The International Steam Pages
Researching the Ultimate Fireless Steam Locomotive - Part 11
Chemical Thermal Energy Storage
Over the past decade, research was undertaken in Japan into high-temperature chemical thermal energy storage using metallic oxides. This research was aimed at storing thermal energy at thermal power stations during off-peak periods, then using that stored energy to generate extra electric power during peak demand hours. A team of research scientists based at the Tokyo Institute of Technology included Dr Yukitaka Kato, Dr Yamashita and Dr Yoshizawa who undertook research into the thermal reaction of magnesium oxide with steam. Another research team that included Dr Matsuda, Dr Kyaw, Dr Masanobu and Dr Hasatoru at Nagoya University based their investigation on the thermal reaction of calcium oxide and carbon dioxide.
The injection of steam [H2O] into a container containing powdered magnesium oxide [MgO] produced magnesium hydroxide [Mg(OH)2] at a temperature of 300-degrees C to 350-degrees C (570-degrees F to 660-degrees F). The reaction released between 391-KJ/Kg and 556-KJ/kg or 168-BTU/lb to 239-BTU/lb of heat. The reverse reaction (decomposition) involved heating the magnesium hydroxide until it released the water vapour, leaving behind powdered magnesium oxide. Japanese researchers used a heat pump to transfer heat from a low-grade source and raise its temperature to enable magnesium hydroxide to decompose into the metallic oxide and water vapour.
Magnesium is one of several metallic oxides that will react with steam to form a hydroxide (giving off heat), which can be heated until it decomposes into a metallic oxide and steam. Others include calcium oxide (CaO) and nickel oxide (NiO), the latter having a high density allowing it to occupy a compact package. A portion of the saturated steam in the accumulator of a fireless steam locomotive may be directed to the tank of metallic oxide, to generate the heat needed to maintain constant temperature and pressure levels in the accumulator as saturated water was being flashed into steam for propulsion. This transfer of energy into the accumulator would raise the locomotive's power levels and increase its operating range from the shunting yard to short-distance intercity service. A portion of the heat of formation of the metallic hydroxide may be heat pumped (using a high-pressure line of steam) to a higher temperature either into the accumulator or to a superheater.
Calcium carbonate [CaCO3] decomposes into calcium oxide [CaO] and carbon dioxide [CO2] when heated, a process that needs to be carefully controlled to prevent glazing the calcium oxide, rendering it unfit for further use. Reconstituting the glazed oxide involves grinding it into a powder then reacting it with water to produce calcium hydroxide [Ca(OH)2] and 15,300-calories of heat. The hydroxide can then be reacted with carbon dioxide to form calcium carbonate. When calcium oxide reacts with carbon dioxide, it produces calcium carbonate at temperatures between 700-degrees C and 1031-degrees C (1290-degrees F to 1885-degrees F), the higher temperature occurring at a gas pressure of 5-atms (74-psia) and releasing 237-Watts/Kg or 367-BTU/lb of heat energy.
The range of metallic oxides that would react with carbon dioxide would include beryllium, lead, barium, magnesium and manganese. Limestone (CaCO3), magnesite (MgCO3), and rhodochrosite (MnCO3) all occur quite naturally in nature and should be available at competitive costs. Manganese has the advantage of high density, allowing a thermal storage system using this metal to occupy a compact package that would make it more suitable for mobile operation. The carbon dioxide gas may either be stored in high-pressure containers or in low temperature carbonates that could be decomposed using exhaust heat rejected from an engine. Fireless steam locomotives using heat of formation of metallic carbonates for energy storage may carry most of the carbon dioxide in a low temperature carbonate in a tender unit, with a small amount being carried in an auxiliary pressure tank to enable the locomotive to start and restart.
To generate heat for propulsion, the metallic oxide would need to react with the carbon dioxide inside a thermal reaction chamber. This chamber may be located next to an accumulator of saturated water. It may alternatively occupy the location of a firebox in a firetube boiler. The firetubes may either use high-pressure steam or a liquid metal (like a sodium-potassium mixture) to transfer thermal energy from the reaction chamber to the boiler. The temperature generated by the heat of formation/reaction between the carbon dioxide and the metallic oxide is within the temperature range of solid fueled combustion in a steam locomotive. The chemical reaction chamber may also be built around a series of high-pressure water-tubes in which water would be converted to superheated steam.
This technology could be based on research undertaken by Enginion of Germany ( http://www.autofieldguide.com/articles/070102.html (link is dead) and http://www.enginion.com link broken July 2020) to generate ultra-critical pressure steam at extreme temperature (1000-deg C) by using advanced materials technology. When combined with advanced chemical thermal energy storage technology, this technology could enable a modern fireless steam locomotive to operate well in excess of 30% thermal efficiency. A unique oil-free piston steam engine designed by Viktor Gorodnyanskiy in Russia can be built out of ceramic material and deliver an estimated 35%-efficiency using superheated steam at 650-deg C/1200-deg F, while Enginion technology has shown that high-pressure steam at 1000-deg C/1800-deg F can enable a small, low-powered steam engine to deliver the engine efficiency of a diesel engine. Such technology could enable a future generation of condensing fireless steam locomotives to operate at the efficiency level of diesel engines while using lower costing fuels and incurring lower operating and maintenance costs.
A less efficient fireless steam locomotive using chemical thermal energy storage may use a 1,000-psia accumulator and a low-pressure steam engine (300-psia). Steam from the accumulator may be superheated in the thermal reaction chamber before the hot steam line re-enters the accumulator. A choke valve in the steam line would reduce line pressure from 1,000-psia to 550-psia and temperature from 1000-deg F to 800-deg F on the first pass. On the second pass through the accumulator, a second choke valve in the line would reduce steam line pressure to near 300 psia and steam temperature by the same value as the first pass. Heat rejected from the hot steam line would be transferred into the accumulator to maintain pressure and temperature levels in the accumulator, to allow more of the saturated water to be used for propulsion, raising power output and extending locomotive operating range. Steam at 300-psia and at over 800-degrees F could be expanded in a steam piston engine at short inlet valve cut-off ratios to optimize engine efficiency during branch-line, short-line or commuter services.
In railway operation, safety would be a major factor that would determine which chemical materials may be used for chemical thermal energy storage. Only low-volatility, non-corrosive materials that release water vapour, oxygen or carbon dioxide when heated to high temperature would qualify. Of these, low-cost materials that are easily accessible and that absorb and release large amounts of thermal energy for their weight and volume, would be suitable for mobile operation. Thermal energy storage materials generally exceed the useable life expectancy and energy storage densities of chemical-electrical battery energy storage systems. While many thermal energy technologies have an almost infinite life expectancy, the thermal storage technologies that do eventually deteriorate after prolonged use, are generally more easily reconstituted and at much lower cost than electrical energy storage technologies.
Hybrid Thermal Energy Storage:
When heated, some compounds melt while others decompose or dissociate while still in the solid state. Other compounds like sodium nitrate [NaNO3] will first melt then release an oxygen atom to become sodium nitrite [NaNO2], which can decompose into sodium hyponitrite [NaNO], a process that involves 260-BTU/lb of energy. This phenomena occurs with several metallic nitrates/nitrites/nitrides and chlorates/chlorite/hypo-chlorites [eg; potassium perchlorate KClO4] that release oxygen atoms as they decompose at higher temperatures. Many metallic compounds that can occur as hydroxides, hydrated oxides, sulphates, nitrates, or silicates will melt at one temperature then release water vapour at a higher temperature.
The reverse reaction would occur as the compounds/mixtures are allowed to cool, by transferred from them while adding oxygen or steam. This would result in a series of successive levels of heat of fusion and heat of formation becoming available as a thermal energy supply for use short-distance intercity railway propulsion. Theoretically, a modern fireless steam locomotive using such technology could be developed to deliver over 10,000-Drawbar-Horsepower for traction purposes, using the combination of chemical thermal energy storage as well as the latent heat of fusion thermal energy storage. At the present time, research is underway in a variety of countries involving researchers who are investigating chemical and phase-changing means to store larger quantities of heat at higher temperatures, using combinations of easily and readily available materials. Future developments in fireless steam railway traction would benefit from such efforts.
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