Ultra-high temperature pyrolysis separation of hydrogen and carbon

Abstract

A continuous hydrocarbon pyrolysis process to produce hydrogen gas and carbon includes exposing a hydrocarbon feedstock to oxygen-deficient combustion gas in a hydrocarbon pyrolysis zone. A valveless pulse combustor generates combustion gas at a temperature greater than 2400° C. The hydrocarbon feedstock and combustion gas have a residence time in the hydrocarbon pyrolysis zone of less than 30 seconds, causing pyrolysis of the hydrocarbon feedstock to produce gas containing hydrogen and solid particles containing carbon. The gas and solid particles exit the hydrocarbon pyrolysis zone at a temperature greater than 1200° C. A heat exchanger cools the gas and solid particles to a temperature less than 200° C. A gas absorber removes unwanted gas molecules from the gas to produce an H2-containing gas having an H2 concentration greater than 80% by volume. The H2-containing gas is continuously introduced to an H2-consuming facility.

Description

[Technical field]

[0001] The present disclosure relates to the pyrolysis of hydrocarbons at extremely high temperatures in oxygen deficient or oxygen starved environments, enabling cost-effective yield of hydrogen and high purity carbon with reduced or no greenhouse gas emissions. [Background technology]

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 320,667, filed March 16, 2022, and entitled "PYROLYSIS SEPARATION OF HYDROGEN AND CARBON," which is incorporated herein by reference.

[0003] There is growing interest in reducing greenhouse gas emissions. The main source of greenhouse gas emissions is the burning of gaseous, liquid, or solid fossil fuels to produce heat. In power plants, the heat is converted into electricity, usually by steam turbines or direct drive. All fossil fuels are hydrocarbons, which have both carbon and hydrogen atoms. For example, the chemical formula for methane is CH 4 with 4 hydrogen atoms for every carbon atom. Carbon has an atomic weight of 12 g / mol and hydrogen has an atomic weight of 1 g / mol. The molecular weight of methane is 16 g / mol. The mass percentages of carbon and hydrogen in methane are 75% carbon and 25% hydrogen.

[0004] The balanced chemical reaction for stoichiometrically burning methane is: CH 4 + 2O 2 → CO 2 + 2H 2 O 1 mole of CH 4 The stoichiometric combustion of 1 mole of CO 2 CO is produced. 2 The molecular weight of 1 mole (16 grams) of CH 4 When burned, 1 mole (44 grams) of CO 2is generated.

[0005] An efficient and economical process to process hydrocarbons and capture most of the carbon as carbon solids while converting hydrogen into H 2 Non-limiting examples of potential applications of the captured carbon solids include chemical feedstocks, carbon electrodes, high temperature refractories, batteries, etc. The battery market will continue to grow to support both vehicle electrification and grid energy storage. These examples are not intended to limit the potential applications of the carbon produced via the processes described herein. Carbon solids can be used to generate CO 2 Sequestration is the lowest-value use of carbon.

[0006] Hydrogen gas (H 2 ) is the molecule with the smallest molecular weight of 2 g / mol. For storage and transportation, H 2 It is not economically feasible to liquefy hydrogen gas. High pressure tanks and pipelines have been explored as a way to increase the energy density for the transportation and storage of hydrogen gas. Typically, high pressure gas pipelines are made of metal, often iron and steel. Over time, hydrogen reacts with the metal and embrittles it. Embrittlement of metal under high pressure is prone to breakage. It is well known that natural gas pipelines eventually start leaking at the majority of their joints. If natural gas or methane, with a molecular weight of about 16 g / mol, can easily leak, hydrogen gas, with a molecular weight as low as 2 g / mol, is expected to leak at the same or much higher rates. CH 4 Unlike the leak of H 2 leakage is not considered a greenhouse gas risk. 2 H caused by leakage during long-distance high-pressure gas transportation 2 Loss of this represents a significant economic risk. Summary of the Invention [Problem to be solved by the invention]

[0007] Thus, there is a strong need to efficiently and cost-effectively process hydrocarbons to obtain high quality hydrogen, carbon, and other products, and to produce hydrogen for immediate use with little or no storage and transportation. [Means for solving the problem]

[0008] The present disclosure relates to processes for converting gaseous, liquid, and / or solid hydrocarbons into hydrogen and carbon solids while minimizing carbon dioxide emissions. The disclosed processes involve rapid, very high temperature pyrolysis of hydrocarbons.

[0009] The disclosed hydrocarbon pyrolysis process produces hydrogen gas and carbon by exposing a hydrocarbon feedstock to hot, oxygen-deficient combustion gas, which, in some embodiments, is obtained from combustion gases exiting a valveless pulse combustor (VPC), causing the pyrolysis of the hydrocarbon feedstock to produce hydrogen gas and carbon, as described below.

[0010] The hydrocarbon pyrolysis process disclosed herein demonstrates the pyrolysis of hydrocarbons in oxygen deficient gas at high temperatures (greater than 2400° C.) and short residence times (less than 30 seconds) to produce hydrogen and carbon.

[0011] As used herein, the term hot oxygen-deficient combustion gas has an initial temperature in the range of about 2400° C. to about 3400° C. or higher, i.e., about 2400° C., about 2500° C., about 2600° C., about 2700° C., about 2800° C., about 2900° C., about 3000° C., about 3100° C., about 3200° C., about 3400° C., or higher (any of the values ​​listed can be 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 hot or ultra-hot combustion gas is transferred to the hydrocarbon feedstock, increasing the temperature of the hydrocarbon feedstock.

[0012] As used herein, the terms oxygen deficient, oxygen deficient, or very low excess oxygen refer to less than about 4% by volume, less than about 3% by volume, less than about 2% by volume, less than about 1% by volume, less than about 0.5% by volume, less than about 0.2% by volume, or less than about 0.1% by volume (any of the values ​​listed can be the upper or lower limit of a range). 2 means.

[0013] As used herein, the term short residence time means that the exposure time of the hydrocarbon feedstock to the hot oxygen deficient gas is less than 30 seconds. The total exposure time of the hydrocarbon feedstock to the high temperature may be more than 1 second due to the transport time in the process system equipment. The exposure time may be less than 30 seconds, less than 25 seconds, less than 20 seconds, less than 18 seconds, less than 16 seconds, less than 14 seconds, less than 12 seconds, less than 10 seconds, less than 9 seconds, less than 8 seconds, less than 7 seconds, less than 6 seconds, less than 5 seconds, less than 4 seconds, less than 3 seconds, less than 2 seconds, and less than 1 second (any of the values ​​listed may be the upper or lower limit of a range).

[0014] As used herein, the term hydrocarbons includes, but is not limited to, fossil fuels such as coal, petroleum, natural gas, wood, bio-waste, and the like.

[0015] In some embodiments, the hot oxygen-deficient lean gas is obtained from combustion gases exiting a valveless pulse combustor (VPC) or pulse jet to effect pyrolysis of the hydrocarbon feedstock to produce hydrogen gas and carbon. The VPC not only provides hot combustion gases to the pyrolysis process, but also provides a source of sonic energy. The valveless pulse combustor generates pressure waves of about 20-200 Hz, further improving the efficiency of hydrocarbon processing by pyrolytic separation. Without wishing to be bound by theory, it is believed that the pressure pulses in the form of sonic energy applied by the VPC to the pyrolysis process serve to improve the kinetics of the various reactions that occur during the disclosed pyrolytic separation of hydrogen and carbon.

[0016] In some embodiments, instead of using air (20% oxygen and 80% nitrogen by volume) as the oxygen source for combustion in the VPC, oxygen is provided by adding more than 50% O 2 by volume from air. 2 In some non-limiting embodiments, the oxygen is concentrated to greater than 60% by volume. In some non-limiting embodiments, the oxygen is concentrated to greater than 70% by volume. In some non-limiting embodiments, the oxygen is concentrated to greater than 75% by volume. In some non-limiting embodiments, the oxygen is concentrated to greater than 85% by volume. In some non-limiting embodiments, the oxygen is concentrated to greater than 90% by volume. In some non-limiting embodiments, the oxygen is concentrated to greater than 93% by volume. It is understood that a higher oxygen content allows for a higher flame temperature and a higher combustion gas temperature.

[0017] The disclosed embodiments of the high temperature continuous process add significant and unexpected value to the carbon fraction, enabling and supporting the economic feasibility of this pyrolysis approach to producing hydrogen. The hydrogen produced herein can be advantageously used as a combustion fuel or as a chemical reactant in a continuous process.

[0018] In some disclosed embodiments, hydrogen production is achieved without long-term hydrogen storage, and is carried out by H 2 H from the point of production to the nearest point of use at the pressure required for gas use 2 Hydrogen gas is transported short distances at the pressure required at the point of use, either adjacent or in close proximity to the point of use, as part of a continuous process involving short distance transportation of hydrogen at the pressure required at the point of use.

[0019] Non-limiting potential applications for on-site or point-of-use hydrogen gas production facilities include power generation. For example, the high temperature pyrolysis process can be scaled up to produce enough hydrogen to run a full-sized power plant (e.g., 600 MW). Smaller or larger power plants can also be accommodated. A 600 MW power plant is a non-limiting example.

[0020] Other potential non-limiting applications for on-site or point-of-use hydrogen gas production facilities include hydrometallurgy, where hydrogen is used as part of the process to reduce metal ores to elemental metal form. Other potential non-limiting applications for on-site hydrogen gas production facilities include chemical processes that require hydrogen as a reactant, such as the ammonia production process.

[0021] CO 2 By producing high-value solid carbon products instead of waste gases, 2 The production of hydrogen gas at the point of use on a commercial scale while minimizing or eliminating emissions would be a significant advancement in the art.

[0022] As used herein, wt.% means % by weight. As used herein, vol.% means % by volume. As used herein, mol% means mole %, i.e., the percentage based on the number of moles of gas molecules in the gas stream. In an ideal gas, volume % and mole % are equivalent. As used herein, MTPH means metric tonnes per hour. As used herein, VPC means valveless pulse combustor. As used herein, MW means megawatts. As used herein, MM means one million. As used herein, Btu means British Thermal Unit and is equivalent to approximately 1055 Joules. As used herein, MAF means moisture free and ash free.

[0023] As used herein, the phrases [A], [B], [C], "and / or" and [D] mean that one or more of the cases connected by the "and / or" may occur separately or in combination. Thus, this phrase means that [A] or [B] or [C] or [D] may occur individually, or any combination of two or more cases, such as [A] and [B], [A] and [C], [B] and [C], or [A] and [C] and [D] may occur.

[0024] As used herein, unless expressly stated otherwise or clearly implied, the term "about" means a range of values ​​of plus or minus 10% ("±10%), for example, about 1.0 encompasses values ​​from 0.9 to 1.1.

[0025] Concentrations, amounts, and other numerical data may be expressed or presented in a range format herein. Such range formats are used merely for convenience and brevity. It should therefore be understood that the numerical values ​​explicitly stated as limits of the ranges should be interpreted flexibly to include all individual numerical values ​​or subranges subsumed within the ranges as if each numerical value and subrange were explicitly stated. As an example, the numerical range "about 1 to about 5" should be interpreted to include not only the values ​​of about 1 to about 5 explicitly stated, but also the individual values ​​and subranges within the indicated range. Thus, included in this numerical range are individual values ​​such as 2, 3, 4, and the subranges such as 1 to 3, 2 to 4, 3 to 5, and the like. This same principle also applies to ranges that indicate only one numerical value. Moreover, such interpretation should be applied regardless of the range or the properties being described.

[0026] Throughout this specification, reference to "one embodiment," "an embodiment," or similar language means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment of the invention. Thus, the appearances of "in one embodiment," "in an embodiment," and similar language throughout this specification do not necessarily all refer to the same embodiment. Furthermore, in the following description, reference is made to several embodiments and examples of the various components and processes of the invention described, but all described embodiments and examples should be considered to be illustrative in all respects and not limiting in any way. Furthermore, the described features, structures, properties, processes, or methods of the invention can be combined in any suitable manner in one or more embodiments.

[0027] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory, and are not intended to limit the invention as claimed. It is to be understood that the specific aspects and features of the disclosed invention may be freely combined with other specific aspects and features of the disclosed invention. It is to be understood that the various embodiments are not limited to the arrangements and instruments shown in the drawings. It is also to be understood that the embodiments may be combined or other embodiments may be utilized, and structural changes may be made without departing from the scope of the various embodiments of the invention, unless so claimed. Therefore, the following detailed description is not to be taken in a limiting sense.

[0028] So that the manner in which the above-mentioned and other features and advantages of the invention are obtained can be readily understood, a more particular description of the invention as briefly set forth above will be made by reference to specific embodiments thereof which are illustrated in the accompanying drawings, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings, with the understanding that these drawings depict only typical embodiments of the invention and are therefore not to be considered as limiting its scope. [Brief description of the drawings]

[0029] [Figure 1] FIG. 1 illustrates a hydrocarbon pyrolysis process in which the produced hydrogen gas is directly consumed in a hydrogen-fired power plant. [Diagram 2] FIG. 2 illustrates the process of FIG. 1 omitting the cyclone gas / particle separator. [Diagram 3] FIG. 2 illustrates the process of FIG. 1 with an optional secondary heating zone for carbon particles exiting the cyclone gas / particle separator and the underflow of the baghouse gas / particle separator. [Figure 4] FIG. 2 illustrates the process of FIG. 1, showing an alternative location of the gas processor at the end of the process after combustion of H2-containing gas in the H2 power plant. [Diagram 5] FIG. 2 shows the process of FIG. 1 with a heat exchanger installed after the H2 power plant. [Figure 6] FIG. 6 illustrates the process of FIG. 5 with a fugitive particle scrubber and gas absorber installed between the hydrogen and carbon pyrolysis separation process and the H2 power plant. [Figure 7] FIG. 6 illustrates the process of FIG. 5 with a fugitive particle scrubber and gas absorber installed after the H2 power plant, as well as an optional secondary heating zone for carbon particles exiting the cyclone gas / particle separator and the underflow of the baghouse gas / particle separator. [Figure 8] FIG. 8 shows a variation of the equipment layout shown in FIGS. 4 and 7, in which equipment modules can be moved within the process based on design objectives, with the gas processor being moved near the end of the process and positioned between the fugitive particle scrubber and the gas absorber, as shown. [Figure 9] FIG. 6 shows a variation of the installation layout shown in FIGS. 3 and 5 in which the gas processor is moved closer to the end of the process. [Figure 10] FIG. 7 illustrates a variation of the process of FIG. 6 for supplying H2-containing reactant gas to a hydrometallurgical production facility. [Figure 11]FIG. 7 illustrates a variation of the process of FIG. 6 in which an H2-containing reactant gas can be used as a reactant in a chemical production facility. [Figure 12] These figures show transmission electron microscope (TEM) images at three different magnifications and inset fast Fourier transform (FFT) images of carbonized solid carbon particles that were removed from the system at 1200°C (sample S-1200, images a1, a2, and a3), carbonized solid carbon particles that were removed from the system at 2500°C (sample S-2500, images b1, b2, and b3), graphitized solid carbon particles that were removed from 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). [Figure 13A] FIG. 1 shows X-ray diffraction (XRD) patterns of heat-treated samples S-1200, S-2500, S-2700 and graphite sample G-ref. [Figure 13B] FIG. 1 shows X-ray diffraction (XRD) patterns of heat-treated samples S-1200, S-2500, S-2700 and graphite sample G-ref. [Figure 14] FIG. 1 shows Raman spectra of heat-treated samples S-1200, S-2500, S-2700 and graphite sample G-ref. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] The present disclosure relates to a continuous hydrocarbon pyrolysis process to produce hydrogen gas and carbon. The process includes exposing a hydrocarbon feedstock to oxygen-deficient combustion gas in a hydrocarbon pyrolysis zone. Preferably, the combustion gas is generated by a valveless pulse combustor. When the hydrocarbon feedstock and combustion gas enter the hydrocarbon pyrolysis zone, the combustion gas has a temperature greater than 2400° C. The hydrocarbon feedstock and combustion gas have a residence time in the hydrocarbon pyrolysis zone of less than 30 seconds, causing pyrolysis of the hydrocarbon feedstock to produce gases comprising hydrogen and solid particles comprising carbon.

[0031] FIG. 1 illustrates an embodiment of the disclosed hydrocarbon thermal cracking process. The hydrocarbon thermal cracking process illustrated in FIG. 2For local consumption, H 2 In a disclosed embodiment, the facility provides for on-site production of H 2 However, H 2 It will be appreciated that other equipment requiring a continuous source of may be used.

[0032] A valveless pulse combustor (VPC) is used as the heat source for the pyrolysis process. The fuel and the oxygen-containing gas stream are mixed in the combustion chamber of the VPC. The oxygen content in the oxygen-containing gas stream is enriched, preferably greater than 85% by volume. In some embodiments, the oxygen content in the oxygen-containing gas stream is greater than 90% by volume. In some embodiments, the oxygen content in the oxygen-containing gas stream is greater than 93% by volume. When oxygen is enriched from atmospheric air, nearly all of the remaining gas in the oxygen-containing gas stream is N 2 There are very small amounts of other gases present, such as CO from the ambient air. 2 may also be present in the oxygen-containing gas stream in the low ppm range.

[0033] The advantage of the VPC is that it can be operated with near stoichiometric combustion. This means that the oxygen content in the combustion gases leaving the VPC is very low. In some embodiments, the oxygen content in the combustion gases is 4% by volume. 2 In some embodiments, the oxygen content in the combustion gas is less than 3% by volume. 2 In some embodiments, the oxygen content in the combustion gas is less than 2% by volume. 2 The oxygen content in the combustion gases can even be less than 1% by volume. In many combustion technologies, the oxygen in the combustion gases is often more than 5% by volume, and can be as much as 10% by volume. When using hydrocarbons as fuels, most combustion technologies cannot operate with less than 2% by volume of oxygen in the combustion gases and still produce low amounts of CO. The presence of large amounts of CO is an indicator of incomplete or inefficient combustion. 2% by volume O 2 CO can be less than 100 ppm. Less than 1% by volume O 2In this case, the CO can be less than 300 ppm.

[0034] When an oxygen-containing gas stream containing more than 85% oxygen by volume is introduced, the combustion gas temperature exceeds 2400° C. At 90% oxygen by volume, the combustion gas temperature leaving the VPC can reach as high as 3000° C. or more. At 94% oxygen by volume, the combustion gas temperature leaving the VPC can reach as high as 3300° C. or more.

[0035] Non-limiting examples of methods for concentrating oxygen from air to produce an oxygen-containing gas having an oxygen content greater than 85% by volume include pressure swing absorption, membrane absorption, vacuum pressure swing absorption, ionic liquid-based absorption, special liquid chemistry-based absorption, aqueous salt gas absorption, and aqueous suspended solid gas absorption.

[0036] The fuel used in the VPC is hydrogen (H 2 ) gas. When hydrogen is used as fuel, a fraction of the hydrogen produced in the pyrolytic separation of hydrogen and carbon is diverted as fuel for the VPC to generate the heat required to drive the pyrolysis process that converts hydrocarbons into carbon and hydrogen. 2 When burning, the amount of O is more than the 85% by volume required for high-temperature combustion. 2 Some N from the gas stream 2 At the same time, water vapor becomes the main gas component in the combustion gas. 2 Even if it is burned, CO 2 does not occur. H 2 The balanced chemical reaction for the stoichiometric combustion of is: 2H 2 + O 2 → 2H 2 O

[0037] The fuel used by the VPC may be a hydrocarbon gas such as natural gas, methane, propane, etc. The fuel used may be a solid hydrocarbon fuel such as lignite, brown coal, subbituminous coal, bituminous coal, anthracite, etc., where the coal is a dry powder with less than 1% moisture by mass and less than 150 μm in particle size. The fuel used may be a solid hydrocarbon such as dried solid biowaste such as forest waste, agricultural waste, sawdust, wood chip waste, human or animal feces waste, plastic waste, rubber waste, automobile tire waste, etc., where the solid hydrocarbon fuel is a dry powder with less than 1% moisture by mass and less than 150 μm in particle size. The fuel used may be a liquid hydrocarbon such as gasoline, diesel, biodiesel, biofuel, waste cooking oil, etc.

[0038] Pyrolytic separation of carbon and hydrogen is achieved by injecting a hydrocarbon feedstock into the combustion gas stream from the VPC at temperatures above 2400 °C. 2 The content is so low, e.g., 2 vol.% or less, and more preferably 1 vol.% or less, that it does not react with the hydrocarbon feedstock in the hydrocarbon pyrolysis zone. 2 There is almost no trace of O in the combustion gas stream with a temperature above 2400°C. 2 When reacted with CO or CO 2 resulting in a substantially oxygen-free combustion gas stream. The absence of oxygen in the combustion gas stream reduces the amount of carbon produced by pyrolytic separation of hydrogen and carbon.

[0039] The combustion gas stream, which is hotter than 2400°C, immediately heats the hydrocarbon feedstock to a temperature above 1200°C, causing the hydrocarbon feedstock to pyrolyze. The sonic pulses of the VPC assist in the energy transfer to efficiently and quickly heat the hydrocarbon feedstock. The feed rate of the hydrocarbon feedstock is controlled such that the combustion gas stream and particles exit the hydrocarbon pyrolysis zone at a temperature above 1200°C. In some embodiments, the combustion gas stream and particles exit the hydrocarbon pyrolysis zone at a temperature above 1300°C. In some embodiments, the combustion gas stream and particles exit the hydrocarbon pyrolysis zone at a temperature above 1400°C. In some embodiments, the combustion gas stream and particles exit the hydrocarbon pyrolysis zone at a temperature above 1500°C. In some embodiments, the combustion gas stream and particles exit the hydrocarbon pyrolysis zone at a temperature above 1,600°C. In other words, when a larger amount of hydrocarbon feedstock is combined with the combustion gas stream, the cooling of the combustion gas stream may be greater. Similarly, when a smaller amount of hydrocarbon feedstock is combined with the combustion gas stream, the combustion gas stream is cooled less and the temperature of the combustion gas stream and particles is higher when they exit the hydrocarbon pyrolysis zone. Similarly, a hotter combustion gas stream can thermally process a larger amount of the hydrocarbon feedstock.

[0040] In some embodiments, the amount of hydrocarbon feedstock combined with the combustion gas stream is controlled so that the temperature of the gases and particles exiting the hydrocarbon pyrolysis zone is greater than 2,500° C. At particle temperatures greater than 2500° C., preferably in the range of 2700° C. to 3000° C. or greater, the solid carbon particles transition from carbonized material to layered graphitized material. Under these conditions, the solid carbon particles are greater than 98% carbon as characterized by CHNSO analysis. The percent graphitization is greater than 80% as characterized by X-ray diffraction (XRD). Operating at a high enough temperature to graphitize the solid carbon particles converts the hydrocarbon feedstock into high value solid carbon materials.

[0041] The higher the temperature of the combustion gases, the more work can be done on the incoming hydrocarbon feedstock because of the greater difference between the temperature of the combustion gases and the >1200°C temperatures at which the solid carbon products and gases exit the hydrocarbon pyrolysis zone.

[0042] The residence time of the gas and particles in the hydrocarbon pyrolysis zone is less than 30 seconds. In non-limiting embodiments, the residence time of the 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 (any of the values ​​listed can be the upper or lower limit of a range). The total exposure time of the hydrocarbon feedstock to high temperatures can be more than 1 second due to transport times in the process system equipment.

[0043] 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, subbituminous coal, bituminous coal, anthracite, the coal being a dry powder with less than 1% moisture by mass and less than 500 μm in particle size. The hydrocarbon feedstock used may be a solid hydrocarbon such as forest waste, agricultural waste, solid biowaste made by drying human or animal manure, the hydrocarbon feedstock being a dry powder with less than 1% moisture by mass and less than 500 μm in particle size. The fuel used may be a liquid hydrocarbon such as gasoline, diesel, biodiesel, biofuel, waste cooking oil, etc.

[0044] In the oxygen-deficient hydrocarbon pyrolysis zone, hydrocarbons begin to carbonize at temperatures above 600 to 700 °C. Hydrocarbons are molecules that consist of at least carbon and hydrogen. Methane is one of the simplest hydrocarbons, with the molecular formula CH 4where each molecule of methane has one carbon atom and four hydrogen atoms. Carbonization of methane means that all non-carbon atoms are removed 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. Rather, carbon finds other carbon atoms to form a carbon matrix of six-membered rings that expand to form graphite-like layers. Multiple layers are then stacked on top of each other until enough carbon atoms are bonded together to no longer exist as a gas and / or vapor. The solid particles precipitate from the gas and / or vapor phase to form submicron solid particles with morphology and properties similar to carbon black grades. In contrast, the most common method of producing carbon black from methane is the carbonization of methane by a specialized incomplete combustion reaction, in which part of the methane is burned to generate heat and the remaining methane is carbonized.

[0045] In the disclosed pyrolysis process, hydrocarbons are injected into a hot combustion gas stream that has a low oxygen content. The oxygen reacts with the hydrocarbons and burns, producing heat, CO or CO. 2 , and H 2 Generate O 2 As mentioned above, there is a small amount of O 2 (less than 1% by volume of the combustion gas) will cause the above reaction, and then O 2 The content is zero. 2 In a depleted environment, the hydrocarbons are carbonized. In the case of methane, submicron particles of carbon black, made almost entirely of carbon, are formed. O 2 does not exist. As a result, hydrogen atoms bond to H 2 The products of the pyrolysis reaction are solid carbon and H 2 When the temperature of the gas and carbon solids leaving the hydrocarbon pyrolysis zone is above 1200°C, carbonization is complete and the hydrocarbons are converted to H 2 It is separated into gas and solid carbon particles.

[0046] If the hydrocarbon feedstock is solid, it may be a hydrocarbon gas, a hydrocarbon vapor, or H 2Gases begin to destructively distill from the hydrocarbon feedstock solids at temperatures above about 300°C. The hydrocarbon gases may be methane, ethane, propane, etc. Hydrocarbon vapors range from coal tar vapors to vapors of smaller organic compounds (ring structures like benzene, polycyclic organic molecules, molecules that are liquid at room temperature such as ethanol, methanol, decane, etc.). These organic molecules are examples of solid and liquid hydrocarbons that may destructively distill from coal particles and exist in the vapor phase. Heating these gases and vapors to temperatures above 1200°C carbonizes them and produces H, as produced from the methane gas mentioned above. 2 It produces gases, other carbonizing gases, and submicron particles similar to carbon black.

[0047] Larger solid char particles remain from the solid hydrocarbon feed particles. When the temperature rises above 1200°C, these char particles are carbonized and H is released from the char particles. 2 It produces gases, other carbonizing gases, and large carbon particles.

[0048] Solid hydrocarbons such as dry coal, dry plant material, and dry feces are converted into simple CH2O3 of methane. 4 It should be noted that solid hydrocarbons have a much more complex molecular structure than solid hydrocarbons. Often these solid hydrocarbons are characterized with equipment that measures the weight percent of carbon (C), hydrogen (H), nitrogen (N), and sulfur (S). The mass percent of oxygen (O) is determined by subtracting the sum of the mass percent of C, H, N, and S from 100 mass percent. This is sometimes called CHNSO analysis. The other carbonization gases mentioned above are gases containing N, S, and O that are emitted from the carbon matrix as it carbonizes and becomes purer carbon.

[0049] When the hydrocarbon feedstock is a liquid hydrocarbon such as diesel, the liquid hydrocarbon is sprayed as fine droplets, preferably having a droplet size of less than 500 μm, into the combustion gas stream at temperatures above 2400° C. The fine droplets of liquid hydrocarbon vaporize immediately. When heated to temperatures above 1200° C., the liquid hydrocarbon vapor carbonizes and produces H. 2Gas is produced. Small amounts of other carbonized gases are also produced, so long as N, S, and O atoms are present in the molecular structure of the liquid hydrocarbon. Submicron particles similar to carbon black produced from methane gas are produced. Small amounts of larger carbon char particles are also formed.

[0050] Regardless of the hydrocarbon feedstock, carbon particles that reach temperatures above 1200° C. contain greater than 90% carbon by weight as determined by CHNSO analysis. For most hydrocarbon feedstocks, once the carbon particles reach temperatures above 1200° C., the carbon content exceeds 95% by weight.

[0051] After the hydrocarbon pyrolysis zone, the particle-containing gas stream is sent to a heat exchanger that reduces the gas and particle temperature to less than 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. (any of the values ​​listed can be the upper or lower limits of a range). Considering the ideal gas law and the equation PV=nRT, where P is pressure, V is volume, n is moles of gas, R is the ideal gas constant, and T is temperature in Kelvin, reducing the temperature from 1200° C. to 200° C. at constant pressure results in a 1 / 3.1 reduction in volume. T in / T out = (1200+273.15) / (200+273.15) = 3.1 The volume reduction due to cooling of the gas allows for smaller downstream piping and equipment, including gas particle separators, gas treaters, gas scrubbers, gas adsorption units, etc. The maximum temperature for continuous operation of a baghouse, a type of gas particle separator, is typically less than 200°C, depending on the bag material available.

[0052] The heat recovered from the heat exchanger is valuable and can be used to perform work, making the disclosed process more efficient. Non-limiting uses of the recovered heat include preheating gas or feedstock, and generating superheated steam to drive turbines to produce electricity.

[0053] The cooled particle-laden gas is sent to a downstream gas / particle separator. Typically a cyclone is followed by a baghouse as shown in Figure 1. If all the particles are so small that few emerge from the cyclone underflow, then only the baghouse is used as shown in Figure 2.

[0054] Carbon particles that reach temperatures above 1200°C in the hydrocarbon pyrolysis zone are mostly composed of sp 2 It is an amorphous solid of carbon. When a resistivity meter probe is placed on the particle, it will show a resistance of about 20 ohms or less at 1 cm intervals. The 1 cm interval between the resistivity meter probes spans many particles of the powdered carbon product. The bulk density may be too low for physical electrical connection between the particles. To measure the electrical resistivity of carbon particles, especially those such as carbon black recovered from the baghouse that have a low bulk density, it may be necessary to compress the powder to increase the bulk density. sp 2 The bonds are not regular, but rather link the carbon atoms within the particles together as an amorphous solid. X-ray diffraction may show the beginnings of a layered structure that may represent a low level of graphitization. The hydrocarbon pyrolysis zone does not reach temperatures where significant graphitization occurs.

[0055] FIG. 3 illustrates an optional addition to the process of FIG. 1, where carbon particles exiting the underflow of the cyclone and / or baghouse or other gas / particle separator are advanced to a secondary heating zone. The carbon particles are ramped to a temperature greater than 2200° C. with a residence time in the secondary heating zone of less than 10 minutes, preferably less than 5 minutes, and more preferably less than 2 minutes. The heat source in the secondary heating zone may be any means capable of heating the carbon particles to the target temperature. One preferred method is an induction furnace. Another preferred method is an electric arc furnace. Heating the carbonized coal particles to temperatures greater than 2200° C. drives the reorganization of the amorphous structure into a layered graphite structure. The graphitized carbon can be used as a feedstock for higher value markets, such as carbon refractory components, carbon electrodes, and battery production for the growing automotive and grid storage markets.

[0056] Referring again to the process shown in FIG. 1, the cooled, particle-free gas is then sent to a gas processor. This machine may be a single-stage, two-stage, or multi-stage centrifugal fan. This machine may also be a positive displacement blower. This machine may also be a large capacity gas compressor, such as a screw compressor. The specific type of gas processor is selected based on the overall system requirements, which are identified by the vacuum required in the upstream portion of the system and the pressure required in the downstream portion of the system. In FIG. 1, the gas processor may be placed after the gas / particle separator in the hydrogen and carbon pyrolysis separation process, before any downstream equipment that may be present in the process, and before any downstream equipment, such as the H2O power plant shown in FIG. 1. 2 It is located before the contained gas point-of-use facility.

[0057] Figure 4 shows the H 2 H at power generation facilities 2 1 shows an alternative location for the gas processor, installed at the end of a combined hydrogen and carbon pyrolysis separation process, which can be combined with combustion of the contained gases.

[0058] In Figure 1, cooled, particle-free H 2 The gas contained is H 2 It is transported to the power generation facility, where it is mixed with air (approximately 20% by volume O 2 and approximately 80% by volume of N 2 If free CO is present in the gas stream, it will be burned to produce CO 2 Similarly, S or N that is not in the oxide form (N 2 (except for H) are likely to burn and become oxides. 2 The power plant may be one that originally burned coal or liquid hydrocarbons but has been modified to burn hydrogen in the combustor as a replacement for the previous fuel, thereby preserving the infrastructure and capital invested in the plant.

[0059] H 2 The power generation equipment is H 2may be burned to generate superheated steam, which may then be used to drive a turbine to generate electricity. 2 The power generation equipment is H 2 Alternatively, the fuel may be burned and the resulting combustion gas may directly drive a turbine to generate electricity.

[0060] In the system depicted in FIG. 2 The emissions are from CO produced when hydrocarbons are burned in the VPC to generate heat for the process. 2 , CO produced during carbonization of hydrocarbon feedstocks that have oxygen as part of the carbon matrix 2 , and CO produced in the water-gas shift reaction 2 The water-gas reaction occurs when water vapor in the hot combustion gas reacts with carbon to produce H 2 and CO. H 2 The mixture of carbon and CO is called water gas because it is the product of a reaction between carbon and water. The water gas shift reaction occurs when CO reacts with water vapor to produce H. 2 , CO 2 The water-gas shift reaction is a reaction in which CO in water gas is converted to H by exposing it to water steam. 2 and CO 2 For historical reasons surrounding the development of this reaction, the conversion of CO, H 2 , and possibly some CO 2 Water gas with a composition of is mainly CO 2 , H 2 , and possibly some CO. The combustion vapors react with carbon in the form of carbon gas, carbon vapor, and carbon solids, and with water gas, e.g., H 2 and CO. The water vapor in the combustion gas can convert this water gas CO, or the CO produced during carbonization of hydrocarbons containing O in the organic matrix, into H. 2 and CO 2 Depending on the efficiency of the power plant, the CO generated in the above process can be converted to 2 is the amount of CO produced when the original fuel is burned to run a power plant.2 As mentioned, the process also produces carbon products that can be sold into existing and future markets.

[0061] As shown in Figure 1, H 2 The combustion exhaust gas from the power generation equipment is discharged into the atmosphere through the exhaust stack. The combustion gas is almost entirely composed of water vapor and unreacted N2 from the inflowing air, which is generated by the following combustion reaction: 2 It is. 2H 2 + O 2 → 2H 2 O + heat

[0062] Alternatively, as shown in Figure 5, a highly efficient heat exchanger can be used as the H 2 By installing it after the power generation equipment and cooling the exhaust gas temperature to less than 100°C, a considerable amount of water can be condensed from the steam in the combustion gas and saved. The heat exchanger can generate superheated steam, which can be used to generate electricity using the secondary turbine if a secondary turbine is installed. By installing a secondary turbine or multiple microturbines, H 2 Power plants begin to approach the efficiencies of combined cycle natural gas fired power plants rather than the inherently lower efficiencies of coal or liquid hydrocarbon power plants.

[0063] H from the pyrolysis separation process of hydrogen and carbon 2 The contained gas contains some N2O, derived from a gas stream containing 85% or more by volume of oxygen used to combust hydrocarbons in the VPC. 2 Combustion of hydrocarbon fuels in the VPC produces some CO 2 Carbonization of hydrocarbons can also produce CO and / or CO if oxygen is present in the molecular structure. 2 The combustion water produced during the combustion of hydrocarbon fuels reacts with the hydrocarbon feedstock in the high temperature pyrolysis zone to produce CO and H. 2 and / or, more preferably, CO 2 and H 2See the above discussion of the water-gas reaction and the water-gas shift reaction.

[0064] Figure 6 shows the pyrolysis separation process of hydrogen and carbon and the H 2 Between the power generation equipment and the H 2 More than 90% by volume of H in power generation equipment 2 The configuration is shown with optional equipment installed to feed the gas stream. A set of equipment that may be used includes a flocculent particle scrubber. The combination of a cyclone and a baghouse separates over 99% of the particles from the gas stream. Some flocculent particle discharge may pass through the baghouse. This is especially true if the process produces sub-micron carbon black-like particles. If flocculent particles are undesirable for the gas absorber, a flocculent particle scrubber can be installed. The scrubber may be one of many water spray-based scrubber designs. Another example of a scrubber that may be used is an electrostatic precipitator. These two suggestions are non-limiting examples.

[0065] After the migrating particles are removed, the gas absorber is 2 Remove other gases except H 2 H exceeding 80% or 90% by volume for power generation equipment 2 Generate a gas flow. The gases that can be removed are N 2 , CO 2 , CO, SO x , NO x , H 2 S, N.H. 4 etc. These are non-limiting examples of gases that can be removed in a gas absorber. Methods of gas absorption can include pressure swing absorption, membrane absorption, vacuum pressure swing absorption, ionic liquid based absorption, ammonia liquid based absorption, aqueous salt gas absorption, aqueous suspended solid gas absorption, etc. These are non-limiting examples.

[0066] Many of the removed gases have utility in the chemical industry. 2The absorbent gas, removed from the contained gas, can be stored on-site until the loadout is full, after which it can be shipped as product. 2 It can be sold to the food processing industry or sequestered using various techniques to keep it from entering the atmosphere as a greenhouse gas.

[0067] High concentration hydrogen gas (H 2 ) flow, which is free of fugitive particles, is a more efficient alternative to retrofitting existing coal-fired or liquid hydrocarbon-fired power plants using new, highly efficient turbine-based combined cycle (H 2 ) It is an ideal fuel for use in power plants.

[0068] An example of an alternative installation is shown in Figure 7. The secondary heating zone is shown to show that it can be present or absent in any configuration depending on whether a carbonized or graphitized product is desired. This installation is shown as an alternative option, H 2 It is shown that the fugitive particle scrubber and gas absorption equipment can be installed after the power plant. One example where this configuration might be done is a retrofitted coal-fired or liquid hydrocarbon-fired power plant. In a retrofitted power plant, H 2 The contained gases are burned. The ultimate goal is to produce CO 2 The goal is to minimize emissions of hydrogen and other gases. 2 Total CO in exhaust gas from continuous processes leading to combustion of contained gases 2 and other target gases, 2 A gas absorber may be installed after the power plant.

[0069] FIG. 8 is a variation of FIG. 4 and an alternative to FIG. 7, showing that equipment modules can be moved within the process based on design objectives. The gas treater is moved near the end of the process between the fugitive particle scrubber and the gas absorber. The type of gas treater is selected based on the vacuum level required for the upstream equipment and the pressure of the downstream equipment. The reason for having the gas treater at that location is that the gas absorber may require high pressure. The basic process after pyrolysis separation of hydrogen and carbon may also require a gas treater at the location shown in FIG. 1.

[0070] Figure 9 is an alternative that is a variation of the equipment arrangement of Figures 3 and 5. The secondary heating zone is shown to show that it can be present or absent in any configuration depending on whether a carbonized or graphitized product is desired. The gasifier is moved near the end of the process.

[0071] FIG. 10 is a variation of FIG. 6. After pyrolytic separation of hydrogen and carbon, a fugitive particle scrubber and gas absorber are used to extract more than 80% by volume of H 2 A reactant gas containing more than 80% by volume H is produced. 2 Reactant gases containing H can be used as reactants in hydrometallurgical production facilities. 2 H is used as a reducing agent to produce elemental metals from metallic ores. 2 CO absorbed from the gas 2 Sequestration of CO2 can result in reduced, low or extremely low CO2 emissions depending on the capacity of the gas absorber. 2 Commercial hydrometallurgical processes with (greenhouse gas) emissions become possible.

[0072] FIG. 11 is a variation of FIG. 6. After pyrolytic separation of hydrogen and carbon, a fugitive particle scrubber and gas absorber are used to extract more than 90% by volume of H 2 A reactant gas containing greater than 90% by volume H is produced. 2Reactant gases containing H can be used as reactants in chemical production facilities. An example of a commercial process that requires large amounts of hydrogen is ammonia production. 2 CO absorbed from the gas 2 By sequestrating the CO2, reduced, reduced or extremely reduced CO2 can be produced depending on the capacity of the gas absorber. 2 Chemical production processes can be carried out that involve (greenhouse gas) emissions.

[0073] It should be understood that the disclosed invention is not limited to the specific equipment layouts shown in Figures 1-11. It should be understood that equipment modules can be moved around within process variations based on the design goals of the disclosed invention.

[0074] Other features and advantages of the present invention will be apparent from the following various examples. The following examples illustrate various aspects and embodiments of the present invention, as well as methods of making and practicing them. The examples do not limit the claimed invention. Although methods and materials similar or equivalent to those described herein can be used to practice the present invention, suitable methods and materials are described below. Based on this disclosure, one skilled in the art can identify and employ other components and methodologies useful in practicing the present invention. EXAMPLES

[0075] Example 1 600 MW is a common size for a coal-fired power plant. Calculations of the calorific value in Btu / hr required to produce 600 MW of electricity at a 35% efficient coal-fired power plant are shown in Table 1. According to the calculations summarized in Table 2, 210.63 MTPH of coal would need to be burned to operate a 35% efficient 600 MW coal-fired power plant that burns the same coal used as the feedstock for the pyrolytic separation of hydrogen and carbon. 35% efficiency is the average high efficiency for coal-fired power plants. Table 2 summarizes the calculations for burning 210.63 MTPH of coal with 10% moisture as received to operate a 35% efficient 600 MW coal-fired power plant.

[0076] [Table 1]

[0077] [Table 2]

[0078] The model coal has 5.0% ash and 10.0% moisture by mass. 210.63 MTPH of as-received coal x (1-10.0% moisture) x (1-5.0% ash) equals 180.09 moisture-free and ash-free (MAF) coal. Table 3 shows the CO2 emissions from burning 210.63 MTPH of as-received coal with the indicated CHNSO values. 2 The mass balance for calculating the MTPH of the coal is shown below. This coal is used in the on-site 41% efficient H 2 Enough H to operate the power generation equipment 2 The same amount is used as a feedstock for pyrolytic separation of hydrogen and carbon to produce gas. When 210.63 MTPH of as-received coal or 180.09 MTPH of MAF coal is combusted, 533.42 MTPH of CO is produced. 2 Generates 533.42 MTPH of CO 2 is the CO2 emitted when 210.63 MTPH of as-received coal is burned in a 600 MW coal-fired power plant with an efficiency of 35%. 2 is the amount.

[0079] O 2 Negative values ​​of O 2 is the amount of O required to stoichiometrically react with each element in coal and burn it into its oxide form. 2 The total amount of oxygen required to burn coal is 452.50 MTPH.

[0080] [Table 3]

[0081] Example 2 There is enough hydrogen to power a 600MW hydrogen plant using Pittsburgh No. 8 coal as feedstock and operating at 41% efficiency. 2 The mass balance for pyrolysis of hydrogen and carbon to produce fuel gas containing 0.5% to 1.0% is shown in Table 4. The CHNSO analysis of the coal feedstock was 80.78% by weight carbon, 5.24% by weight hydrogen, 1.74% by weight nitrogen, 2.09% by weight sulfur, and 10.15% by weight oxygen by MAF based variance. The preferred moisture and ash content of the coal feedstock for the hydrogen and carbon pyrolysis separation process is less than 1% by weight moisture and less than 10% ash. For the mass balance summarized in Table 4, 610.55 MTPH of coal feedstock with 0.5% moisture and 5.0% ash was used. 0.5% moisture or less is a more preferred embodiment. 5% ash or less is a preferred embodiment. The mass balance summarized in Table 4 below is consistent with FIG. 6. FIG. 6 illustrates the process for pyrolysis separation of hydrogen and carbon, gas absorption, and adjoining or in situ H 2 H at power generation facilities 2 Combination of fuel gases and H 2 is manufactured on-site, and H 2 This indicates that there is no long-term storage of gas and that transportation is very short.

[0082] CO 2 Without gas absorption, the mass balance summary in Table 4 shows that a 600 MW H 2 307.5 MTPH of CO2 produced by pyrolysis separation of hydrogen and carbon linked to power generation facility 2 The mass balance for coal combustion in Table 3 shows that a 600 MW coal-fired power plant with an efficiency of 35% produces 533.42 MTPH of CO. 2 (533.42-307.5) / 533.42=42.4%. A 41% efficient 600 MW H2O was produced by pyrolysis separation of coal-based hydrogen and carbon without a gas absorption device. 2 Enough H to operate the power generation equipment 2 H 2 Generated in contained fuel gas is 35% less CO compared to a 600MW coal-fired power plant with 35% efficiency 2 In one embodiment, the CO 2The reduction in CO emissions is greater than 35%. 2 The reduction in emissions is more than 40%. The mass balance is 69.13% by volume of fuel gas. 2 One embodiment is a gas containing more than 65% H 2 It is a gas, a fuel gas.

[0083] Mass balance summary shows that in the pyrolysis separation of hydrogen and carbon, 465.63 MTPH of carbon was produced, with hydrogen (H) at an efficiency of 41%. 2 ) enough H to operate the generating equipment 2 Gas is produced. This carbon can also simply be buried and sequestered. As mentioned above, carbon has value in various markets and can easily be sold into these markets.

[0084] [Table 4-1]

[0085] [Table 4-2]

[0086] [Table 4-3]

[0087] After pyrolytic separation of hydrogen and carbon, gas absorption techniques can be used. For example, H 2 H for power generation facilities 2 H in the fuel gas 2 If it absorbs 50% of all gases other than H 2 The composition of the fuel gas contains more than 80% by volume of H 2 According to the mass balance, the CO 2 A 50% absorption of 153.75 MTPH of CO from the entire process. 2 It emits CO 2 80% absorption of 61.75 MTPH of CO 2 It emits CO2 90% absorption of 30.75 MTPH of CO 2 Table 5 shows the H2O absorption rate for gas absorption between 50% and 90% and for no gas absorption. 2 H in the fuel gas 2 Volume percent of and H 2 Residual CO in contained fuel gas 2 For example, 50% gas absorption is H 2 H in the fuel gas 2 This means that 50% of each gas other than CO is absorbed and removed from the gas stream. In addition, the CO from the hydrogen and hydrogen pyrolysis separation process with gas absorption is 2 Emissions, H 2 H for power generation facilities 2 CO produced at a 35% efficient 600 MW coal-fired power plant using the same coal used in the pyrolytic separation of hydrogen and carbon to produce contained fuel gas 2 It should be noted that the percentage of gas absorption is based on moles or volume of gas, not mass of gas.

[0088] To operate a 600MW coal-fired power plant with an efficiency of 35%, approximately 533.42 tons of CO 2 occurs. H 2 If all gases other than 153.75 MTPH are absorbed, the CO2 will be 153.75 MTPH after the gas absorption in the hydrogen and carbon pyrolysis separation equipment. 2 H is emitted from the product fuel gas produced in the process described herein when coal is used as a hydrocarbon feedstock. 2 CO compared to emissions from a 600MW coal-fired power plant with 50% non-gas absorption. 2 The reduction rate is (533.42-153.75) / 533.42=71.2%. 2 After absorbing 50% of the gas other than H, the remaining fuel gas is 81.75% by volume. 2 With reference to the data shown in Table 5, one embodiment of the hydrogen-containing fuel gas produced by the present process contains more than 80% by volume H 2Another embodiment of the hydrogen-containing fuel gas produced by the present process is greater than 90% by volume H 2 Combining the pyrolytic separation of hydrogen and carbon, H 2 One result of the overall process, including gas absorption before the power plant, is that CO emissions from a 600 MW coal-fired power plant using the same coal are reduced by 10%. 2 Compared to emissions, CO 2 In another embodiment, the reduction in CO emissions is greater than 70% compared to a comparable MW coal-fired power plant using the same coal. 2 More than 80% reduction in CO emissions compared to a comparable MW coal-fired power plant using the same coal. 2 That's more than a 90% reduction in emissions.

[0089] [Table 5]

[0090] Example 3 Table 6 shows the results of the process of CNG by pyrolysis separation of carbon and hydrogen to obtain H 2 H that can be burned in power generation facilities 2 The calculations convert 600 MW of electricity to the amount of heat (Btu / hr) required to produce 600 MW of electricity in a 58% efficient combined cycle CNG-fired power plant. According to the calculations summarized in Table 7, 79.04 MTPH of CNG would need to be burned to operate a 600 MW combined cycle CNG-fired power plant with an efficiency of 58%. 58% is the average efficiency of a natural gas combined cycle power plant.

[0091] [Table 6]

[0092] [Table 7]

[0093] Table 8 shows the CO produced when 79.04 MTPH is burned. 2 The mass balance for calculating the MTPH of 79.04 MTPH of CNG is shown below. When 79.04 MTPH of CNG is burned, 217.36 MTPH of CO is produced. 2 217.36 MTPH is the CO produced when 79.04 MTPH of CNG is burned in a 600 MW combined cycle CNG-fired power plant with an efficiency of 58%. 2 Represents the amount of negative O 2 is the amount of O required to stoichiometrically react with each element in CNG and burn it to its oxide form. 2 The total amount of oxygen required for the combustion of CNG is 316.17 MTPH.

[0094] [Table 8]

[0095] Example 4 Table 9 shows the results of pyrolysis of compressed natural gas (CNG) to produce hydrogen and carbon, enough to generate electricity for a 600 MW hydrogen power plant operating at an efficiency of 41%. 2 The mass balance for producing CNG is shown in Table 9. CNG is 75% carbon and 25% hydrogen by mass. For the mass balance summarized in Table 9, 130.63 MTPH of CNG feedstock was used for the hydrocarbon pyrolysis separation process. The mass balance summarized in the table below includes pyrolysis separation of hydrogen and carbon, gas absorption, adjacent or in situ H 2 H at power generation facilities 2 This corresponds to Figure 6, which shows the combination of gas combustion. 2 is produced on-site and H 2 The gas is not stored and is transported for very short periods of time.

[0096] CO 2 Without gas absorption, the mass balance is 600 MW H with an efficiency of 41%. 2 Pyrolysis separation of hydrogen and carbon connected to power plant produces 220.84 MTPH of CO 2The mass balance for CNG combustion in Table 8 shows that a 600 MW combined cycle CNG-fired power plant with 58% efficiency produces 217.36 MTPH of CO 2 (217.36-220.84) / 217.36=-1.6% CO 2 The reduction is solely due to the pyrolytic separation process of hydrogen and carbon. In other words, pyrolytic separation of hydrogen and carbon produces roughly the same amount of CO as burning CNG in a combined cycle CNG power plant, due to the high efficiency of the combined cycle CNG power plant, which is 58%. 2 The mass balance is H 2 After pyrolysis and separation of carbon and before gas absorption, the fuel gas was 77.83 vol.% H 2 One embodiment is a gas that is greater than 70% H 2 It is a gas, a fuel gas.

[0097] Mass balance summary shows H with efficiency of 41% 2 Enough H to power the generating set 2 In the process of producing gas, the process produces 72.87 MTPH of carbon. The particle size of the carbon is submicron size similar to carbon black. It produces significantly more CO than a highly efficient combined cycle CNG-fired power plant. 2 The lack of carbon dioxide emissions and the production of a valuable solid carbon product are advantages over simply burning CNG in a power plant. As mentioned above, carbon has value in a variety of markets and can be readily sold into these markets as well as utilized to develop new markets.

[0098] [Table 9-1]

[0099] [Table 9-2]

[0100] [Table 9-3]

[0101] After pyrolytic separation of hydrogen and carbon, gas absorption techniques can be used. For example, H 2 H for power generation facilities 2 H in the fuel gas 2 If it absorbs 50% of all gases other than H 2 The composition of the fuel gas contains more than 80% by volume of H 2 According to the mass balance, the CO 2 A 50% absorption of 110.42 MTPH of CO from the entire process. 2 It emits CO 2 80% absorption of 44.17 MTPH of CO 2 It emits CO 2 90% absorption of 22.08 MTPH of CO 2 Table 10 shows the H in the fuel gas when all other gases are absorbed in the proportions shown. 2 % by volume of CO remaining in the fuel gas 2 of MTPH and CO generated from a 58% efficient combined cycle 600 MW CNG-fired power plant 2 CO compared to 2 It should be noted that the percentage of gas absorption is based on moles or volume of gas, not mass of gas. The table below shows the H 2 For non-gas, gas absorption rates range from 50% to 90%.

[0102] When CNG is burned in a 600MW combined cycle CNG-fired power plant with an efficiency of 58%, approximately 217.36 tonnes of CO 2 If 50% of the non-hydrogen gases are absorbed from the combustion gases derived from hydrocarbon pyrolysis separation, then (217.36-110.42) / 217.36=49.2% of the CO emissions will be generated compared to the emissions of a 58% efficient combined cycle CNG-fired power plant. 2 Reductions will be made. 2 After absorbing 50% of the gas other than 100%, the remaining fuel gas is 87.53% by volume H 2Referring to the data in Table 10, the H produced by pyrolytic separation of hydrogen and carbon and gas absorption is 2 One embodiment of the contained fuel gas is greater than 85% by volume H 2 H produced by pyrolytic separation of hydrogen and carbon and gas absorption 2 Another embodiment of the contained fuel gas is greater than 90% by volume H 2 Combining pyrolysis separation of hydrogen and carbon using CNG as the feedstock, H 2 One result of the overall process, including gas absorption prior to the power plant, is a reduction in CO emissions compared to a comparable sized MW combined cycle CNG-fired power plant. 2 In another embodiment, the reduction in CO emissions is greater than 50% when using gas absorption technology compared to an equivalent size MW combined cycle CNG-fired power plant. 2 In yet another embodiment, the reduction in CO emissions is greater than 60% when using gas absorption technology compared to an equivalent size MW combined cycle CNG-fired power plant. 2 In yet another embodiment, the reduction in CO emissions is greater than 70% when using gas absorption technology compared to an equivalent size MW combined cycle CNG-fired power plant. 2 The goal is to reduce emissions by more than 80%.

[0103] [Table 10]

[0104] Example 5 Pittsburgh No. 8 coal was the hydrocarbon feedstock for the pyrolytic separation process of hydrogen and carbon disclosed herein. The solid carbon particles were separated and subjected to a secondary heating zone. Table 11 shows three samples of carbonized solid carbon particles that exited the system at 1200°C (S-1200), graphitized solid carbon particles that exited the system at 2500°C (S-2500), graphitized solid carbon particles that exited the system at 2700°C (S-2700), as well as a reference synthetic graphite (G-ref) made from a standard graphite synthesis process known in the art. Additional samples heated to different temperatures are also reported in Table 11: 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 varies from 80.78% in the as-received coal feedstock, 95.23% in the 1200°C product, to over 99% in the samples at 2500°C and above. CHNSO analysis is reported on MAF basis. After high temperature treatment, meaning above 2500°C, the ash content is less than 1% by mass at 2500°C and less than 0.13% by mass at 2700°C. Almost all the mineral matter (clay, sulfides, carbonates, silica, sulfates, etc.) in the coal samples was vaporized as metals or compounds. As seen in Table 11, the low ash content of S-2500 and S-2700 was similar to that of the reference synthetic graphite G-ref. Samples S-2500, S-2700 and G-ref contained about 99.90% by mass carbon on MAF basis, with negligible amounts of other elements. The data in Table 11 show that at processing temperatures above 1200°C, the samples carbonize to greater than 95% carbon on a MAF basis. Samples with greater than 90% carbon on a MAF basis are also likely to carbonize. Further analysis is required to show that at higher temperatures, such as 2500°C and 2700°C, a transition from amorphous carbonized carbon to graphitized carbon occurs. This analysis is presented below.

[0105] [Table 11]

[0106] The carbon contents of S-2500, S2700 and G-ref were above 100% within the range of systematic error. For these samples, the oxygen content was assumed to be zero and the carbon contents were calculated by difference.

[0107] Figure 12 shows the transmission electron microscope (TEM) images of all the samples, observed at three different magnifications for each sample. Images a1, a2, and a3 in Figure 12 show the amorphous structure of S-1200 treated at 1200°C, and the fast Fourier transform (FFT) images showed hollow circles. High-temperature samples S-2500 (images b1, b2, b3), S-2700 (images c1, c2, c3) and reference sample G-ref (images d1, d2, d3) after high-temperature treatment showed ordered layered structures mixed with amorphous structures. The interlayer distance of S-2700 was about 0.34 nm. Multiple dots with 6-fold symmetry observed in the FFT images of S-2700 and G-ref indicate more carbon layers compared to S-2500. This is consistent with the interlayer distance and average crystallite height analysis by XRD (Figure 13 and Table 12). G-ref exhibits a typical homogeneous microcrystalline structure, with multiple dot sets with six-fold symmetry well observed in the FFT image. The FFT images of S-2500 and S-2700 are less developed than G-ref, indicating that some regions of the solid carbon particles are still amorphous.

[0108] Figures 13A and 13B show the XRD patterns of heat-treated samples S-1200, S-2500, S-2700 and G-ref. Table 12 summarizes the relevant XRD data for each sample. S-1200 shows a typical amorphous structure without a clear crystalline structure, and as a result, no XRD data is shown in Table 12. The other samples show a graphitic structure, exhibiting a sharp peak at 26.5° and three small peaks at 42.3°, 44.3° and 77.3°, which correspond to the (002), (100), (004) and (110) facets of graphite, respectively. The peak intensity of G-ref is much larger than that of S-2500 and S2700, which means it has a highly ordered carbon structure. According to Scherrer's formula, the interlayer spacing of S-2500 and S-2700 was about 0.3369 nm and 0.3366 nm, respectively, and the graphitization degree was 82.69% to 85.59%, respectively. G-ref had a graphitization degree of 88.49%. In one or more embodiments of the disclosed invention, the graphitization degree is greater than 80%. This data indicates that high process temperature can destroy the bridge bonds of amorphous carbon produced at low carbonization temperature (e.g., less than about 1200°C) and is essential for the morphology change from amorphous carbon to graphitic carbon layer stacks. S-2700 reached a stacking height of 26.97 nm and an interlayer number of 81.12 layers, while S-2500 showed a lower stacking height of 19.26 nm and a lower interlayer number of 58.18 layers. The stacking height of G-Ref, which has an intermediate layer number of 151.34 layers, was 50.57 nm, which was 2 to 3 times that of S-2500 and S-2700. By approaching the processing temperature to 3000°C, the results such as stacking height, number of layers, graphitization percentage, FFT image, etc. are expected to approach those of the reference graphite sample G-ref. Depending on the target market, a lower or higher processing temperature can be selected to graphitize the carbon particles less or more. It will be understood that the higher the degree of graphitization, the higher the expected value in the market. A higher processing temperature requires greater operating costs and may also reduce the processing capacity to reach and maintain the high processing temperature.

[0109] [Table 12]

[0110] Figure 14 shows the Raman spectra of all samples. -1 The D band around 1590 cm represents defects and disorder at the edges of the graphite layers. -1 The G band near the center is the vibration of the in-plane C-C bonds of graphitic carbon. I D / I G is used to represent the degree of disorder in the carbon structure. D / I G The value of I D / I G The ratio decreased from 0.83 in S-1200 to 0.51 in G-2500-1. D / I G The I value for S-2700 was reduced to 0.16. High and ultra-high temperature treatments can transform amorphous carbon into an ordered carbon structure. The G-ref sample had an I value of 0.10. D / I G It has the lowest defect value of 2700cm. -1 The nearby peak is a typical graphite peak, which becomes more developed after high temperature treatment.

[0111] Exposing a hydrocarbon to the high temperature hydrogen and carbon pyrolysis separation process disclosed herein results in a carbon product with increased value compared to the hydrocarbon feedstock. The increased value can be measured in a variety of ways. For example, increasing the carbon content increases the value. Thus, the carbon content can be increased from 75% by weight in methane gas to a solid carbon product with more than 95% carbon by weight. When coal is used as the hydrocarbon feedstock, the carbon content can be increased from about 80% by weight, including other elemental impurities, to more than 95% by weight carbon by reduction of HNSO and reduction of mineral contaminants from the carbon matrix. In the case of biowaste, wood, and lignite, the carbon content of the dry solid hydrocarbons can be as low as 50% or less by weight. The high temperature hydrogen and carbon pyrolysis separation process can produce carbon products with a carbon content of about 90% or more by weight from these solid hydrocarbon feedstocks while removing HNSO and mineral contaminants. If the temperature is raised to a sufficiently high temperature, greater than 2500°C and reaching 3000°C, the carbon content can approach and exceed 99%. Furthermore, characterization of the graphitization degree of the carbon indicates a degree of graphitization of about 80% or more. The increase in graphitization degree can also be considered as an increase in commercial value. Carbonized carbon and graphitized solid carbon have at least twice the commercial value per ton in the marketplace compared to the hydrocarbon feedstock.

[0112] (Embodiment) Various embodiments are listed below, and it will be understood that the embodiments listed below can be combined with all aspects and other embodiments in accordance with the scope of the present invention.

[0113] Embodiment 1: A continuous hydrocarbon pyrolysis process for producing hydrogen gas and carbon comprising exposing a hydrocarbon feedstock to oxygen-deficient combustion gas in a hydrocarbon pyrolysis zone, the combustion gas being generated by a valveless pulse combustor, the combustion gas entering the hydrocarbon pyrolysis zone at a combustion gas temperature greater than 2400° C., and the hydrocarbon feedstock and the combustion gas having a residence time in the hydrocarbon pyrolysis zone of less than 30 seconds to effect pyrolysis of the hydrocarbon feedstock to produce gas comprising hydrogen and solid particles comprising carbon. Embodiment 2: The hydrocarbon pyrolysis process of embodiment 1, wherein the hydrocarbon feedstock is selected from gaseous, liquid, and solid hydrocarbon materials. Embodiment 3: The hydrocarbon pyrolysis process of embodiment 1 or 2, wherein the valveless pulse combustor is operated by burning the fuel with an oxygen source having an oxygen content of greater than 50% by volume. Embodiment 4: The hydrocarbon pyrolysis process of embodiment 1 or 2, wherein the oxygen source has an oxygen content of greater than 85% by volume. Embodiment 5: The hydrocarbon pyrolysis process of embodiment 1 or 2, wherein the oxygen source has an oxygen content of greater than 90% by volume. Embodiment 6: The hydrocarbon pyrolysis process of any of the previous embodiments, wherein the oxygen-deficient combustion gas has an oxygen content of less than 2% by volume. Embodiment 7: The hydrocarbon pyrolysis process of any of the previous embodiments, wherein the oxygen-deficient combustion gas has an oxygen content of less than 1% by volume. Embodiment 8: A hydrocarbon pyrolysis process according to any of the previous embodiments, wherein the residence time in the hydrocarbon pyrolysis zone is less than 5 seconds. Embodiment 9: A hydrocarbon pyrolysis process according to any of the previous embodiments, wherein the residence time in the hydrocarbon pyrolysis zone is less than 2 seconds. Embodiment 10: A hydrocarbon pyrolysis process according to any of the previous embodiments, wherein the gases and solid particles produced in the hydrocarbon pyrolysis zone exit the hydrocarbon pyrolysis zone at a temperature greater than 1200° C. Embodiment 11: A hydrocarbon pyrolysis process as described in embodiment 10, comprising cooling the gas and solid particles exiting the hydrocarbon pyrolysis zone in a heat exchanger to a temperature of less than 200°C. Embodiment 12: The hydrocarbon pyrolysis process of embodiment 11, comprising separating the solid particles from the gas. Embodiment 13: The gas is treated to remove unwanted particles and gas molecules, and contains more than 80% H by volume. 2 H with concentration 2 13. A hydrocarbon pyrolysis process as recited in embodiment 12, comprising producing a contained gas. Embodiment 14: The gas is treated to remove unwanted particles and gas molecules, and contains more than 90% H by volume. 2 H with concentration 2 13. A hydrocarbon pyrolysis process as recited in embodiment 12, comprising producing a contained gas. Embodiment 15: H 2 14. A hydrocarbon pyrolysis process as described in embodiment 13, comprising continuously introducing the contained gas into a power generation facility without long-term storage. Embodiment 16: H 2 14. A hydrocarbon pyrolysis process as recited in embodiment 13, comprising continuously introducing the contained gas into a hydrometallurgical production facility without long-term storage. Embodiment 17: H 2 15. A hydrocarbon pyrolysis process as described in embodiment 14, comprising continuously introducing the contained gas into a chemical production facility without long-term storage. Embodiment 18: The hydrocarbon pyrolysis process of embodiment 12, wherein the solid particles have a carbon content of greater than 90% by weight as characterized by CHNSO analysis. Embodiment 19: The hydrocarbon pyrolysis process of embodiment 12, comprising heating the solid particles to a temperature greater than 2500° C. Embodiment 20: The hydrocarbon pyrolysis process of embodiment 19, wherein the solid particles comprise carbon having a percent graphitization greater than 80% as characterized by X-ray diffraction.

[0114] Embodiment 21: A valveless pulse combustor for combusting a fuel and a source of oxygen to produce a combustion gas, the source of oxygen having an oxygen content greater than 85% by volume, the combustion gas being oxygen deficient; a hydrocarbon pyrolysis zone configured to receive a combustion gas and a hydrocarbon feedstock, the combustion gas entering the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., the hydrocarbon feedstock and the combustion gas having a residence time within the hydrocarbon pyrolysis zone of less than 30 seconds to effect pyrolysis of the hydrocarbon feedstock to produce gases and solid particles comprising hydrogen gas and carbon, and the gases and solid particles produced in the hydrocarbon pyrolysis zone exiting the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; a heat exchanger configured to cool the gas and solid particles exiting the hydrocarbon pyrolysis zone to a temperature of less than 200°C; A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon, comprising: Embodiment 22: A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as described in embodiment 21, comprising a gas / particle separator that separates solid particles from the gas. Embodiment 23: A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as described in embodiment 22, wherein the gas / particle separator is selected from a cyclone gas / particle separator and a baghouse gas / particle separator. 24. Removing unwanted gas molecules from a gas and purifying the gas with more than 80% H by volume. 2 H with concentration 2 2. A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as described in any of the previous embodiments, comprising a gas absorber producing a contained gas.

[0115] Embodiment 25: A combined system for continuous hydrocarbon pyrolysis to produce hydrogen gas and to receive and combust the hydrogen gas to produce electricity, comprising: a valveless pulse combustor for combusting a fuel and a source of oxygen to produce a combustion gas, the source of oxygen having an oxygen content greater than 85% by volume, the combustion gas being oxygen deficient; a hydrocarbon pyrolysis zone configured to receive a combustion gas and a hydrocarbon feedstock, the combustion gas entering the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., the hydrocarbon feedstock and the combustion gas having a residence time within the hydrocarbon pyrolysis zone of less than 30 seconds, causing pyrolysis of the hydrocarbon feedstock to produce gases and solid particles comprising hydrogen gas and carbon, and the gases and solid particles produced in the hydrocarbon pyrolysis zone exiting the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; a heat exchanger configured to cool the gas and solid particles exiting the hydrocarbon pyrolysis zone to a temperature of less than 200°C; a gas / particle separator that separates solid particles from the gas; Removes unwanted gas molecules from the gas and produces H with more than 80% by volume. 2 H with concentration 2 a gas absorber for producing a continuous source of contained gas; H 2 Connected to a continuous source of contained gas, H 2 A power generation facility that burns the contained gas to generate electricity; A complex system including:

[0116] The described embodiments and examples are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is therefore indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are embraced within their scope.

Claims

1. 1. A continuous hydrocarbon pyrolysis process for producing hydrogen gas and carbon comprising exposing a hydrocarbon feedstock to oxygen-deficient combustion gas in a hydrocarbon pyrolysis zone, the combustion gas being generated by a valveless pulse combustor, the combustion gas entering the hydrocarbon pyrolysis zone at a combustion gas temperature greater than 2400° C., and the hydrocarbon feedstock and the combustion gas having a residence time in the hydrocarbon pyrolysis zone of less than 30 seconds to effect pyrolysis of the hydrocarbon feedstock to produce gas comprising hydrogen and solid particles comprising carbon.

2. 10. The hydrocarbon pyrolysis process of claim 1, wherein the hydrocarbon feedstock is selected from gaseous, liquid, and solid hydrocarbon materials.

3. 10. The hydrocarbon pyrolysis process of claim 1, wherein the valveless pulse combustor is operated by burning a fuel with an oxygen source having an oxygen content of greater than 50% by volume.

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

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

6. 2. The hydrocarbon pyrolysis process of claim 1, wherein the oxygen-deficient combustion gas has an oxygen content of less than 2% by volume.

7. 2. The hydrocarbon pyrolysis process of claim 1, wherein the oxygen-deficient combustion gas has an oxygen content of less than 1% by volume.

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

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

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

11. 11. The hydrocarbon pyrolysis process of claim 10, comprising the step of cooling the gas and solid particles exiting the hydrocarbon pyrolysis zone to a temperature of less than 200°C in a heat exchanger.

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

13. The gas is treated to remove unwanted particles and gas molecules, and contains more than 80% H by volume. ２ H having a concentration ２ 13. The hydrocarbon pyrolysis process of claim 12, further comprising the step of producing a contained gas.

14. The gas is treated to remove unwanted particles and gas molecules, and contains more than 90% H by volume. ２ H having a concentration ２ 13. The hydrocarbon pyrolysis process of claim 12, comprising the step of producing a contained gas.

15. H ２ 14. The hydrocarbon cracking process of claim 13, comprising the step of continuously introducing the contained gas into a power generation facility without long term storage.

16. H ２ 14. The hydrocarbon pyrolysis process of claim 13, comprising the step of continuously introducing the contained gas into the hydrometallurgical production facility without long-term storage.

17. H ２ 15. The hydrocarbon pyrolysis process of claim 14, comprising continuously introducing the contained gas into a chemical production facility without long-term storage.

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

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

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

21. a valveless pulse combustor for combusting a fuel and a source of oxygen to produce a combustion gas, the source of oxygen having an oxygen content greater than 85% by volume, the combustion gas being oxygen deficient; a hydrocarbon pyrolysis zone configured to receive combustion gases and a hydrocarbon feedstock, the combustion gases entering the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., the hydrocarbon feedstock and the combustion gases having a residence time in the hydrocarbon pyrolysis zone of less than 30 seconds to effect pyrolysis of the hydrocarbon feedstock to produce gases and solid particles comprising hydrogen gas and carbon, and the gases and solid particles produced in the hydrocarbon pyrolysis zone exiting the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; a heat exchanger configured to cool the gas and solid particles exiting the hydrocarbon pyrolysis zone to a temperature of less than 200°C; 1. A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon, comprising:

22. 22. A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as described in claim 21 including a gas / particle separator that separates solid particles from the gas.

23. 23. The continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as recited in claim 22, wherein the gas / particle separator is selected from a cyclone gas / particle separator and a baghouse gas / particle separator.

24. Remove unwanted gas molecules from the gas and create more than 80% H by volume. ２ H having a concentration ２ 22. A continuous hydrocarbon pyrolysis system for producing hydrogen gas and carbon as claimed in claim 21 including a gas absorber producing a contained gas.

25. 1. A combined system for continuous hydrocarbon pyrolysis to produce hydrogen gas and to receive and combust the hydrogen gas to produce power, the combined system comprising: a valveless pulse combustor for combusting a fuel and a source of oxygen to produce a combustion gas, the source of oxygen having an oxygen content greater than 85% by volume, the combustion gas being oxygen deficient; a hydrocarbon pyrolysis zone configured to receive combustion gases and a hydrocarbon feedstock, the combustion gases entering the hydrocarbon pyrolysis zone at a temperature greater than 2400° C., the hydrocarbon feedstock and the combustion gases having a residence time within the hydrocarbon pyrolysis zone of less than 30 seconds, causing pyrolysis of the hydrocarbon feedstock to produce gases and solid particles comprising hydrogen gas and carbon, and the gases and solid particles produced in the hydrocarbon pyrolysis zone exiting the hydrocarbon pyrolysis zone at a temperature greater than 1200° C.; a heat exchanger configured to cool the gas and solid particles exiting the hydrocarbon pyrolysis zone to a temperature of less than 200°C; a gas / particle separator for separating solid particles from the gas; Remove unwanted gas molecules from the gas and create more than 80% H by volume. ２ H having a concentration ２ a gas absorber for producing a continuous source of contained gas; H ２ connected to a continuous source of containing gas, H ２ A power generation facility that burns the contained gas to generate electricity; A composite system including:

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