Heat treatment of coke produced from carbon oxides.

Abstract

Using a process that also includes the production of methane from the reaction gas, carbon pitch or dry coke is produced by reacting a mixture of carbon dioxide and hydrogen in a reactor at a predetermined temperature and pressure while feeding an iron catalyst to the reactor. The reaction product is cooled. The vessel is heated at a predetermined rate and the reaction product can be graphitized in the reactor under reduced pressure while injecting an inert gas stream. The vessel is heated to a temperature of 1600°C to 2800°C and maintained at that temperature for several hours. The vessel is cooled, and the reaction product is removed.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 62 / 926,978, filed October 28, 2019, entitled "Process for Making Synthetic Graphite from Carbon Oxides," the disclosure of which is incorporated herein by this reference in its entirety. [Background technology]

[0002] There are various methods for producing different forms of carbon. For example, U.S. Patent No. 8,679,444, the specification of which is incorporated herein by reference, discloses a novel method for producing carbon fibers ("Noyes Process"), carbon nanotubes, amorphous carbon, and other forms. This disclosure has been extended to produce nanodiamonds (see U.S. Patent No. 9,475,699, the specification of which is incorporated herein by reference) and other forms of carbon. Because of the carbon capture and carbon production cost advantages of using the Noyes process, it would be useful to be able to adapt the Noyes process in such a way as to produce coke materials from carbon oxides (e.g., carbon monoxide and carbon dioxide). Previously, such coke production methods involved passing through a liquid phase. See H. Marsh Introductions to Carbon Science, Chapter 1, page 1, 3rd paragraph: "The former (coke) results from a carbonaceous precursor (e.g., pitch) that passes through a liquid phase during pyrolysis." The Noyes process CHO equilibrium diagram (see U.S. Pat. No. 8,679,444) shows the relationship between hydrocarbon pyrolysis, the Boudouard reaction, and the Bosch reaction.

[0003] The Boudouard and Bosch processes, under the appropriate conditions (i.e., temperature, catalyst, pressure, and gas composition), typically produce anisotropic carbon. This carbon is highly disordered (see Figure 16) and may be graphitizable (see Figure 36). See also H. Marsh's definition of graphitizable carbon, page 30, conclusion: "Graphitizable carbon has passed through a fluid phase during pyrolysis." The Boudouard or Bosch processes do not pass through a fluid phase at any point. Carbon produced using the Noyes process typically contains iron or other catalytic materials because it uses iron or other metals to catalyze a reaction. Depending on the application, it may be beneficial to remove this iron from the carbon product. There are also advantages to producing carbon with a lower surface area or a tighter structure. Therefore, it would be useful to have a way to take carbon and create products with different properties. Summary of the Invention

[0004] According to the present disclosure, the heat treatment process imparts different properties to the carbon feedstock. The carbon feedstock may be Noyes-process carbon (typically, this is carbon nanotubes and carbon fiber with some amorphous or possibly graphitic carbon as well), or other carbon forms. At present, it appears that various forms of carbon may be used, including naturally occurring graphitic carbon, other synthetically produced carbons (including carbon fiber, nanotubes, graphite, and amorphous carbon), and other carbon sources. One method for producing carbon pitch for use in graphitization is to produce coke material. According to this process, a reactant gas mixture of hydrogen and CO2 is heated and injected into a reactor. The presence of nickel, typically in the metallurgy of the piping used to construct the heat exchanger, triggers the Sabatier process reaction, in which a portion of the CO2 reacts with H2 to form methane. Within the reactor, CO2 and H2 react at temperatures of approximately 340°C and 715°C over catalytic materials such as iron, nickel, chromium, and other metals or metal alloys. At these temperatures, carbon oxides and methane are converted into solid carbon and water in the presence of the catalyst. The result is often a mixture of graphitic and pyrolytic carbon species. The ratio of these carbons can be varied by controlling the ratio of methane in the reactor. Pyrolytic carbon is formed during this part of the reaction by converting methane to solid carbon and hydrogen. Graphitic carbon is produced via the Bosch reaction. A catalyst feeder deposits the catalyst into the reactor.

[0005] As carbon is formed in the reactor, various morphologies can be produced by controlling the residence time in the reactor, for example, by converting carbon fibers into coke and its mixtures. The residence time is controlled by the flow rate of the reaction gas through the reactor. The resulting carbon product is then discharged from the reactor. The reaction gas is cooled, condensing water from the reaction gas. The resulting carbon (carbon pitch or coke) can then be used in a graphitization process. According to one embodiment of the disclosed method, coke or carbon pitch is placed in a crucible or other container made of a material capable of withstanding the temperatures involved in the method. The carbon and container are placed in a vacuum furnace, the vacuum pump is turned on, and the furnace is gradually brought to the desired temperature. For example, the furnace temperature can be increased by 20°C per minute until the processing temperature (usually above 1500°C) is reached. In some embodiments, the vacuum pump is then turned off, and a helium flow (or other relatively inert gas such as nitrogen, argon, or neon) is passed through the furnace. In other embodiments, no gas flow is used.

[0006] The furnace is maintained at the desired elevated temperature, often for several hours. The furnace is then cooled and the container is removed. Experiments described below have shown that the resulting carbon has significantly different properties than the original carbon before treatment. For example, testing of the resulting carbon has shown it to have significantly higher thermal and electrical conductivity, more consistent D-spacing, a smaller surface area, and lower iron content, in some experiments significantly less iron. Furthermore, examination of the TEM images of the product revealed that the resulting product had significantly "tighter" spacing, i.e., the carbon atoms appeared to be better aligned in a graphitic fashion.

[0007] This process differs in part from the previous Noyes process due to the use of a different catalyst and different gas feed rates in the reaction. For example, this process may use FeC, Fe2O3, and Fe3O4 rather than elemental iron. The gas feed rates are also different, as addressed in the experimental process described below. However, the end result is that carbon from carbon oxides can be captured or sequestered in the form of coke or carbon pitch. Producing large quantities of coke at competitive rates would greatly benefit steel production. In effect, this process allows steel mills to take carbon oxides emitted from the steel mill, convert them to elemental carbon, return the carbon (in the form of coke) to the blast furnace, and incorporate the captured carbon oxides into the steelmaking process (again, in the form of coke). [Brief explanation of the drawings]

[0008] [Figure 1-8] 1 shows SEM images of carbon feedstocks used in the experiments of the present disclosure. [Figure 9] 1-8 show energy dispersive spectroscopy ("EDS") graphs and charts illustrating the iron percentages of the samples shown in FIGS. [Figure 10-16] TEM image of the carbon raw material before heat treatment. [Figure 17-18] 14 shows a graph of the inner and outer D-spacings of the carbon feedstock shown in FIG. 13. [Figure 19-20] FIG. 17 shows a graph of the inner and outer D-spacings of the carbon feedstocks shown in FIG. 16. [Figure 21-24] TEM image of the product from the 1600° C. heat treatment is shown. [Figure 25-26] 24 shows a graph of the inner and outer D-spacings of the carbon products shown in FIG. 23. [Figure 27-30] TEM image of the product from the 2000°C heat treatment. [Figure 31-32] 31 shows a graph of the inner and outer D-spacings of the 2000° C. treated feedstock shown in FIG. 30. [Figure 33-36] TEM image of the product from the 2400° C. heat treatment is shown. [Figure 37-38] 37 shows a graph of the inner and outer D-spacings of the 2400° C. treated feedstock shown in FIG. 36. [Figure 39] Showing the surface area, density, conductivity, resistivity, EDS (energy dispersive spectroscopy), and TGA (thermographic analysis) of each of the three experimental products; and [Figure 40] 1 shows a diagrammatic representation of an exemplary process flow diagram. DETAILED DESCRIPTION OF THE INVENTION

[0009] This disclosure relates to the effect of heat treating carbon to remove iron and the change in carbon properties by thermally annealing material from a 0.3 ton reactor at different temperatures. In this case, a 0.3 ton reactor is used to make various forms of carbon. However, the process should work with other carbon forms, including those made using the iron acetate catalyzed process disclosed in U.S. Provisional Patent Application No. 62,444,587, the disclosure of which is incorporated herein by reference. Figures 1-8 show SEM images of the carbon feedstock used in this experiment. As shown, Figure 1 is at 5,000x magnification. Figure 2 is a portion of the material shown in Figure 1 but at 10,000x magnification. Figure 3 shows the feedstock carbon at 25,000x magnification. Small iron particles are highlighted in Figure 3. Figure 4 shows the feedstock at 50,000x magnification. Figure 5 shows different parts of the raw material at 5000 times magnification. Figure 6 shows the same part as Figure 5 but at a magnification of 10,000 times. Figures 7 and 8 are close-up images of the raw material shown in Figures 5 and 6, shown at magnifications of 25000 times and 50000 times respectively. Figure 9 shows graphs and charts of energy dispersive spectroscopy (「EDS」) showing the iron ratio of the samples shown in Figures 1 - 8. As shown therein, the iron content of the raw material carbon exceeded 12%. Such an iron content is acceptable if the carbon is intended to be used as coke. However, when the sample is heat-treated to form graphite, part of the heat treatment helps to reduce this iron content. The K ratio referred to in Figure 9 is the X-ray intensity ratio k = I unknown / I standard measured for each element, and calculated by applying matrix corrections for electron backscattering and energy loss (Z), X-ray absorption (A), characteristics and continuous wave induced secondary fluorescence X-rays (F) as originally developed for an electron probe microanalyzer (EPMA) equipped with a wavelength dispersive spectrometer (WDS), and calculating the concentration. By using the K ratio protocol, SEM / EDS has been shown to be able to match the accuracy and precision of EPMA / WDS for major components (concentration C > 0.1 mass fraction) and upper trace range (0.001 < C < 0.01) components even when significant peak interference occurs.

[0010] Figures 10 - 13 show the carbon raw material before heat treatment. By examining these images, especially Figures 12 and 13 in detail, it can be seen that the small pieces of the carbon raw material shown have relatively disordered carbon atoms. That is, the 「lines」 of carbon atoms are scattered and broken, and are not particularly straight except for short stretches. Also, by examining Figures 14 - 16 showing the pretreated carbon raw material in detail, it can be seen that they have the same characteristics.

[0011] Figures 17 and 18 are graphs of the D-spacings of the raw carbons shown in Figure 13. Figures 19 and 20 are graphs of the D-spacings of the carbon raw materials shown in Figure 16.

[0012] Heat Treatment Process Different samples of carbon (from the 0.3 ton per month reactor described above) were subjected to a heat treatment process. Three such experiments are briefly described below. The maximum temperatures in the three experiments were 1600°C, 2000°C, and 2400°C. In each case, the process involved placing 30 grams of carbon feedstock into a graphite crucible (graphite is used because it is known to be able to withstand the temperatures involved). The crucible and feedstock were placed into a vacuum furnace, the furnace was closed, and the vacuum pump was started. The temperature of the furnace was increased at approximately 20°C per minute. For the first two experiments (1600°C and 2000°C), the material was left in the furnace at the specified temperature for 4 hours. The furnace was then cooled to 150°C, the furnace was opened, and the material was allowed to cool to room temperature. The material was then removed from the furnace.

[0013] As outlined below, for the 2400°C experiment, after reaching a temperature of 2000°C, the furnace was held at that temperature long enough to thermally stabilize. The vacuum pump was turned off and a helium flow of 5 standard cubic feet per minute was started through the furnace. The furnace temperature was then increased again at a rate of approximately 20°C per minute until the internal temperature reached 2400°C. The furnace was held at 2400°C for 4 hours, after which it was cooled to 150°C, opened to return to room temperature, and the material removed.

[0014] In each experiment, after the set temperature was reached, the vacuum pump was turned off and a slow gas flow (approximately 5 cubic feet per second) was introduced into the furnace. The gases used were typically nitrogen up to temperatures of approximately 2000°C, argon from 2000°C to approximately 2400°C, and helium above 2400°C. The experiments were performed as follows, with the maximum temperature used as the heading and the experimental steps numbered: 1600℃ 1. Place 30g of material in a graphite crucible. 2. Place the crucible in a vacuum furnace. 3. Close the furnace. 4. Start the vacuum pump. 5. Start the furnace heating element. 6. Start the argon flow. 7. Raise the temperature inside the furnace at a rate of 20°C per minute. 8. Hold at 1600°C for 4 hours. 9. Cool the furnace to 150°C. 10. Open the furnace and allow the crucible to cool to room temperature. 11. Remove the material from the crucible. 2000℃ 1. Place 30g of material in a graphite crucible. 2. Place the crucible in a vacuum furnace. 3. Close the furnace. 4. Start the vacuum pump. 5. Start the furnace heating element. 6. Start the argon flow. 7. Raise the temperature inside the furnace at a rate of 20°C per minute. 8. Hold at 2000°C for 4 hours. 9. Cool the furnace to 150°C. 10. Open the furnace and allow the crucible to cool to room temperature. 11. Remove the material from the crucible. 2400℃ 1. Place 30g of material in a graphite crucible. 2. Place the crucible in a vacuum furnace. 3. Close the furnace. 4. Start the vacuum pump. 5. Start the furnace heating element. 6. Heat the furnace at a rate of 20°C per minute. 7. Hold at 2000°C, hold long enough to stabilize the temperature (nominally 30 minutes), and begin helium flow at 5 scfh [std ft3 / hr]. 8. Stop the vacuum pump. 9. Heat the furnace to 2400°C at a rate of 20°C per minute. 10. Hold at 2400°C for 4 hours. 11. Cool the furnace to 150°C. 12. Open the furnace and allow the crucible to cool to room temperature. 13. Remove the material from the crucible.

[0015] Figure 23, taken from a specific portion of the product shown in Figure 22, shows how the carbon atoms have been ordered. Note the graphitic carbon lines, which indicate much more ordered atomic carbon than the original carbon feedstock had. Figures 27 to 30 show TEM images of the products from the 2000°C heat treatment. The TEM images were taken using an HRTEM (High Resolution Transmission Electron Microscope) device. Figure 27 is at a magnification of 300,000 times, Figure 28 is at a magnification of 600,000 times, Figure 29 is at a magnification of 1 million times, and Figure 30 is at a magnification of 10 million times. Figure 30, taken from a specific portion of the product shown in Figures 28 and 29, shows how the carbon atoms have been ordered. Note the graphitic carbon lines, which indicate much more ordered atomic carbon than the original carbon feedstock had. Figures 31 and 32 plot the inner and outer D-spacings (respectively) of the 2000°C-treated material shown in Figure 30. This tighter D-spacing after treatment also indicates increased ordering of the C atoms. Further testing showed that the electrical conductivity of the carbon product improved, again indicating increased ordering of the carbon atoms in the 2000°C-treated carbon product. Figures 33 to 36 show TEM images of the products from the heat treatment at 2400°C. The TEM images were taken using an HRTEM (High Resolution Transmission Electron Microscope) device. Figure 33 is at a magnification of 600,000 times, Figure 34 is at a magnification of 1,000,000 times, Figure 35 is at a magnification of 5,000,000 times, and Figure 36 is at a magnification of 10,000,000 times. Figure 35, taken from a specific portion of the product shown in Figure 33, and Figure 36, taken from a specific portion of Figure 35, each show how the carbon atoms have been ordered. Note the relatively strong lines of graphitic carbon, indicating much more ordered atomic carbon than was present in the original carbon feedstock.

[0016] Figures 37 and 38 plot the inner and outer D-spacings (respectively) of the 2400°C-treated material shown in Figure 36. This D-spacing after treatment also shows increased order of the carbon atoms. Note in particular the regularity of the D-spacing, which is a significant improvement over that of the 2000°C-treated material.

[0017] The chart below shows the surface area, density, conductivity, resistivity, EDS (energy dispersive spectroscopy), and TGA (thermographic analysis) of the three experimental products, respectively. [Table 1] chart

[0018] Figure 39 plots the surface area (in square meters / gram) of the carbon feedstock (the dots or circles on the far left) and the experimental carbon products at 1600°C, 2000°C, and 2400°C. The iron content was also significantly reduced in the feedstock product processed at 2400°C. This indicates that the carbon morphology becomes more graphitic as the BET decreases (i.e., in the higher temperature samples). It seems likely that the carbon products would become even more graphitic if experiments were conducted at even higher temperatures. The carbon used for graphitization by the present process can be produced by a variety of processes, but a preferred process is described herein. Figure 40 shows a schematic representation of an exemplary process flow diagram. The various elements shown in Figure 40 are categorized as follows: MFC: Mass flow controller CFM: Coriolis flow meter UGA: Universal Gas Analyzer VTA: Vent to atmosphere X1:Catalyst supply device E1: Heat exchanger E2: Heat exchanger H1:tubular furnace H2:tubular furnace R1: Fluidized bed reactor K2: Air compressor F1: Bag filter F2: Particulate guard filter E3: Glycol heat exchanger V3: Condensation tank V1: Pressure vessel (low pressure) V2: Pressure vessel (high pressure) E4: Heat exchanger K1: Recirculation compressor

[0019] As shown in Figure 40, H2 and CO2 enter the process through designated mass flow controllers (MFCs). The amount of gas entering the system is controlled to maintain the gas composition within the reaction process and can be from 0.1 standard liters per minute ("sl / m") to 40 sl / m of H2 and 2.0 sl / m to 38 sl / m of CO2. CO2 and H2 enter the process before (upstream of) the Coriolis flow meter (CFM), where the mass balance is measured. A universal gas analyzer (UGA1) measures the composition of the reaction gas before the gas passes to reactor R1.

[0020] The gas composition entering the reaction process has a hydrogen content varying between 2% and 89.2%, a CO2 content varying between 2% and 60%, a CH4 content varying between 0.05% and 65.7%, and a CO content varying between 5% and 60%. These reaction gases enter the outer tube of the E1 tube-in-tube heat exchanger, where they are preheated by the hot gases exiting reactor R1, typically measured between 340°C and 550°C. Heat exchangers E1, E2, and the piping up to fluidized bed reactor R1 are made from INCONEL®, e.g., product name HASTELLOY®.

[0021] The catalytic material typically comprises less than about 22% by weight (wt%) chromium and less than about 14% by weight nickel (often less than about 8% by weight nickel). In some embodiments, the catalytic material comprises 316L stainless steel. 316L stainless steel comprises from about 16% by weight chromium to about 18.5% by weight chromium and from about 10% by weight nickel to about 14% by weight nickel.

[0022] When the reactant gas enters reactor R1, the Sabatier process begins as CO2 and H2 react in the presence of nickel in the metallurgy of the piping used in the construction of the heat exchanger.

number

[0023] A catalyst supply X1 deposits catalyst into reactor R1. Various grades of catalyst material can be used. For example, the catalyst material can be an iron-, chromium-, molybdenum-, cobalt-, tungsten-, or nickel-containing alloy or superalloy grade. Such materials are commercially available from a number of sources, for example, from Special Metals Corp. of New Hartford, New York, under the trade name INCONEL®, or from Haynes, Int'l, Inc. of Kokomo, Indiana, under the trade name HASTELLOY® (e.g., HASTELLOY® B-2, HASTELLOY® B-3, HASTELLOY® C-4, HASTELLOY® C-2000, HASTELLOY® C-22, HASTELLOY® C-276, HASTELLOY® G-30, HASTELLOY® N, or HASTELLOY® W), or as stainless steel.

[0024] In this example, using a 0.3 ton / month (carbon production) reactor, the catalyst feeder X1 was loaded with iron catalyst FeC, Fe2O3, or Fe3O4, and the iron feed rate to the reactor was 5 g / h to 50 g / h. Once carbon was formed in the reactor R1, various morphologies were produced by controlling the residence time within the reactor, e.g., by converting carbon fibers to coke or mixtures thereof. The residence time was controlled by the flow rate of the reaction gas through reactor R1, typically 40 sl / m to 215 sl / m. The resulting carbon product was then entrained in the gas stream and transported out of the reactor. The reaction gas exited reactor R1 and entered the inner tube of heat exchanger E1, where the reaction gas (and carbon) exiting the reactor was used to preheat the reaction gas passing from Coriolis flowmeter CFM1 to tubular furnaces H1 and H2.

[0025] The catalytic material can include stainless steel, where the catalyst typically includes less than about 22% by weight (wt%) chromium and less than about 14% by weight nickel (often less than about 8% by weight nickel). In some embodiments, the catalytic material includes 316L stainless steel. 316L stainless steel includes between about 16% by weight chromium and about 18.5% by weight chromium, and between about 10% by weight nickel and about 14% by weight nickel.

[0026] Compressed air from air compressor K2 is used at a controlled rate to cool the reaction gas (and carbon) exiting heat exchanger E1, avoiding thermal damage to the bag filter media used in bag filter housing F1. The reaction gas (and carbon) exiting heat exchanger E1 enters heat exchanger E2 and passes through its inner tube, while cooling air from compressor K2 passes through its outer tube. The compressed air used to cool the reaction gas is vented to the atmosphere (VTA) to dissipate its heat. The reaction gas passing through the inner tube of heat exchanger E2 must be kept sufficiently hot to prevent premature condensation of water from the reaction gas, i.e., before it enters heat exchanger E3. Particulate guard filter F2 captures any carbon not captured upstream by bag filter F1. Note that the water of reaction is the result of the reverse water-gas shift reaction.

[0027] The gas stream then flows downstream of baghouse filter F1 to glycol heat exchanger E3. From heat exchanger E3, the reaction gas enters condenser V3, where the reverse water-gas shift occurs. The water collected in condenser V3 is pumped to a carboy for disposal or use. The gas exiting condenser V3 then passes through a second Coriolis flowmeter, CFM2, where a mass balance is measured and then through Universal Gas Analyzer UGA2, which is used to determine the gas composition. Measurements from the first set of Coriolis flowmeters, CFM1 and UGA1, and the second set of Coriolis flowmeters, CFM2 and UGA2, allow the gas conversion of the entire process to be determined. Measurements during the above experiment indicated that the carbon conversion rate of the process ranged from 6.3 grams per hour to 1480.2 grams per hour.

[0028] The gas then flows to pressure vessel (low pressure) V1, the low-pressure side of recycle compressor K1, which is used to circulate the gas through the closed-loop process. The gas is then pressurized by compressor K1 to the required process pressure. Pressure vessel (high pressure) V2 acts as a stabilizer, removing gas pulses from compressor K1. Heat exchanger E4 is used to cool the gas from the high-pressure side of the compressor and protect the flow valves used to control the pressure in the system. [Example]

[0029] Carbon dioxide and hydrogen were fed into a continuous flow reactor at a temperature of 590°C and a pressure of 50 psi. The CO feed rate was set at 2.2 sl / m and the H feed rate at 8.7 sl / m. The iron catalyst feed rate was set at 5 grams per hour. These conditions were used for 112 hours of operation. During this time, the average gas composition of the reactor was 29.2% H, 46.1% CH, 38.75% CO, and 47.2% CO. The gas composition was set to flow through the reactor at 128 sl / m. The reaction produced 7.74 kg of carbon pitch (or coke) over the 112-hour run time. Thus, according to the present disclosure, processing of carbon feedstocks can be customized to produce carbon products with desired properties. That is, carbon produced as described herein can be heat treated to not only remove impurities but also to increase the graphitization of the carbon product, thereby increasing the electrical conductivity of the carbon product. Furthermore, these processes use carbon dioxide (such as that removed from refinery flue gas) to make carbon pitch for producing synthetic graphite, or "dry" coke from those very refinery reactor flue gases. This "dry" carbon pitch or coke is not produced from petroleum tar or other "wet" feedstocks as is conventionally known. Furthermore, the "dry" coke, which can then be used to make synthetic graphite, typically has a significant carbon fiber content, which can be increased or decreased based on the operating parameters of production.

[0030] While specific embodiments of the present invention have been described, those skilled in the art will recognize that various modifications and changes can be made by those skilled in the art without departing from the spirit and scope of the invention. The present invention may be embodied in other specific forms without departing from its structure, methods, or other essential characteristics as broadly described herein and as hereinafter claimed. The described embodiments are to be considered in all respects only as illustrative and not restrictive. Another aspect of the present invention may be as follows. [1] feeding a reaction mixture containing carbon dioxide and hydrogen into a reactor at a predetermined temperature and a predetermined pressure at a first predetermined feed rate, wherein a portion of the reaction mixture is converted to methane as the reaction mixture is fed into the reactor; feeding the catalyst to the reactor at a second predetermined feed rate; maintaining the reaction process for a predetermined period of time to produce a solid carbon reaction product; removing the solid carbon reaction product from the reactor and cooling the solid carbon reaction product; condensing water and other gaseous impurities from the solid carbon reaction product; placing a quantity of solid carbon reaction product into a reaction vessel; loading the reaction vessel into a vacuum furnace equipped with a vacuum pump; closing the furnace and beginning to heat the furnace to increase the temperature of the reaction vessel; starting the vacuum pump; increasing the temperature of the furnace at a first predetermined rate; maintaining the temperature of the reaction vessel at a first predetermined temperature for a first predetermined time; increasing the temperature of the furnace at a second predetermined rate until the reactor temperature reaches a second predetermined temperature; maintaining the reaction vessel temperature at a second predetermined temperature for a second predetermined time; cooling the reaction vessel at a rate sufficient to ensure that the treated solid carbon reaction product does not oxidize upon opening of the furnace; opening the furnace and allowing the reaction vessel to cool to a handling temperature; and removing the treated solid carbon reaction product from the reaction vessel; A method for producing synthetic graphite, comprising: [2] The method according to [1], further comprising the step of introducing a flow of a relatively inert gas into the furnace at a predetermined flow rate. [3] A method for treating a mixture of amorphous carbon and fibrous carbon to increase order and conductivity, comprising: placing a quantity of carbon-based material, including amorphous or fibrous carbon or a combination thereof, into a reaction vessel; loading the reaction vessel into a vacuum furnace equipped with a vacuum pump, closing the furnace, and starting to heat the furnace to increase the temperature of the reaction vessel; starting the vacuum pump; increasing the temperature of the furnace at a first predetermined rate; maintaining the temperature of the reaction vessel at a first predetermined temperature for a first predetermined time; increasing the temperature of the furnace at a second predetermined rate until the reactor temperature reaches a second predetermined temperature; maintaining the temperature of the reaction vessel at a second predetermined temperature for a second predetermined time; cooling the reaction vessel at a rate sufficient to ensure that the treated carbon-based material does not oxidize upon opening the furnace; opening the furnace and allowing the reaction vessel to cool to a handling temperature; and removing the carbon-based material from the reaction vessel; A method comprising: [4] The method according to [3], wherein the first predetermined rate is about 20°C per minute. [5] The method according to [3], wherein the first predetermined temperature is about 2000°C and the first predetermined time is about 30 minutes. [6] The method according to [3], wherein the second predetermined temperature is about 2400°C and the second predetermined rate is about 20°C per minute. [7] The method according to [3], wherein the second predetermined time is approximately 4 hours. [8] The method according to [3], further comprising the step of introducing a flow of a relatively inert gas into the furnace at a predetermined flow rate. [9] feeding a reaction mixture containing carbon dioxide and hydrogen into a reactor at a predetermined temperature and a predetermined pressure at a first predetermined feed rate, wherein a portion of the reaction mixture is converted to methane while the reaction mixture is being fed into the reactor; feeding the catalyst to the reactor at a second predetermined feed rate; maintaining the reaction process for a predetermined period of time to produce a predetermined amount of carbon pitch reaction product; removing the reaction product from the reactor and cooling the reaction product; condensing water and other gaseous impurities from the reaction products; and recovering the reaction product; A method for producing carbon pitch, comprising:

[10] The method according to [9] above, wherein the reaction mixture has a hydrogen content of 2% to 89.2% and a carbon dioxide content of 2% to 60%.

[11] The method according to [9], wherein after the reaction mixture is fed to the reactor, the converted methane constitutes 0.5% to 65.7% of the reaction mixture.

[12] The method according to [9] above, wherein the predetermined temperature is 340°C to 540°C.

[13] The method according to [9], wherein the predetermined pressure is 14 to 610 pounds per square inch.

[14] The method according to [9] above, wherein the predetermined time is 1 to 1250 hours.

Claims

1. feeding a reaction mixture comprising carbon dioxide and hydrogen to a reactor at a temperature of 340°C to 715°C and a pressure of 14 psi to 610 psi at a feed rate of 40 sl / m to 215 sl / m, wherein a portion of the reaction mixture is converted to methane as it is fed to the reactor; feeding an iron catalyst into the reactor at a feed rate of 5 grams / hour to 50 grams / hour; maintaining the reaction process for 1 to 1250 hours to produce a solid carbon reaction product; removing the solid carbon reaction product from the reactor and cooling the solid carbon reaction product; condensing water and other gaseous impurities from the solid carbon reaction product; placing the solid carbon reaction product in a reaction vessel; loading the reaction vessel into a vacuum furnace equipped with a vacuum pump; closing the furnace and beginning to heat the furnace to increase the temperature of the reaction vessel; starting the vacuum pump; increasing the temperature of the furnace at a rate of about 20°C per minute; maintaining the temperature of the reaction vessel at about 2000° C. for about 30 minutes; increasing the temperature of the furnace at a rate of about 20°C per minute until the reactor temperature reaches about 2400°C; maintaining the reactor temperature at about 2400°C for about 4 hours; cooling the reaction vessel at a rate sufficient to ensure that the treated solid carbon reaction product does not oxidize upon opening of the furnace; opening the furnace and allowing the reaction vessel to cool to a handling temperature; and removing the treated solid carbon reaction product from the reaction vessel; A method for producing synthetic graphite, comprising:

2. 10. The method of claim 1, wherein the temperature of the step of feeding the reaction mixture to the reactor is from 340°C to 590°C.

3. A method as described in claim 1 or 2, further comprising the step of introducing a flow of gas selected from helium, nitrogen, argon, and neon into the furnace.

4. The method of claim 3, wherein the step of introducing a flow of gas selected from helium, nitrogen, argon, and neon into the furnace is performed at a flow rate of approximately 5 cubic feet per second.

5. 1. A method for treating a mixture of amorphous carbon and fibrous carbon to increase order and conductivity, comprising: placing a carbon-based material including amorphous carbon and fibrous carbon into a reaction vessel; loading the reaction vessel into a vacuum furnace equipped with a vacuum pump; closing the furnace and beginning to heat the furnace to increase the temperature of the reaction vessel; starting the vacuum pump; increasing the temperature of the furnace at a rate of about 20°C per minute; maintaining the temperature of the reaction vessel at about 2000°C for about 30 minutes; increasing the temperature of the furnace at a rate of about 20°C per minute until the temperature of the reaction vessel reaches about 2400°C; maintaining the temperature of the reaction vessel at about 2400°C for about 4 hours; cooling the reaction vessel at a rate sufficient to ensure that the treated carbon-based material does not oxidize upon opening the furnace; opening the furnace and allowing the reaction vessel to cool to a handling temperature; and removing the treated carbon-based material from the reaction vessel; A method comprising:

6. The method of claim 5, further comprising introducing a flow of gas selected from helium, nitrogen, argon, and neon into the furnace.

7. The method of claim 6, wherein the step of introducing a flow of gas selected from helium, nitrogen, argon, and neon into the furnace is performed at a flow rate of approximately 5 cubic feet per second.

8. feeding a reaction mixture comprising carbon dioxide and hydrogen to a reactor at a temperature of 340°C to 715°C and a pressure of 14 psi to 610 psi at a feed rate of 40 sl / m to 215 sl / m, wherein a portion of the reaction mixture is converted to methane as it is fed to the reactor; feeding an iron catalyst into the reactor at a feed rate of 5 grams / hour to 50 grams / hour; maintaining the reaction process for 1 to 1250 hours to produce a carbon pitch reaction product; removing the reaction product from the reactor and cooling the reaction product; condensing water and other gaseous impurities from the reaction products; and recovering the reaction product; A method for producing carbon pitch, comprising:

9. 9. The method of claim 8, wherein the temperature of the step of feeding the reaction mixture to the reactor is from 340°C to 590°C.

10. 10. The process according to claim 8 or 9, wherein the reaction mixture has a hydrogen content of from 2% to 89.2% and a carbon dioxide content of from 2% to 60%.

11. 10. The process of claim 8 or 9, wherein the converted methane comprises 0.5% to 65.7% of the reaction mixture after it is fed to the reactor.

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