Chapter 11

Fuel Processing
Subsystem Design

Lecture Notes
Dr. Sammia Shahid
Why is Fuel Cell Technology
Important?
Why is Fuel Cell Technology
Important?
Since conversion of the fuel to energy
takes place via an electrochemical
process, not combustion

It is a clean, quiet and highly efficient
process- two to three times more
efficient than fuel burning.
Fuel Cell
Fuel Cell Stack
Importance of Hydrogen
Fuel Cells require highly purified
hydrogen as a fuel

Researchers are developing a wide
range of technologies to produce
hydrogen economically from a variety of
resources in environmentally friendly
ways
Importance of Hydrogen
Hydrogen is a secondary energy
resource, meaning it must be made
from another fuel

Hydrogen can be produced from a wide
variety of energy resources including:
Fossil fuels, such as natural gas and coal
Nuclear energy
Renewable resources, such as solar, water,
wind and biomass
Hydrogen Production
The biggest challenge regarding hydrogen
production is the cost

Reducing the cost of hydrogen production
so as to compete in the transportation
sector with conventional fuels on a per-mile
basis is a significant hurdle to Fuel Cells
success in the commercial marketplace
Hydrogen Production
There are three general categories of
Hydrogen production

Thermal Processes
Electrolyte Processes
Photolytic Processes
HYDROGEN GENERATION
PROCESSES
Steam reforming of Natural Gas/Naphtha
Partial oxidation of hydrocarbons
Thermal cracking of Natural Gas
Coal/Bio mass Gasification
Electrolysis Electricity from renewable sources like
solar, wind, hydel etc.
HYDROGEN PRODUCTION

World wide production
From Natural gas (mostly steam reforming) - 48%
Oil (mostly consumed in refineries) 30%
Coal 18%
Electrolysis 4%

Nearly all H
2
production is based on fossil fuels at present.

H
2
OPTIONS FOR PAKISTAN
Hydrocarbon Liquid Fuels
Natural Gas
Solar / Wind power for electrolysis
Coal
Bio-mass
Other options like Chlor-Alkali Units & Co-generation
electricity from Bagasse at sugar mills


STORAGE OPTIONS
Storage as gas under pressure (250 350 bar)
Cryogenic storage as liquid hydrogen
(Temp. 253
0
C)
Storage as metallic hydrides
Carbon adsorption and glass microsphere
storage techniques (under development)

Fuel Processing


Reformer

A vessel within which fuel and other gaseous recycle
stream(s) are reacted with water vapor and heat, usually in
the presence of a catalyst, to produce
hydrogen-rich gas for use within the fuel cell.

There are a number of different sources of hydrogen and
methods for reforming.
Steam reformation
Fuel reacts with water over a catalyst
Requires heat input

Partial oxidation
Fuel reacts with air (w/o catalyst)
Typically produces heat

Auto-thermal
Combination of above (fuel, water, air)
No net heat required or produced

Other e.g., Cyclic
Oxidation states of metals
Alternatively pass fuel and oxidant over parallel beds
Calcium oxide, calcium carbonate for carbon
absorption
Fuel Processing
Fuel Processor
Fuel Processing Subsystem
Fuel processing subsystem will probably consists of at
least three primary reactor processes:

1. Fuel Reforming (labeled no. 3)

2. Water gas shift reaction (labeled no. 4)

3. Carbon monoxide clean-up (labeled no. 5)
Fuel Processing Subsystem
The overall goal of fuel reforming is to convert a hydrocarbon
(HC) fuel into a hydrogen-rich gas. The primary conversion
may be accomplished with or without a catalyst via one of
five major types of fuel-reforming processes:

1. Steam reforming (SR)
2. Partial oxidation (POX) reforming
3. Auto thermal reforming (AR)
4. Gasification
5. Anaerobic digestion (AD)

Fuel Reforming Overview
Steam Reforming


Steam reforming is endothermic reaction:
C
x
H
y
+ x H
2
O x CO + (x + 1/2y) H
2

The SR typically has a H
2
yield of 76% on a dry basis.

Catalytic system: CuO/ZnO, CuO/SiO
2
, CuO/ZnO/SiO
2
For Methanol: 250-260
0
C
Ethanol : >300
0
C
Advantages : Maximum Hydrogen generation
Disadvantages: Indirect Heat transfer


Partial Oxidation Reforming

POX is an exothermic reaction that combines a HC fuel with some
oxygen to partially oxidize the fuel into a mixture of CO and H2. e.g.
the complete combustion of propane is:
C
3
H
8
+ xO
2
yCO
2
+ zH
2
O
Advantages:
Any type of hydrocarbon
Direct Heat transfer
Disadvantages:
Low H
2
production
Dilution of gas with N
2
Soot formation

Auto thermal Reforming

Combination of Steam Reforming and partial
oxidation and water gas shift reaction in a single process.
CH
4
+H
2
O CO+3H
2
H=+206.16 kJ/mol
CH
4
+1/2O
2
CO+2H
2
H= -36 MJ/kmol

Reactions are balanced in such a way net energy
requirement is Zero (H = 0)

C + 1/2O
2
CO
2


C + H
2
O

CO
2
+ H
2

C + CO
2
2CO
CO + H
2
O CO
2
+ H
2

CO + 3H
2
CH
4
+H
2
O


Gasification of solid fuels
Stationary fuel cell systems may also utilize fuel gases
produced from solid fuels through a process known as
gasification.
The process of gasification typically reacts a solid fuel
containing carbon (such as coal) at high temperature (700
1400C) under pressure with O
2
and

H
2
O

to produce H
2
,
CO
2
, CO and other gases.
Catalytic decomposition

CH
3
OH 2 H
2
+ CO

Mostly suitable for Alcohols
Soot formation and carbon deposition for
Hydrocarbons

Desulphurisation

Gas phase Desulphurisation
ZnO + H
2
S ZnS (s) + H
2
O (g)
2 to 3 kg ZnO sufficient for one year Automobile operation

Liquid Fuel Desulphurisation
Gasoline 30-40 ppm 1-2ppm Sulphur
For high sulphur Fuels hydro treatment followed by gas phase
Desulphurisation

Adsorption
Chemical reaction
High temperature & Low temperature Shift reaction

CO + H
2
O CO
2
+ H
2

HT Shift: Iron and Chromium Oxide Catalyst.
Temperature 350-450
0
C
LT Shift: Copper and Zinc Oxide Catalyst.
Temperature 200-250
0
C
Carbon Monoxide Clean-up

Chemical
Preferential oxidation
CO + O
2
CO
2
H
2
+ O
2
H
2
O
Pt, Pd, Rh, Ru are catalysts (~ 120
0
C)
Methanation
CO + 3 H
2
CH
4
+ H
2
O
Ru, Rh are catalysts. Temperature 100-220
0
C
Physical
Pressure Swing Adsorption (PSA)
Membranes-Metal or polymeric
Solvent Absorption
Pressure Swing Adsorption
Pressure Swing Adsorption (PSA) processes rely on the fact that under
pressure gases tend to be attracted to solid surfaces, or adsorbed.

The higher the pressure, the more gas is adsorbed; when the pressure is
reduced, the gas is released, or desorbed.

PSA processes can be used to separate gases in a mixture because
different gases tend to be attracted to different solid surfaces more or
less strongly.

If a gas mixture such as air, for example, is passed under pressure
through a vessel containing an adsorbent bed that attracts nitrogen more
strongly than it does oxygen, part or all of the nitrogen will stay in the bed,
and the gas coming out of the vessel will be enriched in oxygen. When the
bed reaches the end of its capacity to adsorb nitrogen, it can be regenerated
by reducing the pressure, thereby releasing the adsorbed nitrogen. It is then
ready for another cycle of producing oxygen enriched air.
Pressure Swing Adsorption
Pressure swing adsorption is known to be one of the
most economic and widespread commercial processes for
hydrogen purification.

It can produce 99.99% pure hydrogen.

A PSA unit operates with atleast two adsorption beds.

Each adsorption process is batch process.

Primary
Reformer

CO + H
2
O = CO
2
+ H
2
- - - - - - - - - - - - - - - -
-
H
2


Fuel
Air
H
2
O
H
2
,CO,N
2
H
2
, CO
2
, N
2
To Fuel
Cell
Fuel Processor using Membrane
Reactor
Novel Reformer Technologies

Solvent enhanced reforming
Calcium Oxide along with steam reforming catalyst is
added. Composition 90% H2, 10% CH4, 0.5% CO2
and <50ppm CO
Downstream processing load is reduced.
Ion transport membrane reforming
Oxygen on one side of the membrane (1-5 psig)
Methane & steam on the other side of the membrane (100-
500 psig)
Plasma Reformers
HT plasma (3000-10000
0
C) is generated by electric arc in
plasmatron
Heat Exchangers


A device used to transfer heat from a fluid (liquid or gas) to another fluid
where the two fluids are physically separated.

Heat exchangers are needed to cool fuel cells and maintain a consistent
operating temperature.

They are used primarily by the lower-temperature fuel cells (AFC, PEMFC
and PAFC).

The typical cooling mechanism is water.

There are a number of types of heat exchangers:
Gas - Gas
Gas - Liquid
Condensers
Humidifiers

Some of the development areas to date are:
Size and weight reduction (transportation markets)
Heat transfer and size (portable power markets)
Power Conversion and Electronics


Fuel cells produce direct current or DC power. Today, most
of our buildings and appliances require alternating current or
AC power to operate.

Consequently, a conversion device is necessary as part of
the fuel cell system.

There are in fact many "appliances" that can or do use DC
power, such as computers and lighting.

Today, the issue with this technology is to reduce the
efficiency losses, increase the reliability, and the cost.
General Power Electronics Capabilities

Convert direct current (DC) to alternating current (AC) when
required.
Control current and/or voltage
Feedback to control system
Surge and short-circuit protection
Connect to and manage energy storage
Connect to and/or control loads
Dedicated load
Motor controller, motors
Synchronize
Electrical grid
Other generators
Balance of Plant
Balance of plant refers to supporting and/or auxiliary
components based on the power source or site-specific
requirements and integrated into a comprehensive power
system package.

Filters
Filters remove solid material from a medium, such as a gas
(air) or fluid. In the case of air, filters can be installed as part
of a heating/cooling system through which air flows for the
purpose of removing particulates before or after the air
enters the mechanical components. In the case of a liquid or
gas, it could be a pre-step to reformation (e.g. sulfur
removal).
Auxiliary Components
Seals and Gaskets


A gasket or seal is used to prevent the leakage of fluids and
to maintain the pressure in an enclosure. Specifically, a
gasket is used between two static surfaces to provide a seal.
Sealing is an important issue for all applications. Some of the
developmental areas today include:
High temperature seals
SOFC and MCFC applications
Fuel processing components
Good performance versus:
Load swings
Thermal gradients
Rapid transients (pressure, temperature)
Multiple cycles
Valves

A device used in piping to control the fuel supply to any
section of a system of piping or to fuel utilization equipment.

Automatic. A device consisting essentially of a valve and
operator that controls the fuel supply to the burner during
normal operation of the equipment. The operator may be
actuated by application of fuel pressure on a flexible
diaphragm, by electrical means, by mechanical means or by
other means.

Diaphragm Type. A device consisting essentially of an
automatic valve actuated by means of the application of fuel
pressure upon a flexible diaphragm.
Electric Type. A device actuated by electrical energy for
controlling the fuel supply. These consist of the following:
Modulating. A valve designed so the valve opening is controlled
within narrow limits throughout the entire range from the "full
open to the "closed" position.
Motor. An electric control valve that is automatically closed by a
spring or other mechanical means in the event the electric circuit
is broken.
Solenoid. A valve that is opened or closed by the action of an
electrically excited coiled wire magnet upon a bar of steel
attached to the valve disc.
Step (Manual). A valve having a rotating plug usually with three
positions and different rates of fuel flow for each. The plug is
actuated by a solenoid or motor-driven rack and pinion and a cam
arrangement. This apparatus and a combination push-button
switch determine the position assumed by the plug.
Valves
Burner. A manually or mechanically operated valve which permits
control of the flow of fuel.
Combustion (input) Control. An automatic control valve for
regulating fuel input.
Latching Type. A manual gas valve which requires at least two
separate actions or movements to turn the valve on, as for example,
pushing in on the valve handle to unlatch the valve before the valve
handle can be rotated to turn on the fuel.
Lubricated Plug. A valve of the plug-and-barrel type that has
bearing surfaces designed to be re-lubricated without disassembly of
the valve.
Main Burner, Individual. A valve that controls the fuel supply to an
individual main burner.
Valves
Valves
Semi-Automatic. A valve that is opened manually and closed
automatically, or vice versa.
Shutoff, Manual. A manually operated valve in a fuel line for
the purpose of completely turning on or shutting off the fuel
supply to fuel utilization equipment.
Shutoff, Manual Main. A manually operated valve in the fuel
line for the purpose of completely turning on or shutting off the
fuel supply to fuel utilization equipment, except to a pilot
provided with independent shutoff valves.
Shutoff, Safety. A valve that is automatically closed by the
safety control system or by an emergency device. Such valve
may be of the automatic or manually opened type.
TYPES OF FUEL CELLS
Temp.C Application
Alkaline (AFC) 70-90 Space
Phosphoric Acid 150-210 Commercially available
(PAFC)
Solid Polymer 70-90 Automotive application
(PEMFC)
Moltan Carbonate 550-650 Power generation
(MCFC)
Solid Oxide 1000-1100 Power generation
(SOFC)
Direct Methanol 70-90 Under development
(DMFC)