Ultrahigh temperature pyrolysis separation of hydrogen and carbon

Abstract

A continuous hydrocarbon pyrolysis process for producing hydrogen and carbon includes exposing a hydrocarbon feedstock to an oxygen-deficient combustion gas within a hydrocarbon pyrolysis zone. The temperature of combustion gas generated by the valveless pulse combustor is higher than 2400 DEG C. A residence time of the hydrocarbon feedstock and the combustion gas within the hydrocarbon pyrolysis zone is less than 30 seconds to pyrolyze the hydrocarbon feedstock and produce a gas comprising hydrogen and solid particles comprising carbon. The gas and solid particles exit the hydrocarbon pyrolysis zone at a temperature above 1200 DEG C. The heat exchanger cools the gas and solid particles to a temperature below 200 DEG C. The gas absorber removes unwanted gas molecules from the gas and produces an H2-containing gas having an H2 concentration greater than 80 vol% H2. The H2-containing gas is continuously introduced into the H2 consuming device.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 320,667, filed on March 16, 2022, entitled “PYROLYSIS SEPARATION OF HYDROGEN AND CARBON”. This prior application is incorporated herein by reference. Background Art

[0003] The present invention involves the pyrolysis of hydrocarbons at ultra-high temperatures in an oxygen-depleted or oxygen-deficient environment, allowing for the cost-effective harvesting of hydrogen and high-purity carbon with reduced or no greenhouse gas emissions.

[0004] There is growing interest in reducing greenhouse gas emissions. The main source of greenhouse gas emissions is the burning of gaseous, liquid and / or solid fossil fuels to produce heat. In power plants, the heat is usually converted into electricity through a turbine or direct drive. All fossil fuels are hydrocarbons, which means that the material has both carbon atoms and hydrogen atoms. For example, the chemical formula of methane is CH4, with 4 hydrogen atoms for every carbon atom. The atomic weight of carbon is 12g / mol, the atomic weight of hydrogen is 1g / mol, and the molecular weight of methane is 16g / mol. The weight percentage of carbon and hydrogen in methane is 75wt% carbon and 25wt% hydrogen.

[0005] According to stoichiometry, the balanced chemical reaction for methane combustion is:

[0006] CH4+2O2→CO2+2H2O.

[0007] According to stoichiometry, burning 1 mol of CH4 produces 1 mol of CO2. The molecular weight of carbon dioxide is 44 g / mol. Burning 1 mol (16 g) of CH4 produces 1 mol (44 g) of CO2.

[0008] There is a need to process hydrocarbons by efficient and economical methods to release hydrogen in the form of H2 gas while capturing most of the carbon in the form of solid carbon. Non-limiting examples of potential uses for the captured solid carbon include chemical feedstocks, carbon electrodes, high temperature refractory materials, and batteries. The battery market will continue to grow to support vehicle electrification and grid energy storage. These embodiments are not intended to limit the potential uses of the carbon produced by the methods described herein. The solid carbon can be sequestered to prevent it from being emitted into the air in the form of carbon dioxide. Sequestration would be the lowest value use of the carbon.

[0009] Hydrogen (H2) is the molecule with the lowest molecular weight at 2g / mol. It is not economically feasible to liquefy H2 for storage and transport. High-pressure tanks and pipelines are one of the methods discussed to increase the energy density of hydrogen transport and storage. High-pressure transport gas pipelines are usually made of metal, usually iron and steel. Hydrogen reacts with metals over time, causing them to become brittle. Brittle metals under high pressure are susceptible to damage. It is well known that natural gas pipelines will eventually begin to leak at most of their connections. If natural gas or methane, with a molecular weight of about 16g / mol, leaks easily, then hydrogen, with a lower molecular weight of 2g / mol, would be expected to leak just as much or significantly more. While leaking H2 would not be considered a greenhouse gas risk, unlike leaking CH4, the loss of H2 leaks during the transportation of H2 gas at high pressure over long distances is a significant economic risk.

[0010] Therefore, there is an urgent need to process hydrocarbons in an efficient and cost-effective manner to harvest high-quality hydrogen, carbon and other products. Hydrogen needs to be produced for immediate use so that there is little or no storage and transportation. Summary of the invention

[0011] The present invention relates to a method for converting gaseous, liquid and / or solid hydrocarbons into hydrogen and solid carbon while minimizing carbon dioxide emissions. The disclosed method involves rapid ultra-high temperature pyrolysis of hydrocarbons.

[0012] The disclosed hydrocarbon pyrolysis method produces hydrogen and carbon by exposing a hydrocarbon feedstock to a high temperature, oxygen-depleted combustion gas. As described below, in some embodiments, the high temperature, oxygen-depleted combustion gas is obtained from the combustion gas leaving a valveless pulse combustor (VPC) to pyrolyze the hydrocarbon feedstock and produce hydrogen and carbon.

[0013] The hydrocarbon pyrolysis process disclosed herein shows the pyrolysis of hydrocarbons in an oxygen-depleted gas at high temperatures (>2400° C.) and short residence times (<30 seconds) to produce hydrogen and carbon.

[0014] As used herein, the initial temperature of the term "high temperature oxygen-depleted combustion gas" is in the range of about 2400°C to about 3400°C or higher, i.e., about 2400°C, 2500°C, 2600°C, 2700°C, 2800°C, 2900°C, 3000°C, 3100°C, 3200°C, 3300°C, 3400°C or higher, wherein any of the stated values ​​may form the upper or lower limit of the range. As used herein, the term "ultra-high temperature" includes combustion gas temperatures above 3000°C. Upon initial contact with the hydrocarbon feedstock, the combustion gas immediately begins to cool because energy in the form of heat from the high temperature or ultra-high temperature combustion gas is transferred to the hydrocarbon feedstock to increase the temperature of the hydrocarbon feedstock.

[0015] As used herein, the terms "oxygen-depleted," "oxygen deficiency," or "very low excess oxygen" refer to less than about 4 vol%, 3 vol%, 2 vol%, 1 vol%, 0.5 vol%, 0.2 vol%, 0.1 vol% O2, wherein any of the stated values ​​may form the upper or lower limit of a range.

[0016] As used herein, the term "short residence time" refers to that the hydrocarbon feedstock is exposed to the high temperature oxygen-depleted gas for less than 30 seconds. Due to the transportation time within the process system equipment, the total time that the hydrocarbon feedstock is exposed to the high temperature may be greater than 1 second. The exposure time can be less than 30 seconds, 25 seconds, 20 seconds, 18 seconds, 16 seconds, 14 seconds, 12 seconds, 10 seconds, 9 seconds, 8 seconds, 7 seconds, 6 seconds, 5 seconds, 4 seconds, 3 seconds, 2 seconds and 1 second, wherein any of the values ​​can form the upper or lower limit of the range.

[0017] As used herein, the term "hydrocarbon" includes, but is not limited to, fossil fuels such as coal, oil and natural gas, wood, biogenic waste, and the like.

[0018] In some embodiments, the high temperature oxygen-depleted gas is obtained from the combustion gas discharged from a valveless pulse combustor (VPC) or a pulse jet to pyrolyze the hydrocarbon feedstock and produce hydrogen and carbon. The VPC not only provides hot combustion gas for the pyrolysis process, but the VPC also provides an acoustic energy source. The valveless pulse combustor generates pressure waves of about 20 Hz to 200 Hz to further improve the efficiency of the hydrocarbon processing separated by pyrolysis. Without being bound by theory, the pressure pulses in the form of acoustic energy added to the pyrolysis process by the VPC are used to improve the reaction kinetics of the various reactions occurring in the disclosed pyrolysis separation process of hydrogen and carbon.

[0019] In some embodiments, instead of using atmospheric air of about 20vol% oxygen and 80vol% nitrogen as the oxygen source for combustion in the VPC, the oxygen in the air is concentrated to an amount greater than 50vol% O2. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 60vol%. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 70vol%. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 75vol%. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 85vol%. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 90vol%. In some non-limiting embodiments, oxygen is concentrated to an amount greater than 93vol%. It should be understood that higher oxygen contents allow for higher flame temperatures and higher combustion gas temperatures.

[0020] The disclosed high temperature continuous process embodiments impart significant and unexpected value to the carbon fraction, thereby enabling and supporting the economic viability of this pyrolysis process to produce hydrogen. The hydrogen produced herein can be advantageously used as a combustion fuel or chemical reactant in a continuous process.

[0021] In some disclosed embodiments, hydrogen production is co-located adjacent to or near the point of hydrogen use as part of a continuous process, long-term H2 storage is not performed, and H2 transportation distances from the production point to nearby points of use at the pressure required for H2 gas use are short. By doing so, hydrogen storage requirements are minimized or eliminated. Transportation of hydrogen at the pressure required at the point of use is short distance.

[0022] Non-limiting potential uses of co-sited or point-of-use hydrogen production facilities include power generation. For example, the high temperature pyrolysis process can be scaled up to produce enough hydrogen to run a full-size power plant, such as 600MW. Smaller or larger power plant sizes can be supported. A 600MW power plant is a non-limiting example.

[0023] Another non-limiting potential use of co-located or point-of-use hydrogen production facilities includes hydrometallurgy, where hydrogen is used as part of the process of reducing metal ores to elemental metal form. Another non-limiting potential use of co-located hydrogen production facilities includes chemical processes that require hydrogen as a reactant, such as ammonia production processes.

[0024] Producing hydrogen on a commercial scale at the point of use while minimizing or eliminating CO2 emissions by producing a valuable solid carbon product rather than a CO2 waste gas is a significant advance in the art.

[0025] As used herein, wt% means percent by weight.

[0026] As used herein, vol% means volume percentage.

[0027] As used herein, mol% means molar percentage, i.e., the percentage based on the number of moles of gas molecules in the gas stream. In an ideal gas, vol% and mol% are equal.

[0028] As used herein, MTPH means metric tons per hour.

[0029] As used herein, VPC stands for Valveless Pulse Combustor.

[0030] As used herein, MW means megawatt.

[0031] As used herein, MM means millions.

[0032] As used herein, Btu means British Thermal Unit, which is equivalent to about 1055 joules.

[0033] As used herein, MAF means moisture and ash free.

[0034] As used herein, the expression [A], [B], [C] "and / or" [D] means that one or more instances connected by the expression "and / or" may appear alone or in combination. Thus, the expression [A] or [B] or [C] or [D] may appear alone or in combination of any two or more instances, such as [A] and [B], [A] and [C], [B] and [C], [A], [C] and [D], etc.

[0035] As used herein, unless expressly stated otherwise or clearly implied otherwise, the term "about" means a range of values ​​plus or minus 10% ("±10%"), for example, about 1.0 includes values ​​of 0.9 to 1.1.

[0036] Concentration, quantity and other numerical data can be represented or presented in range format herein.It should be understood that such range format is only used for convenience and simplicity, and therefore should be flexibly interpreted as not only including the numerical value clearly listed as the limit of the range, but also including all single numerical values ​​or sub-ranges contained in the range, as if each numerical value and sub-range are clearly listed.As an illustration, the numerical range of "about 1 to about 5" should be interpreted as not only including the value of about 1 to about 5 clearly listed, but also including the single value and sub-range in the indicated range.Therefore, included in the numerical range are single values ​​such as 2,3 and 4 and sub-ranges such as 1-3,2-4 and 3-5.The same principle applies to the range of only listing a numerical value.In addition, no matter how the described range or feature is, this explanation should be applicable.

[0037] References in this specification to "one embodiment," "an embodiment," or similar language mean that a particular feature, structure, or characteristic described in conjunction with that embodiment is included in at least one embodiment of the present invention. Therefore, the phrases "in one embodiment," "in one embodiment," and similar language appearing throughout the specification may, but do not necessarily, all refer to the same embodiment. Furthermore, although the following description relates to several embodiments and examples of various components and processes of the described invention, all described embodiments and examples are to be considered in all respects merely illustrative and not limiting in any way. Furthermore, the described features, structures, characteristics, processes, or methods of the present invention may be combined in any suitable manner in one or more embodiments.

[0038] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory descriptions and are not limitations of the claimed invention. It should be understood that the specific aspects and features of the disclosed invention can be freely combined with other specific aspects and features of the disclosed invention. It should be understood that the various embodiments are not limited to the arrangements and means shown in the drawings. It should also be understood that these embodiments can be combined, or other embodiments can be utilized, and unless otherwise stated, structural changes can be made without departing from the scope of the various embodiments of the present invention. Therefore, the following detailed description should not be considered restrictive. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to facilitate understanding of the implementation of the above and other features and advantages of the present invention, the invention briefly described above will be described in more detail with reference to the specific embodiments shown in the accompanying drawings. It should be understood that these drawings only depict typical embodiments of the present invention and are therefore not to be considered as limiting the scope thereof. The present invention will be described and explained with additional specificity and detail through the use of the accompanying drawings, in which:

[0040] Figure 1 A hydrocarbon pyrolysis process is shown wherein the hydrogen produced is directly consumed by a hydrogen combustion power plant.

[0041] Figure 2 Shows Figure 1 The method omits the cyclone gas / particle separator.

[0042] Figure 3 Shows Figure 1 A process having an optional secondary heating zone for the carbon particles exiting the underflow of the cyclone gas / particle separator and the baghouse gas / particle separator.

[0043] Figure 4 Shows Figure 1 A method wherein the replacement location of the gas treatment machine is located at the end of the method after the H2 power plant combusts the H2-containing gas.

[0044] Figure 5 Shows Figure 1 A method wherein a heat exchanger is installed after the H2 power generation device.

[0045] Figure 6 Shows Figure 5 A method wherein a fugitive particle scrubber and a gas absorption device are installed between a pyrolysis separation process of hydrogen and carbon and an H2 power generation device.

[0046] Figure 7 Shows Figure 5 A method wherein a fugitive particle scrubber and a gas absorption device are installed after the H2 power generation device. Figure 7Also shown is an optional secondary heating zone for the carbon particles exiting the cyclone gas / particle separator and baghouse gas / particle separator underflow.

[0047] Figure 8 Shows Figure 4 and Figure 7 A variation of the plant arrangement shown, where plant modules can be moved around in the process based on design goals. As shown, the gas handler is moved to the end of the approach process between the fugitive particle scrubber and the gas absorption plant.

[0048] Fig. 9 Shows Figure 3 and Figure 5 A variation of the plant arrangement shown, in which the gas treatment machine is moved closer to the end of the process.

[0049] Fig.10 Shows Figure 6 A variant of the method in which a H2-containing reaction gas is supplied to the hydrometallurgical production plant.

[0050] Fig.11 Shows Figure 6 A variant of the method in which the H 2 -containing reaction gas can be used as a reactant in a chemical production plant.

[0051] Fig.12 Transmission electron microscope (TEM) images and fast Fourier transform (FFT) insert images of three different magnifications of carbonized solid carbon particles leaving the process at 1200°C (sample S-1200, images a1, a2 and a3), graphitized solid carbon particles leaving the system at 2500°C (sample S-2500, images b1, b2 and b3), graphitized solid carbon particles leaving the system at 2700°C (sample S-2700, images c1, c2 and c3) and a reference synthetic graphite sample (G-ref, images d1, d2 and d3) are shown.

[0052] Fig.13A and 13B X-ray diffraction (XRD) patterns of heat treated samples S-1200, S-2500, S-2700 and graphite sample G-ref are shown.

[0053] Fig.14 Raman spectra of heat treated samples S-1200, S-2500, S-2700 and graphite sample G-ref are shown. DETAILED DESCRIPTION

[0054] The present disclosure relates to a continuous hydrocarbon pyrolysis process for producing hydrogen and carbon. The process includes exposing a hydrocarbon feedstock to an oxygen-depleted combustion gas in a hydrocarbon pyrolysis zone. The combustion gas is preferably produced by a valveless pulse burner. When the hydrocarbon feedstock and the combustion gas enter the hydrocarbon pyrolysis zone, the temperature of the combustion gas is greater than 2400° C. The residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds to pyrolyze the hydrocarbon feedstock and produce a gas containing hydrogen and solid particles containing carbon.

[0055] Figure 1 Embodiments of the disclosed hydrocarbon pyrolysis process are shown. Figure 1 The hydrocarbon pyrolysis process shown provides on-site production of H2 for local consumption of H2 by adjacent equipment. In the disclosed embodiment, the equipment is an H2 thermal power generation equipment. However, it should be understood that different equipment requiring a continuous source of H2 can be used.

[0056] A valveless pulse combustor (VPC) is used as a heat source for the pyrolysis process. The fuel and oxygen-containing gas stream are mixed in the combustion chamber of the VPC. The oxygen content in the oxygen-containing gas stream is concentrated, preferably greater than 85 vol%. In some embodiments, the oxygen content in the oxygen-containing gas stream is greater than 90 vol%. In some embodiments, the oxygen content in the oxygen-containing gas stream is greater than 93 vol%. If oxygen is concentrated from the atmosphere, almost all of the remaining gas in the oxygen-containing gas stream is N2. There are very small amounts of other gases. For example, CO2 from ambient air will also be present in the oxygen-containing gas stream in the low ppm range.

[0057] One advantage of VPCs is that they can operate at near stoichiometric combustion. This means that the oxygen content in the combustion gas leaving the VPC is very low. In some embodiments, the oxygen content in the combustion gas is less than 4vol% O2. In some embodiments, the oxygen content in the combustion gas is less than 3vol% O2. In some embodiments, the oxygen content in the combustion gas is less than 2vol% O2. The oxygen content in the combustion gas can even be less than 1vol%. For many combustion technologies, the oxygen in the combustion gas is typically greater than 5vol%, and can even be as high as 10vol% or more. If hydrocarbons are used as fuel, most burner technologies cannot operate with less than 2vol% O2 in the combustion gas and still produce low CO content. The presence of a large amount of CO indicates incomplete or insufficient combustion. At 2vol% O2, CO can be <100ppm. At <1vol% O2, CO can be less than 300ppm.

[0058] When the incoming oxygen-containing gas stream has >85 vol% oxygen, the temperature of the combustion gases can exceed 2400° C. At 90 vol% oxygen, the temperature of the combustion gases leaving the VPC can be as high as 3000° C. or higher. At 94 vol% oxygen, the temperature of the combustion gases leaving the VPC can be as high as 3300° C. or higher.

[0059] Non-limiting examples of methods for concentrating oxygen from air to produce oxygen-containing gases having an oxygen content > 85 vol% include pressure swing absorption, membrane absorption, vacuum pressure swing absorption, ionic liquid-based absorption, specialty liquid chemical-based absorption, aqueous salt gas absorption, and aqueous suspended solid gas absorption.

[0060] The fuel used by the VPC can be H2 gas. If hydrogen is used as the fuel, a portion of the hydrogen produced in the pyrolysis separation of hydrogen and carbon is diverted to the VPC as fuel to generate the heat required to drive the pyrolysis process to convert hydrocarbons into carbon and hydrogen. If H2 is burned in the VPC to generate the heat required for pyrolysis, steam will be the main gas component in the combustion gas, along with some N2 from the >85vol% O2 gas stream required for high temperature combustion. No carbon dioxide is produced when H2 is burned. The balanced chemical reaction for the stoichiometric combustion of H2 is:

[0061] 2H2+O2→2H2O.

[0062] The fuel used in VPC can be hydrocarbon gas, such as natural gas, methane, propane, etc. The fuel used can be solid hydrocarbon fuel, such as lignite, brown coal, sub-bituminous coal, bituminous coal, anthracite, wherein the coal is a dry powder with a moisture content of less than 1wt% and a particle size of less than 150μm. The fuel used can be solid hydrocarbon, such as solid biowaste from dry forest waste, farm waste, sawdust, wood chip waste, human or animal fecal waste, plastic waste, rubber waste, automobile tire waste, etc. The solid hydrocarbon fuel is a dry powder with a moisture content of less than 1wt% and a particle size of less than 150μm. The fuel used can be liquid hydrocarbon, such as gasoline, diesel, biodiesel, biofuel, waste cooking oil, etc.

[0063] The pyrolytic separation of carbon and hydrogen is accomplished when the hydrocarbon feedstock is injected into the combustion gas stream above 2400°C leaving the VPC. Because the O2 content in the combustion gas from the VPC is very low, for example, less than 2 vol%, and even more preferably less than 1 vol%, there is almost no O2 reacting with the hydrocarbon feedstock in the hydrocarbon pyrolysis zone. The reaction between the hydrocarbon feedstock and the trace amount of O2 in the combustion gas stream above 2400°C will produce CO or CO2 and produce a combustion gas stream that is essentially oxygen-free. The lack of oxygen in the combustion gas stream reduces the amount of carbon produced by the pyrolytic separation of hydrogen and carbon.

[0064] The combustion gas stream above 2400°C immediately heats the hydrocarbon feedstock to a temperature above 1200°C, which causes the hydrocarbon feedstock to undergo pyrolysis. The sonic pulses of the VPC facilitate energy transfer, thereby effectively and quickly heating the hydrocarbon feedstock. The feed rate of the hydrocarbon feedstock is controlled so that the combustion gas stream and particles leave the hydrocarbon pyrolysis zone at a temperature of>1200°C. In some embodiments, the combustion gas stream and particles leave the hydrocarbon pyrolysis zone at a temperature of>1300°C. In some embodiments, the combustion gas stream and particles leave the hydrocarbon pyrolysis zone at a temperature of>1400°C. In some embodiments, the combustion gas stream and particles leave the hydrocarbon pyrolysis zone at a temperature of>1500°C. In some embodiments, the combustion gas stream and particles leave the hydrocarbon pyrolysis zone at a temperature of>1600°C. In other words, if a larger amount of hydrocarbon feedstock is combined with the combustion gas stream, the combustion gas stream may have greater cooling. Similarly, if a smaller amount of hydrocarbon feedstock is mixed with the combustion gas stream, the combustion gas stream is less cooled, resulting in a higher temperature when the combustion gas stream and particles leave the hydrocarbon pyrolysis zone. Similarly, a hotter combustion gas stream may be able to heat and process a larger amount of hydrocarbon feedstock.

[0065] In some embodiments, the amount of hydrocarbon feedstock combined with the combustion gas stream is controlled so that the temperature of the gas and particles leaving the hydrocarbon pyrolysis zone is above 2500°C. When the particle temperature exceeds 2500°C, preferably in the range of 2700°C to 3000°C or higher, the solid carbon particles are converted from carbonized materials to layered graphitized materials. Under these conditions, the solid carbon particles are characterized by CHNSO analysis, carbon>98%. Characterized by X-ray diffraction (XRD), the graphitization percentage>80%. Operating at a sufficiently high temperature to graphitize the solid carbon particles results in the conversion of hydrocarbon feedstock into high-value solid carbon materials.

[0066] The higher the temperature of the combustion gas stream, the more work can be done on the incoming hydrocarbon feedstock because of the greater temperature difference between the combustion gas temperature and the >1200°C of solid carbon products and gases exiting the hydrocarbon pyrolysis zone.

[0067] The residence time of gas and particles in the hydrocarbon pyrolysis zone is less than 30 seconds. In non-limiting embodiments, the residence time of gas and particles in the hydrocarbon pyrolysis zone is less than 30 seconds, 25 seconds, 20 seconds, 18 seconds, 16 seconds, 14 seconds, 12 seconds, 10 seconds, 9 seconds, 8 seconds, 7 seconds, 6 seconds, 5 seconds, 4 seconds, 3 seconds, 2 seconds and 1 second, wherein any of the values ​​can form the upper or lower limit of the range. Due to the transportation time in the process system equipment, the total time that the hydrocarbon feedstock is exposed to high temperature may be greater than 1 second.

[0068] The hydrocarbon feedstock may be a hydrocarbon gas, such as natural gas, methane, propane, etc. The hydrocarbon feedstock used may be a solid hydrocarbon fuel, such as lignite, brown coal, sub-bituminous coal, bituminous coal, anthracite, wherein the coal is a dry powder with a moisture content of less than 1 wt% and a particle size of less than 500 μm. The hydrocarbon feedstock used may be a solid hydrocarbon, such as solid biowaste from dry forest waste, farm waste, human or animal fecal waste, etc. The hydrocarbon feedstock is a dry powder with a moisture content of less than 1 wt% and a particle size of less than 500 μm. The fuel used may be a liquid hydrocarbon, such as gasoline, diesel, biodiesel, biofuel, waste cooking oil, etc.

[0069] In the oxygen-depleted hydrocarbon pyrolysis zone, at temperatures above 600°C to 700°C, hydrocarbons begin to carbonize. Hydrocarbons are molecules composed of at least carbon and hydrogen. Methane is one of the simplest hydrocarbons, with the molecular formula CH4, which means that each methane molecule has one carbon atom and four hydrogen atoms. The carbonization of methane means that all atoms except carbon are driven away from the carbon atom, leaving only carbon. In the case of methane, one carbon atom and four hydrogen atoms do not leave the process as atoms. Instead, the other carbon atoms find each other and form a carbon matrix composed of 6-membered rings that stretch to form graphite-like layers. Multiple layers are then stacked on top of each other until enough carbon atoms are bound together to no longer exist as a gas and / or vapor. Solid particles are deposited from the gas and / or vapor phase to form submicron-sized solid particles with morphology and properties similar to different grades of carbon black. In contrast, the most common method for making carbon black from methane is to carbonize methane in a specialized incomplete combustion reaction, in which some of the methane is burned to produce heat to carbonize the remaining methane.

[0070] In the disclosed pyrolysis process, hydrocarbons are injected into a low oxygen content, high temperature combustion gas stream. There is virtually no oxygen to react with the hydrocarbons to burn and produce heat, CO or CO2, and H2O. As mentioned above, the small amount of O2 present (<1 vol% of the combustion gas) will do this, but then the O2 content is zero. In an O2-depleted environment, the hydrocarbons carbonize. Taking methane as an example, submicron-sized carbon black particles are almost entirely composed of carbon. There is no oxygen to burn the hydrogen atoms. As a result, the hydrogen atoms combine together to become H2 gas. The products of the pyrolysis reaction are solid carbon and H2 gas. If the temperature of the gases and carbon solids leaving the hydrocarbon pyrolysis zone is above 1200°C, carbonization is nearly complete, with the hydrocarbons separated into H2 gas and solid carbon particles.

[0071] If the hydrocarbon feedstock is solid, hydrocarbon gases, hydrocarbon vapors, H2 gas begin to destructively distill from the hydrocarbon feedstock solid at temperatures above about 300°C. The hydrocarbon gas may be methane, ethane, propane, etc. The hydrocarbon vapor may range from coal tar vapor to vapors of smaller organic compounds, such as ring structures like benzene, polycyclic organic molecules, and molecules that are liquid at room temperature, such as ethanol, methanol, decane, etc. These organic molecules are examples of solid and liquid hydrocarbons that can be destructively distilled from coal particles and exist in the gas phase. When these gases and vapors are heated to above 1200°C, they carbonize and produce H2 gas, other carbonized gases, and submicron particles similar to carbon black (such as those formed by the methane gas described above).

[0072] Large solid carbon particles remain in the solid hydrocarbon raw material particles. When the temperature of these carbon particles rises to above 1200°C, they carbonize and generate H2 gas, other carbonized gases and large carbon particles from the carbon particles.

[0073] It should be noted that solid hydrocarbons, such as dry coal or dry plant matter or dry manure, have a more complex molecular structure than the simple CH4 of methane. Such solid hydrocarbons are usually characterized in an instrument that measures the weight of carbon (C), hydrogen (H), nitrogen (N) and sulfur (S). The oxygen (O) weight % is then obtained by subtracting the sum of the C wt%, H wt%, N wt% and S wt% from 100 wt%, which is called the CHNSO analysis. The other carbonizing gases mentioned above are gases containing nitrogen, sulfur and oxygen, which are discharged from the carbon matrix as it is carbonized into increasingly pure carbon.

[0074] If the hydrocarbon feedstock is a liquid hydrocarbon, such as diesel, the liquid hydrocarbon is sprayed into the combustion gas stream at >2400°C in the form of fine droplets, preferably with a droplet size of less than 500 μm. The fine droplets of liquid hydrocarbon evaporate immediately. When the liquid hydrocarbon vapor is heated to above 1200°C, it carbonizes and produces H2 gas. Small amounts of other carbonized gases are also produced, depending on the N, S and O atoms present in the molecular structure of the liquid hydrocarbon. The production of submicron particles is similar to the formation of carbon black from methane gas. Small amounts of larger carbon char particles may also be formed.

[0075] Regardless of the hydrocarbon feedstock, carbon particles reaching >1200°C will be greater than 90 wt% carbon in a CHNSO analysis. For most hydrocarbon feedstocks, when the carbon particles reach >1200°C, the carbon content will be greater than 95 wt%.

[0076] After the hydrocarbon pyrolysis zone, the particle laden gas stream enters a heat exchanger that reduces the gas and particle temperature to <200°C. In some embodiments, the heat exchanger reduces the gas and particle temperature to less than 200°C, less than 175°C, less than 150°C, less than 125°C, or less than 100°C, wherein any of the stated values ​​may form the upper or lower limit of the range. Considering the ideal gas law and the equation PV=nRT, where P is pressure, V is volume, n is the number of moles of gas, R is the ideal gas constant, and T is the temperature in Kelvin, at constant pressure, reducing the temperature from 1200°C to 200°C will result in a volume reduction of approximately 3.1 times, T in / T out =(1200+273.15) / (200+273.15)=3.1. The volume reduction caused by cooling the gas allows for smaller downstream piping and equipment (including gas particle separators, gas handlers, gas scrubbers, gas adsorption, etc.). The bag house is a gas particle separator that operates continuously with a maximum temperature typically below 200°C, depending on the available bag material.

[0077] The heat captured from the heat exchanger has value that can be used to do work and otherwise make the disclosed method more efficient. Non-limiting uses for the recovered heat include preheating gases or raw materials, and generating superheated steam to drive a turbine to generate electricity.

[0078] The cooled particle laden gas then flows downstream to a gas / particle separation device. Typically, Figure 1 As shown, a cyclone separator will be used, followed by a bag house. If all particles are so small that almost none of them will leave the underflow of the cyclone separator, then only a bag house will be used, such as Figure 2 shown.

[0079] The carbon particles reaching >1200°C in the hydrocarbon pyrolysis zone are primarily amorphous solids of sp2 carbon, in which three carbons are connected by two single bonds and one double bond. The probes of an ohmmeter were placed on the particles, demonstrating that their resistance was less than about 20 ohms at 1 cm intervals. The 1 cm interval between the probes of the ohmmeter was spanned by many particles of the powdered carbon product. The packing density may be too low for physical electrical connections between the particles. It may be necessary to compress the powder to a greater packing density to measure the resistance of the carbon particles, especially the low packing density carbon black-like particles collected from the baghouse. The sp2 bonds are not ordered, but instead connect the carbon atoms in the particles together to form an amorphous solid. X-ray diffraction can show the beginning of a layered structure that is considered to be a low level of graphitization. No temperature of significant graphitization is reached in the hydrocarbon pyrolysis zone.

[0080] Figure 3 Shows the Figure 1An optional addition to a process wherein the carbon particles discharged from the underflow of a cyclone separator and / or bag house or some other gas / particle separation device enter a second heating zone. In the second heating zone, the carbon particles are raised to a temperature of >2200°C in a residence time of less than 10 minutes, preferably less than 5 minutes, and even more preferably less than 2 minutes. The heat source of the second heating zone can be any device capable of heating the carbon particles to the target temperature. A preferred method is an induction furnace. Another preferred method is an electric arc furnace. Heating the carbonized coal particles to >2200°C causes the amorphous structure to reorganize into a layered graphite structure. The graphitized carbon can be used as a feedstock for higher value markets, such as carbon refractory parts, carbon electrodes, battery production for the growing automotive and grid storage markets, etc.

[0081] Reference again Figure 1 The method shown, the cooled and particle-free gas then enters a gas treatment machine. The machine may be a single, two or multi-stage centrifugal fan. The machine may be a positive displacement blower. The machine may be a high capacity gas compressor, such as a screw compressor. The specific type of gas treatment machine will be selected based on the requirements of the overall system, as dictated by the vacuum required in the upstream portion of the system and the pressure required in the downstream portion of the system. Figure 1 In the process of pyrolysis separation of hydrogen and carbon, the gas treatment machine is located after the gas / particle separator equipment and before the downstream equipment that may exist in the process, and before the H2-containing gas use point equipment, such as Figure 1 The power generation equipment shown.

[0082] Figure 4 Another location of the gas treatment plant is shown, which is located at the end of the combined pyrolytic separation process of hydrogen and carbon and the combustion of the H2-containing gas in the H2 power plant.

[0083] exist Figure 1 In the process, the cooled and particle-free H2-containing gas is delivered to a nearby H2 power plant where it is burned in the presence of air of about 20 vol% O2 and 80 vol% N2. If there is any fugitive carbon monoxide in the gas stream, it will be burned to carbon dioxide. In addition to N2, any other non-oxide fugitive S or N gases may also be burned to their oxide forms. The H2 power plant may be a power plant that originally burned coal or liquid hydrocarbons, but which has undergone a conversion to burn hydrogen in the burner instead of the previous fuel. In this way, the base equipment and the capital invested in the equipment are preserved.

[0084] H2 power plants can burn H2 to produce superheated steam that drives turbines to generate electricity. H2 power plants can burn H2 and use the combustion gases to directly drive turbines to generate electricity.

[0085] exist Figure 1In the described system, CO2 emissions are minimized, including CO2 produced when burning hydrocarbons in the VPC to generate process heat, CO2 produced when carbonizing hydrocarbon feedstocks containing oxygen as part of the carbon matrix, and CO2 produced in the water gas shift reaction. The water gas reaction is a chemical reaction of steam and carbon in the high temperature combustion gas to produce H2 and carbon monoxide. A mixture of H2 and carbon monoxide is called water gas because this gas mixture is the product of the reaction of carbon and water. The water gas shift reaction is a reaction between carbon monoxide and steam to produce H2 and carbon dioxide. For historical reasons, it is called the water gas shift reaction, which converts the CO in the water gas into H2 and CO2 by exposing the CO in the water gas to steam. Therefore, the water gas with a composition of CO, H2 and possibly some CO2 is "shifted" to be mainly CO2, H2 and possibly some CO. The combustion steam can react with carbon in the form of carbon gas, carbon vapor and solid carbon to produce water gas, such as H2 and CO. The steam in the combustion gases can convert the CO of this water gas or the CO produced during the carbonization of hydrocarbons containing O in an organic matrix into H2 and CO2. Depending on the efficiency of the power plant, the CO2 produced by the above process is less than or about the same as the CO2 produced if the power plant is operated by burning the original fuel. This process also produces a carbon product, which, as already discussed, can be sold to existing or future markets.

[0086] The combustion exhaust gas from the H2 power generation equipment can be discharged into the air through the exhaust stack, such as Figure 1 The combustion gases are almost entirely steam and unreacted N2 from the incoming air according to the following combustion reaction:

[0087] 2H2+O2→2H2O+heat.

[0088] Or, if Figure 5 As shown, a high efficiency heat exchanger can be installed after the H2 power plant to cool the exhaust gas temperature to below 100°C, thereby condensing and saving a large amount of water from the steam in the combustion gases. If a two-stage turbine is installed, the heat exchanger can produce superheated steam, which can be used to generate electricity. By installing a two-stage turbine or several micro-turbines, the H2 power plant will begin to approach the efficiency of a combined cycle CNG power plant, rather than the initially lower efficiency of a coal or liquid hydrocarbon power plant.

[0089] The H2-containing gas leaving the pyrolysis separation process of hydrogen and carbon contains some N2 from the gas stream containing >85 vol% oxygen used to burn the hydrocarbons in the VPC. The combustion of hydrocarbon fuels in the VPC will produce some carbon dioxide. Carbonization of hydrocarbons can also produce CO and / or CO2 if oxygen is present in the molecular structure. The combustion water produced when burning hydrocarbon fuels will likely react with the hydrocarbon feedstock in the high temperature pyrolysis zone to produce CO and H2 and / or more preferably CO2 and H2. See the previous discussion on the water gas reaction and the water gas shift reaction.

[0090] Figure 6 A configuration is shown in which optional equipment is installed between the pyrolysis separation process of hydrogen and carbon and the H2 power plant to remove unwanted particles and gases, thereby providing a gas stream with greater than 90 vol% H2 to the H2 power plant. One set of equipment that can be used includes a fugitive particle scrubber. A combination of a cyclone separator and a bag filter house separates more than 99% of the particles from the gas stream. Some fugitive particle emissions may pass through the bag filter house. This is particularly true when a process produces submicron carbon black-like particles. If the fugitive particles are detrimental to the gas absorption equipment, a fugitive particle scrubber can be installed. The scrubber can be one of a variety of water spray-based scrubber designs. Another example of a scrubber that can be used is an electrostatic precipitator. These two suggestions are non-limiting examples.

[0091] After removing the fugitive particles, the gas absorption equipment removes other gases besides H2 to produce a gas stream of more than 80vol% or 90vol% H2 for the H2 power generation equipment. The gases that can be removed are N2, CO2, CO, SO x 、NO x , H2S, NH4, etc. These are non-limiting examples of gases that can be removed using gas absorption equipment. Methods for gas adsorption may include pressure swing adsorption, membrane adsorption, vacuum pressure swing adsorption, adsorption based on ionic liquids, adsorption based on ammonia liquids, aqueous salt gas adsorption, aqueous suspended solid gas adsorption, etc. These are non-limiting examples.

[0092] Many of the gases removed have value in the chemical industry. Therefore, the absorbed gas removed from the H2-containing gas can be stored on site until the tank is full and then shipped out as a product. The CO2 can be sold to the food processing industry or sequestered through various technologies to prevent it from entering the atmosphere as a greenhouse gas.

[0093] A gas stream of greater than 90 vol% H2 with fugitive particulates removed is an ideal fuel for new, high-efficiency turbine-based combined cycle H2 combustion power plants, rather than retrofitting existing coal-fired and liquid hydrocarbon-fired power plants.

[0094] Another way to install the device is as follows Figure 7As shown. The second heating zone shown indicates that the second heating zone may be present or absent in any configuration, depending on whether a carbonized product or a graphitized product is desired. The device shows that, as an alternative, a fugitive particle scrubber and a gas absorption device may be installed after the H2 power generation device. One example in which this configuration can be implemented is in a converted coal-fired power plant or a liquid hydrocarbon-fired power plant. The converted power plant burns coal gas containing H2. The ultimate goal is to limit the emission of carbon dioxide and other gases as much as possible. Therefore, the gas absorption device can be installed after the H2 power generation device to absorb CO2 and other target gases from the combined exhaust gas from the continuous process of pyrolysis separation of hydrogen and carbon until the combustion of the H2-containing gas.

[0095] Figure 8 for Figure 7 An alternative diagram is also Figure 4 A variation of this, showing that equipment modules can be moved around in the process based on design goals. The gas handler is moved to the near end of the process between the fugitive particle scrubber and the gas absorber. The type of gas handler will be selected based on the vacuum required for the upstream equipment and the pressure of the downstream equipment. The reason for placing the gas handler in this location is because the gas absorber may require high pressure. Potentially, for the basic process after the pyrolytic separation of hydrogen and carbon, in Figure 1 The locations shown may still require a gas handler.

[0096] Fig. 9 for Figure 3 and Figure 5 The second heating zone shown indicates that the second heating zone may be present or absent in any configuration, depending on whether a carbonized product or a graphitized product is desired. The gas treatment machine is moved toward the end of the process.

[0097] Fig.10 for Figure 6 A variant of the invention. After pyrolytic separation of hydrogen and carbon, a fugitive particle scrubber plant and a gas absorption plant produce a reaction gas containing more than 80 vol% H2. The reaction gas containing more than 80 vol% H2 can be used as a reactant in a hydrometallurgical production plant. In hydrometallurgy, H2 is used as a reducing agent to produce elemental metals from metal ores. The sequestration of the CO2 absorbed from the H2-containing gas makes it a commercial hydrometallurgical process with reduced, low or very low CO2 (greenhouse gas) emissions, depending on the capacity of the gas absorption plant.

[0098] Fig.11 for Figure 6A variant of the invention. After the pyrolytic separation of hydrogen and carbon, a fugitive particle scrubber device and a gas absorption device produce a reaction gas containing more than 90 vol% H2. The reaction gas containing more than 90 vol% H2 can be used as a reactant in a chemical production device. An example of a commercial process requiring large amounts of hydrogen is ammonia production. Depending on the capacity of the gas absorption device, the sequestration of the CO2 absorbed from the H2-containing gas makes this a chemical production process with reduced, low or very low CO2 (greenhouse gas) emissions.

[0099] It should be understood that the disclosed invention is not limited to Figure 1-11 Specific equipment arrangement shown. It should be understood that equipment modules can be moved around as the process changes, based on the design objectives of the disclosed invention.

[0100] According to the following different embodiments, other features and advantages of the present invention are apparent. The following examples illustrate different aspects and embodiments of the present invention, and how to make and practice them. These embodiments do not limit the claimed invention. Although methods and materials similar or equivalent to the methods and materials described herein can be used in the practice of the present invention, suitable methods and materials are described below. Based on this disclosure, those skilled in the art can identify and adopt other components and methods for implementing the present invention.

[0101] Example 1

[0102] 600MW is a common size for coal fired power plants. Table 1 lists the calculations of the heat required to produce 600MW of electricity in a coal fired power plant with an efficiency of 35%, in units of Btu / hr. The calculations summarized in Table 2 show that in order to operate a 600MW coal fired power plant with an efficiency of 35%, which burns the same coal used as the feedstock for the pyrolysis separation of hydrogen and carbon, 210.63MTPH of coal needs to be burned. For coal fired power plants, 35% efficiency is an average to high efficiency. The calculations summarized in Table 2 show that 210.63MTPH of as-received coal containing 10% moisture is burned to operate a 600MW coal fired power plant with an efficiency of 35%.

[0103] Table 1. In a 35% efficient coal fired power plant, 600MW of electricity is converted into the MM Btu / hr of heat required to produce the electricity.

[0104] 600 MW / hr power plant 35％ Efficiency of a typical coal-fired power plant 1,714 MW / hr Actual output 3,412,141 Btu / MW 5,849,384,571 Btu / hr for a 600MW power plant 5.12E+07 MMBtu / yr for a 600MW power plant

[0105] Table 2. MTPH of coal required to operate a 600MW coal-fired power plant at 35% efficiency

[0106]

[0107] The model coal is 5.0wt% ash and 10.0wt% moisture. 210.63MTPH Original Coal * (1-10.0% Moisture) * (1-5.0% Ash) 180.09 Moisture Ash-Free (MAF) Coal. Table 3 shows the mass balance of MTPH calculated for CO2 produced when burning 210.63MTPH of original coal with the CHNSO values ​​shown. This coal is the same coal used as the feedstock for pyrolysis to separate hydrogen and carbon, and can produce enough H2 gas to operate an on-site H2 power plant with an efficiency of 41%. 533.42MTPH CO2 is produced when burning 210.63MTPH original coal or 180.09MTPH MAF coal. 533.42MTPH CO2 represents the amount of CO2 produced if 210.63MTPH of original coal is burned in a 600MW coal-fired power plant with an efficiency of 35%.

[0108] Negative values ​​for O2 represent the amount of O2 required to react stoichiometrically with each element in the coal and burn it into oxide form. The total amount of oxygen required to burn coal is 452.50 MTPH.

[0109] Table 3. Mass balance of a 600MW coal-fired power plant burning MAF coal at 35% efficiency.

[0110]

[0111]

[0112] Example 2

[0113] Table 4 shows the mass balance for the pyrolytic separation of hydrogen and carbon using Pittsburgh 8 Seam Coal as a feedstock, which produces sufficient H2-containing fuel gas to drive a 600MW hydrogen power plant operating at 41% efficiency. The CHNSO analysis of the coal feedstock is 80.78wt% carbon, 5.24wt% hydrogen, 1.74wt% nitrogen, 2.09wt% sulfur and 10.15wt% oxygen on a MAF basis. The preferred moisture and ash content of the coal feedstock entering the pyrolytic separation process of hydrogen and carbon is <1wt% moisture and <10% ash. The mass balance summarized in Table 4 uses a 610.55MTPH coal feedstock with a moisture content of 0.5% and an ash content of 5.0%. A moisture content of 0.5% or less is a more preferred embodiment. An ash content of 5% or less is a preferred embodiment. The mass balance summarized in Table 4 below is with Figure 6 Match, Figure 6A combination of pyrolytic separation of hydrogen and carbon, gas absorption, and combustion of a fuel gas containing H2 in a nearby or on-site H2 power plant is shown, wherein H2 is produced on-site, no long-term storage of the H2 gas is performed, and the transportation distance of the H2 gas is very short.

[0114] Without CO2 gas absorption, the mass balance summary in Table 4 shows that the pyrolysis separation of hydrogen and carbon coupled to a 600MW H2 power plant with a 41% efficiency produces 307.5 MTPH of CO2. The mass balance of coal in Table 3 shows that a 600MW coal-fired power plant with a 35% efficiency produces 533.42 MTPH of CO2. (533.42-307.5) / 533.42=42.4%, and sufficient H2 is produced in the H2-containing fuel gas to operate a 600MW H2 power plant with a 41% efficiency without using any gas absorption equipment through pyrolysis separation of hydrogen and carbon, which reduces CO2 emissions by 42.4% compared to a 600MW coal-fired power plant with a 35% efficiency. One embodiment is a CO2 emission reduction of greater than 35%. Another embodiment is a CO2 emission reduction of greater than 40%. The mass balance also shows that after pyrolysis separation of H2 and carbon, the fuel gas is 69.13 vol% H2 gas. One embodiment is a fuel gas that is greater than 65% H2 gas.

[0115] The mass balance summary shows that 465.63 MTPH of carbon is produced in the pyrolysis separation of hydrogen and carbon, which produces enough H2 gas to power an H2 power plant with an efficiency of 41%. The carbon can be landfilled and sequestered. As mentioned earlier, the carbon has value in a variety of markets and can be easily sold into these markets and used to develop new markets.

[0116] Table 4. Mass balance for pyrolytic separation of hydrogen and carbon using Pittsburgh 8 coal as feedstock to produce fuel gas containing H2 for a 600 MW production facility with 41% efficiency.

[0117]

[0118]

[0119]

[0120]

[0121]

[0122] Gas absorption technology can be used after the pyrolytic separation of hydrogen and carbon. For example, absorbing 50% of all gases except H2 in the H2-containing fuel gas for an H2 power plant can change the composition of the H2-containing fuel gas to >80 vol% H2. The mass balance shows that when 50% of CO2 is absorbed in the gas absorption step, 153.75 MTPH of CO2 is emitted from the entire process. For 80% CO2 absorption, 61.75 MTPH CO2 will be emitted. For 90% CO2 absorption, 30.75 MTPH CO2 will be emitted. Table 5 shows the volume % of H2 in the H2-containing fuel gas and the MTPH CO2 remaining in the H2-containing fuel gas for 50% to 90% gas absorption and no gas absorption. For example, 50% gas absorption means that 50% of each gas except H2 in the H2-containing fuel gas is absorbed and removed from the gas stream. In addition, the percentage reduction in CO2 emissions for the pyrolysis separation of hydrogen and carbon with gas absorption is shown compared to CO2 produced in a 35% efficient 600MW coal-fired power plant using the same coal used in the pyrolysis separation of hydrogen and carbon to produce the H2-containing fuel gas for the on-site H2 power plant. It should be noted that the percentage of gas absorption is based on the number of moles or volume of gas, not on the mass of gas.

[0123] A 600MW coal-fired power plant operating at 35% efficiency will produce about 533.42 tons of CO2. At a 50% absorption rate for all gases except H2, 153.75MTPHCO2 is emitted after gas absorption for the pyrolysis separation device for hydrogen and carbon. When coal is used as a hydrocarbon feedstock, when 50% of the gases other than H2 gas are absorbed from the product fuel gas produced by the method described herein, the CO2 reduction is (533.42-153.75) / 533.42=71.2% compared to the emissions of a 600MW coal-fired power plant. After absorbing 50% of the non-H2 gases, the remaining fuel gas is 81.75vol% H2. Referring to the data shown in Table 5, one embodiment of the H2-containing fuel gas produced by the method is>80vol% H2. Another embodiment of the H2-containing fuel gas produced by the method is>90vol% H2. One result of the overall process combining pyrolysis separation of hydrogen and carbon and including gas absorption prior to the H2 power plant is a greater than 70% reduction in CO2 emissions compared to CO2 emissions from a 600MW coal-fired power plant using the same coal as feedstock. Another embodiment is a >80% reduction in CO2 emissions compared to a MW coal-fired power plant of the same size using the same coal as feedstock. Another embodiment is a >90% reduction in CO2 emissions compared to a MW coal-fired power plant of the same size using the same coal as feedstock.

[0124] Table 5. The comparison of the vol% H2 and MTPH CO2 summarized in the mass balance shown in Table 4 for the pyrolysis separation of hydrogen and carbon when gas absorption is added after pyrolysis shows the reduction in CO2 emissions compared to an equivalent sized MW coal-fired power plant.

[0125] Gas absorption% <![CDATA[vol% of H2]]> <![CDATA[MTPHCO2]]> <![CDATA[Reduction of CO2]]> 0％ 69.13％ 307.5 42.4％ 50％ 81.75％ 153.75 71.2％ 60％ 84.84％ 123 76.9％ 70％ 88.19％ 92.25 82.7％ 80％ 91.80％ 61.5 88.5％ 90％ 95.73％ 30.75 94.2％

[0126] Example 3

[0127] CNG can be processed by pyrolysis separation of carbon and hydrogen to produce H2 that can be burned in an H2 power plant. Table 6 lists the calculations for converting 600MW of electricity into the heat in Btu / hr required to produce 600MW of electricity in a combined cycle CNG fired power plant with an efficiency of 58%. The calculations summarized in Table 7 show that in order to operate a 600MW combined cycle CNG fired power plant with an efficiency of 58%, 79.04MTPH of CNG needs to be burned. The average efficiency of a combined cycle CNG fired power plant is 58%.

[0128] Table 6. In a 58% efficient combined cycle CNG fired power plant, 600 MW of electricity is converted into the MM Btu / hr of heat required to produce that electricity.

[0129] 600 MW / hr power plant 58％ Efficiency of a standard CNG power plant 1,034 MW / hr Actual output 3,412,141 Btu / MW 3,529,801,034 Btu / hr for a 600MW power plant 3.09E+07 MMBtu / yr for a 600MW power plant

[0130] Table 7. MTPH of CNG required to operate a 600MW combined cycle CNG fired power plant at 58% efficiency.

[0131]

[0132] Table 8 shows the mass balance for calculating the MTPH of CO2 produced when 79.04 MTPH is combusted. 79.04 MTPH of CNG produces 217.36 MTPH of CO2 when combusted. 217.36 MTPH represents the amount of CO2 that would be produced if 79.04 MTPH of CNG were combusted in a 600 MW combined cycle CNG combustion power plant with an efficiency of 58%. The negative value for O2 represents the amount of O2 required to react stoichiometrically with each element in the CNG and combust it into oxide forms. The total amount of oxygen required to combust CNG is 316.17 MTPH.

[0133] Table 8. Mass balance of CNG fired at a 600MW combined cycle CNG fired power plant with 58% efficiency.

[0134]

[0135]

[0136] Example 4

[0137] Table 9 shows the mass balance for the pyrolysis separation of hydrogen and carbon using compressed natural gas (CNG) as a feedstock, which produces enough H2 gas to drive a 600MW hydrogen power plant operating at 41% efficiency. Compressed natural gas is 75wt% carbon and 25wt% hydrogen. The mass balance summarized in Table 9 uses 130.63MTPH of CNG feedstock for the hydrocarbon pyrolysis separation process. The mass balance summarized in the following table is Figure 6 Match, Figure 6 A combination of pyrolytic separation of hydrogen and carbon, gas absorption, and combustion of the H2 gas in a nearby or on-site H2 power plant is shown, wherein the H2 is produced on-site, no storage of the H2 gas is performed, and the transportation distance of the H2 gas is very short.

[0138] If CO2 gas absorption is not performed, the mass balance shows that the pyrolytic separation of hydrogen and carbon coupled to a 600MW H2 power plant with a 41% efficiency produces 220.84MTPH of CO2. The mass balance of burning CNG in Table 8 shows that a 600MW combined cycle CNG combustion power plant with an efficiency of 58% produces 217.36MTPH of CO2. (217.36-220.84) / 217.36=-1.6%, and CO2 is reduced only by the pyrolytic separation process of hydrogen and carbon. In other words, due to the high efficiency of 58% of the combined cycle CNG combustion power plant, the amount of CO2 produced by the pyrolytic separation of hydrogen and carbon is approximately the same as the amount of CO2 produced by burning CNG in the combined cycle CNG combustion power plant. The mass balance also shows that after pyrolytic separation of H2 and carbon and before gas absorption, the fuel gas is 77.83vol% H2 gas. One embodiment is a fuel gas of greater than 70% H2 gas.

[0139] The mass balance summary shows that 72.87 MTPH of carbon is produced in the process of producing enough H2 gas to drive a H2 power plant with an efficiency of 41%. The particle size of the carbon is submicron, similar to carbon black. Producing a valuable solid carbon product while not producing significantly more CO2 than a high efficiency combined cycle CNG combustion power plant is an advantage of the power plant burning only CNG. As mentioned earlier, the carbon has value in a variety of markets and can be easily sold into those markets or used to develop new markets.

[0140] Table 9. Mass balance of pyrolytic separation of hydrogen and carbon using CNG as feedstock to produce fuel gas containing H2 for a 600 MW production plant with an efficiency of 41%.

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] Gas absorption technology can be used after the pyrolysis separation of hydrogen and carbon. 50% absorption of all gases except H2 produces a fuel gas for an H2 power plant with greater than 80 vol% H2. The mass balance shows that when 50% of CO2 is absorbed in the gas absorption step, 110.42 MTPH of CO2 is emitted from the entire process. For 80% CO2 absorption, 44.17 MTPH CO2 will be emitted. For 90% CO2 absorption, 22.08 MTPH CO2 will be emitted. When all other gases are absorbed at the percentages shown, Table 10 shows the vol% of H2 in the fuel gas, the MTPH CO2 remaining in the fuel gas, and the percentage of CO2 emission reduction compared to the CO2 produced in a 600MW combined cycle CNG combustion power plant with 58% efficiency. It should be noted that the percentage of gas absorption is based on the moles or volume of the gas, not on the mass of the gas. The following table shows the percentage of gas absorption other than H2 gas, from 50% to 90%.

[0147] If CNG is burned in a 600MW combined cycle CNG combustion power plant with an efficiency of 58%, about 217.36 tons of CO2 will be produced. If 50% of the gases other than hydrogen are absorbed from the fuel gas separated by pyrolysis of hydrocarbons, the CO2 will be reduced by (217.36-110.42) / 217.36=49.2% compared to the emissions of a combined cycle CNG combustion power plant with an efficiency of 58%. After absorbing 50% of the non-H2 gases, the remaining fuel gas is 87.53 vol% H2. Referring to the data in Table 10, one embodiment of the H2-containing fuel gas produced by pyrolysis separation of hydrogen and carbon plus gas absorption is>85 vol% H2. Another embodiment of the H2-containing fuel gas produced by pyrolysis separation of hydrogen and carbon plus gas absorption is>90 vol% H2. One result of the overall process combining pyrolytic separation of hydrogen and carbon with CNG as a feedstock and including gas absorption prior to the H2 power plant is a >50% reduction in CO2 emissions compared to an equivalent sized MW combined cycle CNG fired power plant. Another embodiment is a >60% reduction in CO2 emissions when the gas absorption technology is used in an equivalent sized MW combined cycle CNG fired power plant. Another embodiment is a >70% reduction in CO2 emissions when the gas absorption technology is used in an equivalent sized MW combined cycle CNG fired power plant. Another embodiment is a >80% reduction in CO2 emissions when the gas absorption technology is used in an equivalent sized MW combined cycle CNG fired power plant.

[0148] Table 10. The vol% H2 and MTPH CO2 comparisons shown in the mass balance summary shown in Table 9 for the pyrolysis separation of hydrogen and carbon when gas absorption is added after pyrolysis show the reduction in CO2 emissions compared to an equivalent sized MW coal-fired power plant.

[0149] Gas absorption% <![CDATA[vol% of H2]]> <![CDATA[MTPHCO2]]> <![CDATA[Reduction of CO2]]> 0％ 77.83％ 220.84 -1.6％ 50％ 87.53％ 110.42 49.2％ 60％ 89.77％ 88.34 59.4％ 70％ 92.13％ 66.25 69.5％ 80％ 94.61％ 44.17 79.7％ 90％ 97.23％ 22.08 89.8％

[0150] Example 5

[0151] Pittsburgh #8 coal seam coal is the hydrocarbon feedstock for the pyrolysis separation process of hydrogen and carbon disclosed herein. Solid carbon particles are separated and passed through a secondary heating zone. Table 11 lists three samples of carbonized solid carbon particles (S-1200) leaving the process at 1200°C, graphitized solid carbon particles (S-2500) leaving the system at 2500°C, graphitized solid carbon particles (S-2700) leaving the system at 2700°C, and a reference synthetic graphite (G-ref) made by a standard synthetic graphite process known in the industry. Other samples heated to different temperatures are also listed in Table 11, including 1000°C (S-1000), 1500°C (S-1500), 1800°C (S-1800), 2000°C (S-2000), and 2900°C (S-2900). Table 11 shows that high temperature heat treatment affects the carbon content of solid carbon particles. The carbon content ranges from 80.78% in the raw coal feedstock to 95.23% in the 1200°C product to >99% in samples treated above 2500°C. The CHNSO analysis is reported on a MAF basis. After high temperature treatment, i.e. above 2500°C, the ash content is less than 1 wt% at 2500°C and less than 0.13 wt% at 2700°C. Almost all the minerals in the coal samples, including clays, sulfides, carbonates, silica and sulfates, etc., evaporate as metals or compounds. As shown in Table 11, the low ash content of S-2500 and S-2700 is similar to the reference synthetic graphite G-ref. On a MAF basis, samples S-2500 and S-2700 as well as G-ref contain about 99.90 wt% carbon, while other elements are negligible. The data in Table 11 show that for treatments above 1200°C, the samples are carbonized with >95% carbon on a MAF basis. Samples with greater than 90% carbon on a MAF basis are also considered carbonized. Further analysis is required to show that the transformation from amorphous carbonized carbon to graphitized carbon occurs at higher temperatures, such as 2500°C and 2700°C. This analysis is shown below.

[0152] Table 11. Proximate and ultimate analysis of coal hydrocarbon feedstocks and samples processed at various high temperatures.

[0153]

[0154] M, water content

[0155] A. Ash content

[0156] VM, volatile matter content

[0157] FC, fixed carbon content

[0158] ad, air dry basis

[0159] d, dry basis

[0160] MAF, without moisture and ash

[0161] a , through the difference

[0162] C and O, the carbon contents of S-2500, S2700 and G-ref are over 100% and within the systematic error. The carbon contents were obtained by difference, assuming that the oxygen content of these samples was zero.

[0163] Fig.12 Transmission electron microscopy (TEM) images of all samples at three different magnifications for each sample. Fig.12 Images a1, a2, and a3 show the amorphous structure of S-1200 treated at 1200°C, where the fast Fourier transform (FFT) images are shown as hollow circles. After high temperature treatment, the high temperature samples S-2500 (images b1, b2, and b3) and S-2700 (images c1, c2, and c3) and the reference sample G-ref (images d1, d2, and d3) show an ordered layered structure mixed with some amorphous structures. The interlayer distance of S-2700 is about 0.34nm. The multiple groups of points with six-fold symmetry observed in the FFT images of S-2700 and G-ref indicate that there are more carbon layers compared to S-2500. This is consistent with the interlayer distance and average crystallite height analysis performed by XRD (Figure 13 and Table 12). G-ref shows a typical uniform microcrystalline structure, in which multiple groups of points with good six-fold symmetry are observed in the FFT image. The FFT images of S-2500 and S-2700 are not as clear as those of G-ref, indicating that some areas of the solid carbon particles are still amorphous.

[0164] Fig.13A and 13BThe XRD patterns of heat-treated samples S-1200, S-2500, S-2700 and G-ref are shown. Table 12 summarizes the relevant XRD data for each sample. S-1200 is a typical amorphous structure without an obvious crystal structure; as a result, no XRD data is shown in Table 12. The other samples show a graphite structure with a sharp peak at 26.5° and three small peaks at 42.3°, 44.3°, and 77.3°, corresponding to the (002), (100), (004), and (110) crystal planes of graphite, respectively. The peak intensity of G-ref is much greater than that of S-2500 and S2700, which means that it has a higher-order carbon structure. According to the Scherrer formula, the interlayer spacings of S-2500 and S-2700 are 0.3369 nm and 0.3366 nm, respectively, and the degree of graphitization is 82.69% to 85.59%, respectively. The degree of graphitization of G-ref is 88.49%. In one or more embodiments of the disclosed invention, the degree of graphitization is >80%. The data show that high processing temperatures can break bridge bonds in amorphous carbon produced at lower carbonization temperatures, such as below about 1200°C, and are critical to the morphological change of carbon layer stacking from amorphous carbon to graphite. S-2700 achieves a stacking height of 26.97nm with 81.12 interlayers, while S-2500 shows a lower stacking height of 19.26nm and 58.18 layers. The stacking height of 50.57nm of G-Ref with 151.34 interlayers is two to three times higher than that of S-2500 and S-2700. It is expected that higher processing temperatures (close to 3000°C) will bring graphite results (such as stacking height, number of layers, graphitization percentage, and FFT images) closer to those of the reference graphite sample G-ref. Depending on the target market, lower or higher processing temperatures can be selected to achieve more or less graphitization of carbon particles. It will be appreciated that the higher the degree of graphitization, the greater the expected value in the market. Higher processing temperatures may require higher operating costs and may also result in reduced production to achieve and maintain higher processing temperatures.

[0165] Table 12 Structural parameters of synthetic graphite samples

[0166]

[0167]

[0168] d (002) Calculated by the Bragg equation: d (002) =λ / 2sinθ (002) ;

[0169] Lc (002) is the average crystallite height: Lc (002) =0.89λ / (β 002) ×cosθ(002) );

[0170] N is the carbon layer accumulation in the microcrystal: N = Lc (002) / d (002) +1;

[0171] G is the degree of graphitization: G = (0.3340-d (002) ) / (0.3440-0.3354);

[0172] I D / I G It is the intensity of the D peak divided by the intensity of the G peak.

[0173] The Raman spectra of all samples were Fig.14 Shown in. 1358cm -1 The nearby D band represents defects and disorder at the edge of the graphene layer; 1590 cm -1 The G band at is the vibration of the CC bond in the plane of graphite carbon. D / I G Used to describe the degree of disorder in carbon structure. D / I G The values ​​are shown in Table 12. D / I G The S-1200 has a lower I / O ratio than the G-2500-1, which is 0.83. D / I G The G-ref sample has the least defects, and I D / I G The value is 0.10.2700cm -1 The nearby peaks are typical graphite peaks, which become more developed after high temperature treatment.

[0174] Compared with hydrocarbon feedstock, hydrocarbons are exposed to the high temperature pyrolysis separation process of hydrogen and carbon disclosed herein to produce carbon products with increased value. The increased value can be measured in different ways. For example, the increase in carbon content increases its value. Therefore, the carbon content can be increased from 75wt% in methane gas to a solid carbon product with a carbon content greater than 95wt% carbon or more. In the case of coal as a hydrocarbon feedstock, the carbon content can be increased from about 80wt% (containing other element impurities) to 95wt% carbon or more with the reduction of HNSO in the carbon matrix and the reduction of mineral contaminants. In the case of biowaste, wood and lignite, the carbon content of dry solid hydrocarbons can be as high as 50wt% or less. The high temperature pyrolysis separation process of hydrogen and carbon can produce carbon products from these solid hydrocarbon feedstocks, which have about 90wt% carbon or more, while removing HNSO and mineral contaminants. If heated to a sufficiently high temperature, above 2500°C and reaching 3000°C or more, the carbon content approaches and exceeds 99%. In addition, the characterization of graphitization of carbon can show a degree of graphitization of about 80% or more. The increase in the degree of graphitization can also be seen as an increase in commercial value. Carbonized carbon and graphitized solid carbon have a commercial value per ton on the market that is at least twice that of the raw hydrocarbon.

[0175] Implementation

[0176] Various embodiments are listed below. It should be understood that according to the scope of the present invention, the embodiments listed below can be combined with all aspects and other embodiments.

[0177] Embodiment 1. A continuous hydrocarbon pyrolysis method for producing hydrogen and carbon, comprising exposing a hydrocarbon feedstock to an oxygen-depleted combustion gas in a hydrocarbon pyrolysis zone, wherein the combustion gas is generated by a valveless pulse burner, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a combustion gas temperature greater than 2400°C, wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so as to pyrolyze the hydrocarbon feedstock and produce a gas containing hydrogen and solid particles containing carbon.

[0178] Embodiment 2. A hydrocarbon pyrolysis method according to Embodiment 1, wherein the hydrocarbon feedstock is selected from gaseous hydrocarbon materials, liquid hydrocarbon materials and solid hydrocarbon materials.

[0179] Embodiment 3. A hydrocarbon pyrolysis method according to Embodiment 1 or 2, wherein the valveless pulse burner is operated by burning a fuel and an oxygen source, the oxygen content of the oxygen source being greater than 50 vol% oxygen.

[0180] Embodiment 4. A hydrocarbon pyrolysis method according to Embodiment 1 or 2, wherein the oxygen content of the oxygen source is greater than 85 vol% oxygen.

[0181] Embodiment 5. A hydrocarbon pyrolysis method according to Embodiment 1 or 2, wherein the oxygen content of the oxygen source is greater than 90 vol% oxygen.

[0182] Embodiment 6. The hydrocarbon pyrolysis method according to any of the preceding embodiments, wherein the oxygen content of the oxygen-depleted combustion gas is less than 2 vol% oxygen.

[0183] Embodiment 7. The hydrocarbon pyrolysis process according to any of the preceding embodiments, wherein the oxygen content of the oxygen-depleted combustion gas is less than 1 vol% oxygen.

[0184] Embodiment 8. The hydrocarbon pyrolysis method according to any of the preceding embodiments, wherein the residence time in the hydrocarbon pyrolysis zone is less than 5 seconds.

[0185] Embodiment 9. The hydrocarbon pyrolysis method according to any of the preceding embodiments, wherein the residence time in the hydrocarbon pyrolysis zone is less than 2 seconds.

[0186] Embodiment 10. The hydrocarbon pyrolysis method according to any of the preceding embodiments, wherein the gas and solid particles produced in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200°C.

[0187] Embodiment 11. The hydrocarbon pyrolysis process of embodiment 10, comprising cooling the gas and solid particles leaving the hydrocarbon pyrolysis zone to a temperature below 200°C in a heat exchanger.

[0188] Embodiment 12. A hydrocarbon pyrolysis method according to Embodiment 11, wherein the hydrocarbon pyrolysis method comprises separating the solid particles from the gas.

[0189] Embodiment 13. A hydrocarbon pyrolysis method according to Embodiment 12, wherein the hydrocarbon pyrolysis method includes treating the gas to remove unwanted particles and gas molecules, thereby producing a H2-containing gas having an H2 concentration greater than 80 vol% H2.

[0190] Embodiment 14. A hydrocarbon pyrolysis method according to Embodiment 12, wherein the hydrocarbon pyrolysis method includes treating the gas to remove unwanted particles and gas molecules, thereby producing a H2-containing gas having an H2 concentration greater than 90 vol% H2.

[0191] Embodiment 15. A hydrocarbon pyrolysis method according to Embodiment 13, wherein the hydrocarbon pyrolysis method comprises continuously introducing the H2-containing gas into a power generation device without long-term storage.

[0192] Embodiment 16. A hydrocarbon pyrolysis method according to Embodiment 13, wherein the hydrocarbon pyrolysis method comprises continuously introducing the H2-containing gas into a hydrometallurgical production device without long-term storage.

[0193] Embodiment 17. A hydrocarbon pyrolysis method according to Embodiment 14, wherein the hydrocarbon pyrolysis method comprises continuously introducing the H2-containing gas into a chemical production device without long-term storage.

[0194] Embodiment 18. A hydrocarbon pyrolysis method according to Embodiment 12, wherein the carbon content of the solid particles as characterized by CHNSO analysis is greater than 90 wt%.

[0195] Embodiment 19. The hydrocarbon pyrolysis method according to Embodiment 12, wherein the hydrocarbon pyrolysis method comprises heating the solid particles to a temperature greater than 2500°C.

[0196] Embodiment 20. The hydrocarbon pyrolysis method of Embodiment 19, wherein the solid particles comprise carbon having a graphitization percentage greater than 80% as characterized by X-ray diffraction.

[0197] Embodiment 21. A system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon, comprising: a valveless pulse burner, which burns fuel and an oxygen source to produce combustion gas, wherein the oxygen source includes an oxygen content greater than 85 vol% oxygen, and wherein the combustion gas is oxygen-depleted; a hydrocarbon pyrolysis zone, which is configured to receive the combustion gas and a certain amount of hydrocarbon feedstock, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a temperature greater than 2400°C, wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so that the hydrocarbon feedstock is pyrolyzed and produces gas and solid particles containing hydrogen and carbon, wherein the gas and solid particles produced in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200°C; and a heat exchanger, which is configured to cool the gas and solid particles leaving the hydrocarbon pyrolysis zone to a temperature below 200°C.

[0198] Embodiment 22. A system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to Embodiment 21, wherein the system includes a gas / particle separator to separate solid particles from the gas.

[0199] Embodiment 23. A system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to Embodiment 22, wherein the gas / particle separator is selected from a cyclone gas / particle separator and a baghouse gas / particle separator.

[0200] Embodiment 24. A system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to any of the preceding embodiments, the system comprising a gas absorber to remove unwanted gas molecules from the gas and produce an H2-containing gas having an H2 concentration greater than 80 vol% H2.

[0201] Embodiment 25. A combined system for continuous hydrocarbon pyrolysis to produce hydrogen and to receive and burn the hydrogen to generate electricity, comprising: a valveless pulse burner, the valveless pulse burner combusting a fuel and an oxygen source to produce a combustion gas, wherein the oxygen source comprises an oxygen content greater than 85 vol% oxygen, wherein the combustion gas is oxygen-depleted; a hydrocarbon pyrolysis zone, the hydrocarbon pyrolysis zone configured to receive the combustion gas and a certain amount of hydrocarbon feedstock, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so as to pyrolyze the hydrocarbon feedstock and produce a gas and solid particles comprising hydrogen and carbon, wherein the gas and solid particles generated in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200°C; a heat exchanger, which is configured to cool the gas and solid particles leaving the hydrocarbon pyrolysis zone to a temperature less than 200°C; a gas / particle separator, which is used to separate solid particles from the gas; a gas absorber, which is used to remove unwanted gas molecules from the gas and produce a continuous source of H2-containing gas with an H2 concentration greater than 80 vol% H2; and a power generation device, which is connected to the continuous source of H2-containing gas and burns the H2-containing gas to generate electricity.

[0202] The described embodiments and examples are to be considered in every respect as merely illustrative and not restrictive. Therefore, the scope of the invention is indicated by the appended claims rather than by the foregoing description. All changes within the meaning and scope of the equivalents of the claims are included within the scope of the claims.

Claims

1. A continuous hydrocarbon pyrolysis method for producing hydrogen and carbon, comprising exposing a hydrocarbon feedstock to an oxygen-depleted combustion gas in a hydrocarbon pyrolysis zone, wherein the combustion gas is produced by a valveless pulse burner, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a combustion gas temperature greater than 2400° C., wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so as to pyrolyze the hydrocarbon feedstock and produce a gas containing hydrogen and solid particles containing carbon.

2. The hydrocarbon pyrolysis method according to claim 1, wherein the hydrocarbon feedstock is selected from the group consisting of gaseous hydrocarbon materials, liquid hydrocarbon materials and solid hydrocarbon materials.

3. The hydrocarbon pyrolysis process of claim 1, wherein the valveless pulse burner operates by combusting a fuel and an oxygen source, the oxygen content of the oxygen source being greater than 50 vol% oxygen.

4. The hydrocarbon pyrolysis process of claim 3, wherein the oxygen source has an oxygen content greater than 85 vol% oxygen.

5. The hydrocarbon pyrolysis process of claim 3, wherein the oxygen source has an oxygen content greater than 90 vol% oxygen.

6. The hydrocarbon pyrolysis process of claim 1, wherein the oxygen content of the oxygen-depleted combustion gas is less than 2 vol% oxygen.

7. The hydrocarbon pyrolysis process of claim 1, wherein the oxygen content of the oxygen-depleted combustion gas is less than 1 vol% oxygen.

8. The hydrocarbon pyrolysis process of claim 1, wherein the residence time in the hydrocarbon pyrolysis zone is less than 5 seconds.

9. The hydrocarbon pyrolysis process of claim 1, wherein the residence time in the hydrocarbon pyrolysis zone is less than 2 seconds.

10. The hydrocarbon pyrolysis process of claim 1, wherein the gas and solid particles produced in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200°C.

11. A hydrocarbon pyrolysis process according to claim 10, comprising cooling the gases and solid particles leaving the hydrocarbon pyrolysis zone to a temperature below 200°C in a heat exchanger.

12. The hydrocarbon pyrolysis process of claim 11, comprising separating the solid particles from the gas.

13. A hydrocarbon pyrolysis process according to claim 12, comprising treating the gas to remove unwanted particles and gas molecules, thereby producing a H2-containing gas having a H2 concentration greater than 80 vol% H2.

14. The hydrocarbon pyrolysis process of claim 12, comprising treating the gas to remove unwanted particles and gas molecules to produce a H2-containing gas having a H2 concentration greater than 90 vol% H2.

15. The hydrocarbon pyrolysis process of claim 13, comprising continuously introducing the H2-containing gas into a power generation device without long-term storage.

16. The hydrocarbon pyrolysis process of claim 13, comprising continuously introducing the H2-containing gas into a hydrometallurgical production facility without long-term storage.

17. The hydrocarbon pyrolysis process of claim 14, comprising continuously introducing the H2-containing gas into a chemical production facility without long-term storage.

18. The hydrocarbon pyrolysis process of claim 12, wherein the solid particles have a carbon content greater than 90 wt% as characterized by CHNSO analysis.

19. The hydrocarbon pyrolysis process of claim 12, comprising heating the solid particles to a temperature greater than 2500°C.

20. The hydrocarbon pyrolysis process of claim 19, wherein the solid particles comprise carbon having a graphitization percentage greater than 80% as characterized by X-ray diffraction.

21. A system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon, comprising: a valveless pulse combustor that combusts a fuel and an oxygen source to produce a combustion gas, wherein the oxygen source comprises an oxygen content greater than 85 vol% oxygen, wherein the combustion gas is oxygen-depleted; a hydrocarbon pyrolysis zone configured to receive the combustion gas and a quantity of hydrocarbon feedstock, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so as to pyrolyze the hydrocarbon feedstock and produce gas and solid particles comprising hydrogen and carbon, wherein the gas and solid particles produced in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; and A heat exchanger configured to cool the gases and solid particles exiting the hydrocarbon pyrolysis zone to a temperature below 200°C.

22. The system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to claim 21, comprising a gas / particle separator to separate the solid particles from the gas.

23. The system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to claim 22, wherein the gas / particle separator is selected from the group consisting of a cyclone gas / particle separator and a baghouse gas / particle separator.

24. The system for continuous hydrocarbon pyrolysis to produce hydrogen and carbon according to claim 21, the system comprising a gas absorber to remove unwanted gas molecules from the gas and produce a H2-containing gas having a H2 concentration greater than 80 vol% H2.

25. A combined system for continuous hydrocarbon pyrolysis to produce hydrogen and receiving and burning said hydrogen to generate electricity, comprising: a valveless pulse combustor that combusts a fuel and an oxygen source to produce a combustion gas, wherein the oxygen source comprises an oxygen content greater than 85 vol% oxygen, wherein the combustion gas is oxygen-depleted; a hydrocarbon pyrolysis zone configured to receive the combustion gas and a quantity of hydrocarbon feedstock, wherein the combustion gas enters the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., wherein the residence time of the hydrocarbon feedstock and the combustion gas in the hydrocarbon pyrolysis zone is less than 30 seconds, so as to pyrolyze the hydrocarbon feedstock and produce gas and solid particles comprising hydrogen and carbon, wherein the gas and solid particles produced in the hydrocarbon pyrolysis zone leave the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; a heat exchanger configured to cool the gases and solid particles exiting the hydrocarbon pyrolysis zone to a temperature below 200° C.; a gas / particle separator, the gas / particle separator being used to separate the solid particles from the gas; a gas absorber for removing unwanted gas molecules from the gas and producing a continuous source of H2-containing gas having a H2 concentration greater than 80 vol% H2; and A power generation device connected to a continuous source of H2-containing gas, the power generation device combusting the H2-containing gas to generate electricity.

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