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Utilizing Waste Hydrogen for Energy Recovery Using Fuel Cells and Associated Technologies

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Utilizing Waste Hydrogen for Energy Recovery Using Fuel Cells and Associated Technologies UTILIZING WASTE HYDROGEN FOR ENERGY RECOVERY USING FUEL CELLS AND ASSOCIATED TECHNOLOGIES Copyright Material IEEE Paper No. PCIC-2004-14 Paul Buddingh, P.Eng. Vince Scaini, P.Eng. Leo Casey, PhD Member, IEEE Member, IEEE Member, IEEE Universal Dynamics SatCon Power Systems SatCon Technology 100-13700 International Place 835 Harrington Crt. 161 First Street Richmond, BC V6V 2X8 Burlington, ON L7N 3P3 Cambridge, MA 02142-1228 Canada Canada USA Abstract- Electrochemical and other process industries one could argue that we will eventually be using 100% frequently vent or flare hydrogen byproducts to the hydrogen fuel without the motivation of environmental atmosphere. This paper will discuss hydrogen power benefits. conversion methods including fuel cells and combustion Hydrogen has higher energy per unit of mass, but lower technologies. This paper presents an overview of some of the energy per unit volume than any other fuel. By weight, practical implementation methods available, and the hydrogen “carries” three times the energy of our most challenges that must be met. The pros and cons of distributing common fuels. For example, 1 kg of hydrogen has power to either the AC power system or DC process bus are approximately the same amount of energy as 1 US gallon of examined. This technology is expected to become cost- gasoline (approximately 3 kg). The major downside of competitive as energy prices continue to climb and fuel cell hydrogen is its poor volumetric energy density, making proficiency matures. storage and transportation a fundamental challenge. To help resolve this problem, the hydrogen industry is currently Index Terms – Hydrogen, Fuel Cells, DC/DC Converters, certifying 10,000 psi hydrogen cylinders. Even at these Inverters extreme pressures, a hydrogen cylinder of 1 ft inside diameter 4 ft long (about 23 US gallons by volume at 10000 psi, or I. INTRODUCTION 15,000 US gallons at atmospheric pressure) would contain the equivalent energy of a conventional 5 US gallon gasoline The amount of waste hydrogen produced varies widely container at atmospheric pressure. In addition to the depending on the process in a particular plant. This paper certification of high-pressure storage cylinders, one must also examines alternatives for plants that produce more than 4 consider the challenge of the compressors required to boost metric tones of hydrogen per day. Power generation greater the gas to 10,000 psi. Currently, there are several than 1 megawatt is the focus of this paper. commercially available hydrogen compressors available that achieve these pressures. TABLE 1 Hydrogen is actually safer than media reports of the past GENERATION SYSTEM ATTRIBUTES [1] suggest. The infamous burning and subsequent explosion of Efficiency the Heindenberg airship is used as an example when the Type Size (%) dangers of hydrogen are discussed. However, it was actually Reciprocating Engines 50 kW-6 MW 33-37 the flammable coating of the Dirigible’s balloon that caused most of the damage. The small size of the hydrogen molecule Micro Turbines 10 kW-300 kW 20-30 results in free hydrogen (a leak) dispersing very quickly in the Fuel Cell, PAFC 50 kW-1 MW 40 atmosphere, and its chances of creating an explosion are Fuel Cell, MCFC 250 kW-3 MW 47-50 somewhat less than conventional fossil fuel vapors. Fuel Cell, SOFC 5 kW-3 MW 45-65 The great advantage of many electrochemical plants is the Fuel Cell, PEMFC <1 kW-1 MW 34-36 continuous production of hydrogen that may be utilized continuously to produce power. II. HYDROGEN BASICS III. HYDROGEN POWER TECHNOLOGIES Hydrogen is often discussed favorably as an environmental friendly fuel. The combustion of hydrogen produces no carbon A. Fuel Cells dioxide (CO2), particulate, or sulfur emissions. What is not so obvious is that as technology has advanced over the last Fuel cells convert chemical energy into electrical energy. several hundred years we have increased our use of This principle has been known for close to two centuries and hydrogen fuel. As the conventional fuel of choice, progressed the first kilowatt-sized fuel cells were developed over forty from wood to coal then to oil and natural gas, the percentage years ago. It is the direct conversion of fuel to electricity that of carbon in our fuel has declined and the percentage of enables fuel cells to have high efficiencies when compared to hydrogen increased. Taking this progression to the extreme, the heat engines in common use today. The basic schematic of a typical fuel cell is shown in Fig. 1. TABLE 2 “Every fuel cell consists of a fuel electrode (anode) and an COMPARISON OF FUEL CELL TYPES [1][2] oxidant electrode (cathode), separated by an ion conducting Operating Charge External Fuel Cell Type electrolyte. Incoming gaseous fuel is ionized to produce Temp. (°C) Carrier Reformer hydrogen ions and electrons at the anode. The electrolyte will Proton Exchange conduct only ions; electrons flow away from the anode Membrane Fuel 80-100 H+ Yes through an external circuit. Oxygen atoms at the cathode Cell (PEMFC) react with migrating hydrogen ions from the electrolyte and Phosphoric Acid + 180-205 H Yes combine with electrons from the external circuit to produce Fuel Cell (PAFC) water”.[2] The water produced can be in the form of liquid or Molten Carbonate 2- 600-700 CO3 No gas depending on the fuel cell operating temperature. Fuel Cell (MCFC) The electrolyte current flows via H+ ions in acid electrolytes, Solid Oxide Fuel 2- 600-1000 O No carbonate ions flow in molten carbonate electrolytes and Cell (SOFC) oxide ions flow in solid oxide electrolytes for the different fuel cell types. The chemical reaction for an acid electrolyte 1) Proton Exchange Membrane Fuel Cell (PEMFC). The system such as a Proton Exchange Membrane Fuel Cell PEMFC uses an ion exchange membrane as an electrolyte, (PEMFC) is as follows: typically constructed of fluorinated sulfonic acid polymer or a + - similar polymer. Anode: H2 → 2H + 2e (1) + - Water management in the membrane is important for its Cathode: ½ O2 + 2H + 2e → H2 O (2) performance in that the water byproduct should not evaporate Overall: H2 + ½ O2 → H2 O (3) faster than it is produced due to the membrane hydration requirement. Thermal ratings of the polymer along with where: problems of water balance limit the temperature of the H2 hydrogen gas PEMFC. This low temperature limitation dictates that a rich H2 + H positive hydrogen ion gas with minimal carbon monoxide (CO) (10 ppm desirable) or - e negatively charged ion no CO be used as a fuel. CO contaminates the membrane, as O2 oxygen gas do many other impurities, thereby reducing its efficiency or H2 O water destroying it. Hence, when hydrocarbon fuels such as natural gas are used, a “reformer” fuel processor is required to Load 2e- produce H2 gas free of contaminates. Available H2 gas from a chlor-alkali cell line can only be used as a fuel if the gas is processed to remove all Fuel In Oxidant In contaminants such as chlorine gas (Cl2). To date the level of 1/ O acceptable Cl2 contamination with any fuel cell is not known 2 2 to any certainty. (Low temperature fuel cells such as PEMFCs H 2 Positive Ion are more susceptible to chlorine poisoning, Stable Or performances of PEMFCs have been demonstrated up to 10,000 h.) Their high power density, low operating H O Negative Ion 2 temperature, and fast step response to load change make the H2O PEMFC the system of choice for vehicle applications. 2) Phosphoric Acid Fuel Cell (PAFC). The electrolyte used Depleted Fuel / Depleted Oxidant/ Product Gases Out Product Gases Out for PAFCs is 100% phosphoric acid concentrate. Due to low temperature operation, CO poisoning of the electro-catalyst is Anode Electrolyte Cathode an issue if not addressed. Therefore, the use of a fuel processor (reformer) is also required. The use of concentrated (Ion Conductor) acid and temperatures above 100°C make water management Fig. 1 Hydrogen-Oxygen Fuel Cell Basic Schematic [1] less of an issue when compared to PEMFCs. The PAFC is in commercial production. To date over 75 MW worth of PACFs Although the schematic in Fig. 1 may seem simple enough, are installed worldwide in stationary generation applications. other components such as the fuel processors and electrical Typical plants are in the range of 50 kW to 200 kW capacity, power converters are required for a full fuel cell system. with the largest installed plant to date being 11 MW. Power conditioning options for use in electro-chemical plants 3) Molten Carbonate Fuel Cell (MCFC). The electrolyte are outlined in section IV Power Distribution Methods. used is a mixture of alkali carbonates retained in a ceramic The types of fuel cells are generally named for their matrix. The alkali carbonates become a highly conductive electrolyte used. Table 1 lists the fuel cell types predominately molten salt with the high temperatures present in the MCFC. It available today along with operating temperatures and charge is the carbonate ions in the salt that provide the ionic carriers. conduction. Similar to the hydrogen ions of (1), the MCFC has The following sub-sections give a brief description of the the following electrochemical reactions: fuel cells listed in Table 1. Detailed information on the 2- - construction and operation of these various fuel cells can be Anode: H2 + CO + 2CO3 → H2 O + 3CO2 + 4e (4) - 2- obtained from the references given. Cathode: O2 + 2CO2 + 4e → 2CO3 (5) - = Overall: H2 + O2 + CO→ H2 O + CO2 (6) Cathode: ½ O2 + 2e → O (8) Overall: H2 + ½ O2 → H2 O (9) where: H2 hydrogen gas where: - CO3 carbonate ion H2 hydrogen gas - e negatively charged ion e- a negatively charged ion CO2 carbon-dioxide gas O2 oxygen gas H2 O water H2 O water 4e- Load Carbon monoxide (CO) as well as hydrocarbons (CH4) can be used as fuels to produce an H2 stream that is internally reformed.
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