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Gaseous Fuels

Gaseous Fuels:

Benefits: No ash. SO2 easy to remove from fuel.


Easy to achieve to achieve premixed combustion
(low NOx, low soot)

Drawbacks: Difficult to store and transport.


Natural gas:

High energy content per CO2.

Sources: NG wells, LNG from overseas, Coalbed


methane, Shale gas.

It is natural so varied composition.

Vs Coal: less C, S, N, metals, ash per MJ.

Vs Gasoline: Octane # of 120.

Vs Diesel: Cetane # of 0.

Transportation: Heavy/Light duty trucks, rail


marine.
Syngas:

Syngas: Gasification is a thermo-chemical


process that converts carbon containing
feedstocks to:
1) Feedstock + O2 CO2 and H2O.
2) C + CO2 2CO
3) C + H2O H2 + CO

Upgrading: Water Shift Reaction:


1) CO+H2O CO2 + H2
Particulate, tar, CO2 and SO2 Removal
Catalytic Methanation.
2) 3H2 + CO CH4 + H2O
Water Removal Result: High Energy Syn-NG

Syngas via Biomass Gasification:


Biomass is partially combusted (fuel rich,
=3-5) resulting in: Low energy syngas
(compared to NG) N2, CO2, and H2O Heat
Ash.
Nexterras Gasification Technology at
Kamloops BC: Biomass is fed to base of fuel
pile Air is fed from the base Air moves up,
fuel moves down Syngas exits at 260-371C

Syngas via coal gasification: Similar to


biomass gasification: Used to reduce pollutants
from coal (esp. ash, SO2, Hg, CO2, NOx)
Integrated Gasification Combined Cycle
Gasification Gas Cleaning Combined Gas
Turbine Steam Cycles Carbon Sequestration?

PlascoSyngas: Plasco (Ottawa) converts garbage


(MSW) to electrical energy via syngas The MSW
waste stream is converted into a crude syngas
using recycled heat. Plasma torches refine the
crude gas into a cleaner syngas. Removal of
sulphur, acid gases and heavy metals Syngas is
used to fuel internal combustion engines that
efficiently generate electricity.

The plaso conversion system recovers


1.2MWH electricity, 300L potable quality water, 510kg commercial salt, 150 kg construction
aggregate and 5kg agricultural fertilizer from
every tonne of waste converted.
Solid Fuels
Solid Fuels:

Benefits: High Density, relatively easy to store


and transport, cheap (almost no processing).

Drawbacks: Many pollutants in fuel (sulfur,


nitrogen, ash), difficult to remove pollutants from
fuel, non-premixed combustion (high NOx, smoke).

Trend to more processing (Syngas, Clean Coal)


Coal:

Benefits: High energy density, plentiful, relatively


inexpensive. Greater fossil fuel reserve to
production ratio than oil and natural gas.

Types of coal:
1.
Low rank coals 47%:
lignite 17% Power Generation
Sub-bituminous 30% Power Generation,
Cement Manufacture, Industrial uses. (*)
2.
Hard coal 53% :
Bituminous 52%

Thermal-Steam Coal (*)

Metallurgical-Coking Coal: Manufacture of


iron and steel.
Anthracite 1%: Domestic/Industrial including
smokeless fuel.

Disadvantages: High CO2 emissions Coal-fired


power plants are responsible for 40 percent of all
U.S. carbon dioxide emissions Reuters, 2007.
Sulfur content results in SO2 Nitrogen content
results in NOx Mercury Radioactive compounds
in fly ash Ash Difficult to remove pollutants from
fuel.
Solid Biomass Fuels:

Forestry Biomass e.g.: Mill Waste, Harvest Residues.


Agricultural Biomass: Energy crops (switch grass),
agricultural waste (Corn Stover).

Benefits: Renewable, Low net Greenhouse Gas


Emissions, Supports Rural Economy.

Drawbacks: Dispersed supply far from markets,


Existing users, Impact on ecosystems, Low energy
density, Expensive, High water content, Ash.

Challenges:

Low Density: Solution: Pellets (Twice the


density.)

Moisture Content: Solution: Drying (Via Solar,


Via Biomass, Via Fossil Fuel). Drying helps
reduce moisture to below 10% compared to
20 to 60%.

Torrefaction: Torrefaction removes moisture and


volatiles from biomass, leaving bio-coal. Added
value of torrefied biomass via Higher energy
density More homogeneous composition
Hydrophobic behavior Elimination of biological
activity Improved grindability.
Municipal Solid Waste:

Benefits: Renewable, Uses waste, Source close to


energy users.

Drawbacks: Variable fuel content, many potential


pollutants (Sulfur, Nitrogen, Mercury, Radioactive,
Ash, Difficult to remove pollutants from fuel), High
water content, Low energy density, Chlorine
(dioxins), Metals, Odor.

The heating value of a fuel is the difference between the


enthalpy of the reactants and the enthalpy of the
products when the fuel burns completely with air,
reactants and products being at the same temperature T
and pressure P. This experiment is done in a calorimeter.

The higher heating value (HHV) is obtained when


all the water formed by combustion is a liquid.
The lower heating
value (LHV) is
obtained when all the
water formed by combustion is a vapor. The higher
heating value exceeds the lower heating value by
the energy that would be released were all water in
the products condensed to liquid (Hvap WATER =
44.01 kJ/mol).
Heat of Combustion: Consider a quantity of fuel and
air at TO (298K) React and cool products to TO
Measure heat release (q) If work, kinetic energy and
potential energy changes are
negligible, then the equation.
Adiabatic Flame Temperature Equation:

Equilibrium
Gibbs free energy: At equilibrium, the Gibbs function, G,
is at a minimum for an isothermal, isobaric fixed-mass
system.

Equilibrium Gibbs function change :

Stoichiometry for Practical Fuels, Struct.


Chemical Compounds and Structures:

Alkanes (CnH2n+2):

Normal isomers (e.g. butane). (1o) 2+ (2o)


6 (less primary bonds, less
knocking/catching fire under high
pressure).

Branched isomers (isooctane, 2, 2, 4-

trimethyl pentane. More stable.


(1o)5+(2o)1+(3o)1+(4o)1.
More primary (C-C) bonds.

Alkenes (CnH2n): Ethylene (C2H4)


Alkynes (CnH2n-2): Acetylene (C2H2)
Aromatic Hydrocarbons: Ring
structure. Very stable. Soot
precursor. E.g. Benzene.
Poly-Aromatic Hydrocarbons: e.g.
Pyrene (C16H10)
Alcohols: -OH group.
Esters: -O-C=O group. E.g. Methyl Oleate.
Ethers: E.g. Dimethyl Ether: H3C-O-CH3, Methyl Tertbutyl ether: (H3C)3-C-O-CH3.

Conservation of Mass
Combustion: exothermic process where fuels are rapidly
oxidized.
Flame:

Premixed Flame: The thin zone propagates through a


fuel-oxidizer mixture.

Non-premixed (diffusion) flame: Fuel and oxidizer,


initially separate, diffuse into a common region and
sustain combustion, and combustion products
diffuse out of that zone.
Partial Pressure, mole fraction, mass fraction
equations:

Equivalence Ratio, Excess Air:

Factors affecting equilibrium:

Pressure effect on equilibrium: Higher pressure will


shift equilibrium to side with lesser moles, hence
reducing dissociation. This can be proved via
examining the following equation:

For exothermic reactions, as temperature


increases, equilibrium favors left hand side and viceversa. This can also be examined by considering
changes in T in the equation above.
Dissociation rules of thumb: Dissociation of species
must be taken into account to accurately calculate the
correct Adiabatic Flame Temperature.

For T>2200K Add the species CO, H2 and OH


1)
CO2CO + O2
2)
2 OH H2O + O2
3)
H2O H2 + O2

For T>2400K: Add the species H and O


1)
H2 2 H
2)
O2 2 O

For T>3000K
1)
Add the specie NO
2)
NO N2 + O2
3)
NO important as a pollutant above 1700K

For T>3500K
1)
Add the specie N
2)
N2 2N CO and

H2 will be present at any temperature for fuel


rich combustion.
Chemical Kinetics
Global Reaction Rate:

(50% or more EA used to


ensure complete combustion
and no CO/UHC emissions)
Adiabatic Conditions:

W=0, Q=0. Therefore, HR=HP.


Heating Values of Hydrocarbon Fuels:

m+n denotes
overall
reaction order.
Global reactions are only accurate close to
conditions used to determine their constants.
Global Reaction: A single reaction containing
initial reactants and final products,
representing an entire combustion process.
e.g. 2H2 + O2 2H2O
Elementary Reaction: A chemical reaction in
which species react directly to form products in

a single reaction step and with a single


transition state. e.g. H + O2 OH + O
Kinetic theory equations: Assumes molecules react
instantaneously when they collide if their kinetic energy
>> the energy barrier.

Chemical Time Scales:

Explosive Characteristics of Fuels: A characteristic of


combustion is that chemical reactions are fast thus
explosive. An example is the auto-ignition of fuel in an
HCCI (homogeneous charge compression ignition) engine.

Overall Reaction: H2+ O2 H2O

Chain Initiation: This step produces relatively few


radicals yet gets the chain reaction going. Does not
control overall explosive behavior.

Chain Branching: Chain branching provides


exponential growth in the radical population which is
essential to oxidize the fuel.

These steps provide the


rapid growth in the
radicals.

Radicals are highly


reactive.

Radicals consume the fuel.

Chain branching controls explosive behavior and


produces the very fast reaction times
Chain Propagation: H2 + OH H2O + H

Produces product without consuming radicals.


Chain Termination: These eliminate radicals and
prevent explosive behavior.

Third body reactions:

Trimolecular reactions: Often use a third body M to


remove energy from the transition state and
stabilize the molecule. E.g. A + B + M C + M

Reverse Reaction Equations:

At equilibrium:

From before:

As xi P = [ ]i RT:

Combining equilibrium equation and above:

Types of reactions:

Homogeneous Reaction: A reaction that occurs with


gaseous participants only. For example, auto ignition
inside a rapid compression engine.

Heterogeneous Reaction: Involves the reaction of a


gaseous species with a solid surface or large object
such as a catalytic filter. For example, pollutant
reduction occurring in a cars catalytic converter.
Reaction Mechanisms:

Reaction pathway for methane:

CH4 + OH CH3 + H2O

CH3 + O CH2O + H

CH2O + OH HCO + H2O

HCO + M H + CO + M

CO + OH CO2 + H
Alkane oxidation:

Three Main Steps:


1.
Fuel C2H4, C3H6, CH4, radicals
2.
C2H4, C3H6, CH4, and others CO, H2
3.
CO CO2 , H2 H2O

Chain Initiation:

RH R + H where RH is an alkane

This provides the first radicals (i.e. H)

H Abstraction:

RH + OH R + H2O

RH + X R + XH where X is any radical

For alkane: CnH2n+2 + X CnH2n+1 + XH

Scission: The breaking up of a hydrocarbon


during combustion based on where a radical site
may be.

The molecule will sever bonds on the carbon


atom one away from the radical:

C-C bonds weaker than C-H bonds.


CnH2n+1 C2H4 + Cn-2H2n-3.
As Cn-2H2n-3 same as CmH2m+1, the cycle repeats.
More C2H4 (ethylene) formed that any other
species.
Original alkane not that important as ethylene
quickly forms.
Conversion to C2H4 occurs without significant
temperature increase.

CnH2n+1 C3H6 + Cn-3H2n-5.


As Cn-3H2n-5 same as CmH2m+1, the first cycle
repeats.

Thus less C3H6 formed than C2H4.


CO Oxidation:

CO + OH CO2 + H.

Often rate limiting reaction for hydrocarbon


oxidation.

CO oxidation inhibited by the presence of


hydrocarbons due to the competition for OH.

Peak temperature occurs as CO oxidized


Releases 2/3 of fuel energy.

Fuel begins to break down to form UHCs.

UHCs will start to become oxidized into CO

CO will become oxidized into CO2

Radicals will favor UHC oxidation over CO


oxidation. Therefore, CO will not be destroyed
until UHCs are burned out.

Thermal Oxidation:

Convert Hazardous Volatile Organic Compounds


(VOC) to non-hazardous gases. E.g. C CO2, H
H2O, S SO2, Cl HCl.

High temperatures used to convert VOCs to CO2.


Reactions occur in the gas phase.

Typically the VOCs are very dilute in air thus little


heat rise.

Advantages: Wide range of compounds can be


removed Very high destruction efficiency

Disadvantages: High energy consumption


Other pollutants can form (i.e.NOx)

A high Destruction and Removal Efficiency (DRE)


is achieved by increasing the 3Ts:
1.
Time (added length)

2.
Temperature (added fuel)
3.
Turbulent Mixing with Oxygen (added air)
T99: Temperature needed to destroy 99% of a
compound in 1 second.

PFR: Steady state, steady flow. No mixing in the


axial direction (i.e. diffusion << convection).
Uniform velocity profile (1D flow). Frictionless flow.
Ideal gas behavior.

NOX Emissions
Ground Level Ozone:

Characteristics: A colourless gas with a strong


smell. Major component of summer smog.

Effects: It causes lung irritation, difficulty in


breathing and damage to crops, forests and
vegetation.

Sources: Ozone is not directly emitted into the


atmosphere. It is produced photochemically from:

Volatile Organic Compounds (VOC) which are


emitted by evaporation and combustion.

Nitrogen Oxides (NOx) which are emitted by


combustion.

Greatest level of ground level is at noon when NO2


forms NO and O in the presence of light. This O
atom reacts with O2 to form O3 (Ozone).
Nitrogen oxides:

Source (U.S. data): Combustion engines for


transportation (40%) Stationary combustion
mostly from electric utilities (56%).

Composition: Most important nitrogen oxide is


NO but NO2 and N2O also can be present.

NOx Formation:
1.
Thermal NO (N2 from air)
2.
Fuel NO (N from fuel)
3.
Prompt NO (N2 reacting with HCs)

Thermal NO:

Forms at high temperatures during


combustion (global reaction): 1/2 N2 + 1/2 O2
= NO

Zeldovich Mechanism (detailed reactions):


1.
N2+O NO + N
2.
N + O2 NO + O
3.
N + OH NO + H

Reaction (1) is the rate limiting step. It is very


temperature sensitive due to its:
1. High activation energy Rfr = 1.8 1011 * exp
(38,370/T) [N2] [O] in kmol/m3/s
2. Strong temperature dependence of [O]

Thermal NO formation is kinetically controlled.


Slow rate of formation. Slower than
hydrocarbon combustion. Equilibrium values
generally not reached.

Control:
1.
Reduce Peak Temperature. Exhaust Gas
Recirculation (or Flue Gas Recirculation).
Lowers temperature in cylinder and thus NOx
but also reduces output power.
2.
Reduce time. Quick quench.
3.
Reduce oxygen concentration at highest
temperature zone. Low excess air.
4.
Reduce nitrogen concentration. Oxy-fuel
burners.

Prompt NOx: NN bond scission by flame


radicals. Occurs only in flame fronts.

Fuel NOx: Forms from nitrogen in fuel during


combustion:

CxHyNz + mO2 NO + .

Heavy oil contains 0.2-1.2% N and coal contains


1.2-1.6% N.

Mechanism:
1.
Fuel N HCN
2.
Then, NO formation similar to Prompt NOx

These reactions are fast Typical conversion: 4070%

Fuel NO formation is controlled by stoichiometry

NO formation is weakly dependent on


temperature

Under fuel rich conditions, conversion of fuel


nitrogen to N2 is favored: N + NO N2+O

Control: Staged combustion. Operate under


fuel rich conditions to convert fuel N to N2 then
burn off CO and hydrocarbons.

Staging Methods:
1.
Overfire Air. Separate air injection. NOx
Reduction by 40 to 60 percent.
2.
Low NOx burners. Staging within burner.
NOx Reduction of 30 to 55 percent

Catalytic Converter:
Application: Gasoline (SI) engines Engine
Modifications: fuel air ratio controlled to near
stoichiometric (equivalence ratio of approx. 1),
need oxygen sensor, computer control & air/fuel
control Fuel Change
Lead and sulfur eliminated Problems
Poor performance at low startup temperature
Selective Catalytic Reduction:
NO converted to N2 by NH3 (ammonia) and a
platinum catalyst in the presence of oxygen:
4 NO + 4 NH3 +O2 4 N2 + 6 H2O
T from 500-800K
Over 90% removal can be achieved
Catalysts can become fouled by aluminum
sulfates from fuel sulfur.

Applications:
Gasoline (S.I.) engines:
Conditions: Premixed Combustion, =1, high
pressure.
NOx formation. Mostly thermal NOx with
equilibrium O. Some prompt NO and thermal
NOx with super equilibrium O.
NOx Control: EGR (5-15%), Catalytic converter.

Stationary Gas Turbine Engines:


Conditions: Premixed Combustion, <1, high
pressure.
NOx formation: At =0.7, mostly thermal NOx
with super-equilibrium O
NOx Control: Lean burn

Aviation Gas Turbine Engines:


Conditions: Non-Premixed Combustion, <1,
high pressure.

NOx formation: Mostly thermal NOx with


equilibrium O.

NOx Control: RQL: Rich Burn, Quick Quench, Lean


Burn.
Furnaces and Boilers:
Conditions: Non-premixed Combustion, overall
<1, atmospheric pressure.
NOx Formation: Thermal NOx with equilibrium O,
Fuel NOx
NOx Control: EGR (Low excess air, Reburn),
SCR Staged Combustion (low NOx burners)
Diesel Engines:
Conditions: Non-premixed Combustion, overall
<1, high pressure.
NOx Formation: Mostly thermal NOx with
equilibrium O.
NOx Control: EGR (up to 50%), SCR.