CARBON AND NET-HYDROGEN LIQUIDS PRODUCTION

CROSS-REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to and the benefit of U.S. Provisional Patent Application Nos. 62/209,274 filed August 24, 2015, 62/209,851 filed August 25, 2015, 62/212,510 filed August 31 , 2015, 62/218,476 filed September 14, 2015, 62/233,958 filed September 28, 2015, and 62/372,173 filed August 8, 2016, the entireties of which are incorporated by reference herein.

BACKGROUND

[0002] Finite deposits of fossil fuels are mined and burned to produce energy for manufacturing goods and providing services to propel the remarkably successful industrial revolution that civilization with some 7 Billion human participants now depends upon. Fossil substances such as coal, oil, and natural gas accumulated during more than a million years in a time period 60 million to 250 million years ago are burned each year to meet the energy demands of the world's growing population.

[0003] Rapid burning of fossil fuels that were slowly collected and stored for millions of years in sealed subterranean formations has caused dramatic recent changes in the composition of the earth's atmosphere. Atmospheric concentrations of carbon dioxide and methane along with manmade substances have increasingly changed the global climate particularly during the last 100 years by blocking radiation of heat from the earth's surface to the sky. Global warming has resulted because the earth's rapidly altered atmosphere traps increasingly more solar energy than during the millions of years before the industrial revolution.

[0004] In addition to increased concentrations of carbon dioxide in the global atmosphere, the world's oceans and other components of the hydrosphere have collected considerably more carbon dioxide and other greenhouse gases during the industrial revolution. This has extensively caused changes in the carrying capacity of the hydrosphere along with acidification and destruction of carbonate deposits of limestone and other formations to cause additional releases of carbon dioxide. SUMMARY

[0005] FUTILE COMBUSTION OF CARBON DILEMMA: Earth's entire present and expected human population cannot earn enough discretionary income to pay the cost of repairing damages that have occurred and are predicted to increasingly occur so long as the carbon in fossil fuels continues to be burned to support human earning endeavors. The invention embodiments disclosed herein provide profit driven collection of carbon and hydrogen from substances that rot or burn to overcome the ominous carbon combustion dilemma that has been created by the industrial revolution. Such carbon can be utilized to produce equipment that collects more energy from solar, wind, moving water and geothermal resources (every day in many applications) compared to burning the carbon one time.

[0006] Carbon enhanced equipment can thus sustainably continue to produce energy. Coproduced hydrogen is combined with nitrogen and/or carbon dioxide from the air (or preemptively collected from more concentrated sources such as power plants, mineral calciners, ethanol refineries, bakeries, waste digesters, breweries, decaying permafrost and other unstable clathrates) to make liquid fuels that can be stored in existing gasoline, diesel or jet fuel tanks at ambient temperature and pressure.

[0007] Therefore utilization of such liquids in the world's 1 .2 Billion engines (soon to be 2 billion engines) can provide net-hydrogen benefits including lower fuel cost, extended engine life with lower maintenance costs, and greater power production when needed along with enabling such engines to actually clean the air that enters the engine.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figures 1 A, 1 B, 1 C, and 1 D show system embodiments for accomplishing the principles of the invention.

[0009] Figures 2A, 2B, 2C, 2D, 2E and 2F show embodiments produced by processes in accordance with the principles of the invention.

[0010] Figure 3 shows another system embodiment that performs in accordance with the principles of the invention. [0011] Figure 4 shows process embodiments that perform in accordance with the principles of the invention.

[0012] Figure 5 shows process embodiments that perform in accordance with the principles of the invention.

[0013] Figure 6A shows the top view of embodiment features in accordance with the principles of the invention.

[0014] Figure 6B shows a partially cut-away side view of embodiment features in accordance with the principles of the invention.

[0015] Figure 6C shows a partially cut-away top view of embodiment features in accordance with the principles of the invention.

[0016] Figure 6D shows a partially cut-away top view of embodiment features in accordance with the principles of the invention.

[0017] Figures 7A, 7B, 7C, 7D, 7E and 7F show representative embodiments of the invention.

DETAILED DESCRIPTION

[0018] Figure 1A shows embodiment 100 for converting substances that rot or burn into carbon and hydrogen. In an illustrative operation methane from a renewable resource or natural gas is charged into system 100 through port 134 and is distributed by groove 136 to flow upward between tubes 104 and 106. Annular curvilinear wall 132 directs the methane into seed particles and/or filaments that are distributed through spaced holes in rotating slide valve 144, which is normally sealed against a bearing plate until a spaced hole lines up with a bearing plate port as it is rotated at an adaptively controlled speed such as by heat-blocking chain drive assembly including motor 1 18, sprocket 120 chain 122 sprocket 124 and hollow drive tube 128.

[0019] Radiative, convective and conductive heat transfer from one or more resistive or inductive heaters 1 12 drives the dissociation reaction on the heated seed particles. Occasional cleaning of the inductive or resistive heaters and/or insulator curtain 1 10 to remove excess carbon deposits can be provided by admitting an oxidant such as air or oxygen through port 142 of valve 140 for delivery through orifices 1 16 of tube nipple 1 14. This occasional delivery of oxidant to the zone requiring cleaning quickly converts excess deposits of incandescent carbon into carbon monoxide and/or carbon dioxide to restore the electrical and/or radiative properties of the resistive and/or inductive components 1 12 and/or the radiation transmitting and/or re-radiating properties of insulator curtain 1 10.

[0020] In some modes of operation the insulator curtain 1 10 is allowed to collect carbon deposits for the purpose of serving initially as a blocking curtain to keep components 1 12 from being fouled by carbon deposits from methane dissociation. After suitable loading of carbon deposits curtain 1 10 can be removed to serve as a filter media, reinforcement web for roofing, pavement, or concrete and in various other durable product applications. Similarly curtain wall 108 can be removed after achieving suitable loading of carbon deposits to serve in similar or other durable goods applications.

[0021] Rotary union 128 connects stationary tube 126 to provide delivery of gases through rotating tube 128 from the zone proximate to heating elements 1 12. Gas delivery may include hydrogen, un-reacted feedstock hydrocarbon, e.g., methane and occasional flows of carbon monoxide, carbon dioxide and nitrogen if air is utilized instead of oxygen for removal of excess carbon deposits.

[0022] Seed particles 130 can consist of various ceramics, metals, intermetallics, and graphene or graphite and can range in shape, size and aspect ratio from nano, micro or macro spheroids to filaments and serve as radiation receivers that are rapidly heated to suitable temperatures for supporting dissociation of the methane into carbon and hydrogen as summarized by Equation 2. Upon satisfactory growth to form larger particles and/or filaments 150 as carbon is deposited from dissociated donor feedstock, various batch or continuous unloaders or conveyers of the grown carbon can be utilized including rotating gears and reciprocating piston types 152 and 154 that receive the grown carbon in the "load" position and are cyclically stroked to compact the carbon into smaller volumes in reduced cross section area exit passageways or grates to exclude gases such as hydrogen and/or unreacted donor gas back into the pathway for filtration and travel upward to combustion zone 1 12 and/or through valve 140 to fitting 138 for collection. Suitable stroke drivers include rack and pinion, gear drives, crank and cam actuators, hydraulic and pneumatic cylinders (not shown). [0023] Figure 1 B shows delivery of feedstock hydrocarbon through one or more tubes 133, 135, etc., to a region near radiant tube assembly 1 10, 1 12 for the purpose of deflecting or spraying away particles and/or filaments that are receiving carbon depositions. Tubes 133, 135 etc., can be straight, curved, or helical with orifices that are suitably oriented to spray against or deflect particles and filaments to prevent radiation from penetrating into the zone of carbon growth as hydrogen is co-produced. The orientation of orifices in tubes 133, 135, etc., for delivery of feedstock fluids can be more or less tangential to radiant heating tube 1 12 and/or presented in other suitable patterns for keeping one or more radiant tubes 1 10-1 12 relatively clean in operation. In operation adaptive control of the pressure that the hydrocarbon spray pattern is variably regulated can provide a reduced or greater rate of carbon particle and filament deposition compared to carbon deposits on curtain or screen media 1 10.

[0024] Figure 1 C shows a top view of radiant tube assembly which can include a transparent, translucent, or opaque tube 1 12 that is porous or not to gas flow. Hydrocarbon or another suitable carbon donor fluid is sprayed through orifices in a suitable number of delivery tubes such as 133, 135, 137 and/or other tubes to deflect carbon growth particles and/or filaments away from tube 1 12 to prevent fouling. The spray pattern from tubes 133, 135, 137, etc., for reducing or preventing fouling can be oriented at any suitable angle or pattern and can be presented from straight, curved, helical or other shapes of the feedstock delivery tubes. Similar feedstock delivery tubes with spray cleaning arrangements can be utilized in embodiment 300 to reduce or prevent fouling of radiant tube heater assembly 312.

[0025] In some applications, circulation of particles from one portion of the carbon deposition zone such as from side to side and/or bottom to top is provided by directed flow of gases such as feedstock, produced hydrogen or another gas such as argon. In other instances such circulation can be by accomplished by one or more suitable mechanical conveyer(s) such as shown in Figure 1 D. In an exemplary application a helical fin conveyer 160 is rotated by fins, spokes or other connectors fastened to drive assembly 1 18-120-122-124-144 to lift particles and/or filaments from lower elevations towards the upper elevations of the carbon deposition zone around heater tube 1 12 for extending the time at sufficient feedstock dissociation temperature to provide additional carbon deposition and hydrogen production. [0026] Figure 2A shows embodiment 200 comprising particle 210 that may optionally have more or less round deposits of compounds, alloys, intermetallics, or metals such as iron, nickel, cobalt, copper or refractory metals, etc., that serve as substrates and/or catalysts 212 for growing various forms of carbon such as graphene and/or graphite and/or single or multiple wall nano tubes 214 and/or scrolls and/or ellipsoids or spheroids 216 as shown in Figure 2B.

[0027] Some applications utilize one or more constituents of petrolatum or other selections of organic substances to initiate carbon deposition sites that can receive additional carbon from dissociation of a carbon donor substance such as methane to produce various forms of carbon such as graphene and/or graphite and/or single or multiple wall nano tubes 214 and/or scrolls and/or ellipsoids or spheroids 216 as shown in Figure 2B. Similarly seed stock materials such as filament embodiment 204 can optionally include such petrolatum or other organic stimulants or inorganic catalysts 222 to produce carbon deposits in the form of graphene and/or graphite and/or single or multi-walled nanotubes 224 and/or scrolls, and/or ellipsoids or spheroids 226 as shown in Figure 2D.

[0028] Seed catalysts include deposits of intermetallics, metals or alloys such as iron, cobalt, nickel, copper and refractory metals that may be provided by any suitable method including precipitation from suitable solutions such as copper chloride, iron chloride, nickel or cobalt chloride. In other instances such metals are plated to a suitable thickness and heated in a suitable atmosphere to fuse and produce beads of suitable dimensions.

[0029] Substantial amounts of the carbon is deposited on such seed materials and remaining carbon that is not deposited can serve as additional seed stock that can receive additional carbon that is produced by continuing endothermic dissociation of methane. Such deposits can be on the surface contours of the seed and/or in forms similar to the more complex forms disclosed above.

[0030] Carbon deposit configurations that increase the surface to volume ratio and/or the friction and/or interlocking characteristics in applications such as strengthening agents for elastomers such as tyre rubber, architectural materials, engineering polymers, or various types of adhesives are examples of high value products. Figures 2B and 2D illustrate such configurations. In other applications similar configurations can be further converted for specialized purpose carbides, nitrides, borides, silicides and compounds with various halogens for new physical or chemical characteristics, optical properties, and/or to serve as chemical reaction catalysts.

[0031] In some applications it is desirable to provide carbon deposits on long fiber seed stocks to produce higher surface-to-volume ratio features and/or friction and/or interlocking characteristics in applications such as creating high strength fiber reinforcement filaments from low cost filaments. Illustratively carbon fiber filaments made from low cost fabric quality rayon, polyolefins, or polyacrylonitrile copolymers can be converted by such deposit configurations to achieve equal or greater fiber- reinforcement performance compared to high quality PAN sourced carbon filaments.

[0032] In an exemplary embodiment methane can be polymerized to ethane, which is dehydrogenated to ethylene that is polymerized or co-polymerized and stretch oriented during dehydrogenating carbonization to produce low cost feedstock filaments that receive high surface-to-volume deposits from dissociation of a suitable hydrocarbon such as one or more petrolatum constituents, various molecular weights of wax, petroleum jelly, natural gas constituents and/or renewable methane to provide highly desirable fiber strengthening, optical, electronic and/or other specialized physical or chemical capabilities.

[0033] In many applications such low cost prickly, fuzzy, bristly, or wooly carbon fibers and/or particles can reinforce equipment to collect more energy (every day in many applications) from renewable solar, wind, moving water or geothermal resources compared to burning such carbon one time. It is synergistic to utilize such prickly filaments or fibers along with such prickly particles to increase the fatigue endurance strength and other properties of composited components. This provides energy harvesting equipment with exponential energy collection advantages over burning such carbon one time, which causes highly objectionable amplification of the greenhouse gas global warming dilemma.

[0034] Figure 3 shows embodiment 300 in which processes such as summarized by Equations 1 and 2 provide self-fueled or autogenous production of carbon and hydrogen.

CxHy + HEAT xC + 0.5y H ₂ Equation 1 CH ₄ + HEAT C + 2H ₂ Equation 2

[0035] In the processes shown by Equations 1 and 2, heat sufficient in quantity and quality to drive the anaerobic dissociation reactions shown can be produced by combustion of a portion of the feedstock hydrocarbon CxHy such as CH ₄ and/or a portion of the hydrogen that is produced by such reactions. In some instances a portion of the carbon and/or the hydrogen produced by such reactions can be utilized in one or more engine-generators or fuel cells to produce electricity that powers one or more electrolysis cells and/or resistive or inductive heaters to supply or supplement energy for such anaerobic dissociation processes.

[0036] In other instances as shown in Figure 4, a heat engine and generator to provide heat and electricity for driving the dissociation processes can utilize feedstock hydrocarbon and/or dissociated hydrogen for fuel. Heat rejected by such heat engines can be used to preheat the feedstock hydrocarbon and/or combustion air and the electricity can be utilized for electrolysis and/or to produce resistive and/or inductively induced radiative heating of the seed stock or continuing carbon deposition and growth processes.

[0037] In embodiment 300, shown in Figure 3, a portion of such feedstock and/or one or more dissociated fuel products can be combusted within tube 312 which may be transparent, translucent, or opaque to anaerobically heat the feedstock and cause dissociation as shown by Equations 1 and/or 2. Similarly various other feedstocks such as sewage, garbage, forest slash and farm wastes that may contain other elements such as oxygen, nitrogen, sulfur, silicon, etc. , can be processed to yield carbon and hydrogen and derivatives of the other elements found in such feedstocks.

[0038] In an exemplary operation a hydrocarbon feedstock such as natural gas or methane is provided at suitable pressure such as 1 to 100 Bar through fitting 320 into distribution groove 322 for upward passage between steel tube 304 and 306. In some instances it is desirable to insulate the inside of tube 304 and/or the outside of tube 306 with insulative refractory cloth, felt or wool 305 to reduce heat transfer and contact of gaseous molecules with tube 304 and/or 306 to thus improve the insulative characteristics of typical hydrocarbon feedstocks. In some applications the feedstock hydrocarbon such as CH ₄ is directed along an extended length helical pathway that is provided by helical tube or fin 325 that is spiraled to traverse all or a selected portion of tube 304.

[0039] In some applications the feedstock can be heated prior to entering fitting 320 by heat transferred from carbon, hydrogen and/or un-reacted feedstock by one or more counter-current circuits with heat exchange components such as 327A, 327B, 327C, 329, 331 , 333, and/or 344.

[0040] After entering the dissociation system through fitting 320 the feedstock hydrocarbon insulates tube 306 and its contents including collection of heat that escapes or is transferred from tube 306 to heat the feedstock during the upward travel within the annular space between tube 306 and 312. Such preheated hydrocarbon feedstock is turned downward by feature 342 as shown to travel downward and be more intensely heated to cause rapid anaerobic decomposition into the dissociation products shown in Equations 1 and 2.

[0041] Combustion of hydrogen and/or un-reacted or partially cracked hydrocarbon feedstock is provided at suitably located oxidant entry holes and thus flame ports 316 in tube nipple 313. In applications that provide a high percentage of hydrocarbon dissociation into carbon and hydrogen 31 1 , the gases that are produced by hydrogen combustion with air and delivered through bearing-seal or rotary union 323 may include surplus hydrogen (H ₂ ), nitrogen (N ₂ ) and water vapor (H ₂ 0). The water vapor may be removed by condensation and/or a suitable desiccant to provide a suitable mixture of hydrogen and nitrogen for production of various selections of substances such as ammonia as shown by Equation 3.

3H ₂ + N ₂ 2NH ₃ Equation 3

[0042] Equations 4 and 5 can utilize such ammonia as a fuel, fertilizer, or a reagent for production of a wide variety of nitrogenous products such as polyacrylonitrile, ammonium nitrate and urea as shown. Ammonia can also be subsequently utilized to produce many other valuable products including polyacrylonitrile (C ₃ H ₃ N) or PAN for spinning into clothing threads, yarn and woven products or dissociated and crystallized into high strength carbon fibers. [0043] Equation 4 summarizes the processes for production of such polyacrylonitrile that can be dissociated to produce ammonia and carbon filaments 204 and/or carbon fibers 354 or 356.

3NH ₃ + 3CO C3H3N + 3H ₂ 0 + N ₂ Equation 4

[0044] The amount of hydrogen that is admitted into combustor tube 312 and the proportionate amount of oxide such as air the is delivered through the flame ports 316 in tube 313 can be adaptively adjusted by valve assembly 330 to produce a suitable mixture of hydrogen and nitrogen for processes such as depicted by Equations 3 and/or 4. In other instances a portion of the feedstock hydrocarbon such as methane is admitted into combustor tube 312 to provide a mixture of combustion products such as hydrogen (H ₂ ), nitrogen (N ₂ ), carbon monoxide (CO) and/or carbon dioxide (C0 ₂ ) and water vapor (H ₂ 0).

[0045] If needed, the water vapor (H ₂ 0) can be reduced or removed by condensation and/or a suitable regenerative desiccant. Such mixtures or proportions of such reactants can be adjusted and utilized to produce compounds such as PAN, ammonium cyanate, or urea {CO(NH ₂ ) ₂ } as summarized by Equations 5 and/or 6.

2H ₂ + N ₂ + CO CO(NH ₂ ) ₂ Equation 5

2NH ₃ + C0 ₂ CO(NH ₂ ) ₂ + H ₂ 0 Equation 6

[0046] Heat generated by combustion within combustion tube 312 is radiated through transparent or translucent tube 312 or in some applications such heat energy is re-radiated by opaque tube 312. This includes instances that tube 312 is provided as a transparent or translucent tube and becomes increasingly opaque due to carbon deposition on the outside surface.

[0047] Suitable translucent or transparent tubes include various ceramics such as alumina (sapphire), fused silica (quartz), and magnesia. Suitable high temperature opaque materials include ceramics such as silicon carbide, molybdenum disilicide, super alloys, platinum group alloys and refractory alloys. High temperature insulator cloth or felt tube 310 can be made of aluminum oxide fiber and/or silica fiber and/or carbon fiber etc., and can be similarly transparent, translucent or opaque to the radiation from combustion tube 312. The combustion released energy can be transmitted or re-radiated to rapidly heat fibers or particles 326 that are supplied from the hopper 336 as shown at an adaptively controlled rate by rotary distributor 338 as driven through hollow shaft 319 by torque motor 318 and chain drive assembly 320, 322, and 324.

[0048] Hopper feature 336 can serve as a containment wall and can be ribbed or have suitably shaped heat transfer and/or stirring fins 315 and can be rotated along with hollow tube 319 to increase heat transfer to particles or fiber seeds in the hopper which may have rotating or stationary wall features 317 to increase the shear and mixing of particles and/or fibers including additions of seed growth agents such as one or more constituents of petrolatum. The seed hopper can be covered with a suitable lid (not shown) for various heat conservation or atmosphere control purposes such as retaining a suitable cover gas.

[0049] Fibers or particles 326 are supplied as precursors for receiving rapidly deposited carbon from dissociated hydrocarbon such as shown by Equations 1 and 2. Such fibers or particles continue to be rapidly grown by carbon deposition supplied from continuing hydrocarbon dissociation at suitable operating temperatures such as about 1 100°C to 1700°C. The rate of deposition and/or dwell time of particles in the fluidized bed growing zone can be adjusted by admission of gas such as hydrogen and/or feedstock hydrocarbon and/or one or more products of combustion through one or more suitably located ports including passageways 348 in one or more suitably oriented conveyor screws 333. After suitable growth such carbon fibers and/or particles 328 are collected at the bottom of the annular space between tube 306 and 312 including the zone below gas porous separator 334 and the gas porous skirt below combustion tube 312.

[0050] Any suitable batch or continuous processes such as one or more gears, reciprocating piston extruders, helical screw conveyers 333, one of which is shown as being removed along one of the centerlines of rotation, through the bottom plate 343. Such screw conveyers can be rotated at an adaptively controlled speed by controller 125 or 345 to remove such grown carbon products at a rate to maintain the desired density of the fluidized bed for carbon growth processes of the fluidized zone of operation.

[0051] In some embodiments screw conveyers 333 utilize designs that squeeze and densify the collected carbon to exclude gases such as hydrogen and/or hydrocarbons by progressively decreasing the pitch or the profile dimensions of thread features. In other words the conveyer causes the collected carbon to travel within volumes between screw flights that are progressively smaller as gases are squeezed out into slots or holes to gas relief passageways in the barrel tube (not shown) that contains the rotated screw. In certain applications passageway 348 can be helical, ribbed, or otherwise provided with extended heat transfer surfaces by investment casting of the 333 compacting screw conveyer.

[0052] Hydrogen 31 1 and/or remaining hydrocarbon molecules filter through the gas porous skirt and porous filter 334 to supply fuel for combustion within tube 312 and collection from fitting 330 below the counter-current heat exchange with oxidant such as oxygen or air that is supplied through port 332 of proportional control valve 339 and thus to the flame ports 316 in tube nipple 313 as shown.

[0053] Gases passing from combustion tube 312 into stationary tube 346 can be maintained at elevated temperature, further heated, or cooled by heat exchanger 329 depending upon the parameters of further process steps. In some applications heat is transferred from such gases to preheat seed feedstock including coatings such as selected petrolatum constituents that may or may not include metal organic, metal halide, or other metal precursors to thus serve as fibrous, scrolled or bulbous carbon growth stimulators to produce woolly, fuzzy or prickly particles, filaments, or fibers.

[0054] The amount of feedstock hydrocarbon and/or the proportion of the produced hydrogen 31 1 that is combusted with adaptively proportioned oxidant to drive the dissociation reactions such as shown by Equation 1 or 2 depend substantially upon the reaction rates and efficiency of insulative systems and materials 302, 305 and 308. Controller 345 receives information such as temperature, pressure, and dwell time along with the deposition pattern to adaptively provide proportional control of the regulator 347 pressure of the hydrogen and carbon donor feedstock addition, the rate of seed particles and/or filament additions by motor 318, the temperature reached by feedstock preheating operations, the temperature of radiative heaters and dissociation operations in the fluidized bed zone, the regulator 349 pressure of hydrogen and/or unreacted feedstock extraction, the regulator 351 pressure of oxidant addition through proportional control valve 339, and the regulator 353 pressure that gases are extracted at regulated temperature from heat exchanger 329 along with other process instrumentation and control algorithms.

[0055] In order to meet the world's growing demand for carbon-enhanced products that can be stronger than steel, lighter than aluminum, and that are less energy intensive to produce than steel or aluminum, tubular components such as 304 and 306 can be rapidly formed and welded from recycled steel sheet to expedite practical commercialization. Such roll formed and welded tubes can be corrugated or ribbed to increase the section modulus for greater stability and to improve fluid flow control in the respective zones of operation. Subsequently carbon-fiber reinforced tubes such as 304 and 306 can be utilized to improve the return on investment on equipment such as embodiments 100 and 300.

[0056] In some applications heat is transferred from gases in conduit 346 through tubular spirals 325 to preheat feedstock hydrocarbon and/or seed feedstock including coatings such as selected petrolatum constituents that may or may not include metal organic, metal halide, or other metal precursors to thus serve as fibrous, scrolled or bulbous carbon growth stimulators to produce woolly, fuzzy or prickly particles or filaments. Carbon growth stimulators such as selected petrolatum constituents can be adaptively added through conduit 355 to coat carbon filaments or fibers 354 or 356 for initiating growth of friction inducing and/or interlocking surface structures from hydrocarbons such renewable methane, oil, and as natural gas constituents including butane, propane, ethane, and methane. Various felts such as fibrous alumina, silica, polyacrylonitrile, and/or polyimide can be utilized with such petrolatum to form suitable seals and to coat filaments or fibers such as 354, 356, etc., passing through such felts.

[0057] In some applications longer ceramic or carbon fibers or filaments 354, 356, etc., including fiber, twisted groups, yarn, woven, and/or unwoven configurations are supplied from suitable sources such as through feeder tubes, spindles, or from spools 350, 352 etc., to receive carbon deposits such as nano, micro, or macro deposits in the form of tubes, filaments, bulbs, scrolls, etc. Such deposits can be made in suitably selected portions of the heated deposition zone proximate to heaters 1 12 or combustion tube 312. Extended travel for such surface depositions can be provided by suitable placements of turning pins or idlers 358, 359, 360, 361 etc., and the resulting hot prickly, fuzzy, or woolly filaments or fibers can preheat incoming feedstock in the coaxial space between tubes 304 and 306 as shown. Regenerative heat can be exchanged from such processed carbon particles and filaments by heat exchanger 327C and/or 327B to preheat incoming hydrocarbon feedstock in heat exchanger 327A.

[0058] In many instances the resulting prickly, fuzzy, or wooly filaments or fibers are utilized to wrap or otherwise reinforce composited components such as consumer goods, structural components, truss members, various sizes of pressure rated tanks such as rail tank cars 366 or 367 for improved product performances and manufacturing efficiency. In applications that carbon fiber is to be packaged on spools and stored or shipped to another site for unpacking and utilization as improved interlocking reinforcements the surface embodiments may be spikey similar to the perpendicular barbs on barbed wire. This enables unwinding the spooled spikey fiber that can be bonded by composite forming matrix materials with or without interlocking spikey, fuzzy, or wooly particles and/or filaments mixed with selected thermoplastics and thermosets such as activated monomer styrene, epoxy, etc.

[0059] In applications that the prepared fibers are to be utilized directly, surface preparation embodiments such as curved or hooked filaments that form fuzzy or wooly surfaces can be utilized with improved efficiency with or without interlocking spikey, fuzzy, or wooly particles and/or filaments mixed with selected thermoplastics and thermosets such as activated monomer styrene, multi-part epoxies, etc.

[0060] In certain instances including applications such as shown in Figure 4, hydrogen that is co-produced by dissociation of selected carbon and hydrogen donor feedstocks is added to natural gas pipelines. An in-line selective semi-permeable membrane or particle size filter can be utilized to selectively remove such hydrogen from the mixture with natural gas constituents. This system embodiment is highly desirable for utilizing the vast storage capacity of the natural gas pipeline infrastructure for hydrogen storage and to provide convenient and low cost delivery of hydrogen to desired locations such as homesteads and industrial parks along with refineries, net-hydrogen ambient temperature liquid fuel production sites, organic and inorganic chemical and pharmaceutical manufacturing plants. [0061] As provided by Figure 5, in various instances such co-produced hydrogen is combined with nitrogen and/or carbon dioxide from the air or hydrosphere to produce net-hydrogen liquid fuels or reagents that can be stored at ambient temperature and pressure in existing gasoline, diesel, or jet fuel tanks and that can be transported by conventional liquid pipelines, marine tanker vessels, terrestrial tanker trucks, and rail tank cars. An oxide of carbon such as carbon monoxide or carbon dioxide and/or nitrogen for such net-hydrogen ambient temperature liquid fuel preparations can also be preemptively removed from more concentrated sources such as the exhaust pipes, vents or stacks of engines fueled by hydrocarbons, power plants, calciners, wastewater, digesters, landfills, breweries, bakeries, ethanol plants and/or decaying permafrost or other unstable clathrates.

[0062] In numerous applications a net-hydrogen carrier liquid such as one or more fuel alcohols can be prepared and utilized as a solvent for substances such as urea, nitro-methanol, and other solutes or functional additives to increase the energy density or to impart other useful capabilities and functions such as chemical combustion initiators or stimulants, higher or lower vapor pressure, viscosity adjustments, lubricity, polymerization inhibitors, and/or cleaning properties.

[0063] In an illustrative example, fuel alcohol such as methanol can be prepared by reacting hydrogen from Equations 1 or 2 with carbon monoxide or carbon dioxide as shown by Equations 7 and 8.

2H ₂ + CO CH ₃ OH Equation 7

3H ₂ + C0 ₂ CH ₃ OH + H ₂ 0 Equation 8

[0064] The methanol or methanol water solution prepared by Equations 7 and 8 can serve as a solvent for urea from Equations 5 or 6 or other substances to increase energy density or to impart other properties including viscosity, vapor pressure, lubricity, and ignition characteristics to serve as a replacement for gasoline or jet fuels. In other applications a portion of the alcohol such as methanol or ethanol is dehydrated to produce dimethylether (DME) and/or diethylether (DEE) that is added to the replacement for gasoline or jet fuel to serve as a suitable compression ignition fuel to replace diesel fuel. [0065] In some applications ethanol is produced by an ethanol refinery or it can be produced by reacting hydrogen from Equations 1 or 2 with an oxide of carbon as shown by Equations 9 and 10.

4H ₂ + 2CO C ₂ H ₅ OH + H ₂ 0 Equation 9

6H ₂ + 2C0 ₂ C ₂ H ₅ OH + 3H ₂ 0 Equation 10

[0066] In some applications heat rejected by an engine, concentrated solar energy, or produced by a furnace such as embodiment 100 or 300 can be utilized to endothermically react carbon dioxide with a hydrocarbon such as methane as shown by Equation 1 1 to produce carbon monoxide and/or hydrogen for producing a fuel alcohol such as methanol and/or ethanol with less water dilution as summarized by Equations 7 and 9.

CH ₄ + C0 ₂ + HEAT 2CO + 2H ₂ Equation 1 1

[0067] Such wet or dry ethanol and/or other higher energy density similarly produced alcohols can be blended with suitable amounts of methanol, urea, and/or dimethylether and/or other combustion initiators such as selected aldehydes and/or diethylether, and/or other additives to produce customized net-hydrogen liquid fuel replacements for gasoline, diesel, and jet fuels.

[0068] Figures 6A and 6B schematically illustrate certain components of furnace embodiment 600 that can be partially or fully constructed by a factory or partially or fully assembled in the field. In some applications sheet stock is spiral wound to make tubes 306 or 606 and 304 and 604 that are utilized for assembly 100 or 300 according to embodiment 600. In other instances sheet stock is formed into relatively long curved sections that are welded, brazed riveted or otherwise bonded for assembly 600.

[0069] Alternatively, the more or less coaxial tubes 104 or 304 corresponding to 604 and 106 or 306 corresponding to 606 can be fabricated from flat sheets or rolls of relatively thin selections of sheet material such as carbon fiber reinforced composite or steel about "W" wide. Suitable widths "W" can be about 3' to 12' to meet a variety application circumstances. In one mode of fabrication, such composite or sheet steel W wide such as 1018 low carbon or 302 or 310 stainless steel is initially formed into circular tube 606 and bonded or welded along a butt joint or along an overlapped seam that provides for the sheet stock to be formed into transition 605 and to continue to form coaxial tube 604, which is similarly bonded or welded along a butt joint or an overlapped seam. Alternatively more than one wrap of sheet stock can be used for tube 606 and/or 604.

[0070] The assembly of tube 604, transition 605 and tube 606 can be held within a base assembly that includes circular sheet strip 610, plate 612, ring 614, and plate 616 for bonded or welded rigidization to enclose space 618 which can be utilized for tube-inside-tube or other heat exchangers such as 351 and carbon removal systems such as piston-cylinder assemblies depicted by 152 and 154 and/or screw and cylinder conveyers depicted by 333 (cylinders not shown).

[0071] Subsequent similar fabrication of tube 606, transition 605 and tube 604 from W wide sheet stock can be reinforced by circular sheet belt 620 and welded along seam 608. At locations suitable for turning and directing carbon fibers 624, 625 etc., a reinforcing belt that includes suitable tube guides, pins or rollers such as 622, 623, etc., along with suitable gas seals.

[0072] In certain applications a tubular self-sealing ring or belt 650 as shown in the Figure 6D cross section is utilized to receive tubular sections such as 604 or 606 that become pinched and sealed as the component cross-sections interfere and conform to produce one or more constant lines of annular contact. In some instances a sealant adhesive such as a thermoplastic, thermoset polymer, bitumen, pitch or tar 651 can be pre-placed in each receiving slot of ring belt 650 to decrease the friction to aid in the assembly process and subsequently serve as supplemental sealant. After suitable settling of the components together a relatively small number of welds, rivets, or other bonding system provides strengthening of assembly 100 or 300 as shown.

[0073] After adding the needed number of such tubular units and heat generator assemblies 1 12 or 312, suitable gas flow features 132 or 342, seed gate assembly 144 or 338, fiber feed tubes or spools 350, 352, etc. are added and hopper components 336 and 352 are fitted and bonded or welded. Seed gate drive assembly 318, 320, 322, 324, 346 is added to control the particle and/or filament seed addition rate.

[0074] Certain applications utilize more than one gas permeable tube assembly similar to 1 12 that can include resistive or inductive heating elements. Other applications utilize more than one impermeable transparent, translucent, or opaque tube assembly similar to 312 that can include flame ports similar to 316 in tube nipples similar to 313. This provides the construction flexibility to make carbon furnaces 100 or 300 to meet a wide range of hydrocarbon supply situations, e.g., one heater tube to twelve or more heater tubes along with suitable proportionate diameters and heights of system 600.

[0075] Figure 6C shows a top view of an illustrative arrangement of six heater tubes that can include resistive or inductive heating elements and/or that can provide flame heating through transparent, translucent or opaque tubes. In an application, suitably arranged heat resistant tubes 630, 632, 634, 636, 638 and 640 such as quartz, alumina, or a selected superalloy can be utilized to contain hydrogen and/or unreacted hydrocarbon that is combusted with an oxidant such as air or oxygen distributed from flame ports in tube nipples such as 631 , 633, 635, 637, 639, and 641 .

[0076] Such multiple heater tubes along with various embodiments of system 600 are advantageous for enabling rapid field assembly of carbon and hydrogen production systems because each of the heater tube assembly components can be specified in dimensions and materials that are suitable for rapid assembly with a portable crane and hand tools. This advantage along with the weight and cost saving components of embodiment 600 enable rapid and low cost erection of systems with modularized components and computerized manufacturing processes to meet a wide variety of situations. Modular components and systems for rapid field erection are highly desirable for enabling virtually every community to produce selections of durable carbon products that far exceed the fuel value of burning such carbon from sources that rot or burn.

[0077] Co-production of hydrogen enables such communities to utilize existing industrial and space heating furnaces and engines that actually clean the air during operation. Such hydrogen can be synthesized with nitrogen and/or carbon dioxide into net-hydrogen liquid fuels to store and distribute fuel to replace gasoline, diesel and jet fuels.

[0078] Modularized subsystems for production of carbon fibers from polymer precursors, production of smooth, prickly, fuzzy, or wooly particles, filaments, and/or fibers can be delivered by barges, rail cars, and/or highway trucks to rapidly convert the world's economy from dependence upon burning carbon to more profitable operations that convert substances that rot or burn (including fossil and renewable substances) into durable carbon products and hydrogen and/or net-hydrogen liquid fuels that can replace gasoline, diesel, and jet fuels.

[0079] High strength fibers can be produced from organic feedstock polymers such as cellulose (rayon), polyethylene, polypropylene, polybutylene, polymethylpentene, polyacrylonitrile, pitch, and various inorganic materials and ceramics such as silica, alumina, MgAI ₂ 0 ₄ spinel, silicon nitride, silicon carbide, boron carbide, basalt etc.

[0080] Natural gas can be cleaned to remove impurities such as sulfur compounds and cooled to separate condensate collections of butane, propane, and ethane compounds. Each of these separated compound condensates can be dehydrogenated to produce monomers that can be polymerized to suitable thermoplastic precursor polymers. As an example ethane can be separated into hydrogen along with ethylene that is polymerized to suitable molecular weight polyethylene. Propane can be separated into hydrogen and propylene that is polymerized to suitable molecular weight polypropylene. Butane can be separated into hydrogen and butylene that is polymerized to suitable molecular weight polybutylene.

[0081] Accordingly, high strength carbon fibers can be produced from organic hydrogen and carbon donor substances by forming suitable molecular weight polymers that are spun, extruded, or otherwise formed or shaped into fibers that can be zone refined and/or stretched and thermally dehydrogenated to produce carbon fibers (C-Fibers). Suitable donor substances include one or more thermoplastics, petrolatum, wax, pitch, and thermosetting polymers including adhesives such as epoxy and monomer styrene-cross linking mixtures.

[0082] In an illustrative application, embodiment 700 of Figure 7A comprises a mixture of a suitable carbon and/or hydrogen donor 702 and specifically or randomly oriented single or multiple layer graphene particles or platelets such as 704 that are increasingly oriented such as 706, 708, and 710 as the mixture is spun, extruded, stretched or otherwise formed by suitable tooling and/or dies into a filament 712. Various cross sections for decreasing or increasing the potential winding density of filaments such as 712 and/or 762 illustratively include those shown in Figures 7C and 7D compared to the packing factors and various other characteristics provided by other configurations including examples 7E and 7F.

[0083] Such filaments are suitably heated by partial combustion, radiation, electric resistance or induction to dissociate the carbon donor and provide carbon that can be added to said filament and/or oriented graphene platelets to strengthen and provide a filament that can serve as a precursor to receive additional carbon deposition from dissociation of a suitable fluid such as gaseous substance CxHy, e.g., acetylene, natural gas constituents or renewable methane. In certain embodiments the oriented graphene serves as one or more hosts or templates for said additional carbon deposition to form graphene. The resulting filaments can be utilized to form C- Fibers and/or reacted with silicon, nitrogen, boron, or transition metal donor substances such as their respective carbonyls and other compounds to bond and interlock the platelets to strengthen the fibers and/or to produce suitable surface textures.

[0084] In another illustrative embodiment, graphite is subdivided by ball milling or other suitable grinding methods to produce a multitude of graphene platelets of about one to sixty or more layers. The platelets are mixed with one or more suitable polymers such as one or more polyolefins, pitch, petrolatum, wax, or polyactylonitrile in a form such as 700 shown in Figure 7A and extruded, spun, or otherwise formed at a suitable temperature from a relatively large cross section 702 into a filament of much successive smaller cross sections 706, 708, 710 and 712. Such forming process can orient and/or shear the multilayered platelets into additional layers for the purpose of creating an elongated graphene network that can include partially overlapping platelets that can be grown on the edges, surfaces, and/or bonded by interlocking compounds and/or linked by carbon that is derived from dissociation of the polymer and/or from additional carbon that is provided by dissociation of carbon donor fluids such as constituents of natural gas and renewable methane including the process disclosed regarding Figures 1 A, B, C, D, and/or Figure 3.

[0085] In another illustrative application, embodiment 750 of Figure 7B comprises a mixture of a suitable carbon and/or hydrogen donor 752 and specifically or randomly oriented particles or platelets such as single wall or multiple wall tubes 754 that are increasingly oriented such as 756, 758, and 760 as the mixture is spun, extruded, stretched or otherwise formed by suitable tooling and/or dies into an elongated filament 762. Such filaments are suitably heated by partial combustion, radiation, electric resistance or induction to dissociate the carbon donor and provide carbon that can be added to said filament and/or oriented graphene platelets to provide a filament that can serve as a precursor to receive additional carbon deposition from dissociation of a suitable gaseous substance such as CxHy including acetylene, constituents of natural gas or renewable methane. In certain embodiments the oriented tubes serves as one or more templates for said additional carbon deposition to form larger and/or longer tubes. The resulting filaments can be utilized to form C-Fibers and/or reacted with silicon, nitrogen, boron, or transition metal donor substances to form interlocking bonds to strengthen the fibers.

[0086] Alternatively, one of many ways to produce high strength ceramic fibers can be accomplished by melting ceramic substances and blow forming, spinning or extruding fine fibers. Illustratively, various acceptable ceramics including compositions of natural basalt rock can be melted and blow formed, extruded, or spun to produce high strength fibers (B-Fibers). Heat for the melting operations can be from solar, wind, moving water, geothermal energy conversion systems or from combustion of fossil or renewable fuels particularly including hydrogen that is co- produced by any of the durable carbon production operations.

[0087] C-Fibers and B-Fibers can be improved for high strength reinforcement purposes by receiving various selections of deposited carbon such as such as one or more layers of graphene, bulbous or filament-like structures. Utilization of such carbon deposit improved fibers is highly advantageous for mechanically interlocked and/or chemically adhered, i.e. , bonded fiber applications in composites with matrix materials such as asphalt, concrete, gypsum, plywood, prepreg cloths and various other formulations with thermoplastic and thermoset polymers. The process for production of such deposited carbon along with co-production of hydrogen is shown again by process Equation 1 : (CxHy + HEAT xC + .5yH ₂ )

[0088] C-Fibers and B-Fibers can be produced by carbon delivered from various animal and vegetable fats along with any or all of the hydrocarbon constituents of natural gas and oil. Alternatively the methane separated as heavier condensates are collected can be converted to an olefinic intermediate such as ethane, which can be converted to ethylene and polymerized to produce C-Fiber.

[0089] Equally important are nano, micro, or macro particles and filaments of selected carbon allotropes or ceramics that serve as seeds for receiving carbon including depositions of bulbous or filament-like structures to produce prickly, fuzzy, wooly components for mechanical interlocking as mechanical and/or chemically bonded reinforcements in various applications such as rubber and other elastomers, higher modulus thermosets and thermoplastics along with metal composites. It is synergistic to utilize C-Fiber and/or B-Fiber along with prickly, fuzzy, and/or wooly particles and filaments. Even larger benefits are provided by utilizing C-Fiber and/or B-Fiber that has been converted to prickly, fuzzy, or wooly forms 354, 356, etc., in formulated conjunctions with prickly, fuzzy, or wooly nano, micro or macro particles and filaments.

LARGE SCALE CARBON FI BER PRODUCTION:

[0090] Carbon improved fiber, particle and/or filament reinforcement for asphalt, e.g., roadways, concrete, roofing, and countless other building products are provided for improved functionality and reduced maintenance costs. Carbon improved fiber composites can replace steel and aluminum in present applications by providing stronger than steel, lighter than aluminum structures that are less energy intensive and that can cost less along with causing far less environmental impact.

[0091] Modularized subsystems depicted by Figs 6A, 6B, 6C enable production of cost effective autogenous furnaces 100 and/or 300 for various applications including seeded production of prickly, fuzzy, or wooly particles and filaments from hydrocarbon feedstocks. Operating efficiency advantages compared to conventional production systems for carbon black and/or carbon fiber enable lower cost products such as carbon improved fiber reinforced durable goods including energy conversion and transportation equipment that can be lighter than aluminum and stronger than steel. Carbon black products range from customized optical and chemical process blacks to improved mechanical strength reinforcement blacks for elastomers, adhesives, thermoplastics, and thermoset polymers. [0092] Production of carbon curtain products including embodiments 308 and 310 along with fiber 354 and 356 of Figure 3 enables cost-effective production of large carbon reinforced tanks and equipment, reinforcement of roadways and bridges, roofing and other architectural components, marine and rail products. Such carbon improved reinforcement systems can reduce the cost and improve the performance of products such as rail tank cars compared to steel tank cars. In comparison with steel tank cars, carbon reinforced tank cars can withstand far more severe abuse including full-stick dynamite blasts, .357 Magnum bullets fired at close range, bonfires that heat the surface to red hot temperature, and impacts from collisions and derailment wrecks.

[0093] In another illustrative embodiment, ethane separated from a suitable source such as natural gas and/or by conversion of methane to ethylene is polymerized with the aid of one or more suitable catalysts in an adaptively temperature controlled reactor and/or as provided by the teachings of U.S. Patents 3875134; 3974237; 5817904; 71 19240 and various publications that have cited these references. The polymerized ethylene is converted to carbon fiber in suitable processes such as provided by U.S. Patent publications 1834339; 3607672; 3887747; 20130084455 and/or various other publications that have cited these references.

[0094] Such carbon fiber, graphite or amorphous materials can be ball milled or otherwise subdivided to produce fine particles 200 and filaments 204 that can in some instances be treated to form suitably sized surface deposits of metal dots 212 and/or coated with petrolatum constituents to serve as seeds 326. Longer lengths of such carbon fibers in suitably numbered collection sizes as thread, yarn, weaves or felt 350, 352, etc., are fed into the carbon deposition zone around heater tubes 1 12 or 312 to receive carbon deposits by decomposition of a suitable hydrocarbon CxHy such as methane and/or other constituents of natural gas or oil.

[0095] It is advantageous to utilize seed particles 200 and/or filaments 204 that are fractured or otherwise subdivided from carbon-plated materials such as 150, 328, 354 and/or 356 that are harvested from furnace deposition systems. This is because the time at deposition temperature increases the degree of crystallization of the resulting particles and filaments, which in turn can improve the rate of growth and surface filament formation to produce spiky, fuzzy, or wooly particles, filaments, and fibers. In some applications the recirculation dwell time and/or the height of the deposition operation can be extended to increase the degree of crystallization of the various forms of deposited carbon and thus the degree of crystallization of seed particles and filaments that can be adaptively produced by controller 125 or 345.

[0096] Thus various products are produced by utilizing C-Fiber carbon deposit enhanced fibers 354 or 356 along with a suitable matrix material that can contain interlocking particles 202 and/or filaments 206. Similar products can be made by utilizing B-Fiber carbon deposit enhanced 354 or 356 along with a suitable matrix material that can contain interlocking particles 202 and/or filaments 206. Figure 2E schematically depicts the synergistic chemical bonding on expanded surfaces and mechanical interlocking benefits of spiky, fuzzy, or wooly particles 202, filaments 206, and fibers 354 and/or 356.

[0097] In other instances a suitable form such as a strip or hollow tube 230 of a suitable shape and cross section configuration such as shown in Figure 2E of surface width 232, thickness surface 234 and of any suitable straight length or curvilinear radius 236 which can made of a material such as a suitable ceramic or transition metal, intermetallic, or alloy including iron, nickel, cobalt, copper, or refractory metals can be utilized to serve as a carbon donor deposition surface to produce dissociated carbon nanostructures such as tubes, scrolls, bulbs or graphite including nano, micro and macro dimensioned graphene 238. Endothermic dissociation to deposit such carbon on surfaces such as 232 and 234 and/or opposite surfaces is summarized by Equations 1 and 2.

[0098] Numerous alternative cross-sections and shapes of the substrate include the configuration 240 which may include one or more notches 242 that participates with a laser cutter to prepare graphene layers to release from selected ceramics, intermetallics, metals or alloys containing aluminum, iron, nickel, cobalt, copper or refractory metal substrate.

[0099] In some applications such depositions including graphene 238 are separated from the deposition substrate by forces produced by thermal expansion differences upon heating or cooling between the substrate and the carbon graphene and such separation can be enhanced by one or more fluid flows such as air, nitrogen, argon, water, alcohol, etc., impinging on or between the separating graphene and the substrate material. In instances that relatively large area carbon deposits such as graphite or graphene are deposited, one or more laser cutters may be utilized to produce parallel strips of separated graphene that may be bunched or twisted to form carbon fiber. In other instances such large area graphene is formed or rolled to form a graphene product such as a filter or fiber. In some applications suitable specialization of the graphene is provided variation of the doping by substances such as transition metals, silicon, boron etc., and/or by laser machining of orifices or other configurations.