WO2015103391A1 - Processes and apparatus for production and use of fuels sourced from organic wastes - Google Patents

Abstract

Methods and apparatus for the production of an alcohol such as methanol generally include reacting methane with water. The methane can be obtained from collecting the byproduct of various human-implemented process or methane released from naturally occurring processes. Additional steps can be taken to produce ammonia from the products of the reaction of methane and water. Both methanol and ammonia can be used as liquid energy storage fuels that, when subjected for further reactions, can produce hydrogen suitable for use as a fuel in various applications.

Description

PROCESSES AND APPARATUS FOR PRODUCTION AND USE OF FUELS

SOURCED FROM ORGANIC WASTES

Field of Invention

[0001] This disclosure generally relates to processes for the production of fuels for pressurized pipeline carriers designed for gaseous fuels such as methane and/or occasionally using such pipelines to transport liquid fuels.

Background

[0002] About 150 billion cubic meters of natural gas is leaked or flared each year in petroleum production regions of the world. This is approximately equivalent to 25% of the annual utilization of natural gas in the U.S. economy and represents an enormous opportunity cost and operating expense that includes waste disposal costs and supervision by the EPA regarding efforts to reduce pollution and greenhouse gas production. Leaked or flared compounds that include various proportions of carbon and hydrogen (C_xH_y) such as methane are harmful greenhouse gases that can be produced as a byproduct of numerous human-implemented processes. For example, methane can be released into the atmosphere by kerogen or coal mining, petroleum production and transportation practices, waste water treatment processes, aerobic or anaerobic processes, various industrial and agricultural practices.

[0003] Methane produced by these and other processes has been proven to be detrimental to the environment when released into the atmosphere or hydrosphere. In some instances, methane and other greenhouse gases collect and form an optical absorber, filter or radiation barrier in the atmosphere that prevents infrared radiation from escaping through the air into outer space. Instead, the greenhouse gases absorb and re-emit the infrared radiation, which can result in unnaturally and adversely increasing average surface temperatures on earth.

[0004] Other sources of detrimental greenhouse gases such as methane can be produced or accelerated by naturally occurring activities. For example, recent reports have noted the release of methane into the atmosphere as a result of ocean current changes and bottom disturbances such as quakes and tsunamis causing and/or resulting from the release of methane from unstable clathrates. Additional methane releases from vast areas of decaying permafrost calthrates have also been noted to be correlated to increasing regional and/or global temperatures.

[0005] Also of great concern to the environment is the continued use of fossil fuels as a primary means of powering farms, vehicles, factories, homes, etc. As is well known, fossil fuels are a finite resource and have numerous problems relating to pollution produced by conventional combustion of the carbon content of such fuels. Accordingly, an urgent and persistent need exists for collecting fossil and renewable organic materials that rot or burn such as can be illustratively represented as methane prior to its release into the atmosphere and using the collected methane in beneficial ways, such as for production of durable goods, clean energy and/or an energy carrier.

[0006] Moreover, civilization presently depends upon annually burning fossil substances such as coal, oil, and natural gas reserves that took more than one million years to accumulate during geological periods that occurred more than 60 million years ago. Present practices of such rapid burning of finite fossil reserves cause air and water pollution, respiratory illnesses, economic inflation, scarcity, strife, and related hardships for most of the world's population along with global warming and environmental degradation throughout the world.

[0007] Most of the world's existing population of about 1 .2 billion engines are fueled by octane-rated petrol or gasoline and utilize spark-ignition (SI). Diesel engines utilize cetane-rated "diesel fuel" in higher compression ratio engines that rapidly compress and heat the air for achieving compression ignition (CI). Spark-ignited SI engines are lightweight and operate at higher speeds to achieve greater power-to-weight ratios than compression-ignited CI engines. Diesel engines operate at lower speeds and are heavier and are considerably more expensive to manufacture.

[0008] SI engines have compression ratios that range from about 6 to 10 and operate at speeds of about 2000 to 6000 RPM compared to CI engines with compression ratios of 14 to 24 and operate at speeds of about 450 to 2100 RPM. CI engines are more expensive to manufacture, considerably heavier, noisier, require complex high-pressure fuel injection systems, along with larger starter motor systems in comparison with SI engines. [0009] Diesel fuel is pressurized up to about 2,000 Bar (30,000 PSI) in order to produce sufficiently fine sprays of fuel droplets that are directly injected to rapidly achieve ignition in rapidly compressed hot air in efforts to diminish objectionable emissions of unburned fuel smoke. Such fuel pressurization and friction losses incurred to produce higher compression pressures requires CI engines to overcome

considerably greater parasitic losses by achieving much lower heat losses during combustion and expansive work production during the power stroke of operation.

[0010] The most significant operational difference between Spark Ignition SI and Compression Ignition CI engines is that CI engines provide stratified charge injection and combustion of fuel in unthrottled excess air to achieve sufficiently higher fuel efficiencies to justify higher initial cost. SI engines must throttle the air throughout almost all of their useful life to produce the narrow range of homogeneous fuel-air mixtures that achieve spark ignition.

[0011] Octane-rated SI and cetane-rated CI fuels are produced by expensive refineries from crude oil. About 20 to 30 pounds of carbon dioxide is produced along with oxides of nitrogen, particulates and various carcinogens by oil production, transportation, and refinery operations along with exhaust gases from SI and CI engines. In comparison with fossil fueled central power plants, the world's existing SI and CI engines (expected to soon grow to more than two billion engines) produce about as much greenhouse gases and particulates, acid rain, cancer and other illnesses.

[0012] Large amounts of hydrogen and donor substances such as food, sewage, and cellulosic wastes in addition to hydrocarbons C_xH_y that are leaked or flared from fossil fuel production and transportation operations along with intentional burning of such substances produce carbon dioxide, particulates and other greenhouse gases that now contaminate the global atmosphere and cause global warming

Summary

[0013] The instant application relates to the production and utilization of methane to produce methanol and other liquid energy storage fuels. Problematic productions of greenhouse gases such as sourced by landfills, sewage, and agricultural wastes along with coal seam and flare-gas constituents and/or products are overcome by conversion to valuable carbon and co-produced hydrogen that is utilized for improved

hydrocracking processes to produce methane and/or liquids for pipeline transportation to industrial plants that process such feed stocks into durable carbon and net hydrogen fuels. In some embodiments, methane is reacted with water to produce methanol and hydrogen. The hydrogen product can subsequently be used to produce various products including ammonia, urea, formic acid and many other products such as by reacting the hydrogen with nitrogen and/or carbon dioxide from sources such as the atmosphere or by preemptive collection from more concentrated sources. Heat can be applied to either nitrogenous energy carriers such as ammonia or urea or to

carbonaceous energy carriers including fuel alcohols such as methanol in order to produce hydrogen that can be used in a variety of applications including ovens, furnaces, and engines such as fuel cells and/or heat engines.

[0014] The methane used in the processes and apparatus described herein can be obtained from byproducts produced by human-implemented processes. The methane can also be obtained from sources that leak into the atmosphere by naturally occurring events and processes involving virtually anything or substance that ordinarily rots or burns. Such methane can be dissociated into hydrogen for fuel or production of chemicals and carbon for producing durable goods. Each ton of carbon that is thus prevented from rotting or burning prevents 3.66 tons of C0₂ greenhouse gas

production.

[0015] In some embodiments, an exemplary reactor vessel is provided in order to carry out the reaction of methane and water. The reactor vessel can include two concentrically positioned tubular shells. The interior space of the interiorly positioned tubular shell can define a first reaction zone wherein a carbon-donor such as methane and an oxygen donor such as water react to produce methanol and hydrogen. The annular space between the interiorly positioned tubular shell and the exteriorly positioned tubular shell can form a second reaction zone where hydrogen and nitrogen react to produce a nitrogenous substance such as ammonia. The hydrogen for the second reaction zone can be provided by transporting the hydrogen produced in the first reaction zone through the interiorly positioned tubular shell, which may be made of hydrogen or hydrogen-ion permeable materials. The reaction vessel can be a standalone system or can be incorporated into other equipment, such as an engine.

[0016] In some applications natural gas constituents are thermally cracked to produce hydrogen that is used to hydrocrack and condition such constituents to sufficiently decrease the concentration of condensable substances and thus increase the concentration of methane in the mixture for conveyance according to conventional natural gas pipeline standards. Hydrogen utilized in the hydrocracking operation however may exceed the conventional natural gas pipeline standards and such hydrogen can be reduced by suitable methods such as detailed in US Patent

Application 13/027,235 which is included herein by reference. In such instances it can be advantageous to include hydrogen from the hydrocracking procedure and/or to produce and provide additional hydrogen up to about 20% concentration in the pipeline mixture which does not require natural gas burner tip adjustments for purposes of increasing the efficiency of the conditioning operation, and the pipeline transmission efficiency, including serving as a negative Joule-Thomson (J-T) coefficient of expansion agent that heats upon expansion to overcome positive J-T expansion cooling by other constituents, increasing heat transfer rates of the mixture to prevent cold-spot condensations, reducing the carbon dioxide production per energy unit delivered, and/or to enable improved operation of fuel-cell and heat engines. This enables new and highly desirable outcomes for pipelines designed for natural gas conveyance.

[0017] In addition to the embodiments of Figures 1 A, 1 B, and 1 C it is also highly desirable to produce motive shaft power, compressed gases, and/or electricity by operation of embodiments 300, 400, 500, 600, 700, and/or 800 as shown. Operation according to the principles detailed provide for profitable practices to replace flaring and venting of hydrocarbons to the atmosphere.

[0018] This reduces or eliminates methane that would normally be discharged into the atmosphere where it can contribute to a greenhouse effect. The methanol and ammonia produced are high energy fuels that can be transported using existing infrastructure, such as storage tanks and pipelines repurposed from gasoline and/or diesel fuel applications. The conversion of carbonaceous intermediates including alcohols such as methanol and/or nitrogenous substances such as ammonia and urea to hydrogen provides a relatively clean fuel source and can thereby reduce or eliminate dependency on non-renewable and dirtier fuel sources.

[0019] Therefore it is desirable and advantageous to condition aromatic and/or paraffinic substances by the thermal, electrical, and/or chemical processes disclosed herein that enable conventional gas or liquid pipelines to deliver such conditioned substances to markets including deliveries to processes that extract carbon for production durable goods and that enable co-produced hydrogen to be utilized for energy conversion applications.

Brief Descriptions of the Drawings

[0020] Figure 1 A is a flow diagram illustrating a method of producing an alcohol such as methanol and/or ethanol from organic substances such as methane according to various embodiments described herein.

[0021] Figure 1 B shows a process for operation according to various principles and embodiments described herein.

[0022] Figure 1 C shows another process for operation according to various principles and embodiments described herein.

[0023] Figure 2 is a schematic diagram of a reaction vessel suitable for producing methanol from methane according to various embodiments described herein.

[0024] Figure 3A is a schematic diagram of an engine retrofitted to carry various chemical reactions according to various embodiments described herein.

[0025] Figures 3B and 3C show schematic diagrams of subsystems according to various embodiments described herein.

[0026] Figure 4 is a schematic diagram of an engine retrofitted to carry various chemical reactions according to various embodiments described herein.

[0027] Figure 5 is a schematic diagram of an engine retrofitted to carry various chemical reactions according to various embodiments described herein. [0028] Figure 6 is a schematic diagram of an application system suitable for use in the reaction of liquid energy storage fuels according to various embodiments described herein.

[0029] Figure 7 is a schematic diagram of an application system suitable for use in gaining water from the exhaust system of an internal combustion engine according to various embodiments described herein.

[0030] Figure 8 is a flow diagram illustrating an embodiment method according to the principles of the invention.

[0031] Figures 9A and 9B show process steps for operation in accordance with the principles of the invention.

[0032] Figure 10 shows apparatus for operation according to the principles of the invention.

[0033] Figures 1 1 A and 1 1 B show system embodiments for operation in accordance with the principles of the invention.

[0034] Figures 12A-C show system embodiments for operation in accordance with the principles of the invention.

[0035] Figures 13A and 13B show system embodiments for operation in accordance with the principles of the invention.

[0036] Figures 14A-C show system embodiments for operation in accordance with the principles of the invention.

Detailed Description

[0037] Generally as illustrative example, primary production of natural gas mixtures including substances such as ethane, propane butylene and heavier hydrocarbons are converted to methane for efficient transportation through conventional natural gas pipelines. In another example such feed stocks are converted to a liquid mixture or solution or separated liquid fuels for transportation through conventional gasoline, diesel fuel or oil pipelines. [0038] Table 1 compares the properties of substances that can typically be found in primary natural gas mixtures.

TABLE 1 : PRIMARY NATURAL GAS MIXTURE CONTENTS

; SUBSTANCE MELT TEMP BOIL TEMP DENSITY PRESSURE CRITICAL TEMP-PRESSURE i METHANE CH₄ -182 °C -162 "C GAS 1 BAR

i ETHANE C₂H₆ -183 °C -89 °C GAS 1 BAR 32.4 °C - 48.2 BAR

PROPANE C₃H₈ -188 °C -42 °C GAS 1 BAR 97 °C - 42.1 BAR

: BUTANE C₄H₁₀ -138 °C o °c GAS 1 BAR 152.2 "C - 37.5 BAR

; PENTANE C₅H₁₂ -130 °C 36 °C 0.626 LIQUID 1 BAR

; HEXANE C₆H₁₄ -95 °C 69 °C 0.659 LIQUID 1 BAR

[0039] Methane can be separated from other primary natural gas substances by compressing and rejecting heat to cool the mixture followed by turbo-expansion to produce about -100°C to liquefy the ethane, propane, butane, pentene, and/or hexane. The separated methane gas can be transported by conventional natural gas pipeline operation. Additional methane for delivery by gas pipelines can be produced by thermal dissociation of higher molecular weight or mass hydrocarbons C_xH_y in which "x" exceeds the numeric value of one (1 ) such as ethane, propane, butane, pentane and/or hexane to produce carbon. The co-produced hydrogen is utilized to hydrocrack one or more of the higher hydrocarbons to produce methane for delivery by conventional gas pipeline operations.

[0040] In other instances, the methane can remain mixed with other primary natural gas substances for thermal dissociation to produce carbon and hydrogen and the hydrogen can be utilized to hydrocrack the remaining higher molecular mass or weight hydrocarbons to produce methane for transportation by conventional gas pipeline operations.

[0041] In some applications the same or other pipelines can be used to transport the liquids at sufficient pressure to stabilize the separated mixture as a liquid. Depending upon the respective concentrations of ethane, propane, butane, pentane and/or hexane the pressure required for stable pipeline transportation as a liquid mixture is about 100 to 700PSI or more. In accordance with Dalton's and/or Raoult's and/or Henry's Laws the lower the concentration of the more volatile constituents such as ethane, propane and/or butane, the lower the stable liquid transport pressure can be.

[0042] Therefore in some instances to develop the desired characteristics for pipeline transport as a gas selected portions of ethane, propane, and/or butane can be converted to sufficient concentrations of methane for transport by conventional natural gas pipeline. In other embodiments stable liquid mixtures are prepared and transported by a suitable pipeline for liquids. Transformations to provide these suitable

characteristics are illustrated by processes such as summarized by Equations 2A, 2B, 2C, 2D. In other instances the liquid mixture can be transported at certain times by operation of the natural gas pipeline in a liquid transmission mode at a temperature and pressure that is maintained to at least be sufficient to prevent conversion of any constituent to gas.

[0043] In other instances a liquid such as an ether, ketone, aldehyde, or alcohol is produced to serve as a liquid that receives ethane, propane and/or butane to provide for pipeline transport as a pressurized liquid. This is another application according to Henry's Law that provides for the solubility of a gas absorbed in a liquid to be directly proportional to the partial pressure of the gas above the liquid. The operating pressure of the liquid pipeline can be at least approximate the sum of the partial pressures of the mixture constituents in accordance with Dalton's Law and/or Raoult's Law as needed to assure efficient pipeline operation and transmission.

[0044] With reference to Figures 1 A-C, a method for producing a liquid fuel such as carbonaceous or nitrogenous substance such as ammonia, formic acid, or an alcohol such as illustratively shown regarding methanol from methane generally includes one or more events summarized as step 100 of reacting methane with water to produce liquid methanol that can be separated from hydrogen. The reaction of methane and water can be carried out according to Equation 1 A in an electrolysis cell such as disclosed in co-pending U.S. Patent Application Serial No. 13/584,748 and/or by the synergistic combination of an electrolysis and anaerobic digestion system to provide the net process summarized as follows: CH₄ + H₂0 -> CH₃OH (1 A)

[0045] Alternatively, methane and water can be reacted in a thermochemical process that may utilize steam such as supercritical steam as the oxygen donor to supply the heat needed to convert methane to carbon monoxide and hydrogen as shown in Equation 1 B. In instances that production of dry alcohol is preferred carbon dioxide can be reacted with methane to produce carbon monoxide and hydrogen as shown in Equation 1 C. Portions of such carbon monoxide and hydrogen can then combined to produce a liquid fuel such as butanol, propanol, ethanol or methanol as shown in Equation 1 D.

CH₄ + H₂0 CO + 3H₂ (1 B)

CO₂ + CH₄ 2CO + 2H₂ (1 C)

CO + 2H₂ CH₃OH (1 D)

[0046] It is advantageous to utilize waste heat H-1 , H-2 and/or H-3 and to operate one or more fuel cells to produce electricity in energy conversion processes that utilize processes of Equations 1 A, 1 B, 1 C and 1 D including the enthalpy change for the reaction of Equation 1 D of -90.64 kj/mole and the free energy change of -25.34 kj/mole.

[0047] Various alternatives utilize an oxide of carbon such as can be supplied from an anaerobic or aerobic thermal dissociation and/or anaerobic or aerobic digester to react with hydrogen such as may be produced by dissociation of a hydrogen and carbon donor such as methane to produce carbon and hydrogen as shown in Equation 1 E. Equation 1 F summarizes the process for utilizing such carbon dioxide and hydrogen to produce a liquid fuel such as a selected carboxylic acid e.g. formic acid or an alcohol e.g. methanol. Equation 1 G shows the same net production as shown in Equation 1 D for methanol from carbon monoxide such as provided by processes of Equations 1 B and 1 C and hydrogen produced by electrolysis and/or the processes of Equations 1 A. 1 B, 1 C, 1 C, 2A, 2B, and/or 2C. CH₄ + HEAT C + 2H₂ (1 E)

CO + 2H₂ ^ CH₃OH (1 G)

[0048] It is advantageous to utilize waste heat H-1 , H-2 and/or H-3 and to operate one or more fuel cells to produce electricity. Waste heat H-1 , H-2, and /or H-3 can enable energy conversion processes with series-parallel circuit arrangements that utilize processes of Equations 1 D, 1 E, 1 F, and 1 G including the enthalpy change for the reaction of Equation 1 F of -49.3 kJ/mole and the free energy change of 3.48 kJ/mole.

[0049] In some embodiments, the methane is obtained from one or more specific sources which produce methane or other hydrocarbons either as byproducts of another process implemented by humans or in a naturally occurring process. One aim of obtaining methane from one of these specific sources is to prevent hydrocarbons C_xH_y such as methane from otherwise entering the atmosphere where it can potentially serve as a greenhouse gas and contribute to a greenhouse effect. Accordingly, in some embodiments, step 100 is preceded by a step 90 wherein methane is collected from sources that rot or burn.

[0050] Natural gas varies in composition and typically includes a variety of

substances C_xH_y such as butane C₄H ₀, propane C₃H₈, ethane C₂H₆, in a mixture with methane CH₄. Most transportation pipelines and bulk tanks are designed for one phase of hydrocarbon. Natural gas pipelines are designed for gaseous methane and substances that are subject to condensation including ethane, propane, butane, and heavier substances are limited or prohibited. As an illustrative example, natural gas is cooled and/or compressed to condense objectionable concentrations of such

substances.

[0051] Alternatively, natural gas is separated by pressure and/or temperature swing absorption systems to sufficiently separate methane from objectionable amounts of ethane, propane, butane and heavier hydrocarbons. Remaining methane can be safely transported by a conventional natural gas pipeline. Where other troublesome nitrogenous and/or sulfurous substances such as H₂S can be removed by utilization of co-produced hydrogen such as from Step 3 or 132 for hydro-treatment to provide reaction and/or collection to produce soil amendments such as by collection by calcia, magnesia, diatomaceous earth, and/or various forms of subdivided iron or magnetite.

[0052] The condensates removed from primary natural gas mixtures can be heated as shown in Equations 2A, 2B, and 2C to efficiently produce valuable carbon and hydrogen.

C₄H₁₀, + Heat-2A 4C + 5H₂ (2A) C₃H₈, + Heat-2B 3C + 4H₂ (2B) C₂H₆, + Heat-2C -> 2C + 3H₂ (2C)

[0053] It requires less energy such as Heat-2A, Heat-2B, and/or Heat-2C to produce valuable carbon and co-production of hydrogen for applications such as hydrocracking and/or clean fuel production results than it requires for steam reformation that wastes such carbon as an oxide of carbon such as carbon monoxide or carbon dioxide.

[0054] Carbon separated by such favorably suitable techniques can be used to manufacture durable goods and thus eliminate about 3.6 tons of carbon dioxide from entering the atmosphere per ton of durable carbon collected. Hydrogen can separated by processes such as summarized in Equations 2A, 2B, and 2C for hydrocracking reactions to produce methane such as illustratively shown by the exemplary processes qualitatively summarized by Equation 2D. Illustratively primary natural gas and/or heavier hydrocarbons such as can be separated from organic substances is converted by hydrocracking to break C-C bonds for re-speciation to provide a sufficiently high percentage of methane to assure successful transportation by conventional pipeline practices.

[0055] Accordingly, primary natural gas constituents including problematic heavier aromatic hydrocarbons and/or paraffinic compounds C_xH(₂x₊2) are conditioned and/or converted into methane and/or other substances suitable for transportation by conventional pipelines. In addition to reducing or eliminating the requirement for expensive water conditioning and steam generation systems this process overcomes the inefficiencies of steam reforming to produce hydrogen and eliminates the carbon dioxide that conventional steam reforming operations release into the atmosphere.

[0056] Thus, the sources from which the methane can be produced and/or collected are generally not limited. In some embodiments, the methane is obtained from human- implemented processes in which methane is a waste byproduct. Exemplary processes carried out by humans and which produce a waste methane byproduct include, but are not limited to, fossil fuel mining and production, waste water treatment processes, anaerobic or aerobic regions of landfills, industrial process, animal feeding operations and various other agricultural businesses. In each of these examples, methane is typically produced as a byproduct of another desired process and, in some cases, simply allowed to enter the atmosphere or wastefully burned to produce greenhouse gases such as NO_x, CO₂, SO_x etc..

[0057] Accordingly, this methane can be collected rather than released to the atmosphere and used in the methods described herein. In some embodiments, the source of the methane can be a naturally occurring process that results in methane being produced and released into the atmosphere. One non-limiting example of such a naturally occurring process is the release of methane into the atmosphere when unstable clathrates are disturbed by conditions such as ice mass melting, warming due to changes in ocean currents, landslides, volcanic actions, earthquakes, and human activities that disturb these ocean bottom deposits. Recent reports have indicated that sea bottom disturbances due to ocean changes have resulted in disruption of unstable clathrates containing methane and the subsequent release of methane into the atmosphere. Another non-limiting example is methane released into the atmosphere as a result of increasingly widespread warming and decay of permafrost clathrates.

[0058] Any manner of collecting the organic material such as methane and related byproducts can be used. In some embodiments, the methane collection method can include similar or identical processes and/or apparatus described in U.S. Patent Application US 20130156504 and the referenced citations therein.

[0059] Once harvested from one or more of the sources described above, existing infrastructure can be used to store methane and transport methane to a location such as an industrial park where the process described herein can be carried out particularly including conversion of such methane to valuable carbon-enhanced durable goods. The co-produced hydrogen that can be reacted with nitrogen and/or carbon dioxide from the atmosphere or more concentrated sources to produce net-hydrogen fuels that can be stored as liquids in gasoline or diesel fuel tanks and shipped by conventional pipelines for ambient temperature liquids. This existing infrastructure can include storage tanks and pipelines previously used for storage and transportation of other fluids, such as gasoline or diesel fuel. Other infrastructure that can be used includes, but is not limited to, depleted oil and natural gas wells, storage tanks and/or pipelines used for natural gas, natural gas liquids, gasoline, diesel fuel, various grades of oil, and water.

[0060] The carbon and hydrogen donor such as exemplary methane collected from byproducts of man-implemented processes or naturally occurring processes can be used as the sole source of methane for the processes described herein. Alternatively it can be supplemented with other sources of substances that contain hydrogen and carbon such as methane, including commercially produced methane purchased from a third party supplier.

[0061] The water used in the reaction of step 100 can be obtained from any suitable mobile or stationary source. In some embodiments, the water can be obtained from a furnace or engine such as a fuel cell or heat engine exhaust, decaying permafrost, submerged clathrate deposits, or other anaerobic digestion sources. An illustrative collection of such water from an industrial or agricultural process, fuel cell, or engine is shown by embodiment 700 of Figure 7. In certain applications to facilitate water collection, the exhaust of a fuel cell and/or engine including hybridized combinations is cooled as a result of performing work in a turbo-charger or turbo-generator and/or by supplying heat (H-2) for driving an endothermic reaction or process and/or by supplying heat to a thermoelectric system 709 for production of electricity and/or by heat transfer to the atmosphere.

[0062] The reaction of methane and water in step 100 can be carried out using any suitable equipment or set up. In some embodiments, the reaction is carried out in a tubular reaction vessel as described in greater detail below. The reaction vessel can be stand alone or incorporated into or along with other apparatus. In some embodiments, the reaction vessel is incorporated into an engine as also described in greater detail below.

[0063] In many instances harmful methane is co-produced with other greenhouse gases such as carbon dioxide and/or oxides of nitrogen or sulfur. In some

embodiments, the reaction of methane and water is promoted through the use of catalysts. Any catalyst that improves the reaction between components that form methane or methane, carbon dioxide, and water can be used. Illustratively, the production of liquids including alcohols and derivatives such as methanol,

dimethylether, ethanol, diethylether etc., can be facilitated by an electro-chemical cell that converts reactants selected from incipient production of hydrogen, methane, carbon monoxide, and/or carbon dioxide in an anaerobic digestion process. Suitable electrochemical cell and/or process can be of any particular type including those disclosed in U.S. Patent Publication No. 2012/0175269; U.S. Patent No. 8,313,634; and U.S. Patent No. 8,642,817 which are included herein by reference. In some embodiments, improved results can be provided by variously activated catalytic mixtures that can include precious metals or recipes with copper, zinc and alumina, selected types of nanotubes, functionalized graphene, multilayered graphene, activated carbon, graphite foam, barium and/or other perovskite type ceramics, one or more architectural constructs such as disclosed in U.S. Patent Publication No. 2013/0101808 and/or various combinations thereof.

[0064] With continued reference to Figures 1 A-C, the method can include one or more additional steps for processing the products of the reaction of step 100. In step 1 10, the hydrogen produced from the reaction of methane and water is used to produce a nitrogenous substance such as ammonia or urea. In order to carry out such reactions, the hydrogen can be reacted with nitrogen, such as illustrated by Equations 2E and 2F.

N₂ + 3H₂ ^ 2NH₃ (2E)

N₂ +CO + 2H₂ CH₄N₂0 (2F)

[0065] The nitrogen reacted with the hydrogen in step 1 10 can be obtained from any suitable source including oxides of nitrogen from agricultural, chemical or industrial processes. In some embodiments, the nitrogen reacted with the hydrogen is obtained by separation of nitrogen from the atmosphere. Such separation can be carried out using a variety of filtration systems. Non-limiting examples include selectively permeable membranes, pressure and/or temperature swing sorbent systems, or by depletion of oxygen from air used in an oxidation or combustion process such as an "engine" consisting of a combustion engine and/or a fuel cell. In some applications such nitrogen separation and/or oxygen enrichment including production of NO_x is provided by cyclically regenerative pressure and/or temperature swing sorbent systems.

[0066] In operation, such systems can utilize cyclic applications of pressure produced by compressor 403 or system 300 of Figure 3 and/or heat such as heat from a fuel cell engine and/or heat from a combustion engine coolant H-1 , heat from the exhaust gases H-2 and/or regenerative, renewable, or other sources of energy such as resistive or inductive heat H-3 to provide applications with one or multiple parallel sorbent circuits such as 430, 440, 450, 460, 470 or 480 as illustratively shown in Figure 4. Phased operation of such multiple circuits with coordinated valve controls of flows can smooth the output pressure swings, rates of nitrogen separation or oxygen production, and/or increase the system capacity for oxygen separation and/or enrichment. Throughout the present technology disclosure fuel cells and combustion engines are defined as engines including various combinations of fuel cells and combustion engines.

[0067] An exemplary system is based on an oxygen separation process that can utilize a suitable substance such as a perovskite-type ceramic sorbent for oxygen removal from other constituents of air. Such perovskite-type ceramics can selectively adsorb a large quantity of oxygen at temperatures between about 300-700 °C (570- 1300° F). Illustratively, oxygen-deficient perovskite oxides such as Lao.1 Sro.9Coo.5Feo.5O3- δ, and/or Lao.-iSro.gCoo.gFeo.-i Os-a, and/or BaYMn₂O₅₊5 can selectively adsorb oxygen from air at uptake rates that can be increased as pressure is elevated. Release of adsorbed oxygen upon cooling and/or pressure drop provides a cycle for nitrogen and/or oxygen separation. Similarly, ZrO₂ can be synthesized with copper and/or CuO and/or yttria and/or other rare earth oxide selections for stabilization of the selective oxygen adsorption bed in a temperature-pressure swing system.

[0068] In operation, such systems can be operated between relatively higher temperatures such as by addition of H-3 as needed to load the adsorption bed with oxygen and then upon cooling to release the oxygen at relatively lower temperatures such as provided by heat exchange to engine coolant at a temperature corresponding to H-1 and/or by heat exchange to relatively lower temperatures corresponding to H-2. Accordingly, the system can provide regenerative warming to the suitable lower temperatures for oxygen release corresponding to heat exchange with engine coolant and/or engine exhaust temperatures and can provide regenerative or supplemental heating to suitably higher temperatures for oxygen uptake. This temperature-swing oxygen separation system can be combined with a pressure-swing cycle at a lower or higher pressure to increase the uptake of oxygen and swing to a lower or higher pressure to increase the release of separated oxygen. Either or both the temperature- swing and/or the pressure-swing cycles can be provided by regenerative energy exchange methods. The reaction of nitrogen and hydrogen in step 1 10 can be carried out using any suitable equipment or set up. In some embodiments, the reaction of nitrogen and hydrogen can be carried out in the same reaction vessel used to react methane and water and as will be described in greater detail below.

[0069] In some embodiments, the reaction of hydrogen and separated or enriched nitrogen is promoted through the use of catalysts. Any catalyst that improves the reaction between nitrogen and hydrogen can be used. In some embodiments, the catalyst is graphene, multilayered graphene, activated carbon, an iron oxide, various other transition metal compounds, nano structures such as disclosed in U.S. Patent Publication No. 2013/0101808, powder metal heterogeneous or homogeneous substances, or any combination thereof.

[0070] In step 120, the methanol produced in step 100 can be used in a variety of ways to produce a useful product. In some embodiments, the alcohol such as methanol is utilized to form various chemical intermediates such as dimethylether (DME), diethylether (DEE), methylamine, and/or other carbonaceous substances that contain carbon. For example, ammonia and methanol can be reacted to produce urea, nitromethane or guanine or various other compounds and precursors, such as methylamine (CH₃NH₂) and/or other nitrogenous products that contain nitrogen. Such compounds form solutions with water, and alcohols such as methanol, ethanol, propanol, and butanol to improve the conversion of rejected engine heat such as H1 , H2 and/or H3 to produce higher energy products such as H2 and CO as illustratively shown for methylamine in Equation 5A.

[0071] In some preferred embodiments, methane, carbon monoxide, carbon dioxide, methanol and/or ethanol is used as a liquid fuel or in the process of producing other types of fuel, including dimethylether, diethylether and other suitable compounds. The present embodiments provide for the production and utilization of ammonia, urea, nitromethane, nitroethane, nitromethanol, dimethylether, diethylether, acetaldehyde, triethylborane (C₂H₅)₃B and various nitrogenous compounds, each of which can be produced as part of the methods described herein and can be suitable used as fuels and/or fuel-igniters.

[0072] In some embodiments, the methanol produced in step 100 is used as a liquid fuel. This liquid fuel and/or carrier of soluble fuel substances can be shipped by conventional pipelines stored in repurposed tanks and used for transportation

applications. The addition of heat to methanol can desirably lead to the production hydrogen, carbon monoxide, along with pressure as a result of phase change and/or dissociation. Equation 3 illustrates such a reaction.

CH₃OH + H1 + H2 +H3 CO + 2H₂ + Pressure (3) [0073] The various heat sources identified in Equation 3 are generally not limited. In some embodiments, the heat H1 can be obtained engine coolant, H2 from engine exhaust gases, and H3 from renewable energy conversion systems, regenerative shock absorbers, regenerative braking systems, regenerative compressors, spin-down or other off-peak power or any combination thereof. Use of such heat sources can simplify the thermochemical regeneration process to provide self-pressurized hydrogen- characterized fuels for clean combustion and/or use in fuel cells.

[0074] The nitrogenous substance such as ammonia produced in step 1 10 can be used in a similar manner as described above. For example, the addition of heat (such as the heat sources described above) to ammonia can result in the production of nitrogen, hydrogen, and pressure. Equation 4 illustrates such a reaction.

2NH₃ + H1 , H2 and/or H3 -> N₂ + 3H₂ + Pressure (4)

CH3NH2 + H₂0 + H1 + H2 + H3 -> 0.5N₂ + CO + 3.5H₂ + Pressure (5A)

[0075] Equations 4 and 5A are similar to Equation 3 in that the hydrogen- characterized fuel reaction produces higher energy yield upon combustion along with much faster initiation and completion of combustion. Such benefits can also be enhanced by utilization of energy such as regenerative electrical energy to produce and deliver stratified charge oxygen and/or hydrogen to combustion chamber 328 as disclosed in greater detail regarding other embodiments. In some embodiments, the stratified charge oxygen or oxygen enriched zone i.e. reduced presence of nitrogen that supports fuel combustion allows the temperature of combustion to be increased to improve thermal efficiency and/or to reduce or eliminate of NO_x emissions. Such results can be gained by producing the highest combustion temperature in the oxygen or oxygen enriched stratified zone or pattern in the combustion chamber and/or by sufficiently producing work and expanding the products of combustion to reduce the temperature and/or pressure of such gases to below the condition at which oxides of nitrogen are formed or retained. Thus the peak combustion temperature can be considerably above about 2200°C and the temperature at which higher concentrations of nitrogen are encountered by expanding combustion processes and products can be considerably below about 2200°C to improve the operating efficiency of the combustion engine. The hydrogen produced in Equations 3, 4, and 5A-D have a variety of useful applications, including as a fuel source, but the carbon monoxide and nitrogen produced in Equations 3, 4 and 5A-D also have useful applications, including engine applications that benefit by using Joule-Thomson (JT) expansion cooling before TDC and Joule- Thomson (JT) expansion heating with hydrogen after TDC. Such hydrogen- characterized fuel, such as mixtures of carbon monoxide and hydrogen and/or nitrogen and hydrogen will burn fast and completely with unthrottled air, even with spark plug ignition at or after top dead center TDC in two or four stoke engines. Further

improvements in fuel economy and engine life can be greatly improved by stratified charge combustion by injection and ignition at or after TDC of CO + H₂ and/or by N₂ + 3H₂ and/or by H₂.

[0076] In certain embodiments, oxygen produced by a suitable method such as selective separation and/or filtration from air and/or by electrolysis of an oxide

compound such as water (H₂O) or an oxide of carbon (CO_x) or an oxide of nitrogen (ΝΟχ) is injected into combustion chamber 328 and can serve as a stratified charge J-T expansion coolant such as in the core of compressed air before TDC to improve engine operation and BMEP. Controller 356 and/or 701 can provide adaptive control of the temperatures and pressures of such oxygen by systems 300, 400, and/or 700 as needed to meet varying operating conditions and duty cycles. Subsequently near, at, or after TDC a nitrogenous or carbonaceous fuel such as methane or a liquid fuel prepared by one or more of the embodiments herein or a derivative of such methane or liquid fuels is injected into the stratified oxygen and/or oxygen-enriched zone to produce accelerated ignition and completion of combustion of fuel in the combustion chamber. Adaptive timing and control of the pressures of such injections by controller 701 provides acceleration of ignition and combustion events by oxygen or oxygen

enrichment to enable startup of cold engines and smooth transition to hydrogen characterized fuels after engine warmup. These oxygen accelerated ignition and combustion events can be accomplished with or without other inducements such as spark, Lorentz ion thrusting, corona or other chemical plasma agents. Feed Stock Reaction Vessel

[0077] With reference to Figure 2, a reaction vessel 200 suitable for exemplary use in producing a condensable fuel including oxygenated substances such as ketones including acetone, ethers including dimethylether and diethylether, and/or alcohols including selections such as methanol and/or ethanol generally includes a first tubular shell 210 and a second tubular shell 220. The second tubular shell 220 is generally positioned inside of the first tubular shell 210 and the first tubular shell 210 and the second tubular shell are coaxially aligned.

[0078] The first tubular shell 210 has an interior surface 21 1 and an exterior surface 212 and generally defines the outer perimeter of the reaction vessel 200. The material of the first tubular shell is generally not limited and can include, for example steel, stainless steel, super alloys, and ceramics. In some embodiments, the exterior surface 212 is surrounded by an insulation layer 213. The insulation later can be made of, for example, various selections of ceramic fibers, foams, and composites. The second tubular shell 220 generally includes a composite structure in which the interior surface is a hydrogen permeable anode electrode 221 , the exterior surface is a hydrogen permeable cathode electrode 222, and an ion or proton transport or exchange

membrane 223 is positioned there between. The material of the hydrogen permeable anode electrode 221 can include, but is not limited to, semi conductive or conductive but permeable forms of graphene, graphite, nano-structures including tubes, scrolls, bubbles, and other architectural constructs, metals, powder metal compacts,

intermetallic compositions, silicon carbide fibers or layers, carbon fiber mats, felt, or paper like formulations.

[0079] The material of the hydrogen permeable cathode electrode can include, but is not limited to, semiconductive or conductive but permeable forms of graphene, graphite, nano-structures including tubes, scrolls, bubbles, and other architectural constructs, metals, metal powder compacts, intermetallics, silicon carbide, carbon fiber mat, felt, woven cloth, or paper-like configurations. The material of the proton exchange membrane 223 can include, but is not limited to proton conductive perovskites, graphene, boron nitride, and oxynitride compounds. The first tubular shell 210 and the second tubular shell 220 generally cooperate to form a first reaction zone 230 inside of second tubular shell 220 and a second reaction zone 240 between the second tubular shell 220 and the first tubular shell 210. As described in greater detail below, the first reaction zone 230 is generally where feed stock such as methane and/or ethane and water react to produce hydrogen and methanol and/or ethanol and the second reaction zone 240 is generally where hydrogen and nitrogen react to produce ammonia and/or other nitrogenous products.

[0080] In operation, the reaction vessel 200 receives a fluid such as a liquid or gaseous mixture of water vapor and methane and/or ethane in the first reaction zone 230. A first reaction zone inlet can be provided so that this mixture can be introduced into the first reaction zone 230 at a first end of the first reaction zone 230. The methane and/or ethane and water generally react on the surface of the hydrogen permeable anode electrode 221 and produce hydrogen and methanol, ethanol, and/or acetone according to Equation 5B, 5C, and 5D, respectively. In order to improve the reaction yield of methanol and/or ethanol, the hydrogen is continuously removed from the first reaction zone 230 by passing through the proton exchange membrane 223 and/or another suitable filter media. In some embodiments, the reaction vessel 200 can further include controller 250 to adjust a controlled voltage source 205 for supplying voltage to provide selected outcomes such as shown by Equations 1 A, 1 B, 1 C, 1 D, 1 E, and/or across the proton exchange membrane 223.

CH₄ + H₂0 CH₃OH + H₂ (5B) C₂H₆ + H₂0 C₂H₅OH + H₂ (5C) C₃H₈ + H₂0 C₃H₆0 + 2H₂ (5D)

[0081] Applying voltage across this membrane can provide a suitable voltage gradient between hydrogen permeable anode electrode 221 and hydrogen permeable cathode electrode 222 so that the hydrogen delivered to the second reaction zone 240 is pressurized to a desired magnitude. Meanwhile, the methanol and/or ethanol produced in the first reaction zone 230 can be removed from the first reaction zone 230 (and the reaction vessel 200 overall) by providing a first reaction zone outlet at a second end of the first reaction zone 230. In the second reaction zone 240, nitrogen or a source of nitrogen is introduced through a second reaction zone inlet positioned at a first end of the second reaction zone 240. The nitrogen reacts with the hydrogen in the second reaction zone 240 to produce ammonia and/or a nitrogenous substance. Improvement of the yield of ammonia or another nitrogenous substance is obtained by continuously removing ammonia or nitrogenous substance from the second reaction zone 240.

Illustratively removal of ammonia and/or another nitrogenous substance can be carried out by cooling, absorbing, and/or condensing the ammonia and/or nitrogenous substance using a second reaction zone outlet positioned at a second end of the second reaction zone 240.

[0082] Catalysts can be provided in both the first reaction zone 230 and the second reaction zone 240 in order to improve the reaction between reactants. In the first reaction zone 230, the catalyst can be positioned on the surface of the hydrogen permeable anode electrode 221 . Any suitable catalyst known to promote the reaction between methane and water can be used. In some embodiments, the catalyst includes functionalized graphene, multilayered graphene, activated carbon, graphite foam, barium perovskite, copper, various mixtures of copper, zinc oxide, and alumina, copper and zinc formulations, transition metals, and/or transition metal oxides, pyridinium and/or various other organic substances such as substituted or unsubstituted aromatic amines, and any combination thereof. In the second reaction zone 240, the catalyst can be positioned on the interior surface of the first tubular shell 210. Any suitable temperature, pressure, and/or catalyst known to promote the reaction between hydrogen and nitrogen can be used. In some embodiments, the process is favored by elevated pressure and/or temperature for catalyst selections that include graphene, multilayered graphene, activated carbon, oxides of iron and other transition metals, semiconductors, organic enzymes and organic preparations, and/or selections suitable for other temperatures and/or pressures such as localized surface plasmon resonance (LSPR) utilizing nanoparticles activated by radiation. Suitable radiation can include frequencies of the solar spectrum such as ultraviolet, visible and/or infrared radiation at temperatures and pressures relatively near those found in the earth's atmosphere and any combination thereof.

[0083] As noted previously, the reaction vessel 200 can be a stand-alone equipment or can be incorporated into other equipment, such as an engine. Figures 3A-C and 4 show how the reaction vessel is incorporated into an engine such that the engine can be used to produce carbonaceous and/or nitrogenous substances such as fuel alcohols i.e. methanol, ammonia, urea, methylamine, nitromethane, or other liquid fuels. The general system shown in these Figures can be used on a small scale or can be scaled up to produce liquid fuels in sufficient amounts to provide for large fleets of vehicles.

Engine System

[0084] With reference to system 300 of Figure 3A, a retrofitted single or multi-cylinder reciprocating piston engine 302 (such as a spark-ignited or diesel engine) is provided. Illustratively, one or more selected cylinders of the multi-cylinder reciprocating piston engine 302 are adapted to assist in carrying out the processes described herein.

[0085] The engine 302 includes a combustion chamber 328 that is retrofitted with combined fuel-injection device 330 which may also supply ignition in selected

applications and new combustion chamber gas valve functions. The selected cylinders are provided with a fluid selector valve 340 to switch between receiving an oxidant such as oxygen or air from manifold 338A or fuel from manifold 336. When the engine is used to carry out the process described herein, the fuel flowing through manifold 336 can be fuel feed stock such as natural gas, methane, CO_x (i.e. carbon monoxide and/or carbon dioxide), and/or hydrogen such as may be pressurized and provided by system 200, and various other selections.

[0086] In some embodiments, the converted engine also has conventional inlet valve 327A and an exhaust valve 327B, and exhaust director valve 360 to selectively direct compressed gas to four-way valve 309 or to empty the combustion chamber 328 during the exhaust stroke of piston 301 through exhaust passage 338B. In some embodiments, the converted engine also has manifolds 336, 338A, 31 1 and 338B and flow selector valve 340 to direct air or another gas from 338A or fuel or another gas from 336 through reaction chamber 328 and the products to director valve 360, manifold 31 1 and valve 309 into accumulator 371 and/or to valve 308 for delivery through valve 310 to pressure intensifier 315. Intensifier 315 can utilize gas such as fuel or another gas stored in accumulator 371 or that is delivered by manifold 31 1 to pressurize the motion of piston 312 to force smaller piston 314 to produce higher pressure gas delivered from line 313 and/or 324 to outlet port 320P. Accordingly pressurized oxidant such as oxygen or air or another gas originally from manifold 338A or fuel or another a gas originally delivered by manifold 336 or products produced by reactions in chamber 328 can be delivered from port 320P to line 334, or valve 331 A, or valve 331 B for direct injection into chamber 328 or into an inlet valve port by injector 325.

[0087] Similarly fluids such as methane, an oxide of carbon (CO_x) or water can be delivered from manifold 31 1 , accumulator 371 or line 324 to reactor passage 230 for production of products such as hydrogen and a fuel alcohol such as methanol. The process of Figure 8 can be utilized to produce substances such as oxygen as the oxidant, a liquid fuel that can be converted to one or more gases that are supplied through manifold 336 for such processes. In certain modes of operation fuel or other gas supplied from a suitable source through manifold 336 or air or other gases supplied from a suitable source through manifold 338A and/or reaction products produced in chamber 328 and/or combustion gases that pass into manifold 31 1 during the

compression, power and/or exhaust stroke of piston 301 in chamber 328 are stored in accumulator 371 or a similar accumulator for further processing as set out by Equations 1 , 2, 3, 4, 5, 6, and/or 7 and/or by the process steps of Figure 8.

[0088] This can provide many additional modes of operation, including selection of air from manifold 338A and utilization of surplus fuel (such as hydrogen or methane) injected by device 330 to produce carbon monoxide and nitrogen that is separated for delivery of nitrogen to reaction zone 240 and delivery of carbon monoxide to storage for injection and combustion in other cylinders or utilization as a feedstock in zone 230 to produce methanol. Alternatively, the carbon monoxide may be delivered with the nitrogen to subsequently enable production of methanol, ammonia, urea,

methylamine, and other compounds. In another application mode, surplus hydrogen is injected and ignited by device 330 in compressed air to produce water vapor and nitrogen which may be dried by suitably cooling to condense water and/or by a suitable filter to deliver sufficiently dry nitrogen into reaction zone 240. Pressurization of such nitrogen delivery can be carried out according to the pressure produced by piston 301 or by intensifier assembly 312-314-316-318 in block 315 by delivery from chamber 328 through valves 331 A, 331 B and/or 360 and 309 to a storage tank such as 371 through valves 309, 308, 310, 316, and 318 after intensification of pressure by piston 314 as shown.

[0089] In some embodiments, methane delivered at relatively low pipeline distribution pressure through manifold 336 passes through ordinary inlet valve 327A during the intake stroke of chamber 328. In certain modes of operation, additional methane may be transferred from other selected cylinders and/or tank 371 or similar tanks to increase the inventory of methane in chamber 328 and to thus increase the amount and pressure delivered through valve 331 A and/or 331 B and/or 327 and director valve 360 into tank 371 at selected times according to controller 356. During the compression stroke of piston 301 , pressurized methane at such selected times as determined by controller 356 flows from combustion chamber 328 through valve 331 A, 331 B and/or 327B and 360 through valve 309 into tank 371 to produce methane that is stored at 25 to 100 Bar pressure.

[0090] Figure 4 shows portions of an engine such as 402 as embodiment 400 to carry out the process described herein. Coolant fluid such as water from a suitable source flows through connection 460 to gain heat H-1 and/or H-2 from exhaust gases via heat exchangers 406 and 408. The water is heated to produce sufficiently high temperature and pressure steam for combining with the methane in reaction zone 230 to provide conversion to methanol and hydrogen. The methane to be reacted can be, for example, gas stored in tank 371 shown in Figures 3A-C and may be pressurized by piston 301 and/or intensifier 312-314. The methane is delivered from a tank such as 416 or 371 or port 320P along with steam from heat exchangers such as 422 and/or 470 to an embodiment such as system 200 or 414 for production of methanol and hydrogen. The reaction zone 230 of tube 220 of vessel 200 is incorporated in some applications with the engine assembly such as 414 which can be within an exhaust manifold such as 51 1 . The steam and methane react on hydrogen permeable anode electrode 221 to produce methanol and hydrogen as summarized by Equation 1 . Produced methanol is then routed from 414 to heat exchanger 417 for cooling and condensing and is delivered to receiver 416 for storage.

[0091] In some embodiments, the hydrogen produced by a suitable reaction is delivered across proton exchange membrane 223 and is reacted with nitrogen or another supply of reactant (such as CO_x i.e. carbon monoxide or carbon dioxide) to produce additional liquid fuel values such as ammonia, urea, methylamine etc. In some embodiments, the hydrogen passes out of the reaction vessel 200 via through passageway 240 or conduit 418 and is collected for storage and later use. In either process event, it is particularly advantageous to remove the hydrogen from the reaction products in the reaction vessel 200 in order to improve the process yield efficiency of liquid fuel such as an alcohol e.g. methanol production.

[0092] Referring to Figure 3A, in embodiments where the hydrogen passes through the proton exchange membrane, it can be pressurized for delivery through port 320P to conduit 334 to injector 330 for high efficiency direct injection and ignition at or after TDC for Joule-Thomson expansive heating of high speed hydrogen expansion and stratified- charge combustion in un-throttled air in the combustion chamber 328 of engine 302. Engine 302 can also be operated with pressurized hydrogen delivered to the engine via valve 331 A or valve 331 B from port 320P and/or with a mixture of hydrogen and methane supplied by tank 371 that can be compressed by intensifier 315 for delivery through port 320P.

[0093] Further improvements in the operating efficiency of engine 302 can be obtained by admission of pressurized methane from tank 371 through valve 325 at times that intake valve 327A is open to produce momentum pumping for greater air delivery into combustion chamber 328. Subsequent homogeneous or stratified hydrogen combustion enables an extremely wide range of overall fuel/air ratios and helps to ensure accelerated initiation and completion of combustion.

[0094] In some embodiments, pressurized methane from tank 371 and/or intensifier 370 can be delivered through valve 331 A and/or 331 B of valve assembly 330 during the compression stroke of piston 301 to produce Joule-Thomson expansion cooling and thereby reduce the work of compression. Valve assembly 329 or 330 can be configured to replace glow plugs, spark plugs or fuel injectors in conventional engines. Illustratively, in alternate embodiments, a separate port is provided in the head of engine 302 for valve assembly 329 and device 330 can replace the conventional diesel injector.

[0095] Figures 3B and 3C show an illustrative embodiment 380 which can be utilized in processes similar to the operation of injector 330. An injector case 376 houses valve actuator 384 connected by electrical or fluid cables 378 to control the flow of fluids through passageway 394 to valve 374 such as chemical plasma agents and/or fuel selections that are admitted through conduits 381 -382 and/or 388 and/or other fluids such as coolants or oxidants through conduit 387. Controller 383 monitors combustion chamber conditions such as pressure, temperature, combustion patterns, and events such as intake, compression, fluid injections, combustion, to control valve actuator 384 and selector valve 391 .

[0096] Voltage transformer windings 385A-385P can produce the desired current and voltage which is contained by dielectric insulator 373 for operation of actuators 384 and 391 along with ignition energy delivered through connection 386 within insulator material 373 by spark, Lorentz ion acceleration, corona and/or chemical plasma agents as shown. Actuator 391 can utilize a stroke amplifier lever 397 that rotates around fulcrum bearing 398 to amplify unidirectional motion of plunger 379 and accelerate the motion of selector linkage 396 to control flow of fluids from conduit 387 and/or 388 for deliveries from housing 390 to conduit 392 for control by valve 374 and past 393 that can include one or more electromagnets and/or permanent magnets and/or

instrumentation such as fiber optic temperature, pressure, and acoustical

instrumentation for injections into combustion chamber 372.

[0097] In exemplary operation, an oxidant such as oxygen, oxygen enriched air, an oxide of nitrogen, or a suitable peroxide is delivered through conduit 388 for injection into combustion chamber 372 before, at or after TDC and can form a stratified charge. A fuel delivered through conduit 381 -382 or 387 can be injected before, at or after TDC according to timing of delivery initiation and duration of such events by controller 383. In some application instances auto-ignition of the fuel begins upon mixing with the oxidant selection. In certain embodiments the stratified oxidant selection serves as the combustion initiator and fuel including products of combustion that penetrate into surrounding air complete the combustion process. In other instances ignition and/or acceleration of combustion can be induced by spark, Lorentz ions, corona and/or chemical plasma agents.

[0098] With reference to Figure 4, the system 400 can further include a fuel cell engine and/or a heat engine 402, electricity generator 420 and compressor 403. The compressor 403 may be mechanically or electrically driven. Other components of the system can include a microprocessor 401 , heat exchangers 406, 408, 414, 416 and 422 for transfers of heat H-1 from engine coolant, heat H-2 from engine exhaust gases, energy H-3 from regenerative operation by generator 420, compressor 403 and/or other sources to produce chemical fuel potential energy values. In addition to serving in synergistic circuits for methanol and hydrogen production, engine 402 of system 400 may be utilized according to adaptive control by microprocessor 401 to drive other loads and serve in additional combined heat and electricity generation systems. In some embodiments, combined heat and power include electricity alternator 420 and cascaded heat exchanges to a fluid such as air, water, a hydrogen and/or carbon donor such as methane or industrial process fluid selections admitted at connection 424 and delivered through counter current heat exchanger 422 at connection 426 to transfer a portion of H-2. Similarly, a selected fluid admitted through connection 404 and/or reservoir 416 can be heated by portions of H-1 in circuit 406 and/or 417 and/or by portions of H-2 in circuits 408 and/or 414 for production of pressurized and/or hydrogen characterized fuel from ports 426 and/or 418. This enables improved production of electricity and/or thermal energy and/or various other outcomes to meet seasonal demands along with methanol fuel production demands.

[0099] Methanol, ammonia and/or other liquid energy storage fuel selections produced by the systems and method described herein can be used in conjunction with re-purposed gasoline and diesel fuel tanks, such as described in U.S. Patent

Application Nos. 61 /828,645; 6945-8408. US01 ; 6945-9018WO00; 8345WO00. In such applications, fuel alcohols such as methanol store energy densely and can be delivered through ports 404, 410, valve 412 and/or port 424, in cycles to one or more pressure increasing thermochemical converters such as 406, 408, 414, 417, or 422 and/or such as those disclosed in U.S. Patent Application Nos. 2003/0012985, 201 1 /0125391 , and 2013/0283759. The result of using a precursor fuel such as methanol in this manner is the production of pressurized carbon monoxide and hydrogen as shown in Equation 3.

[00100] Engines that utilize hydrogen, either alone or in mixtures with carbon monoxide, nitrogen, and the like (such as the products produced in Equations 3 and 4), can be more efficiently operated as unthrottled engines in which power is controlled by modulation such as adaptive proportional control of the timing and amount of fuel delivered to the engine. Combustion regimes including homogeneous charge, stratified charge, and/or Joule-Thomson expansion cooling before TDC and/or Joule-Thomson expansion heating after TDC and/or Super Speed hydrogen shock wave combustion and/or other combinations including spark, Lorentz, and/or corona ignition in any and all respective permutations are thus enabled for various improvements in fuel efficiency, engine performance, and life.

Reaction of Liquid Energy Storage Fuels

[00101] Figure 5 shows portions of an application system 500 in which a low pressure fuel storage tank 502 can be utilized to supply a liquid energy storage fuel such as a fuel alcohol e.g. methanol and/or ammonia that is intermediately pressurized by pump 504. Pressurized liquid energy storage fuel is then delivered to a counter- current heat exchanger 506 and used to cool hydrogen and/or mixtures of CO and 2H₂ produced by thermochemical regenerator 508 at a suitable location such as the exhaust manifold 51 1 and/or other locations within the exhaust system 509 of engine 510. The liquid energy storage fuel can then be used to perform one or more the pressurizing gas production reactions such as illustratively summarized by Equations 3, 4 or 5A-D.

Depending upon engine conditions including the exhaust temperature and load on the engine, additional heat such as H-3 from off peak and/or regenerative energy sources may be added to expedite the production of hydrogen in endothermic reactor 508. The hydrogen characterized pressurized gas product then flows past check valve 514 into accumulator 516 and/or to adjustable pressure regulator 518 to control the amount of fuel delivered through direct injection devices such as 330 or intake port injectors 520A, 520B, and 520C to control the power produced by unthrottled oxidant intake of engine 510. In certain embodiments, the oxidant delivered to the combustion chambers can include stratified charge oxygen delivered through valves 331 A or 331 B to produce accelerated initiation and/or completion of combustion of fuel in combustion chamber 328.

[00102] Figure 6 shows portions of an application system 600 in which a relatively high, medium or low pressure fuel storage tank 502 can be selected to supply liquid energy storage fuel such as illustrated by a carbonaceous or oxygenated fuel such as methanol and/or a nitrogenous fuel such as ammonia or urea in a suitable solution that is intermediately pressurized by pump 504 to sufficient pressure such as about 100PSI. Pressurized liquid energy storage fuel is then delivered to a counter-current heat exchanger 506 to cool hydrogen and/or mixtures such as CO and H₂ and/or N₂ and H₂ produced by thermochemical regenerator 508 by utilization of H-1 , H-2, and/or H-3 from a heat engine or another system.

[00103] The liquid energy storage fuel can be used to perform pressure increasing steps in which a gas is produced by phase change and/or reactions such as shown by Equations 3, 4 or 5A-D to produce pressures sufficient to supply port injectors 520A, 520B and 520C or sufficiently greater pressure than the combustion chamber pressure of engine 512 to provide direct fuel injection into the combustion chambers through injectors such as 522A, 522B and 522C.

[00104] Accordingly, pressurized gas flows past check valves 514A and 514B into accumulators 516A and 516B and to adjustable pressure regulators 518A and 518B to control the amount of fuel delivered through timed intake port injectors 520A, 520B, and 520C to induce greater entry of unthrottled air into the respective combustion chambers of engine 512 to control the power produced. Turbocharger 620 and/or system 300 may be utilized to provide additional inventories of unthrottled compressed oxidant such as air to further improve the thermal efficiency and power performance of engine 512.The vast majority of fuel cells and heat engines both of which are defined herein as engines operate in atmospheric air with air as the oxidant for operation to produce significant amounts of water that is ordinarily rejected to the surrounding air through their exhaust systems. Air is a mixture of about 78.1 % nitrogen and 20.9% oxygen, along with 1 % argon and other gases including carbon dioxide and varying amounts of water vapor. Such diluted oxygen is ordinarily the key reactant in air that supports such fuel cell and/or heat engine operation by oxidation of the fuel selection. Increasing the oxygen availability and/or activity by increasing the temperature, pressure and/or concentration can greatly increase the oxidation rate and product yield efficiency in such processes.

[0100] In certain embodiments, oxygen is produced by suitable methods such as electrolysis of water by electrolyzer 650 and/or by a suitable filtration system 350 or 652 which separates oxygen from air. In instances that a feedstock such as methanol is converted to DME or another chemical plasma agent by dehydration in an electrolytic medium the electrolyte such as a suitable base or acid such as sulfuric acid can be regeneratively dissociated by electrolyzer 650 to produce pressurized supplies of oxygen and hydrogen.

[0101] Such oxygen is routed through valve 654 to storage in accumulator 656 and/or regulator 655 to injector valve ports 658, 660, and 662 for direct injection of stratified charge oxygen. Such stratified charge oxygen can greatly accelerate ignition and/or completion of combustion of previously or subsequently injected fuel in the combustion chambers of engine 512. In certain embodiments, relatively low pressure oxygen delivered from filtration process 652 is initially loaded into accumulator 656 and pressurized by subsequent additions of oxygen from a pressurizing electrolyzer 650 and/or from intensifier 315. Such oxygen pressurization electrolyzer can improve the J- T expansion cooling benefit and/or the stratification of such oxygen to accelerate initiation and/or completion of combustion of fuel in combustion chambers such as 328.

[0102] Controller 250, 356, 401 , or 701 can adaptively provide a wide variety of operational methods including injection of oxygen to form a stratified oxygen charge within the air in the combustion chamber before TDC followed by direct injection of a fuel such as natural gas, hydrogen, carbon monoxide, carbon dioxide, ammonia, nitrogen or mixtures of selections of such substances near, at, or after TDC. The controller can respond to instrumentation that provides determination of the BMEP, fuel consumption rate, peak combustion temperature, piston speed etc., to adaptively adjust the pressure and/or temperature of oxygen injection, the crank angle at which the injection begins along with the crank angle traversed during injection, the pressure and/or temperature of such fuel injection, the crank angle at which the injection begins along with the crank angle traversed during injection. This enables adaptive control operations that improve the utilization of regenerative energy, fuel efficiency, power production, and reduction or elimination of objectionable noise or exhaust emissions. Additional direct injection of fuel into the combustion chambers of unthrottled engine 512 is provided by injectors 522A, 522B, and 522C to utilize the higher TCR pressures produced by heat addition to gasify and respeciate intermediately pressurized liquid fuel. High speed combustion of hydrogen characterized fuels after TDC improves BMEP and thus engine performance, fuel economy, and actually cleans the air that enters the combustion chambers.

Carbon and Hydrogen Donor Substances

[0103] In many applications it is desired to extend the range, power performance, or fuel economy and/or to provide fuel value by conversion of toxic or otherwise

unfavorable constituents such as may be extracted from flare gas, food and industrial waste streams. Equation 6 illustrates such a process wherein a carbon and/or hydrogen donor substance ("C") can be used.

CH3OH + 3H₂0 + "C" + HEAT 2C0₂ + 5H₂ (6)

[0104] Equation 7 illustrates a process for utilizing a primary fuel (such as methanol) to collect water from sources such as the atmosphere or more concentrated sources such as the exhaust stream of a fuel cell or heat engine that is fueled with a hydrogen donor substance. Reaction 7 provides TCR conversion of methanol to hydrogen and carbon dioxide.

CH3OH + H₂0 C0₂ + 3H₂ (7) [0105] With reference to Figure 7, an embodiment for gaining water from the exhaust system of a fuel cell or internal combustion engine through which combustion products containing water vapor are exhausted is illustrated. Hydrogen containing fuels such as hydrocarbons, alcohols, ammonia, urea, formic acid, etc., produce such water vapor in amounts that may be greater than the amount that may be used for TCR or electrolyzer reactions that beneficially utilize regenerative energy to provide oxygen and hydrogen for improved combustion efficiency. In the spray down and collection sump

configuration shown, spray nozzle and regulator 704 produces a spray pattern of cool water-absorbing fuel 706 from tank 702, delivered through air cooler 707 by pump 704 to flow selector valve 703 to cool and help reduce back pressure on an engine (such as engine 301 -302, 402, 510, or 512) as water is collected by the cool spray 706 to form mixture 708, which can then be pressurized by pump 71 1 for production of oxygen delivered through conduit 727 and hydrogen delivered through conduit 725 by a suitable electrolyzer 712 and can be regulated by pressure regulator 713 for delivery of the remainder to tank 702.

[0106] In certain embodiments, oxygen is separated from air by one or more filters such as a molecular sieve, diffusion membrane, pressure or temperature swing sorption, or another suitable process in module 350. Oxidant such as air or oxygen separated by system 350 and delivered through passageway 354 can be routed to conduit 338A to be directed to pass through intake valve 327A and to be compressed in chamber 328 for delivery through valve 331 A, 331 B and/or 327B and/or 360 and 309 for storage in an accumulator similar to 371 for delivery to port 352 and/or through valve 308 to displace piston 312 and intensify the pressure of oxidant such as air and/or oxygen supplied through valves 310 and 316 by piston 314 for delivery from port 320 for selected applications including, charging oxygen separator module 350 through port 352 to produce oxygen-rich flow from port 354 and nitrogen-rich flow from port 356. Nitrogen from port 356 can be added to the motor of turbocharger 620 to increase the supply of compressed air charged into intake conduit 338A and/or such pressurized nitrogen can be cooled by surrounding air for J-T expansive cooling of gas flowing through exhaust system 710. Such oxygen or oxygen-rich gas can be utilized with or without other sources of oxygen to produce a stratified zone or pattern in combustion chambers such as 328 for stimulation or acceleration of fuel combustion as described herein. Such oxygen can be stored in an accumulator and/or delivered through valve 331 A, 331 B, or through 334 to 330 as a stratified charge in combustion chamber 328 to stimulate or accelerate ignition and/or completion of combustion of fuel in combustion chamber 328. The hydrogen can be similarly stored in an accumulator and/or delivered to combustion chamber 328 as shown in system 300, 500, or 600. Piston assembly 312-314 reciprocates in a fluid pumping cycle and upon return of piston 312 to the starting position fluid is displaced through valve 322 for delivery to conduit 336 or 338A, or to storage in an accumulator similar to 371 or to a turbocharger 620, or to chamber 328 through 330 and/or valves 331 or 331 B.

[0107] Pressurization of spray nozzle and regulator 705 to deliver fuel from tank 702 may be carried out by a suitable pump 704. At times that the ambient air could produce freezing conditions in dilute fuel-water solutions, air cooler 707 may be bypassed through port 719 and/or provided with H-1 , H-2 or H-3 heating to prevent ice formation in locations such as sump collector 708, electrolyzer 712, regulator 713 and/or in or on fins 720, exducer 730 or filter 718.

[0108] Figure 7 illustrates system 700 components including thermo-electric generator 709 and radiator 707 for air cooling the fluid from tank 702 and a component 717 of the system 700 which may be used as an individual system or in conjunction with other embodiments for collection of water from the exhaust. This component 714 of the system operates by circulation of fluid such as fuel from tank 702 through port 721 to port 723 or vice versa through a mist condenser or filter and/or helical fin tube 720 and/or through an annular passageway 715 between component membrane 717 and exhaust pipe 710 to prevent escape of mist droplets and cool the exhaust gases.

Component membrane 717 can be permeable material that provides suitable micropores or channels or otherwise has provisions for admitting water molecules from the exhaust gases to be captured and form a lower vapor pressure mixture with the fuel, which is returned through port 723 to tank 702. [0109] Figure 7 also illustrates another component of the system 700 which may be used as an individual system or in conjunction with other embodiments and which removes water and/or fuel vapors from the exhaust gases. The component includes a spinning exducer 730 to sling water droplets to a higher radius of gyration and collection for delivery by shroud 716 through filter 718 to tank 702. Such cooling of the exhaust gases by the spray down with cool fluid passing through air cooler 707 to form a more diluted mixture decreases the vapor pressure of the constituents of the mixture and improves collection efficiency.

[0110] In many fuel cell applications the process depicted by Equation 7 and Figure 7 helps to assure elimination or removal of carbon monoxide. In other instances, such as production of carbon dioxide for photosynthesis, elimination of carbon monoxide helps to ensure the safety of workers.

[0111 ] The present invention overcomes the difficult problems stated above by enabling existing SI and CI engines to utilize net-hydrogen fuel and achieve higher fuel economy and longer useful life. Net-hydrogen fuels or energy carriers are substances that contain hydrogen that is combined with nitrogen and/or carbon dioxide taken from the atmosphere or preemptively taken from one or more sources of nitrogen and/or carbon dioxide that would be ordinarily be allowed to enter the atmosphere. Accordingly a net-hydrogen fuel or energy carrier can be combusted without causing a net increase in the atmospheric content of nitrogen and/or carbon dioxide. In many instances hydrogen is combined with sufficient nitrogen to store energy and thus reduce or eliminate the amount of carbon dioxide contributed to the atmosphere per energy unit released upon combustion. Illustratively by combining hydrogen with nitrogen to form a nitrogenous compound such as ammonia (NH3) to deliver "X" amount of energy upon combustion, no carbon dioxide is produced. Preparation of various other

carbonaceous and nitrogenous compounds are disclosed as net-hydrogen fuels that provide energy densities comparable to petrol fuels and that can be stored or shipped as ambient temperature liquids in gasoline and diesel fuel tanks and pipelines. This overcomes difficult storage and transportation problems that conventional hydrogen storage technologies encounter. [0112] Figure 9A and 9B show the process steps for converting materials that ordinarily rot or burn including fossil and renewable substances into carbon and hydrogen. Illustratively wet substances such as sewage, garbage and farm wastes can be wet digested in an anaerobic system to produce methane that is thermally and/or electrolytically dissociated to provide separate supplies of carbon and hydrogen.

Relatively dry substances such as fossil hydrocarbons can be thermally dissociated to provide separated supplies of carbon and hydrogen.

[0113] In an embodiment processes, fossil and/or renewable substances that ordinarily rot or burn are separated into carbon that is co-produced with hydrogen for synthesis of net-hydrogen fuels. The carbon is utilized to produce durable goods optionally including equipment that harvests more solar, wind, moving water or geothermal energy compared to one-time burning of such carbon. Accordingly the combination of carbon extraction to produce durable goods from substances that ordinarily rot or burn greatly reduces carbon dioxide contributions to the atmosphere and enables additional greenhouse gas reductions by production of net-hydrogen fuels. This energy conversion regime provides "carbon-negative" environmental protection benefits along with sustainable energy production to support sustainable economic development.

[0114] Carbon dioxide and/or nitrogen is collected from the atmosphere.

Alternatively, carbon dioxide and/or nitrogen can be preemptively collected from sources such as power plants, calciners, ethanol plants, wastewater processors, landfills, and decaying permafrost. Co-produced hydrogen and such carbon dioxide and/or nitrogen are synthesized to produce fuel compounds such as ethers, ketones, aldehydes and alcohols including acetone, ammonia, urea, nitromethane, formic acid, dimethylether, diethylether, acetaldehyde, and/or other suitable compounds.

Substantially conventional pipelines can be used to transport the liquid fuel compounds. Natural gas, gasoline, oil, and diesel fuel tanks can be used to store such liquid compounds.

[0115] In another embodiment fossil and/or renewable substances that ordinarily rot or burn are processed by suitable methods such as hydro-treating and/or hydro- cracking to produce sufficiently concentrated inventories of methane that can be transported by conventional natural gas pipelines and/or higher molecular mass hydrocarbons and/or other compounds that can be cooled, condensed, and transported by conventional liquid pipelines.

[0116] In operation, heat rejected by fuel cells, SI and CI reciprocating, turbine and rotary combustion engines can be utilized to produce chemical and/or pressure potential energy by endothermic release of such hydrogen from the net-hydrogen fuel

compounds.

[0117] Accordingly, engines including fuel cells, SI and CI reciprocating, turbine and rotary combustion engines can operate by utilization of pressure and/or chemical potential energy provided by the endothermic release of such hydrogen from the fuel compounds. In other instances a furnace or other heated devices supply heat such as combustion and/or process gases by an exhaust system that be utilized to supply heat that is converted into chemical and/or pressure potential energy by endothermic release of such hydrogen from the fuel compounds.

[0118] As shown in Figures 9A and 9B, process steps 900 are for converting substances that ordinarily rot or burn including fossil and renewable substances into carbon and hydrogen. Illustratively, in Step 902 wet substances such as sewage, garbage and farm wastes can be wet digested in an anaerobic system to produce methane that is thermally and/or electrolytically dissociated to provide separate supplies of carbon and hydrogen. In Step 904 relatively dry substances such as fossil

hydrocarbons can be thermally dissociated to provide separate supplies of carbon and hydrogen.

[0119] In the present processes fossil and/or renewable substances that ordinarily rot or burn are separated into carbon that is co-produced with hydrogen. In Step 906 the carbon is utilized to produce durable goods optionally including equipment that harvests more solar, wind, moving water or geothermal energy compared to one-time burning of such carbon. In Step 908 carbon dioxide and/or nitrogen is collected from the

atmosphere. Alternatively carbon dioxide and/or nitrogen can be preemptively collected from sources such as the exhaust systems of power plants, calciners, ethanol plants, wastewater processors, landfills, and decaying permafrost.

[0120] In Step 910 co-produced hydrogen from Step 902 or Step 904 and such carbon dioxide and/or nitrogen from Step 908 are synthesized to produce carbonaceous fuel compounds and/or nitrogenous compounds such as alcohols, ammonia, urea, nitromethane, formic acid, dimethylether, diethylether, acetaldehyde, and/or other suitable compounds. In Step 912 conventional and/or new pipelines can be used to transport the fuel compounds. In Step 914 natural gas, gasoline, and/or diesel fuel tanks can be used to store such compounds from Step 910.

[0121] In Step 916 heat from fuel cells, SI and CI reciprocating, turbine and rotary combustion engines is utilized to produce chemical and/or pressure potential energy by endothermic release of such hydrogen from the net-hydrogen fuel compounds. In Step 918 engines including fuel cells, SI and CI reciprocating, turbine and rotary combustion engines operate by utilization of pressure and/or chemical potential energy provided by the endothermic release of such hydrogen from the fuel compounds. In Step 920 furnaces or other heated devices supply heat such as combustion and/or process gases by an exhaust system that is utilized to supply heat that is converted into chemical and/or pressure potential energy by endothermic release of such hydrogen from the fuel compounds produced by Step 910.

System and Apparatus for Separating Hydrogen and Carbon

[0122] Figure 10 shows system 1060 for co-producing and separating hydrogen and carbon from substances that ordinarily rot or burn. Canister assembly 1080 is radiatively and/or conductively insulated by system 1078 and provides a more or less annular space 1062 for passage of carbon and hydrogen donor substances such as natural gas or methane 1002 which can be preheated by countercurrent heat exchanger 1068-1070.

[0123] Certain embodiments are utilized to convert a carbon and hydrogen donor substance such as C_xH_y (e.g. CH₄) into carbon that is plated, trapped, or collected on or by ceramic substances such as interconnected porous forms, felt, paper or fibers 1064 such as graphite, alumina, spinel, magnesia quartz, bauxite, and/or basalt fibers. Such configurations include combinations of such material selections that may be formed into substrates such as a suitable curtain 1064 or tubing as shown around an inductive or resistive heating element 1066. Hydrogen is co-produced as summarized by Equations 1 1 and 12.

[0124] Illustratively, curtain 1064 can include one or more wraps of such ceramic wool, cloth, matt, and/or felt to provide an unwrapped length that is suitable for serving as a component and/or for reinforcing a component of equipment such as storage tanks, pipelines, wind or water turbines, transportation containers and/or chassis assemblies. An exemplary stationary equipment application that also can serve as roofing and/or siding systems such as 1 100 and 1 150 as shown in Figures 1 1 A and 1 1 B.

Carbon Matt/Film Materials

[0125] An illustrative embodiment 1 100 is provided by thin films such as 1 102, 1 103, 1 104, 1 105, and/or 1 125 that are welded, extruded, or otherwise bonded on seams 1 101 A, 1 101 B, 1 101 C, etc., to define the shape and forms of longitudinal passageways that extend through the length "L" of such roofing and/or siding system. Suitable materials for such thin films include various selections of fluoropolymers, polyolefins, acrylics, polyesters, and other formulations that can be transparent, translucent, UV blocking or transmitting, and/or colored to any suitable appearance and performance. Certain zones such as 1 121 that are bonded and suitably formed such as adjacent arches by suitably spaced seams such as on 2 to 20 mm centers that can be filled with a gas such as air, carbon dioxide, or nitrogen to serve as a structural feature for supporting foot traffic and resisting damage by hail, baseballs, and other impacts. An exemplary construction can utilize one or more thickness of film that are suitable for the selected arch spans such as clear 0.12 mm ethylene-tetrafluoroethylene (ETFE) film for layer 1 105, 0.06mm film for layer 1 103, 0.05mm film for layer 1 125 over mat 1 108, and a 0.010 mm polyester or polyolefin film 1 1 12 can be bonded to seal suitable organic or inorganic foam or ceramic fiber form 1 1 10 as shown.

[0126] The carbon curtain cloth or matt 1064 can be formed as shown in layer 1 108 to serve as a black converter of radiant energy from the sun and/or surroundings to provide heat and infrared radiation to heat substances such as air, water, and other fluids that can be contained and/or transported through passageways such as zone 1 123 formed by transparent layers 1 103 and 1 105; zone 1 121 formed by layer 1 103 and 1 125; zone 1 1 19 formed as the inside of tube 1 1 15; zone 1 1 16 formed by layers

1 103 and 1 125; zone 1 1 17 formed by tube 1 1 14; zone 1 1 18 formed by layers 1 102 and 1 103; zone 1 120 formed by layers 1 102 and 1 104; and zone 1 122 formed by layers

1 104 and 1 125. Carbon curtain matt 1 108 can also serve as a thermal flywheel or capacitor to gain and retain heat during the day for heat exchange to one or more circulated fluids in selected passageway zones such as 1 1 16, 1 1 17, 1 1 18, 1 1 19, 1 120,

1 122, 1 123, at other times such as during the night for space and/or air or water heating etc.

[0127] Film 1 105 can be coated 1 106 (i.e. DLC) with suitable material selections such as with carbon as diamond like material (DLC) to certain thicknesses to admit or omit UV and to provide improved strength and scratch resistance. Alternate coatings include first or second surface photovoltaic materials 1 109 to provide conversion of solar energy into electricity and/or photoactive titania to accelerate the weathering and removal of organic contaminant substances that would foul or block radiation collection. A fluid such as air, nitrogen, hydrogen, or carbon dioxide can be circulated through zone 1 1 16, 1 1 18, 1 121 , 1 123 and/or any other passageway to keep the photovoltaic material within the desired temperature range for efficient operation. In certain applications, a fluid such as water or a food preparation recipe is circulated through a passageway such as 1 1 17 within tube 1 1 14 or another fluid such as an antifreeze or fuel within 1 1 19 of tube 1 1 15 to provide process energy.

[0128] Embodiment 1 150 of Figure 1 1 B shows certain zones such as 1 154-1 156- 1 158 that are bonded and suitably formed such as with a flat top or adjacent arches by suitably spaced seams such as on 2 to 20 mm centers that can be filled in zone 1 163 with a suitable liquid or has such as air, carbon dioxide, or nitrogen to serve as a structural feature for supporting foot traffic and resisting damage by hail, baseballs, and other impacts. [0129] Exemplary components of construction such as upper portion 1 152 that can comprise one or more thickness of film that are suitable for the selected arch spans such as clear 0.12 mm ethylene-tetrafluoroethylene (ETFE) film for layer portions 1 154 and 1 156, 0.06mm film for layer 1 158, 0.006mm film for optional layer 1 167 over mat 1 168, and a 0.010 mm polyester or polyolefin film 1 172 can be bonded to seal suitable organic or inorganic foam or ceramic fiber form 1 170 as shown. In some applications upper assembly 1 154-1 155-1 158 is weld bonded or extruded as a unit with suitable width "W" and length "L" to serve as a roofing or siding component of a dwelling or structure. Tubing 1 166 with suitable pressure rating can be placed at suitable locations and orientations to serve as structural members and fluid conduits.

[0130] In some fluid circuits typical tubing 1 166 contains carbon or carbon-enhanced fibers 1 166 that are produced by processes such as embodiment 1060 and can be packed to suitable density within selected tubes 1 166 as shown. In other fluid circuits such as 1 165, carbon or carbon-enhanced matt 1 160 or fibers 1 162 are incorporated in the tube walls or on the tube walls such as partially of fully surrounding the tube. Such arrangements along with control of fluid flow rates in such circuits provide a wide variety capabilities including fluid compatibility and operating temperatures.

[0131] Layer 1 168 can be any suitable thickness and density of carbon or carbon- enhanced matt or fibers to provide suitable specific heat and capacity such as thermal flywheel or capacitance. Optional layer 1 170 can be any suitable insulator comprised of materials such as organic or inorganic foam, expanded pearlite, fiber-crete, or ceramic fiber form as shown. Optional film 1 172 can be utilized to seal and package the assembly for purposes including prevention of moisture accumulation, ease of handling, and to facilitate rapid installation.

[0132] Film 1 154 can be coated with suitable material selections such as with carbon as diamond like material (DLC) to certain thicknesses to admit or omit UV and to provide improved strength and scratch resistance. Alternate coatings include first or second surface photovoltaic materials 1 151 to provide conversion of solar energy into electricity and/or photoactive titania to accelerate the weathering and removal of organic contaminant substances that would foul or block radiation collection. A fluid such as air, nitrogen, hydrogen, or carbon dioxide can be circulated through zone 1 163 and/or any other passageway to keep the photovoltaic material within the desired temperature range for efficient operation. In certain applications, a fluid such as water or a food preparation recipe is circulated through a passageway such as through tube 1 166 or another fluid such as an antifreeze or fuel within 1 164 of tube 1 166 to provide process energy at a higher temperature. In certain embodiments carbon enhanced fibers or other forms of material can be used to partially fill selected tubes such as 1 163 to perform filtration and/or to serve as energy collection and/or thermal capacitor functions.

[0133] In some process applications of embodiment 1060, as shown in Figure 10, ceramic fibers 1064 can be pre-coated with a carbon and/or other nano structure donor such as a suitable substance including a metal organic, hydride, nitride, or carbide, petrolatum, and/or wax or a mixture of selections of such substances which is thermally dissociated to form seeds for carbon deposits to accelerate and/or catalyze the carbon deposition process that follows as additional feed stock C_xH_y is processed to form nanotubes, scrolls, graphene, bulbs, rods, etc., and/or amorphous deposits. Heating element 1066 can be a suitable material such as refractory metals, ceramets, graphite, silicon carbide, molybdenum disilicide etc.

[0134] Such resistive or inductive heating can be utilized with or without other heat sources such as one or more similar heating elements at other locations such as outside of curtain 1064 (not shown) and/or by combustion produced with a combustant delivered through valve 1072 and conduit 1074. Suitable combustants include fluids such as oxygen, oxides of nitrogen and/or carbon or air that partially combusts fuel such as can be preheated in counter current heat exchanger 1062 and/or 1068-1070 and/or the hydrogen produced by the separation from carbon that is deposited or trapped by curtain 1064. One or more combustors such as orifices in a manifold or multiple tubes 1074 can be utilized such as two to twelve combustors stationed around heater element 1066 to supply supplemental heat and/or to clean deposits or debris from one or more elements such as 1066.

[0135] Such oxidants can be utilized including by adaptively proportioned steady or intermittent duty cycles to oxidize and remove carbon deposits to inductive or resistive heater 1066. As an illustrative example the electrical characteristics of 1066 can be monitored by controller 1084 and at times the electrical resistance drops below a predetermined limit, a reactant substance such as air or oxygen can be added or the rate can be increased or proportionally adjusted to convert such carbon deposits into an oxide of carbon for removal.

[0136] The resulting hydrogen product and/or mixtures such as unconverted feedstock and hydrogen and/or products of combustion such as oxides of carbon that pass into conduit 1070 for countercurrent heat exchange and/or delivery to a fuel cell engine or reciprocating or rotary or turbine combustion engines for shaft power production and/or an engine-generator for electricity generation.

[0137] In other applications at least a portion of the co-produced hydrogen is combined with carbon dioxide and/or nitrogen from the air or from more concentrated sources such as the exhaust systems of power plants, calciners, bakeries, decaying permafrost or other unstable clathrates, ethanol plants, fermenters or breweries to produce carbonaceous and/or nitrogenous fuels such as alcohols, aldehydes, ethers, ammonia, urea etc., to serve as net-hydrogen fuels that can be compactly stored. In certain applications a fuel alcohol such as butanol, propanol, ethanol or methanol is produced along with an ignition stimulant such as acetaldehyde, dimethylether, or diethylether. The alcohol such as methanol or ethanol can be utilized wet or dry and can at least partially dissociated by the endothermic reactions summarized in Equations 8 and 9 by utilization of engine coolant to supply heat (H-1 ), engine exhaust or to supply heat (H-2), regenerative heat (H-3) and/or other sources such as combustion of an oxidant and/or fuel such as 266, 276, or 282 to supply heat (H-3 and H-4).

CH₃OH + (H-1 , H-2 and/or H-3)→ CO + 2H₂ (8) C₂H3OH + H₂O + (H-1 , H-2 and/or H-3)→ 2CO + 3H₂ (9)

[0138] This can provide the benefit of converting relatively inexpensive wet fuel alcohols and heat such as H-1 , H-2, H-3, and/or H-4 into increased chemical and/or pressure potential energy. Beneficial production of pressure potential energy can be provided by converting one or two moles of liquid reactants into three or more moles of gases that are self-pressurized compared to utilization of an expensive gas compressor that requires considerable energy to operate.

[0139] Various carbonaceous substances including alcohols such as methanol, ethanol, propanol, butanol and/or ethers such as dimethylether, diethylether,

dipropylether, and/or nitrogenous substances such as ammonia, urea, methylamine, nitromethane, nitroglycerine, ethylene glycol dinitrate etc., generally include separating a carbonaceous substance such as methane into carbon and hydrogen and reacting the hydrogen with an oxide of carbon and/or nitrogen or an oxide of nitrogen. Feedstock such as methane can be obtained from various human-implemented processes or that may be released from naturally occurring processes. Additional steps can be taken to produce a nitrogenous or carbonaceous substance such as ammonia and/or a carbonaceous substance such as alcohols or ethers from the products of the reaction of methane and water.

[0140] Illustratively, methanol, ethanol, ammonia, and urea can be used in liquid energy storage fuel formulas that, when subjected for further reactions, can produce hydrogen suitable for use as a fuel in various applications. Illustratively, representative Equation 10 shows how a safer solution preparation of methylamine with a suitable solvent that can include an alcohol and/or water provides a reduced vapor pressure mixture for storage. Upon heat addition the reagents are vaporized and subsequently reacted to provide hydrogen-characterized pressurized gaseous fuel.

CH₅N + H₂0 + (H-1 , H-2, and/or H-3)→ CO + 3.5H₂ + 0.5 N₂ (10)

[0141] Further advantages of such conversions include increased chemical potential energy of the products compared to the reactants and much more favorable hydrogen- characterized combustion characteristics of the produces including: 1 ) Higher speed of sound and capability of sonic or supersonic flame speeds as fuel penetrates surplus oxidant such as compressed air;

2) Higher diffusion velocity to provide accelerated combustion speed;

3) Wider range of oxidant-fuel ratios suitable for combustion;

4) Assured elimination of particulates;

5) Clean net-hydrogen combustion to reduce or eliminate greenhouse gas emissions compared combustion of original feedstock substance.

Heat Exchanger for Converting Heat into Chemical and/or Pressure Energy

[0142] Figure 12A shows a system 1200 for converting H-1 , H-2, and/or H-3 to potential chemical and/or pressure energy by utilizing one or more pulsed heat exchanges to fluid fuel to provide self-pressurized supplies of vapors and/or hydrogen- characterized fuel products. In an endothermic process for H-2 and/or H-3 heat transfers, the components of system 1200 can be housed within a passageway through which hot exhaust gases 1240 from an engine such as a fuel cell, piston, rotary or gas turbine are directed to provide heat that vaporizes and thus pressurizes pulsed additions of liquid substances. In certain applications such vaporized substances receive additional heat to dissociate and/or respeciate into hydrogen or hydrogen characterized gases.

[0143] Various types of heat exchangers can be utilized to vaporize, dissociate and/or respeciate the fluid that is cyclically pulsed into one or more heat addition passageways. Heat exchangers can be comprised as high surface to volume microchannel configurations, finned tubes, composites that provide conductive pathways between resistive and/or inductive heating elements, and many other types.

[0144] An exemplary embodiment is shown in the sequences of Figures 12B and 12C, carbonaceous liquid fuel such as a fuel alcohol, ether and/or a nitrogenous substance from a conduit or tank 1201 is initially supplied through filter 1203 at pressure P-1 by pump 1205 to a valve 1207 that is operated to supply a continuous or pulsed flow of fluid such as a liquid fuel through a control valve that may include a check valve feature 121 1 into a relatively flat tube that can be configured as coil 1202. In certain heat pressurization or other endothermic processes upon receiving sufficient heat at least some of the pulsed inventory of liquid is vaporized to produce higher pressure which causes elastic expansion of tube 1202 and transport of the fluid particularly including vapors and gases from the point of liquid entry such as the core towards the outer rim of the coil or vice versa in subsequent stages depending upon the selected circuit for fluid travel to accumulator 1224 and/or port 1232.

[0145] Vaporization and pressurization of a fluid that is rapidly heated in coil 1202 causes elastic flattening of coil 1204. Liquid fluid is vaporized and pressurized from P-1 to higher pressure ultimately such as P-2 and flows to elastically expand and fill tube coil 1202 as coil 1204 is compressed toward closed or flattened condition as vapors and/or gases continue to receive heat and flow through subsequent stages that may include 1208, 1214, and/or 1220 and thus produce hydrogen or hydrogen-characterized gases that pass through valve and conduit 1226 to valve 1228 to port 1232 and/or accumulator 1224. In certain applications the parallel coils are restrained from overall growth by restraining bands 1250, 1252, 1254, and/or 1256 around the outside coils. Illustratively restraining bands such as can be reinforced by heat resistant super alloy bands or ceramic fibers such as alumina, quartz, basalt and/or carbon.

[0146] In certain instances fluid entry such as a suitable liquid added at P-1 by pulsed pumping or sequenced operation of valve 1207 to charge tube 1202 or alternatively to charge tube 1204 is facilitated by providing clearance spaces in entry zones such as in zones 1233 and 1235 that may be provided at suitable locations to receive thermal energy from exhaust gases 1240 and/or heaters 1206, 1212, and 1218 as shown in Figure 12B. Such clearance volume and passage ways can be provided by

mismatching features such as corrugations, knurl orientations and/or by suitable ceramic components or super alloy shot.

[0147] After each fluid pulse is pressurized from P-1 as fluid flows forward as described for further heating and/or achievement of higher pressure such as P-2 the entry chamber 1233 or 1235 can be quickly reduced in pressure to P-1 or less by coordinated pulsing of valve 1236 or 1238 to allow momentary fluid flow out of sections 1233 or 1235 through ports 1242 or 1244 to a turbocharger or the intake system of an engine such as a fuel cell or a piston, rotary or turbine engine. Such configurations, thermal fly-wheeling, and pulsed pressurization cycles enhances turbulent heat transfers from exhaust gases and/or heat sources such as 1206, 1212, and/or 1218.

[0148] In subsequent pulsed pressurization as depicted in Figure 12C coil 1204 receives a pulse of liquid feedstock through valve 1209 which is adaptively controlled along with valve 1207 by controller 1217 for delivery through valve 1213 to relatively flat tube heat exchanger 1204. Accordingly liquid is vaporized and pressurized from P-1 to P-2 and flows to elastically expand and fill tube coil 1204 as coil 1202 is compressed toward closed or flattened conditions as vapors may flow through subsequent stages such as 1210, 1216, and/or 1222 to receive additional heat and thus produce hydrogen or hydrogen-characterized gases that pass through conduit and valve 1230 and 1228 to port 1232 and/or accumulator 1224.

[0149] In some instances coils such as 1202 and 1204 etc., are provided with surface features on one or both sides such as etched, knurled, or coined patterns 1223 to enhance staged countercurrent cyclic heat transfers by radiant and/or conductive heat from resistive or inductive coils 1206, 1212, and/or 1218 and/or from exhaust gases 1240 to store energy in staged coils such as 1202-1204, 1208-1210, 1214-1216 and/or 1220-1222 to rapidly heat pulsed flows of reagent fluids. In other instances the coils are excited by one or more transducers such as 1219 to vibrate or enhance natural vibration of coils such as 1202 and 1204 and/or corresponding stages of such coils to enhance heat transfer rates.

[0150] Controller 1217 can control heat addition by one or more resistive or inductive heaters 1206, 1212, and/or 1218 for addition of heat such as can be provided by regenerative vehicle deceleration (braking) or suspension (springs and/or shock absorbers) or other suitable sources such as renewable solar, wind, moving water, or geothermal energy and/or from a storage system such as a capacitor or battery. This enables rapid start up with heat additions by 1206, 1212, 1218 etc., to provide production of pressure potential energy and/or increased rates and/or conversion ratios of products to reactants as illustratively shown by Equations 8, 9, and 10. [0151] Such conversion of H-1 , H-2, and/or H-3 to pressure potential energy provides efficient production of pressure increases from pressure P-1 to P-2 that can be supplied from port 1232 that is suitable for fuel pressurization of fuel cell engines or direct injection of heat engines such as piston, gas turbine, and rotary combustion types for improved energy conversion efficiency including various hybrid combinations of fuel cells and heat engines. Illustratively a heat engine can supply H-1 , H-2, and/or H-3 to produce pressurized fuel that can include or comprise hydrogen and/or hydrogen characterized fuel to a fuel cell or vice versa.

[0152] Considerable improvement in overall energy-conversion efficiency can be achieved in instances that the pressurized fuel is added near, at, or after TDC in a positive displacement engine or to help pressurize flow to power a gas turbine and/or to improve the efficiency of a fuel cell.

[0153] Accordingly the configuration, size and number of stages such as depicted in Figure 12A can be provided in series and/or parallel circuits to develop rapid radiant and/or conductive transfers of considerable capacity as one or more thermal flywheels. Such circuits can include fluid flows that are radially inward, radially outward, counter- current, and parallel and/or various other permutations as needed. This enables considerable storage of heat during times that vehicle braking and/or suspension energy regeneration is available. Pressurization and/or reaction processes such as depicted by exemplary Equations 8, 9, and/or 10 can thus be accelerated or more efficiently accomplished as a result of conversions at temperatures such as about 500 to 2000°C as a result of H-1 , H-2, H-3, and/or H-4 heat additions.

[0154] Fuel such as hydrogen or hydrogen-characterized fuel can be delivered from suitable sources such as port 1232 in pulses or at more or less constant pressure from accumulator 1224 to operate an engine with normally aspirated or supercharged oxidant, with throttled or unthrottled intake, in homogeneous or stratified charge combustion process operations.

[0155] In certain applications, liquid carbon and hydrogen donor feed stock from reservoir 1201 is pressurized sufficiently by pump 1205 to quickly deliver liquid through valve 1207 and subsequently valve 1209 to provide critical or super-critical pressure and/or for heat addition to produce critical or super-critical pressure in zone 1233 and subsequently in zone 1235. Additional heat gain produces super-critical pressure conversion to hydrogen characterized fuel that can be at a higher or lower pressure as needed for direct fuel injection starting before, at or after TDC in a converted SI engine or a higher compression CI engine such as a converted diesel engine.

[0156] It is generally advantageous in accordance with Le Chatelier's principle to alternately produce pulsed super-critical pressure in zones 1233 and 1235 such as about 700 Bar or more for depressurization through subsequent stages constrained by reinforcements 1210, 1216, 1254, and/or 1256 to deliver converted and/or respeciated gases through valve 1228 at a reduced pressure such as about 350 Bar for direct injection starting before, at, or after TDC. In certain instances the pressure of the products can be further reduced by extraction of products such as hydrogen by transfer through a proton membrane with or without galvanic impetus to accelerate separation and/or to re-pressurize the separated hydrogen.

Injector

[0157] An illustrative embodiment 1300 for such operation is shown in Figures 13A and 13B. A fluid fuel such as a gas viz. net-hydrogen gas is delivered by through conduit 1332 to conduit 1302 with or without additional selections such as chemical plasma ignition stimulants such as dimethylether (DME), diethylether (DEE),

acetaldehyde etc., that can be utilized or added from source 1309 through a valve such as a combination of three-way valve and check valve 1304 to a chamber 1318 for compression by a fluid such as a gas or liquid that displaces piston 1316. Fuel compression in chamber 1318 is provided by pressurized fluid such as liquid i.e.

hydraulic oil from port 1312 into chamber 1306. Piston 1316 can be constant or stepped in diameter to provide the area of piston face 1305 to be larger, equal or smaller than the piston face 1307 to provide suitable pressurization of fluid in chamber 1318 for delivery through a suitable valve 1320 such as a check valve. Valve assembly 1308 can be any suitable type including actuation selections such as a solenoid actuated shuttle or spool valve, piezoelectric, solenoid or piezoelectric piloted mechanisms to provide for pressurization of chamber 1306 from port 1312 and depressurization by exhaust through port 1314.

[0158] In operation, a suitable valve operator such as a pneumatic, hydraulic, solenoid, magnetostrictive, or piezoelectric subsystem 1328 extends to displace insulative plunger 1330 to open valve 1332 away from the seat in electrode 1339 to allow suitably pressurized fluid from chamber 1318 to flow through conduit 1322 and through valve 1332 to the combustion chamber 1350 of an engine 1352. Ignition can be provided by a variety of methods including suitable electrode configurations for spark, Lorentz ion thrusting, corona discharge, microwave, laser and/or chemical plasma agents that can be included in the formula for fluid conveyed into the combustion chamber 1350. In certain instances an electrical transformer 1326 is utilized to provide higher voltage for Lorentz and/or corona ignition systems such as can utilize electrode 1341 and 1343 which are insulated by ceramic components 1334, 1340 and 1342 as assembled by retainer 1343. In certain instances a counter electrode 1345 can be provided within ceramic body 1342 at one or more locations proximate to electrode 1341 to stimulate one or more ion currents that can be accelerated toward combustion chamber 1350 by Lorentz and/or magnetic forces exerted by permanent or

electromagnet circuits proximate thereto.

[0159] In certain applications embodiment 1300 is used to deliver gases that can be supplied at various pressures through conduit 1302 such as diminishing pressure as a pressurized storage of gaseous inventory in a tank is depleted. Illustratively accumulator 1224 can be charged during warm engine operation and upon start-up of a cold engine such as after an over-night period diminish in pressure while it supplies hydrogen or hydrogen-characterized fuel until the engine warms up.

[0160] In such instances and others that the gas pressure in conduit 1302 varies, controller 1315 can adaptively vary the stroke and/or rate of cycling or frequency of piston 1316 to control the pressure of fuel gas delivery to valve 1338. The residual gas pressure in chamber 1318 and/or compression spring 1319 assures rapid action of the piston's intake stroke when chamber 1306 is being emptied through port 1314.

Pressurized liquid from port 1312 that is added to chamber 1306 during the compression stroke can be any suitable liquid that can be pressurized by an appropriate pump including selections such as pressurized engine oil, hydraulic fluid, automatic transmission fluid or water or water with suitable antifreeze additives. Accordingly the return of such fluid selections through port 1314 is typically to an appropriate reservoir such as the engine oil pan, transmission pan, or another reservoir for the selected pump.

[0161] In various instances it is desired to operate with ignition stimulated by chemical plasma agents such as dimethylether (DME), diethylether (DEE), or an aldehyde such as acetaldehyde, etc., that can be supplied in adaptively determined amounts by operation of valve 1304 for mixing with fuel added to chamber 1318 and/or by delivery of the same or another chemical plasma agent through conduit 1317 and three way valve and check valve 1317. This enables a low temperature chemical plasma agent (CPA) such as acetaldehyde to be selected for cold engine start up and a higher temperature CPA such as DME to be utilized after the engine is warmed up.

[0162] In instances that a valve operator with a relatively small displacement such as a piezoelectric system 1328 is selected the coefficient of thermal expansion is engineered accordingly. Illustratively housing 1331 , insulative plunger 1330, retainer 1336, adapter 1337, insulator 1340, insulator 1342, and other components that determine the effective stroke of valve 1332 through temperature changes during operation as a result of thermal expansion/contraction differences are made of materials with about the same coefficient of thermal expansion (CTE). In certain embodiments such components can be made of materials that have about zero CTE values such as Invar 37 or Invar 32-5 for electrically conductive components or lithium aluminosilicate glass-ceramic such as Zerodur, or quartz for electrically insulative components.

[0163] Various ignition electrodes and configurations can be provided in conjunction with system 1300 including electrode 1341 , flow director 1354, and one or more features of the combustion chamber such as the piston, cylinder, head gasket, and head. Illustratively the pattern produced by fluid flow shaping features 1354 can be any suitable configuration to produce various shapes of conical fans, striated fan rays, or stratified clouds. Shaping features provided by 1342 and/or 1354 can incorporate and/or include electromagnetic and/or permanent magnetic components to provide magnetic lens to further modify the injected patterns of fuel and/or oxidant ions and thus modify and/or adaptively control the resulting patterns of penetration into the

combustion chamber.

[0164] Further adaptive control of homogeneous or substantially stratified combustion patterns is provided by adaptively controlled timing including initiation and/or duration of one or more corona stimulated ion multiplication events by DC or AC fields including selected microwave frequencies generated from electrode 1356 to the ions generated by electrical inducement such as Lorentz ion thrusting and/or chemical plasma agents such as DME, DEE, or aldehyde selections. Alternately such corona can be stimulated by electrodes 1360 inserted in the combustion chamber including one or more selected locations such as the intake or exhaust valves, head gasket, and/or piston.

Production of Carbon Durable Goods

[0165] Embodiment 1400 of Figure 14A provides a system that can be utilized in parallel and/or series operation with embodiment 1060 or alone for production of carbon for developing enhanced performance of durable goods by deposition of carbon on a receiver such as a ceramic fiber mat or curtain 1416 as summarized by Equation 1 1 .

C_xH_y + (H-1 , H-2, H-3, and/or H-4)→ xC + 0.5H₂ (1 1 )

[0166] The carbon and hydrogen donor C_xH_y can be prepared and delivered by pipelines that either transport gaseous feed stocks such as methane and hydrogen or liquid feed stocks including carbonaceous compounds including oxygenated fuels such as acetone, alcohols, etc., LP gases such as ethane, propane or butane, various dehydrogenated substances such as ethylene, propylene etc., nitrogenous compounds such as ammonia, urea, nitromethanol, etc., and other intermediates such as naphtha, heptane, octane, toluene, casing-head gasoline, and various other petroleum

compounds. [0167] In exemplary instances that the carbon and hydrogen donor C_xH_y is ubiquitous methane CH₄ from fossil or renewable origins the process is summarized by Equation 12.

CH₄ + (H-1 , H-2, H-3, and/or H-4)→ C + 2H₂ (12)

[0168] A suitable heat source including selections such as a furnace or fuel cell or heat engine 1404 including various designs of gas turbines that are converted to operation on net-hydrogen fuel selections. Illustratively a converted gas turbine 604 can be utilized to supply H-3 exhaust heat at temperatures such as about 400°C to 650°C. Higher temperatures for rapid carbon separation from suitable carbon and hydrogen donor substances can be provided by combusting fuel delivered according to adaptive operation by a controller 1401 for operation of valve 1430 for delivery by conduit 1432 that is added to oxidizing exhaust gases initially provided to the turbine inlet 1408. In some instances exhaust gases are further heated by H-3 produced by such fuel combustion with oxidant supplementation such as oxygen or air that is added at 1409.

[0169] In certain applications an oxidant and/or carbon and hydrogen donor substance such as one or more selected carbonaceous and/or nitrogenous compounds are preheated in heat exchanger fin tube assembly 1421 which may be comprised of one or more channels of equal or unequal flow capacities such as 1423 compared to 1425. In the instance depicted this is provided by countercurrent heat exchange with exhaust gases 1410 from heat source 1404 as can be supplemented by fuel

combustion as shown.

[0170] Such preheated carbon and hydrogen donor substance is delivered for adaptive control by valve 1412 to provide carbon deposition on mat or curtain 616 which may be comprised of suitable ceramic or refractory fibers as hydrogen and incompletely reacted feed stock C_xH_y (e.g. methane) is delivered through conduit 1424 for delivery through conduit 1436 as shown. Such hot mixtures of hydrogen and incompletely reacted feed stock that pass into zone 1422 can source further heat transfers or be utilized as fuel delivered through valve 1430 or in an engine such as gas turbine 1404 or other selections such as a fuel cell or piston engine 552.

[0171] In certain applications an oxidant such as air or oxygen can be preheated by passage through a conduit such as 1423 for adaptive control by valve 1414 according to controller 1401 to provide heat generation and higher local temperatures for expedited carbon deposition on curtain 1416 proximate to one or more flame locations 1418 by oxidation such as partial oxidation of preheated carbon and hydrogen donor substances in zone 1422 that remain from initial feed stock added through valve 1412 into chamber 1424.

[0172] Insulation 1428 surrounds exhaust passageway 1426 and more or less coaxial carbon deposition chamber 1424 to assure high temperature heat transfer from ceramic fiber curtain 1416 to carbon and hydrogen donor fluid selections such as can be preheated in twisted fin conduit 1425 that can be made of a suitable heat resisting steel or super alloy. In some applications electrical resistance and/or inductive heating can be provided in carbon deposition canister 1424 by one or more elements 1446 in zone 1422 of embodiment 1400 similar in composition and operation to heating element 1066 as provided in embodiment 1060 of Figure 10. Heating elements such as 1446 can be occasionally cleaned by gas blasts and/or oxidative removal of deposits upon administration of oxidizing gas such as oxygen or air that can be provided from conduit 1423 through valve 1414 as shown.

[0173] Co-generation energy from engine 1404 such as electricity can be produced from a rotating generator driven by output shaft 1444 or thermo-electric energy from generator 1442 at one or more suitable locations such inside of the exhaust gas passageway within conduit 1426 and/or hot gas transfer conduit 1436. In addition to heat H-2 and/or H-3 supplied by the exhaust gases 1410 such electricity can be utilized to provide additional heat H-4 at the temperature desired by one or more elements 1446 for dissociation of a carbon and hydrogen donor feed stock and collection of suitable carbon allotropes by component 1416. Examples of the embodiments:

[0174] A system embodiment for operation of the combustion chamber of a piston engine that includes monitoring the composition, temperature, pressure of the fuel to be injected into the combustion chamber along with the piston speed, combustion chamber pressure and temperature to control the volume and concentration of oxidant such as oxygen, oxides of nitrogen, ozone, etc., that is directly injected into air in the combustion chamber to form a stratified charge of enriched and/or activated oxidant needed to initiate and/or accelerate completion of combustion of the fuel that is injected into the stratified charge of enriched and/or activated oxidant.

[0175] The system of embodiment A in which a portion of the fuel and/or products of partial oxidation or combustion penetrate through the zone of stratified enriched and/or activated oxidant to continue combustion in the air around the zone of stratified enriched and/or activated oxidant.

[0176] The system of embodiment A or B in which the enriched and/or activated oxidant is directly injected into the combustion chamber by a device that can also inject the fuel.

[0177] The system of embodiment A, B or C in which the enriched and/or activated oxidant is directly injected into the combustion chamber by a device that can also inject more than one fuel selection.

[0178] The system of embodiment A, B, C or D in which the enriched and/or activated oxidant is oxygen produced by separation from atmospheric air or by dissociation of a compound containing oxygen or by production of an activated state of oxidant such as ozone or air that is heated, pressurized and/or partially ionized.

[0179] The system of embodiment A, B, C, D or E in which the enriched and/or activated oxidant can be produced from air or a compound that is formed in the combustion chamber.

[0180] The system of embodiment F in which the compound is at least one of water (H₂0) or an oxide of carbon (CO_x). [0181] The system of embodiment F in which the compound passes into the exhaust system of the combustion chamber of an engine before the enriched or activated oxidant is produced.

[0182] The system of embodiment H in which regenerative energy can be used to form the enriched or activated oxidant.

[0183] The system of embodiment I in which the regenerative energy is generated by at least one of vehicle deceleration, vehicle streamlining air flow, vehicle spring action, or heat rejected from the engine such as a fuel cell or heat engine.

[0184] The system of embodiment A or B in which the fuel is selected from at least one of a carbonaceous substance, a nitrogenous substance or a substance that is produced by a reaction of carbonaceous and nitrogenous substances.

[0185] The system of embodiment A, B or K in which the amount of oxidant and/or the amount of activation of the oxidant is adjusted by a controller to produce sufficient initiation and/or acceleration of combustion to provide an improvement in engine operation including at least one of higher BMEP, increased fuel economy, longer engine life, reduction of objectionable exhaust emissions, reduction of engine noise generation, an increased range of fuel characteristics, rapid start up, efficient transition from one duty cycle to another or smooth operation throughout the range of engine operations.

[0186] Another embodiment provides gas and liquid fuel storage of various fuels and reactants and enables relatively low pressure TCR reactions to produce hydrogen characterized fuels with various combinations with the systems of the present embodiments. This provides favorable economics for collection of greenhouse gas constituents such as methane to reduce damages to build environments and other valuable areas of the planet.

[0187] In summary methods and apparatus produce alcohols such as methanol, ethanol, propanol, butanol, etc., and/or ethers such as dimethylether, diethylether, dipropylether, and/or nitrogenous substances such as ammonia, urea, methylamine, nitromethane, nitroglycerine, ethylene glycol dinitrate etc., generally include reacting methane with water and/or separating methane into carbon and hydrogen and reacting the hydrogen with nitrogen an oxide of nitrogen and/or an oxide of carbon. The methane can be obtained from collecting the byproduct of various human-implemented process or methane released from naturally occurring processes. Additional steps can be taken to produce a nitrogenous or carbonaceous substance such as ammonia and/or a carbonaceous substance such as alcohols or ethers from the products of the reaction of methane and water. Illustratively methanol, ethanol, ammonia, and urea can be used in liquid energy storage fuel formulas that, when subjected for further reactions, can produce hydrogen such as net-hydrogen or carbon-negative fuel considering the nitrogen and/or oxide of carbon is taken from and returned to the atmosphere.

Illustratively the amount of carbonaceous substances utilized accordingly in recipes with nitrogenous substances is less than the carbon dioxide that would be produced by rotting or burning the initial carbonaceous feedstock such as methane.

[0188] From the foregoing, it will be appreciated that specific embodiments of the invention have been described herein for purposes of illustration, but that various modifications may be made without deviating from the scope of the invention.

Accordingly, the invention is not limited except as by the appended claims.

Claims

WHAT IS CLAIMED:

1 . A reaction vessel for producing an alcohol such as methanol from methane comprising:

a first tubular shell; and

a second tubular shell positioned within the first tubular shell and being coaxially aligned with the first tubular shell, the second tubular shell comprising:

a hydrogen permeable anode electrode interior surface;

a hydrogen permeable cathode electrode exterior surface; and a proton transfer membrane positioned between the hydrogen permeable anode electrode interior surface and the hydrogen permeable cathode electrode exterior surface;

wherein the areas inside the second tubular shell defines a first reaction zone and the area between the second tubular shell and the first tubular shell define a second reaction zone.

2. The reaction vessel of claim 1 , further comprising:

a first reaction zone inlet in fluid communication with a first end of the first reaction zone for supplying methane and water into the first reaction zone;

a first reaction zone outlet in fluid communication with a second of the first reaction zone for removing methanol from the first reaction zone;

a second reaction zone inlet in fluid communication with a first end of the second reaction zone for supplying nitrogen into the second reaction zone; and

a second reaction zone outlet in fluid communication with a second end of the second reaction zone for removing ammonia from the second reaction zone.

3. The reaction vessel of claim 1 further comprising means for supplying voltage across the proton exchange membrane and between the hydrogen permeable anode electrode and the hydrogen permeable cathode electrode.

4. The reaction vessel of claim 1 , further comprising an insulation layer surrounding an exterior surface of the first tubular shell.

5. The reaction vessel of claim 1 , further comprising a catalyst formed on nterior surface of the first tubular shell.