coke fines, and wherein the coke fines comprise at least one fine selected from the group consisting of a pitch fine coke, a petroleum coke, a fluid coke, a sponge coke, a coal tar pitch coke, a coke breeze, a biochar coke, a gas pyrolysis coke, and any combination thereof.

[0084] Embodiment 3. The modified heavy hydrocarbon fluid of embodiment 1 or embodiment 2, wherein the heavy hydrocarbon fluid comprises at least one hydrocarbon fluid selected from the group consisting of a hydrocarbon pyrolysis tar, an ethylene tar, an atmospheric residue, a vacuum residue, slurry oil, isotropic pitch, synthetic isotropic pitch, coal tar pitch, coal hydrogenated oil, and combinations thereof, wherein the heavy hydrocarbon fluid comprises 2- ring or 3-ring aromatic compounds in an amount of about 25 wt.% or greater, based on a total mass of the heavy hydrocarbon fluid.

[0085] Embodiment 4. The modified heavy hydrocarbon fluid of any preceding embodiment, wherein the graphitization catalyst is at least a catalyst precursor.

[0086] Embodiment 5. The modified heavy hydrocarbon fluid of any preceding embodiment, wherein the graphitization catalyst comprises a Group 13-containing graphitization catalyst and at least one additive.

[0087] Embodiment 6. The modified heavy hydrocarbon fluid of embodiment 5, wherein the at least one additive comprises at least one additive selected from the group consisting of a tin- containing additive, an aluminum-containing additive, a silicon-containing additive, a titanium- containing additive, and any combination thereof.

[0088] Embodiment 7. The modified heavy hydrocarbon fluid of any preceding embodiment, wherein the graphitization catalyst comprises an organic derivative of a metallic compound, wherein the organic derivative has an initial boiling point within about 5% of the initial boiling point of the heavy hydrocarbon fluid.

[0089] Embodiment 8. The modified heavy hydrocarbon fluid of any preceding embodiment, wherein the graphitization catalyst comprises an organo-catalyst having an initial boiling point within 50 °C of a final boiling point of the heavy hydrocarbon fluid.

[0090] Embodiment 9. The modified heavy hydrocarbon fluid of any preceding embodiment, further comprising at least one composition additive selected from the group consisting of a dispersant, a surfactant, conductive carbons, and any combination thereof.

[0091] Embodiment 10. A method for producing modified heavy hydrocarbon fluid for producing graphitic particles for negative electrode for lithium-ion batteries comprising: including at least one graphitization catalyst in a heavy hydrocarbon fluid to produce the modified heavy hydrocarbon fluid, wherein the at least one graphitization catalyst is included in an amount of about 0.1 wt.% to about 50 wt.%, based on a total mass of a carbonaceous precursor, and wherein the heavy hydrocarbon fluid has an initial boiling point of about 200 °C or greater.

[0092] Embodiment 11. The method of embodiment 10, further comprising mixing the at least one graphitization catalyst in the heavy hydrocarbon using a high shear mixing device, wherein the high shear mixing device is selected from a group of mixing devices consisting of an extruder, a bead mill mixer, a high shear homogenizer, and any combination thereof.

[0093] Embodiment 12. The method of any one of embodiments 10-11, further comprising heating the heavy hydrocarbon fluid above a softening point of the heavy hydrocarbon fluid in a high shear mixing device.

[0094] Embodiment 13. The method of any one of embodiments 10-12, further comprising mixing the heavy hydrocarbon fluid with the at least one graphitization catalyst for a mixing period of from about 10 seconds to about 10000 seconds.

[0095] Embodiment 14. The method of any one of embodiments 10-13, coking the mixture of the at least one graphitization catalyst in the heavy hydrocarbon fluid to produce graphite in a coking process that further comprises heating the mixture to at least 2 different heating temperatures, wherein there is a soaking time at each heating temperature from about 1 hour to about 20 hours.

[0096] Embodiment 15. The method of any one of embodiments 10-14, further comprising mixing the heavy hydrocarbon fluid with the at least one graphitization catalyst at a rotating speed from about 50 rotations-per-minute (rpm) to about 5000 rpm.

[0097] Embodiment 16. The method of any one of embodiments 10-15, wherein the graphitization catalyst comprises a Group 13-containing graphitization catalyst and at least one additive.

[0098] Embodiment 17. The method of embodiment 16, wherein the at least one additive comprises at least one additive selected from the group consisting of a tin-containing additive, an aluminum-containing additive, a silicon-containing additive, and combinations thereof.

[0099] Embodiment 18. The method of any one of embodiments 10-17, further comprising blending the modified heavy hydrocarbon fluid with at least an isotropic pitch.

[0100] Embodiment 19. The method of embodiment 18, wherein the blend of the modified heavy hydrocarbon fluid and the isotropic pitch has a Zeta potential from about 40 mV to about 100 mV.

[0101] Embodiment 20. A method for producing carbonaceous precursors for electrodes comprising: including a graphitization catalyst in a carbonaceous precursor, wherein the graphitization catalyst, is included in an amount of about 0.001 wt.% to about 50 wt.%, based on a total mass of the carbonaceous precursors.

[0102] Embodiment 21. The method of embodiment 20, further comprising processing a modified heavy hydrocarbon fluid to produce at least the carbonaceous precursors, wherein the modified heavy hydrocarbon fluid comprises: a heavy hydrocarbon fluid in an amount of about 70 wt.% to about 99.9 wt.%, based on the total mass of the modified heavy hydrocarbon fluid; and the graphitization catalyst, in an amount of about 0.01 wt.% to about 50 wt.%, based on the total mass of the modified heavy hydrocarbon fluid.

[0103] Embodiment 22. The method of embodiment 20 or embodiment 21, wherein the processing comprises heating the modified heavy hydrocarbon fluid at temperature above 400 °Cin at least one of a delayed coker, a needle coker, a vertical mixer with heat chamber with center electrode, a horizontal kiln with rotors or baffles inside, or any combination thereof..

[0104] Embodiment 23. The method of any one of embodiments 20-22, wherein the heavy hydrocarbon fluid comprises from 0.1 µm to 1000 µm of coke fines, and wherein the coke fines are selected from a group of coke fines consisting of a pitch fine coke, a petroleum coke, a fluid coke, a sponge coke, a coal tar pitch coke, a coke breeze, a biochar coke, a gas pyrolysis coke, and any combination thereof.

[0105] Embodiment 24. The method of any one of embodiments 20-23, wherein the carbonaceous precursor comprises from about 0.001 wt % to about 15 wt% of graphitization catalyst.

[0106] Embodiment 25. The method of any one of embodiments 20-24, wherein the heavy hydrocarbon fluid has a Bureau of Mines Co-relation Index (BMCI) of about 90 to about 160.

[0107] Embodiment 26. The method of any one of embodiments 20-25, wherein the graphitization catalyst comprises a boron-containing graphitization catalyst, and wherein the heavy hydrocarbon fluid further comprises at least one additional additive selected from the group consisting of a tin-containing graphitization catalyst, an aluminum-containing graphitization catalyst, a silicon-containing graphitization catalyst, and any combination thereof.

[0108] Embodiment 27. The method of any one of embodiments 20-26, wherein the graphitization catalyst comprises at least one compound selected from the group consisting of oxides and carbides, wherein the carbides comprise at least one carbide from the group of carbides consisting of iron, nickel, titanium, silicon, and boron.

[0109] Embodiment 28. The method of any one of embodiments 20-27, wherein the modified heavy hydrocarbon fluid further comprises at least one additional additive selected from the group of additives consisting of a tin-containing additive, an aluminum-containing additive, a silicon- containing additive, titanium-containing additive, and any combination thereof.

[0110] Embodiment 29. A method for producing graphitic materials for electrodes comprising: carbonizing at least one carbonaceous precursor to form at least carbonized particles by a process comprising heating the at least one carbonaceous precursor to a temperature of about 500 °C to about 1800 °C; and graphitizing at least a portion of the carbonized particles to form at least graphitic particles by a process comprising heating the at least one carbonaceous precursor to a temperature up to about 3400 °C, wherein the graphitic particles comprise a carbon matrix and two or more additives dispersed in the carbon matrix in an amount up to about 50%, based on a total mass of the graphitic particle.

[0111] Embodiment 30. The method of embodiment 29, wherein the temperature of the graphitizing is 3000 °C to about 3400 °C over a graphitization time of about 1 hour or less.

[0112] Embodiment 31. The method of embodiment 29 or embodiment 30, wherein the heating in the graphitization is to a temperature up to about 2800 °C.

[0113] Embodiment 32. The method of any one of embodiments 29-31, wherein the two or more additives comprises boron atoms and at least additional atoms dispersed in the carbon matrix, wherein the additional atoms comprise at least one additional atom selected from the group consisting of tin, aluminum, silicon, and combinations thereof.

[0114] Embodiment 33. The method of any one of embodiments 29-32, wherein the graphitic particles are for a negative anode of a lithium-ion battery, wherein the method further comprises: producing a green coke or a mesophase pitch using a modified heavy hydrocarbon fluid in a delayed coker, a needle coker, or a mesophase pitch reactor, wherein the modified heavy hydrocarbon fluid comprises at least one graphitization catalyst homogenously suspended therein; grinding the green coke or the mesophase pitch; wherein the at least one carbonaceous precursor that is carbonized comprises the ground green coke or ground mesophase pitch, wherein the carbonizing is done at a temperature of about 500 °C to about 1400 °C; and wherein the graphitizing is done at a temperature of about 1800 °C to about 3200 °C.

[0115] Embodiment 34. The method of any one of embodiments 29-33, wherein one of the two or more additives comprises conductive carbons in an amount from about 0.01 wt to about 10 wt%.

[0116] Embodiment 35. The method of any one of embodiments 29-34, wherein the graphitic particles comprise an interplanar d-spacing value d002 from about 3.354 Å to about 3.363 Å.

[0117] Embodiment 36. The method of any one of embodiments 29-35, wherein the graphitic particles have a degree of graphitization from about 89 % to about 100 %.

[0118] While the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure covers all combinations of all those embodiments. EXAMPLES

[0119] Physical properties of the coke and graphite made from a horizontal coking equipment and a vertical coking equipment were measured. The physical properties include the particle size distribution, true density, tap density, 5T compact density, specific surface area, volatile content, degree of graphitization, discharge capacity, and initial Columbic efficiency.

[0120] For example, X-Ray Diffraction (XRD) was used to estimate the degree of graphitization of the coke and graphite, the interplanar d-spacing values d002, and the ratio of peak intensities. Powder XRD was performed using Cu K-α radiation having a wavelength of 1.5406 Å. The 002- peak of graphite is located at a 2θ value of approximately 26°, where θ is the X-ray scattering angle. Based on the 2θ peak position of the 002-peak, the Bragg equation (Equation 1) was used to calculate the interplanar d-spacing values (d002). From the d002value, the extent of graphitization (G) was calculated using the Mering and Maire equation (Equation 2). In Equations 1 and 2, λ is the X-ray wavelength. λ = 2d002×sin θ (Equation 1) G = (0.3440-d002 / (0.3440-0.3354) (Equation 2)

[0121] The interplanar d-spacing values d002may be from 3.35 Angstrom (Å) to 3.37 Å, from 3.354 Å to 3.365 Å, from 3.357 Å to 3.362 Å, or from 3.358 Å to 3.36 Å, for example. When the interplanar d-spacing values d002 is within these ranges, the degree of graphitization of the coke and / or graphite is from 89 % to 100 %, from 90 % to 99 %, from 92 % to 98 %, from 94 % to 96 %, or any value in between. The extent of anisotropy was determined with the I(101) / I(100) peak ratio from XRD patterns. Id / IG, which is the ratio of the intensities of the d and G bands, was determined from Raman Spectroscopy. True density was measured using a helium pycnometer. Surface area was measured using BET analysis. Particle size was measured using laser diffraction.

[0122] The 5T compact density was acquired introducing a specific mass of powder into a die. The powder was subjected to 5 tons of pressure, and the thickness of the compacted powder was recorded. The density was then measured as the ratio between the mass of the powder and the total volume (calculated as the cross-sectional area of the die multiplied by the compaction).

[0123] The horizontal coking equipment used for this experiment comprises two consecutive barrels with a cooling barrel at the end. Each barrel consists of 5 heating zones. The temperature increased from 280 °C to 900 °C across the two barrels with a total residence time of up to 8 hours. The feeding rate ranged from 100 kg / h to 150 kg / h with a rotational speed between 15-35 Hz. The feed was prepared using a high shear mixing device with a rotating element by adding a boron- containing additive, boric acid (around 1 μm) at 7 wt%, to a pitch material (500-1000 μm). The two materials were mixed at a temperature starting at 300 °C and going up to 350 °C with the rotational element setting at 300 RPM. The total mixing time was around 30 seconds.

[0124] The samples were taken from the three different parts of the horizontal coker that represent different residence times: low (first zone), mid (second zone), and high residence time (third zone). The graphite product is based on the high residence time sample.Properties True Tap 5T Specific Volatile Degree of Discharge Initial f i l bic cy,

[0125] The horizontal coking setup allows to better control the volatiles content of the product by changing the temperatures across the different zones. The graphitized product resulting from the horizontal coking setup shows a high degree of graphitization, consistent with anode active materials used in lithium-ion batteries.

[0126] The same properties were measured and recorded in Table 2, but using vertical cokers instead. The two types of vertical coking equipment used for this experiment comprise a vessel with a mixing attachment from the top that rotates. The vessel temperature was increased from room temperature to 400 °C then 600 °C and finally to 900 °C using a temperature ramp rate of 2 to 5 °C / min. The soaking time at each temperature ranged between 1.5 to 10 hours. However, the soaking time at each temperature may have been from 0.5 hour to 30 hours, from 1 hour to 20 hours, from 2 hours to 10 hours, from 5 hour to 7 hours, for example. The loading of the vessel ranged between 100 kg to 300 kg of material. The feed was prepared using a high shear mixing device with a rotating element by adding a boron-containing additive, boric acid (around 1 μm) at 7 wt%, and calcined coke fines (around 1 μm) at 30 wt% to a pitch material (500-1000 μm). The two materials were mixed at a temperature starting at 300 °C and going up to 350 °C with the rotational element setting at 300 RPM. The total mixing time was around 30 seconds. Samples were generated using two types of vertical cokers with varying volumes. The first vertical coker was 15 L, whereas the second vertical coker was 1000 L. Graphite 1 and 2 use cokes from the first and second units as precursors, respectively.Properties True Tap 5T Specific Volatile Degree of Discharge Initial f i l bic cy,

[0127] The vertical coking setup with the attachment allows to control the morphology of the cokes produced. These unique coke precursors result in a final graphite material with varying surface and bulk properties while maintaining the high degree of graphitization and electrochemical performance that is required for lithium-ion battery applications.

[0128] The same properties were measured and recorded in Table 3 below, but using a delayed coking equipment instead. The delayed coking equipment used for this experiment comprises a drum that is 72 inches in length with a 3.5 inches outer diameter pipe and 0.216-inch wall thickness. The temperature at the top of the drum was set to 454 °C whereas the inlet temperature was 499 °C. The recycle tank was maintained at 399 °C. The drum was operated under 90 pounds per square inch gauge (psig) with a recycle stream of 80 % flow rate. The total residence time of the coking experiment was from 8 hours to 10 hours. The feed was prepared by adding a boron- containing additive, boric acid (around 1 μm) at 7 wt%, to a heavy hydrocarbon fluid, vacuum residue slurry oil, into a feed tank. The modified feed oil was constantly agitated in the tank to ensure well dispersion of the additive into the oil. The modified oil was then pumped into the drum.Properties True C t l t V l til D f

[0129] The results show that the additive content is maintained after the long delayed coking process. The graphite resulting from the coke exhibits good degree of graphitization and a high true density, making it a suitable material for lithium-ion battery applications.

[0130] While compositions, methods, and processes are described herein in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0131] All numerical values within the detailed description are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0132] Many alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and that when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

Claims

CLAIMS:

1. A modified heavy hydrocarbon fluid for producing coke and graphitic particles for electrodes comprising: a heavy hydrocarbon fluid in an amount of about 50 wt.% to about 99.9 wt.%, based on a total mass of the modified heavy hydrocarbon fluid; and a graphitization catalyst in an amount of about 0.1 wt.% to about 50 wt.%, based on the total mass of the modified heavy hydrocarbon fluid.

2. The modified heavy hydrocarbon fluid of claim 1, wherein the heavy hydrocarbon fluid comprises from 0.1 µm to 1000 µm of coke fines, and wherein the coke fines comprise at least one fine selected from the group consisting of a pitch fine coke, a petroleum coke, a fluid coke, a sponge coke, a coal tar pitch coke, a coke breeze, a biochar coke, a gas pyrolysis coke, and any combination thereof.

3. The modified heavy hydrocarbon fluid of claim 1 or claim 2, wherein the heavy hydrocarbon fluid comprises at least one hydrocarbon fluid selected from the group consisting of a hydrocarbon pyrolysis tar, an ethylene tar, an atmospheric residue, a vacuum residue, slurry oil, isotropic pitch, synthetic isotropic pitch, coal tar pitch, coal hydrogenated oil, and combinations thereof, wherein the heavy hydrocarbon fluid comprises 2-ring or 3-ring aromatic compounds in an amount of about 25 wt.% or greater, based on a total mass of the heavy hydrocarbon fluid.

4. The modified heavy hydrocarbon fluid of any one of claims 1-3, wherein the graphitization catalyst is at least a catalyst precursor.

5. The modified heavy hydrocarbon fluid of any one of claims 1-4, wherein the graphitization catalyst comprises a Group 13-containing graphitization catalyst and at least one additive.

6. The modified heavy hydrocarbon fluid of claim 5, wherein the at least one additive comprises at least one additive selected from the group consisting of a tin-containing additive, an aluminum- containing additive, a silicon-containing additive, a titanium-containing additive, and any combination thereof.. e odified heavy hydrocarbon fluid of any one of claims 1-6, wherein the graphitization catalyst comprises an organic derivative of a metallic compound, wherein the organic derivative has an initial boiling point within about 5% of the initial boiling point of the heavy hydrocarbon fluid.

8. The modified heavy hydrocarbon fluid of any one of claims 1-7, wherein the graphitization catalyst comprises an organo-catalyst having an initial boiling point within 50 °C of a final boiling point of the heavy hydrocarbon fluid.

9. The modified heavy hydrocarbon fluid of any one of claims 1-8, further comprising at least one composition additive selected from the group consisting of a dispersant, a surfactant, conductive carbons, and any combination thereof.

10. A method for producing modified heavy hydrocarbon fluid for producing graphitic particles for negative electrode for lithium-ion batteries comprising: including at least one graphitization catalyst in a heavy hydrocarbon fluid to produce the modified heavy hydrocarbon fluid, wherein the at least one graphitization catalyst is included in an amount of about 0.1 wt.% to about 50 wt.%, based on a total mass of a carbonaceous precursor, and wherein the heavy hydrocarbon fluid has an initial boiling point of about 200 °C or greater.

11. The method of claim 10, further comprising mixing the at least one graphitization catalyst in the heavy hydrocarbon using a high shear mixing device, wherein the high shear mixing device is selected from a group of mixing devices consisting of an extruder, a bead mill mixer, a high shear homogenizer, and any combination thereof.

12. The method of claim 10 or claim 11, further comprising heating the heavy hydrocarbon fluid above a softening point of the heavy hydrocarbon fluid in a high shear mixing device.

13. The method of any one of claims 10-12, further comprising mixing the heavy hydrocarbon fluid with the at least one graphitization catalyst for a mixing period of from about 10 seconds to about 10000 seconds.. e ethod of any one of claims 10-13, coking the mixture of the at least one graphitization catalyst in the heavy hydrocarbon fluid to produce graphite in a coking process that further comprises heating the mixture to at least 2 different heating temperatures, wherein there is a soaking time at each heating temperature from about 1 hour to about 20 hours.

15. The method of any one of claims 10-14, further comprising mixing the heavy hydrocarbon fluid with the at least one graphitization catalyst at a rotating speed from about 50 rotations-per-minute (rpm) to about 5000 rpm.

16. The method of any one of claims 10-15, wherein the graphitization catalyst comprises a Group 13-containing graphitization catalyst and at least one additive.

17. The method of claim 16, wherein the at least one additive comprises at least one additive selected from the group consisting of a tin-containing additive, an aluminum-containing additive, a silicon-containing additive, and combinations thereof.

18. The method of any one of claims 10-17, further comprising blending the modified heavy hydrocarbon fluid with at least an isotropic pitch.

19. The method of claim 18, wherein the blend of the modified heavy hydrocarbon fluid and the isotropic pitch has a Zeta potential from about 40 mV to about 100 mV.

20. A method for producing carbonaceous precursors for electrodes comprising: including a graphitization catalyst in a carbonaceous precursor, wherein the graphitization catalyst is included in an amount of about 0.001 wt.% to about 50 wt.%, based on a total mass of the carbonaceous precursors.

21. The method of claim 20, further comprising processing a modified heavy hydrocarbon fluid to produce at least the carbonaceous precursors, wherein the modified heavy hydrocarbon fluid comprises:a heavy hydrocarbon fluid in an amount of about 70 wt.% to about 99.9 wt.%, based o e o a ass of the modified heavy hydrocarbon fluid; and the graphitization catalyst, in an amount of about 0.01 wt.% to about 50 wt.%, based on the total mass of the modified heavy hydrocarbon fluid.

22. The method of claim 21, wherein the processing comprises heating the modified heavy hydrocarbon fluid at temperature above 400 °C in at least one of a delayed coker, a needle coker, a vertical mixer with heat chamber with center electrode, a horizontal kiln with rotors or baffles inside, or any combination thereof.

23. The method of claim 21 or claim 22, wherein the heavy hydrocarbon fluid comprises from 0.1 µm to 1000 µm of coke fines, and wherein the coke fines are selected from a group of coke fines consisting of a pitch fine coke, a petroleum coke, a fluid coke, a sponge coke, a coal tar pitch coke, a coke breeze, a biochar coke, a gas pyrolysis coke, and any combination thereof.

24. The method of claim 23, wherein the carbonaceous precursor comprises from about 0.001 wt % to about 15 wt% of graphitization catalyst.

25. The method of any one of claims 20-24, wherein the heavy hydrocarbon fluid has a Bureau of Mines Co-relation Index (BMCI) of about 90 to about 160.

26. The method of any one of claims 20-25, wherein the graphitization catalyst comprises a boron-containing graphitization catalyst, and wherein the heavy hydrocarbon fluid further comprises at least one additional additive selected from the group consisting of a tin-containing graphitization catalyst, an aluminum-containing graphitization catalyst, a silicon-containing graphitization catalyst, and any combination thereof.

27. The method of any one of claims 20-26, wherein the graphitization catalyst comprises at least one compound selected from the group consisting of oxides and carbides, wherein the carbides comprise at least one carbide from the group of carbides consisting of iron, nickel, titanium, silicon, and boron.. e ethod of any one of claims 20-27, wherein the modified heavy hydrocarbon fluid further comprises at least one additional additive selected from the group of additives consisting of a tin-containing additive, an aluminum-containing additive, a silicon-containing additive, titanium- containing additive, and any combination thereof.

29. A method for producing graphitic materials for electrodes comprising: carbonizing at least one carbonaceous precursor to form at least carbonized particles by a process comprising heating the at least one carbonaceous precursor to a temperature of about 500 °C to about 1800 °C; and graphitizing at least a portion of the carbonized particles to form at least graphitic particles by a process comprising heating the at least one carbonaceous precursor to a temperature up to about 3400 °C, wherein the graphitic particles comprise a carbon matrix and two or more additives dispersed in the carbon matrix in an amount up to about 50%, based on a total mass of the graphitic particle.

30. The method of claim 29, wherein the temperature of the graphitizing is 3000 °C to about 3400 °C over a graphitization time of about 1 hour or less.

31. The method of claim 29 or claim 30, wherein the heating in the graphitization is to a temperature up to about 2800 °C.

32. The method of any one of claims 29-31, wherein the two or more additives comprises boron atoms and at least additional atoms dispersed in the carbon matrix, wherein the additional atoms comprise at least one additional atom selected from the group consisting of tin, aluminum, silicon, and combinations thereof.

33. The method of any one of claims 29-32, wherein the graphitic particles are for a negative anode of a lithium-ion battery, wherein the method further comprises: producing a green coke or a mesophase pitch using a modified heavy hydrocarbon fluid in a delayed coker, a needle coker, or a mesophase pitch reactor, wherein the modified heavy hydrocarbon fluid comprises at least one graphitization catalyst homogenously suspended therein;grinding the green coke or the mesophase pitch; e e n the at least one carbonaceous precursor that is carbonized comprises the ground green coke or ground mesophase pitch, wherein the carbonizing is done at a temperature of about 500 °C to about 1400 °C; and wherein the graphitizing is done at a temperature of about 1800 °C to about 3200 °C.

34. The method of any one of claims 29-33, wherein one of the two or more additives comprises conductive carbons in an amount from about 0.01 wt to about 10 wt%.

35. The method of any one of claims 29-34, wherein the graphitic particles comprise an interplanar d-spacing value d002 from about 3.354 Å to about 3.363 Å.

36. The method of any one of claims 29-35, wherein the graphitic particles have a degree of graphitization from about 89 % to about 100 %.

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