Hydrogen as a molecule, H2, comprises 0.2% of the atmospheric gas throughout the earth. It is volatile. When mixed with Oxygen, another molecule, O2, it explodes forming water H2O. The clean burn makes it an ideal fuel for vehicles. However, storage of Hydrogen leaves opportunities for explosion, requires strong walled cylinders for the compressed gas, which leaks through the materials of most containers, and, as with the Hindenberg, leaves the vehicle vulnerable to explosion from electrical charges as lightning and static electricity.
Rather than carrying the kilograms of Hydrogen on the vehicle, one could generate Hydrogen onboard the vehicle. Forming Hydrogen from Electrolysis from water takes too much power to efficiently carry this out, but dropping a mass of Calcium metal in water produces Hydrogen in an instant in selectable quantities.
Over the years, DuBrucq has shown students an experiment that lets them experience elements, molecules, reactions that run to completion, pH changes, speed of reaction, solution, precipitation, states of matter, and to top it off how fossils form. It is relevant to this effort because the initial reaction places Calcium (Ca) metal from a long term stored reagent bottle into water (H2O). The apparatus contains water and Calcium shavings in a test tube with a stopper with one hole. A tube in that hole goes from that hole to an inverted stopper with two holes onto which an inverted test tube is placed. The second hole in the upper stopper has a tube at the surface of the stopper inside the test tube and extending out to vent into the atmosphere. The Calcium metal surface reacts with the water producing bubbles, which rise to the water surface. In a minute or so, one can remove the inverted tube, keeping it inverted and replace it with another. Then with a match, light a splint and blow out the flame. Insert the glowing splint into the inverted test tube. “BOOOOK”, a reaction occurs leaving water droplets on the inner walls of the test tube.
What happened? Calcium reacted with water forming Ca(OH)2 and H2, Calcium hydroxide and Hydrogen. Testing the pH of the water before the Calcium is added and after the reaction has run, the liquid is changed from neutral pH 7 to basic. pH 13. The reaction of a solid plus a liquid has resulted in a chemical solution of Calcium hydroxide in the water causing the pH change and permanent escape of Hydrogen gas.
The gas molecule H2, Hydrogen, combined with another gas molecule in the air, O2, Oxygen, and the “BOOOOK” indicates the speed of reaction was immediate, quick. Compared with the speed of reaction of the old reagent Calcium and water combination, it was instantaneous. Did this reaction go to completion? Yes. How can one tell? The reaction formed water, H2O, which appears as a liquid on the walls of the inverted test tube. It can be vapor, and it can precipitate to fog combining to form full droplets and cling to the test tube walls. In the case of a fuel cell using the hydrogen, the output is the desirable, clean, pure water. The same byproduct occurs when using Hydrogen in a combustion engine rather than gasoline, ethanol, diesel fuel, jet fuel or kerosene. All these hydrocarbons burned in engines give off hydrocarbons and Carbon dioxide.
The solution of Calcium hydroxide in water gives a basic solution, high pH. When the reaction is completed, place a straw or glass tube into the solution. Have someone gently blow bubbles in the solution. Check the pH. And watch the solution. Upon completion of this reaction, the pH is returned to 7, neutral, and the dissolved Calcium component is now sediment in the bottom of the test tube. What happened? Ca(OH)2 and CO2 from one's breath combined forming Ca(CO3)2 and H2O. The Calcium carbonate separated out as a precipitate or sediment leaving the water pure with a neutral pH.
To get a bit archeological, if one tosses a mosquito into the test tube as the sediment settles, one gets the initial stages of fossil formation. Kids love this part.
The invention here applies these reactions specifically where the end product is needed for Hydrogen fuel cells and applies the Calcium hydroxide to dispose of Carbon dioxide in exhaust where that occurs. It is water in and water out in both the combustion of Hydrogen and Oxygen and in Calcium hydroxide capture of Carbon dioxide. And the sediment can be sold to cement factories for roads and sidewalks, buildings and support walls. Or it could be used in a reduction reaction in a sealed atmosphere where generated Hyrdogen is passed over the Calcium carbonate or Calcium hydroxide releasing the metal Calcium and setting free either Carbon dioxide or water which must be trapped by a severely cold getter or water trap to pull it from the reversible reaction. The apparatus for this reaction is referred to as a reduction chamber. Two types are proposed in this patent.
Recent demonstrations of the experiment used a new bottle of the reagent Calcium that came in a wax sealed jar in a sealed can. Using water displacement from an inverted 250 ml graduated cylinder to catch the Hydrogen, when 0.5 gram of the Calcium was dropped in the water, the reaction went to completion instantaneously leaving the water converted to a concentrated solution of Calcium hydroxide and 250 ml of gaseous Hydrogen displacing the water. Repeating the experiment with the new Calcium, this time using gas displacement of an inverted glass vase over the water-Calcium reaction, run to completion, upon tipping the vase about 15 degrees from inverted vertical, a spontaneous explosion happened during both tries leaving a ring of water condensed in the vase in a region of the cylinder about four inches from the base of the inverted vase. Also, watching the reaction, some six to eight inches outside the vase neck, radiating red lines were seen extending outward centered from the vase opening. These red spectral lines were about two inches long. Observers of the Hindenberg explosion reported they saw red emissions from the explosion. Since red emissions are not among the strong lines of Hydrogen stated the commentary from the PBS special on the Hindenberg explosion, observers' reports were discounted. Since these lines emerged from the Oxygen source region of the air, not the Hydrogen source, which would have been in the vase, the lines are most likely from breaking apart the Oxygen molecule or light emitted in water formation. The placement of the water from the explosion inside the vase indicates a gas volume compression to the liquid/vapor water volume being several inches from the vase opening indicates the spacial compression of the reaction.
The equation for these reactions start with Calcium, MW 40.08, displacing two Hydrogen atoms, MW 2, in the Hydrogen releasing reaction so the weight ratio for vehicle bearing is 20.04 gm of Calcium produces a gram of Hydrogen molecules for fuel using 36 grams of water, MW 18, using two atoms plus 20% more water to allow residual water to make the Calcium hydroxide solution. Ingredient weights for the reaction are 20.04 kg Ca and 43.2 kg water for each kilogram of Hydrogen, generated as needed, a ratio of 63.6:1. Recoverable water from H2 combustion is 9 kg., drinking water for a day. If the driver using Hydrogen requires 1 kg H2 for every 25 miles, 763.2 kg of reagents must be on board for a 300 mile excursion. It is not recommended for aircraft.
Compare this with the weight of the Hydrogen tank to contain compressed Hydrogen. New types of compressed gas containers for Hydrogen are still too heavy to carry sufficient Hydrogen for 300 miles of travel before refueling according the NREL R&D as reported in a web search for mass added for carrying Hydrogen. According to Michael Heben at NREL, graphite containers are 10× the weight of the gas compressed within them. DOE requires 2.5× the PSI testing for these units so 10,000 PSI containers, usually spherical, must withstand 25,000 PSI pressure to be allowed for vehicular use.
Another aspect of the invention relates to a method of purifying large quantities of Calcium metal anticipating its use in generating Hydrogen onboard electric vehicles for both fuel cell use and Hydrogen fueled engines. Because Calcium metal has no trade applications and is semi-reactive, little effort has been put forth to prepare it in quantities regardless of its abundance in nature in molecular configurations. Generating Hydrogen fuel as needed rather than carrying a supply in compressed air tanks can improve the safety of future vehicles. It can be termed “cold cracking Calcium.”
Generation of Hydrogen by metal hydrolysis at the point of use is a replacement for hydrogen storage onboard vehicles. This idea is not novel or without significant engineering and economic hurdles. A system similar to the Calcium system is supposedly in operation in South Africa patented by Francois P. Cornish, U.S. Pat. No. 4,702,894. His system uses Aluminum, needing electrical energy from the coil on the engine to drive the reaction using the Hydrogen to fuel a small internal combustion engine rather than to power a fuel cell. Cornish method numbers show that he can generate hydrogen hydolyzing 9.7 grams of Aluminum wire per minute, enough Hydrogen to drive about 349 miles in a day assuming 1 kg of Hydrogen allows one to drive 25 miles. With May, 2006 prices of Aluminum, the cost per mile is $0.85, and fuel cost per day of constant Hydrogen generation is $297.44. The Aluminum cost is unrealistic economically.
“Hydrogen Refueling System Based on Autothermal Cycle Reforming” by General Electric—EER group of Ravi V. Kumar et al. reports using Nickel with Calcium Oxide and Calcium Carbonate to generate Hydrogen, which they then compress to feed to vehicles. It is one type of Hydrogen generator plant.
Compressed Hydrogen is not cheap either. Hydrogen can be produced with a commercial electrolyzer for about $10/kg in electricity costs. A small-scale production means may be in the $25/kg range. Used as fuel, as Cornish does, a kilogram of Hydrogen is about equal to a gallon of gasoline. At current prices, gasoline at $2.80/gallon has almost a four times price advantage.
The Department of Energy is still researching high temperature thermo-chemical reactions and other methods of Hydrogen generation for Hydrogen production distribution after it has been produced, not in situ production. University of Nevada, Las Vegas (UNLV) is researching fixed site Hydrogen production, not direct production in a vehicle. See: http://shgr.unlv.edu/report/STCH%20Quarterly%20Report%20004.pdf.
In the patent search for cold cracking Calcium, the only locatable Calcium purification for metallic Calcium products is in medical supplements for raising Calcium levels for strengthening bones. For reagent grade chemicals, the cost is about $150 per kilogram, which indicates there are some means of purifying this overlooked element, but either because of short run requirements or the process itself, it is not, under current practice, an economical end. Pfiser has a method of using Calcium carbonate—Aluminum bricketts and super heating them to about 1.500° C., to extract Calcium, which clumps on the walls as it condenses.
The Discovery: When using Hydrogen for fuel, whether feeding a combustion engine or fuel cell or other device, Calcium driven reaction with water may be the enabling means for in situ, generating it where it is being used. This reaction is spontaneous, starts itself, and continues to completion because Hydrogen gas exits the reaction medium. In contrast with most other alkaline metals, Calcium plus water is not explosive. It is the tortoise compared with Lithium, Sodium, Magnesium, and even Potassium.
Another marvel of Calcium is that its hydroxide, a strong base, converts quickly to carbonate with addition of Carbon dioxide forming Calcium carbonate, which precipitates as a sediment settling out of the water leaving the water clear and pH neutral. This second half of the discovery is applying the liquid bi-product of Hydrogen generation to removal of Carbon dioxide from major emitter situations as industrial stack gas, heavy vehicles' exhaust, and smoke from coal or other conglomerate fuel burn for power generation. The applications of these long known reactions are the discoveries. Both eliminate Carbon dioxide release in the atmosphere. Hydrogen burn gives water, not Carbon dioxide: and Calcium hydroxide devours Carbon dioxide from those polluting entities that must use Carbon Fuels from petroleum products to burning telephone books and newspapers, garbage, plant stalks and even crematorium outgases.
And to add to the economics of this discovery, the sediment, Calcium carbonate, can be sold to the cement industry to be part of the concrete that builds our roads and structures. It can also capture sulfates from smoke emissions. Because both systems output as an isolated, pure bi-product, clean, neutral pH water, collection systems are designed to capture this water. Theoretically, the yield from Hydrogen combustion is 9 kg of water generated from 63 kg Calcium. It can quench the vehicle occupants' thirst. This leaves sweet, clean air, clean water from both reactions, and solid footings from sales of the one solid bi-product.
Another use of the bi-product, either Calcium hydroxide or Calcium carbonate is a simple, effective, method of purifying Calcium metal and preparing the metal in consistent sized pellets for the purpose of generating Hydrogen gas onboard vehicles, making fuel available as one drives, flies or sails a Hydrogen powered vehicle.
The need has additionally arisen to provide a method of economical Hydrogen availability for fuel cells, some powering electric vehicles and some in permanent installations. Portable capability to provide this Hydrogen will enhance use of Hydrogen.
The need has additionally arisen to have Hydrogen fueled vehicles be serviced at conventional filling stations throughout the U.S. and around the world. With the designed Hydrogen distribution, the service station attendant can remove and replace three standard dimensional vessels in the Hydrogen fueled vehicle per every 400 or so miles driven. Instead of gassing up, one just removes empty Calcium and water vessels and provides full ones and removes the full Calcium hydroxide vessel and replaces it with an empty one and the vehicle is back on the road again. This is implemented by standard fuel plant design for Hydrogen powered vehicles, which is altogether possible with this technology. These spent vessels are then picked up and serviced and ones filled and ready to install are supplied to the filling station owner.
Additionally, the need has arisen to provide a safe and effective method of fueling a power need which uses available and unused power by power distribution companies and untapped natural energy generating situations as solar, wind, water movement and tidal sources that can tap the activity for power and store that power in pure metallic Calcium pellets to be used at a later date in whatever place it is needed. This is like an energy battery, but rather than releasing electrons, it releases Hydrogen molecules from water.
FIG. 1—The in situ Hydrogen generator system—Chemistry.
FIG. 2—Details of the Hydrogen generator system—components
FIG. 3—Details of Hydrogen generator system—changes with motion.
FIG. 4—Details of Hydrogen generator system—handling Hydrogen.
FIG. 5—Side view Hydrogen Generator systems—post. Hydrogen generation
FIG. 6—Side view Hydrogen Generator system—start of Hydrogen generation.
FIG. 7—Carbon Dioxide Capture on truck exhaust.
FIG. 8—Carbon Dioxide Capture on truck exhaust with non-reverse valves.
FIG. 9—Hydrogen fuel piston system with crankshaft.
FIG. 10—Calcium Recovery by Hydrogen Reduction.
FIG. 11—Harvesting Calcium from Hydrogen Reduction.
FIG. 12—Installing a Hydrogen Generator in an Automobile.
FIG. 13—Installing a rack of Hydrogen Generators in a Truck.
FIG. 14—Installing a Hydrogen Generator in a stationary Fuel Cell unit.
FIG. 15—Sulfate capture using Calcium carbonate in Stack gas emission.
Starting with
FIG. 16—The full cold cracking Calcium apparatus.
FIG. 17—Cryogenic getter and the movement and removal of the ice.
FIG. 18—The getter system with cold-transfer to the conveyor belts.
FIG. 19—The Calcium conveyor belt with steam hydrolysis of CaO.
FIG. 20—The Calcium conveyor belt with Electrolysis unit saturating Calcium molecules with Hydrogen reducing the molecule to Calcium metal and water caught by Cryogenic getter.
FIG. 21—The Calcium metal dust is dropped into the smelter where the Electrolysis output of Oxygen super-heats the fuel to melt the calcium into pellets taking place in an Argon/Hydrogen atmosphere.
FIG. 22—The details of Calcium pellet production is shown as one way pellet.
With the choice of Calcium metal as the Alkaline metal to free Hydrogen from water, we must realize that pure Calcium reacts instantaneously with water contact. Argon gas storage of Calcium prior to use keeps it fresh for rapid, but safe, reaction. The tooling and handling of these Calcium units must be smooth and reliable with little wasted motion to provide Calcium for the water exposure for smooth, continuous Hydrogen generation. Therefore, the Calcium form should be in pellets of common mass to reliably react with a measure of water to give a specific output of Hydrogen. The Calcium pellet will feed into a dispenser dropping into the water by gravity. This same principle will provide orderly feed to the Calcium managing the rate of Hydrogen generation.
The water supply of the unit is proportional to the mass of Calcium provided. Testing reagent consumption to reaction completion, the appropriate volume of water needed to process the Calcium mass is provided per Calcium infusion. The design of this solid unit defines dimension and components of the Calcium Hydrogen generating unit.
In practice, this unit will be a consistent one to another so the unit filled and ready to generate Hydrogen can replace a unit expended of water and Calcium. The expended unit will have containers of base, Calcium hydroxide, which will be transferred to equipment to capture Carbon dioxide and other chimney or exhaust pipe gases. This process will take another fixed form system replaceable as the Calcium hydroxide is expended. This process will convert Calcium hydroxide to Calcium carbonate. The Calcium carbonate will be reduced in a Reduction tube recovering metallic Calcium replenishing the process. Currently, Calcium metal is not a marketable metal. With reduction working, we can produce Calcium throughout the world where energy is generated locally as with water wheels or wind generators. Oxygen is a by-product of the process making it available for medical needs in these areas. This simplistic design is expanded in the final set of figures,
A Hydrogen piston engine design is shown where the Hydrogen forced the piston down, air or Oxygen is added and a spark converts it to water, which pulls the piston up.
Final figures show Hydrogen generating units in an automobile, a truck and a fixed fuel cell unit. These need service or replacement periodically depending on water and Calcium capacity and the rate of Hydrogen consumption by the fuel cell or motor.
This series should make the operation of the Hydrogen generator obvious to the reader/viewer.
To reduce Carbon dioxide 4 release from the reduction reaction, the water 2 and CO2 4 is released in a lighted greenhouse 55 where the plants 54 photosynthesize the CO2 into Oxygen 7.
In practice, “filling stations” will have Calcium to fill the Hydrogen Generating System units. They will replace the Calcium hydroxide container with clean ones with appropriate water levels in the vehicles coming to the station. The Calcium hydroxide containers are turned over to the servicing group, who will transfer the Ca(OH)2 reaction bottles to the Carbon dioxide catchers and replace them with empties. The gas station attendants will put the water in the system units once they are installed in the automobiles and other vehicles and will put the water in the water reservoirs of system units before pushing the rack back in trucks. Calcium will feed into these units as Hydrogen is needed to propel the vehicles. Used systems are returned to the service location. These closed systems are safe. Any mess will be cleaned up in the recycling process of the systems unit. If the Calcium reservoir is pierced, determined by a test as to its ability to hold increased air pressure, that unit will be disposed of before any Calcium or water is added to the unit.
Oxygen can be supplied by having Liquid Nitrogen generation done in close proximity to the smoke stack. The Calcium Carbonate is available from the exhausted precipitate caused by running truck exhaust through Calcium hydroxide from converting a water-Calcium mix to Calcium hydroxide and Hydrogen. This would be one more procedure in the Stack Gas Scrubber invention described in DuBrucq's May 17, 2007 filing, Liquid Nitrogen Enabler Apparatus, application Ser. No. 11/750,149. It provides a use of the by-product. Calcium carbonate, from this Hydrogen generation.