Fuel Cell System Fuel Processing


Fuel cell fuel requirements - why is fuel processing required? Desulphurisation - removing organic sulphur from fuel Steam reforming - getting hydrogen from hydrocarbons and alcohol Carbon formation and pre-reforming - avoiding an accumulation of
carbon deposits in a fuel cell system Internal reforming - using the heat from the stack of high temperature fuel cells Direct hydrocarbon oxidation - aka dry-reforming. Burning the methane so most of the heat is converted directly into electricty Partial oxidation (POX) and autothermal reforming - produce syngas or combination POX + steam forming Hydrogen generation by pyrolysis or thermal cracking - heat in the absense of air so hydrocarbon cracks into hydrogen and solid carbon Carbon Monoxide removal - cool the product gas and pass it through shift reactors to reduce CO to reasonable level (to CO2)

Stationary vs. Mobile applications Electrolysers Biological production

Fuel cell fuel requirements
PEMFC Temperature (°C) 50-100 AFC 50-200 PAFC 180-220 MCFC 600-700 SOFC 850-1000

The lower the temperature, the more intolerant of other compounds...

* Note that diluent just means diluting agent.

Natural gas and petroleum liquids contain organic sulphur compounds (Natural gas odour for leak detection) Sulphur levels deactivate some catalysts and reduce lifetime of fuel processors and even poison the PEM anode catalyst. Hydrodesulphurisation (HDS) reactor converts organic sulphur containing compounds into hydrogen sulphide and then absorbed onto a bed of zinc oxide to form zinc sulphide; this is used for PEM and PAFC systems. Internal reforming MCFC or SOFC systems use a reformer reactor or absorbents (e.g. activated carbon), molecular sieves or sulphur-tolerant catalysts.

Steam reforming
oxygenolysis reactions (methane or hydrocarbon + water converted to carbon monoxide and hydrogen >500°C) and usually happen simultaneously with a water-gas shift reaction (carbon monoxide and water converted to carbon dioxide and hydrogen) with the resulting mix of carbon monoxide, carbon dioxide and hydrogen with methane and steam. computer models and graphs can be used to determine the mix from reactor temperature, operating pressure, feed gas composition and proportion of steam fed in. By no means will all of the carbon monoxide be converted to carbon dioxide and for fuel cell systems that require low CO, further processing is required (last slide). Temperatures > 600°C favour the production of hydrogen instead of methane. Dry (or CO2) reforming can be carried out without steam (MCFC) and mixed reforming using steam and CO2. Can also be used for alcohols as well as hydrocarbon fuels.

Carbon formation and pre-reforming
require a way to minimise the risk of carbon deposits forming in fuel cell systems and clogging catalysts carbon formation can occur from pyrolysis, from disproportionate CO (Boudouard reaction) Can add steam to reactions to promote the shift reaction and carbon gasification reaction. Minimum steam to do this needs to be calculated (usually steam/carbon ratio of 2.0 3.0) Carburisation occurs on metals ('metal dusting') reduced by using copper-coated stainless steal in preheaters Can also reduce risk of carbon formation in a fuel cell system by carrying out pre-reforming of fuel gas before it is fed into reformer reactor (also known as 'sweetening' the gas ); converts heavyweight hydrocarbons via steam reforming at 250-500°C to produce mainly methane.

Internal reforming
utilising the heat of the stack to sustain the reforming of lowweight hydrocarbons such as methane (MCFC or SOFC) cooling requirements of the stack are reduced -> electrical efficiency Uses one of two approaches, or a combination: IIR (Indirect internal reforming) - close thermal contact with stack, but reforming and electrochemical separate DIR (Direct internal reforming) - reforming reactions carried out within the anode compartment of the stack Advantages cf external reforming: cost reduced, less steam required and methane conversion is high with DIR, system efficiency is higher (due to cooling) can be applied to several hydrocarbon fuels

Direct hydrocarbon oxidation
aka Dry reforming hydrocarbon oxidized direction within the fuel cell, converting it directly to electricity with maximum efficiency main issue is carbon formation, but reduced with use of copper or special ceramic anodes for SOFC such as ceriadoped zirconia. probably has particular benefits for proton-conducting fuel cells still being being developed

Partial oxidation and auto-thermal reforming
hydrocarbons converted to hydrogen via partial oxidation (POX) which can be carried out at high temperatures (12001500°C) without a catalyst. attractive for heavier petroleum such as diesels. does not scale down well from large scale systems with a catalyst and reduced temperature, process is known as catalytic partial oxidation (CPO or CPOX) POX and CPOX are usually less efficient than steam reforming and oxidation reactions (heat goes to reforming reaction). does not require steam and therefore makes the system more simple (e.g. for micro-cogen) Autothermal reforming - both steam and air fed with fuel to a catalytic reactor (combination of POX and steam reforming); this also requires no complex heat management engineering (good for mobile applications)

Hydrogen generation by pyrolysis
also called thermal cracking of hydrocarbons heat hydrocarbon in the absence of air and it decomposes into hydrogen and solid carbon suited especially to simple hydrocarbon fuels (reduced byproducts) H produced is very pure C has to be removed from reactor, and this can be tricky. cracking proprane proposed to provide hydrogen for small PEMFC systems.

Carbon monoxide removal
cool the product gas from the steam reformer and pass it through a reactor containing a catalyst which promotes the shift reaction (may need more than one shift reactor) -> converts CO to CO2. Often cool -> shift -> cool -> shift steps. [PAFC] For PEMFC further CO removal needed. One of three ways: Selective oxidation reactor - air added, catalyst absorbed CO; catalyst $$$ and need to be carefully controlled. Methanation - the opposite of steam reformation, but chews hydrogen Palladium/platinum membranes - works but $$$ Shift reaction via bacteria is being researched Pressure Swing Absorption (PSA) - H first absorbed and then on depressurisation of reactor, desorbed.

Stationary vs. mobile applications
conventional industrial steam reformers for hydrogen production for oil refineries and chemical plants (ammonia nitrogen production) are quite large and don't scale down well for the much smaller hydrogen quantities needed for fuel cell systems natural gas is usually the fuel of choice; such a fuel cell system can consist of HDS unit (sulphur removal), steam reformer for conversion to H and CO. (PEMFC requires CO removal). there are six temperature changes involved in the natural gas processes example PAFC process: page 255 of Fuel Cell Systems Explained

FCVs: either provide the motive power for a vehicle (PEM or AFC) or auxillary power (hybrid) requirements: compact (weight, volume), quick starting, match power demand and operate efficiently over wide range, low-CO input, low levels of pollution examples pages 264-270 of Fuel Cell Systems Explained

uses electricity to divide water into hydrogen and oxygen (basically a fuel cell in reverse). Efficiency = 1.48 / cell voltage (1.6 - 2.0 V) electrolytes include alkaline liquids, but usually solid PEM (in the past potassium hydroxide used) usually only makes sense to use electrolysis where FC is mobile application such as boats or cars converting surplus electricity into useful peak power (hydro, wind, solar, ... off peak coal-generated power).

Biological production
biological alternatives to the various reforming and shiftreaction processes (rather than biofuels) include: photosynthesis using unicellular microorganisms that use either hydrogenase or nitrogenase reactions fermentation using bacteria to produce hydrogen anaerobically various stepwise processes that use a combination of bacteria to predigest complex organic molecules to make less complex organic material that can then be transformed using hydrogen-producing organisms. however, difficult to develop biological processes because of limits to growth, limited range of feedstocks, comparative rate of hydrogen to other gases produced is low

These slides are just a summary of information available in Chapter 8 "Fuelling Fuel Cells " (p229) of the book: Fuel Cell Systems Explained Second Edition James Larminie Oxford Brookes University, UK Andrew Dicks University of Queensland, Australia (Former Principal Scientist, BG Technology, UK)

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