Fuel Cell System

Fuel Processing

Maree
Overview
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 AFC PAFC MCFC SOFC
Temperature (°C) 50-100 50-200 180-220 600-700 850-1000

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

* Note that diluent just means diluting agent.

Desulphurisation
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 low-
weight 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 ceria-
doped 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 (1200-
1500°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 by-
products)
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
Stationary
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
Mobile
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
Electrolysers
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 shift-
reaction 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
Reference
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)