Phosphoric acid fuel

N.D. Kackley, S.A. McCatty, J.A. Kosek, "Improved Anode Catalysts for Coal Gas-Fueled Phosphoric Acid Fuel Cells," Final Report DOE/MC/25170-2861, prepared for... 

Daimler-Benz displayed its first NECARI experimental fuel cell vehicle at a press conference in Ulm, Germany, and New Jersey s H Power Corporation launched its methanol-fueled phosphoric acid fuel cell bus during Earth Day activities in Washington. 

White phosphorus may be made by several methods. By one process, tri-calcium phosphate, the essential ingredient of phosphate rock, is heated in the presence of carbon and silica in an electric furnace or fuel-fired furnace. Elementary phosphorus is liberated as vapor and may be collected under phosphoric acid, an important compound in making super-phosphate fertilizers. 

AFC = all line fuel ceU MCFC = molten carbonate fuel ceU PAFC = phosphoric acid fuel ceU PEFC = polymer electrolyte fuel ceU and SOFC = solid oxide fuel ceU. 

Phosphoric Acid Fuel Cell. Concentrated phosphoric acid is used for the electrolyte ia PAFC, which operates at 150 to 220°C. At lower temperatures, phosphoric acid is a poor ionic conductor (see Phosphoric acid and the phosphates), and CO poisoning of the Pt electrocatalyst ia the anode becomes more severe when steam-reformed hydrocarbons (qv) are used as the hydrogen-rich fuel. The relative stabiUty of concentrated phosphoric acid is high compared to other common inorganic acids consequentiy, the PAFC is capable of operating at elevated temperatures. In addition, the use of concentrated (- 100%) acid minimizes the water-vapor pressure so water management ia the cell is not difficult. The porous matrix used to retain the acid is usually sihcon carbide SiC, and the electrocatalyst ia both the anode and cathode is mainly Pt. 

Hydrogen use as a fuel in fuel cell appHcations is expected to increase. Fuel cells (qv) are devices which convert the chemical energy of a fuel and oxidant directiy into d-c electrical energy on a continuous basis, potentially approaching 100% efficiency. Large-scale (11 MW) phosphoric acid fuel cells have been commercially available since 1985 (276). Molten carbonate fuel cells (MCFCs) ate expected to be commercially available in the mid-1990s (277). 

Poly(vinyl nitrate) has been prepared and studied for use in explosives and rocket fuel (104,105). Poly(vinyl alcohol) and sulfur trioxide react to produce poly(vinyl sulfate) (106—111). Poly(vinyl alkane sulfonate)s have been prepared from poly(vinyl alcohol) and alkanesulfonyl chlorides (112—114). In the presence of urea, poly(vinyl alcohol) and phosphoms pentoxide (115) or phosphoric acid (116,117) yield poly(vinyl phosphate)s. 

Phosphoric Acid Fuel Cell This type of fuel cell was developed in response to the industiy s desire to expand the natural-gas market. The electrolyte is 93 to 98 percent phosphoric acid contained in a matrix of silicon carbide. The electrodes consist of finely divided platinum or platinum alloys supported on carbon black and bonded with PTFE latex. The latter provides enough hydrophobicity to the electrodes to prevent flooding of the structure by the electrolyte. The carbon support of the air elec trode is specially formulated for oxidation resistance at 473 K (392°F) in air and positive potentials. 

The bipolar plate material of the PAFC is graphite. A portion of it has a carefully controlled porosity that sei ves as a resei voir for phosphoric acid and provides ffow channels for distribution of the fuel and oxidant. The plates are elec tronically conductive but impervious to gas crossover. 

Because of this extreme sensitivity, attention shifted to an acidic system, the phosphoric acid fuel cell (PAFC), for other applications. Although it is tolerant to CO, the need for liquid water to be present to facilitate proton migration adds complexity to the system. It is now a relatively mature technology, having been developed extensively for stationary power usage, and 200 kW units (designed for co-generation) are currently for sale and have demonstrated 40,000 hours of operation. An 11 MW model has also been tested. 

Tetrapropylene is manufactured from propylene (containing 50% propane) with the use of a phosphoric acid catalyst at 70-bar pressure and 200°C. Under these conditions a product mixture is obtained which has to be purified by distillation. Unconverted propane is obtained as the first fraction, followed by tripropylene which can either be sent back to the polymerization or used as motor fuel. The third fraction consists of the desired tetrapropylene. 

Surfactants are prepared which contain carboxylic acid ester or amide chains and terminal acid groups selected from phosphoric acid, carboxymethyl, sulfuric acid, sulfonic acid, and phosphonic acid. These surfactants can be obtained by reaction of phosphoric acid or phosphorus pentoxide with polyhydroxystearic acid or polycaprolactone at 180-190°C under an inert gas. They are useful as polymerization catalysts and as dispersing agents for fuel, diesel, and paraffin oils [69]. 

In a simple version of a fuel cell, a fuel such as hydrogen gas is passed over a platinum electrode, oxygen is passed over the other, similar electrode, and the electrolyte is aqueous potassium hydroxide. A porous membrane separates the two electrode compartments. Many varieties of fuel cells are possible, and in some the electrolyte is a solid polymer membrane or a ceramic (see Section 14.22). Three of the most promising fuel cells are the alkali fuel cell, the phosphoric acid fuel cell, and the methanol fuel cell. 

If an acid electrolyte is used, water is produced only at the cathode. An example is the phosphoric acid fuel cell ... 

In the phosphoric acid fuel cell as currently practiced, a premium (hydrogen rich) hydrocarbon (e.g. methane) fuel is steam reformed to produce a hydrogen feedstock to the cell stack for direct (electrochemical) conversion to electrical energy. At the fuel electrode, hydrogen ionization is accomplished by use of a catalytic material (e.g. Pt, Pd, or Ru) to form solvated protons. 

Recent testing in phosphoric acid fuel cells has shown improved performance using promoted Ft on carbon catalysts in the air cathode. The promoters are oxides of the base transition metals, e.g., Ti (O,... 

Fhosphoric acid does not have all the properties of an ideal fuel cell electrolyte. Because it is chemically stable, relatively nonvolatile at temperatures above 200 C, and rejects carbon dioxide, it is useful in electric utility fuel cell power plants that use fuel cell waste heat to raise steam for reforming natural gas and liquid fuels. Although phosphoric acid is the only common acid combining the above properties, it does exhibit a deleterious effect on air electrode kinetics when compared with other electrolytes ( ) including such materials as sulfuric and perchloric acids, whose chemical instability at T > 120 C render them unsuitable for utility fuel cell use. In the second part of this paper, we will review progress towards the development of new acid electrolytes for fuel cells. 

Reforming 573 K Shift-Conversion Phosphoric Acid, 473 K or Proton Exchange Membrane Fuel Cells, 363 K... 

PAFC, phosphoric acid fuei ceii MCFC, moiten carbonate fuei ceii SOFC, soiid oxide fuei ceii PEMFC, proton exchange membrane fuei ceii DMFC, direct methanoi fuei ceii AFC, alkaiine fuel cell. 

Medium-temperature phosphoric acid fuel cells (PAFCs). The electrolyte is 85 to 95% phosphoric acid the working temperatures are 180 to 200°C. Such systems were used to build numerous autonomous power plants with an output of up to about 250 kW, and even some with an output of up to 4 MW, in the United States, Japan, and other countries. 

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