4

Fuels

John Ackland, Jeff White, Richard T. Waibel, and Stephen B. Londerville

CONTENTS
4.1 Gaseous Fuels................................................................................................................................................................... 72
4.1.1 Introduction.......................................................................................................................................................... 72
4.1.2 Natural Gas........................................................................................................................................................... 72
4.1.3 Liquified Petroleum Gas..................................................................................................................................... 73
4.1.4 Refinery Gases...................................................................................................................................................... 73
4.1.5 Combustible Waste Gas Streams....................................................................................................................... 75
4.1.5.1 PSA Tail Gas........................................................................................................................................... 75
4.1.6 Flexicoking Waste Gas........................................................................................................................................ 76
4.1.7 Physical Properties of Gaseous Fuels............................................................................................................... 77
4.2 Gas Property Calculations.............................................................................................................................................. 77
4.2.1 Molecular Weight................................................................................................................................................. 77
4.2.2 Lower and Higher Heating Values.................................................................................................................... 82
4.2.3 Specific Heat Capacity......................................................................................................................................... 82
4.2.4 Flammability Limits............................................................................................................................................ 83
4.2.5 Burning Velocity.................................................................................................................................................. 84
4.2.6 Viscosity................................................................................................................................................................ 84
4.2.7 Derived Quantities.............................................................................................................................................. 84
4.2.7.1 Partial Pressure..................................................................................................................................... 84
4.2.7.2 Adiabatic Flame Temperature............................................................................................................. 85
4.2.7.3 Other Special Cases.............................................................................................................................. 85
4.3 Liquid Fuels...................................................................................................................................................................... 85
4.3.1 Production, Refining, and Chemistry............................................................................................................... 85
4.3.2 Oils......................................................................................................................................................................... 88
4.3.2.1 Light Oils................................................................................................................................................ 88
4.3.2.2 Heavy Oils............................................................................................................................................. 89
4.3.2.3 Residual Oils.......................................................................................................................................... 89
4.3.3 Liquid Naphtha.................................................................................................................................................... 90
4.3.4 Physical Properties of Liquid Fuels................................................................................................................... 90
4.3.4.1 Flash Point.............................................................................................................................................. 90
4.3.4.2 Pour Point............................................................................................................................................... 91
4.3.4.3 Distillation.............................................................................................................................................. 91
4.3.4.4 Viscosity................................................................................................................................................. 91
4.3.4.5 Density, Gravity, Specific Volume, and Specific Weight.................................................................. 91
4.3.4.6 Heat Capacity (Specific Heat).............................................................................................................. 93
References................................................................................................................................................................................... 94

71
 72 The Coen & Hamworthy Combustion Handbook

TABLE 4.1
4.1  Gaseous Fuels Example Pipeline-Quality Natural Gas
Minimum Maximum
4.1.1 Introduction
Major and minor components (vol%)
The term “gaseous fuel” refers to any combustible fuel Methane 75%
that exists in the gaseous state under normal tempera- Ethane — 10.0%
tures and pressures. Gaseous fuels are typically com- Propane — 5.0%
posed of a wide range of chemical compounds. Low Butane — 2.00%
boiling point hydrocarbons (both paraffins and olefins), Pentane and heavier — 5.00%
hydrogen, carbon monoxide, and inert gases (nitrogen Nitrogen and other inerts — 3%–4%
and carbon dioxide) are among the many chemical Carbon dioxide — 3%–4%
constituents of common gaseous fuels. The purpose of Trace components
this section is to introduce many of the common fuel Hydrogen sulfide — 0.25–1.0 grains/100 scf
gas mixtures used as fuel in the hydrocarbon and pet- Mercaptan sulfur — 0.25–1.0 grains/100 scf
rochemical industries. Commonly occurring waste gas
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Total sulfur — 5–20 grains/100 scf

mixtures in flare systems are also described.
4.1.2  Natural Gas
Natural gas is a gaseous fossil fuel that is formed natu-
rally beneath the Earth and is typically found with or
near crude oil reservoirs. According to the U.S. Energy
Information Administration, in 2009, proven natural gas
reserves in the United States totaled approximately 7.717 ×
1012 m3 (2.725 × 1014 ft3).1 Total natural gas consumption in
the United States in 2009 was estimated at 23.344 quadril-
lion Btu, 24.7% of the total U.S. energy consumption.2
Natural gas consists of a fluctuating range of low boil-
ing point hydrocarbons. Methane is the primary chemi-
cal component, and can be present in amounts ranging
from 70% to 99.6% by volume. Ethane can be present in
amounts ranging from 2% to 16% by volume. Carbon
dioxide, nitrogen, hydrogen, oxygen, propane, butane,
and heavier hydrocarbons are also typically present
in the fuel analysis.3 The exact analysis usually varies
somewhat depending on the source of the gas and on
any heating value adjustments or supplementation.
Natural gas quality specifications have historically
been negotiated in individual contracts between the
natural gas producer and the purchaser or pipeline
company. Specification parameters often include upper
and lower limits for heating value, chemical composi-
tion, contaminants, water content, and hydrocarbon
dew point. Table 4.1 outlines general specifications for
pipeline-quality natural gas, as provided by the Gas
Processors Suppliers Association (GPSA).4 Typical com-
mercial natural gas compositions, listed by production
region, are contained in Table 4.2.
In addition to the primary combustible and inert
chemical components discussed earlier, raw natural gas
can also contain undesirable amounts of water, hydrogen
sulfide, and/or carbon dioxide. Before the raw natural
gas can be deposited into a pipeline ­transmission net-
work, these undesirable components must be removed.
Water vapor — 7.0 lb/mmcf
Oxygen — 0.2–1.0 ppmv
Other characteristics
Heating value, 950 1150
Btu/scf-gross saturated
Source: Adapted from Gas Processors and Suppliers Association,
GPSA Engineering Data Book, Vol. I, 10th edn., Tulsa, OK, 1987.
With permission.
Liquids: Free of liquid water and hydrocarbons at delivery tempera-
ture and pressure.
Solids: Free of particulates in amounts deleterious to transmission
and utilization equipment.
Failure to remove the water vapor from raw natural
gas prior to introduction to the pipeline network will
result in increased corrosion rates, formation of solid
hydrate compounds that can restrict or interrupt gas
flow, and freezing of valves and regulators during cold
weather conditions.5 Techniques for the dehydration of
natural gases include the following:
1. Absorption with liquid desiccants: Glycols
(typically triethylene glycol) are used to absorb
water vapor via countercurrent-flow, packed-
bed absorption columns.6
2. Adsorption with solid desiccants: Water vapor
is adsorbed onto a bed of inorganic porous solid
material (silica gel, alumina, molecular sieves,
etc.).6,7
3. Dehydration with calcium chloride: Solid anhy-
drous calcium chloride (CaCl2) absorbs water
from the wet natural gas and forms various
calcium chloride hydrates (CaCl2 × H2O). These
hydrates are removed from the natural gas
stream as a calcium chloride brine solution.6
4. Refrigeration: A refrigeration coil is used to cool
and condense water vapor from the wet natu-
ral gas stream. Separation of the liquid phase
is accomplished via a two-phase, vapor/liquid
separation drum.5
 Fuels 73

TABLE 4.2
Commercial Natural Gas Components and Typical Ranges of Composition
Sample Gas Compositions by Production Region (vol%)
Fuel Gas Tulsa, North
Component OK Alaska Algeria Netherlands Kuwait Libya Sea Alabama Ohio Missouri Pennsylvania
CH4 93 100 87 81 87 70 94 90 94 84 83
C2H6 3 — 9 3 9 15 3 5 3 7 16
C3H8 1 — 3 <1 2 10 1 — <1 — —
C4H10 <1 — 1 <1 1 4 <1 — <1 — —
C5 and — — — — — — — — — — —
higher
CO2 1 — — 1 2 — <1 — 1 1 —
N2 2 1 <1 14 1 1 2 5 1 8 1
O2 — — — — — — — — <1 — —
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H2 — — — — — — — — <1 — —
Total 100 100 100 100 100 100 100 100 100 100 100

Source: Adapted from Reed, R.J., North American Combustion Handbook, Vol. 1, North American Mfg. Co., Cleveland, OH, 1986. (Courtesy of
Fives North American Combustion, Inc.)

Hydrogen sulfide must be removed from the raw nat-
ural gas stream due to air pollution considerations and
corrosion hazards. The hydrogen sulfide content of com-
mercial natural gas rarely exceeds 1.0 grains/100 std. ft3
(0.023 g/m3). A majority of pipeline companies respond-
ing to a 1994 poll limited hydrogen sulfide concen-
trations to less than 0.3  g/100  std. ft3 (0.007  g/m3).8 In
addition, carbon dioxide is often removed from the raw
gas because the inert component weakens the overall
heating value of the gas stream.5 There are numerous
commercial processes (chemical reaction, absorption,
and adsorption) for the removal of acidic components
(H2S and CO2) from raw natural gas streams. The GPSA
Engineering Data Book discusses many of these hydro-
carbon treatment processes in detail.6 Hydrogen sulfide
removed from the raw gas is generally converted to ele-
mental sulfur via the Claus process.6
After the necessary purification processes have been
completed, the commercial-grade natural gas is com-
pressed to approximately 1000  psig (6.9  MPag) and is
introduced to a natural gas pipeline distribution net-
work.5 The gas is recompressed along the path to the
consumer as necessary. Operating pressure at an indi-
vidual natural gas burner located at a process furnace
inside a petrochemical or hydrocarbon processing facil-
ity is reduced to an operating pressure range that typi-
cally varies between 5 and 30 psig (34 and 207 kPag),
depending on the furnace’s heating requirements and
the individual burner’s design specifications.
4.1.3  Liquified Petroleum Gas
Liquified petroleum gas (LPG) is the general term used
to describe a hydrocarbon that is stored as a liquid under
moderate pressure, but is a gas under normal atmospheric
conditions. LPG is vaporized for use as a fuel. The pri-
mary chemical components of LPG are propane, propyl-
ene, normal butane, isobutane, and butylene.8 The GPSA
Engineering Data Book contains industry standard prod-
uct specifications for commercial propane (predomi-
nantly propane and/or propylene), commercial butane
(predominantly butane and/or butylene), and commer-
cial butane–propane mixtures.4 LPG produced via the
separation of heavier hydrocarbons from natural gas is
mainly paraffinic, containing primarily propane, normal
butane, and isobutane. LPG derived from oil-refinery gas
may contain varying small amounts of olefinic hydrocar-
bons such as propylene and butylene.8
Most of the LPG used in the United States consists
primarily of propane.9 Due to their relatively high boil-
ing point, LPG mixtures containing high concentra-
tions of normal butane (boiling point = 31°F or −1°C at
atmospheric pressure) or isobutane (boiling point = 11°F
or −12°C at atmospheric pressure) are preferred for use
in warm climates. Conversely, LPG mixtures containing
high concentrations of propane (boiling point = −44°F
or −42°C) are typically preferred for use in cold climates.5
LPG is often used in the hydrocarbon or petrochemical
industry as a fuel gas supplement or as a standby/start-
up fuel. However, due to its value as both a common pet-
rochemical feedstock and a marketable commodity, LPG
is not typically preferred as a primary processing fuel.10
4.1.4  Refinery Gases
Although commercial natural gas and LPG are often
used as fuels in processing plants, internally generated
refinery fuel gases serve as the primary fuel component
for most refineries, petrochemical plants, and hydrocar-
bon facilities. It is not usual for a process unit to produce
 74 The Coen & Hamworthy Combustion Handbook

its own fuel supply. Often, fuel gas streams from vari-
ous processing units are delivered to a common mixing
point within the plant, before the new gas mixture is
returned to the processing units as refinery gas. Refinery
fuel gases contain an extremely wide variety of chemi-
cal constituents, including paraffins, o ­ lefins, diolefins,
aromatics, mercaptans, organic sulfides, ammonia,
hydrogen sulfide, carbon monoxide, carbon dioxide, etc.
Because plants must operate in a manner best suited to
maximize profit, the individual fuel gas streams origi-
nating at each process unit will vary in composition and
quantity, depending on numerous economic and tech-
nical factors.11 Table 4.3 contains typical chemical com-
positions of fuel gas streams originating from various
process units within a petroleum refinery.8
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to ensure a well-mixed, homogeneous fuel gas mixture.
However, static mixers are often impractical in the pet-
rochemical and hydrocarbon processing industries,
typically due to pressure drop limitations of the refin-
ery fuel gas system.
Another problem often associated with the com-
bustion of refinery fuel gases is the presence of liquid
hydrocarbons in the refinery fuel gas stream, which
can accelerate the coking and plugging rates of down-
stream gas burner components. Sources of unwanted
liquid hydrocarbons in refinery fuel gas streams include
condensation of heavier fuel gas components (C5 and
higher) due to natural cooling of the fuel gas stream,
liquid entrainment into absorber or fractionator over-
head gas streams, and lubrication oil contamination of

It is very important that the refinery fuel gas leaving
the common mixing point is a homogenous mixture of
the fuel gas streams supplied. If the individual fuel gas
supply streams vary significantly in calorific value, and
if the supply streams are not combined in a homoge-
neous manner, the calorific value of the nonhomoge-
neous refinery fuel gas mixture will also vary widely
and often instantaneously. Unless the gas burners and
control systems at each processing furnace have been
designed to accommodate instantaneous changes in
fuel gas calorific value, the process will likely be impos-
sible to control. All of the combustion performance
parameters—including burner stability, emissions con-
trol, heat transfer efficiency, and heat flux—will suffer
as a result of the nonhomogeneous fuel mixture.10 Static
mixers are often used in various segments of industry
the fuel gas stream. Potential solutions for the problems
associated with these liquid hydrocarbons include liq-
uid extraction of the heavier chemical components (C5
and heavier) and filtration/coalescence of liquid compo-
nents from the gas stream. In addition, increasing the
velocity of the flowing gas through burner components
(tips, risers, etc.) has been proven to cool the hardware
and inhibit the cracking reactions that eventually lead
to plugging and coking.
Wet fuel gas can introduce problems in cooler cli-
mates associated with the condensation and subsequent
freezing of water vapor inside the fuel gas system. If the
water vapor reaches the dew point in a cold atmospheric
environment, there is danger of frost stoppage, freezing,
or bursting of lines—a considerable fire safety hazard
that merits serious thought. Options to combat water

TABLE 4.3
Composition of a Typical Refinery Gas
Refinery Fuel Gas Source (Dry Gas)
Fuel Gas Cracked Gas Coking Gas Reforming Gas Combined Refinery Combined Refinery
Component (%) (%) (%) FCC Gas (%) Gas—Sample 1 (%) Gas—Sample 2 (%)
CH4 65 40 28 32 36 53
C2H4 3 3 7 7 5 2
C2H6 16 21 28 9 18 19
C3H6 2 1 3 15 8 6
C3H8 7 24 22 25 20 14
C4H8 1 — — — — —
C4H10 3 7 7 0 2 1
C5 and higher 1 — — — — —
H2 3 4 5 6 3 3
CO — — — — — —
CO2 — — — — — —
N2 — — — 7 8 3
H2O — — — — — —
O2 — — — — — —
H2S — — — — — —
Total 100 100 100 100 100 100

Source: Adapted from Nelson, W.L., Petroleum Refining Engineering, 3rd edn., Marcel Dekker, New York, 1949.
 Fuels 75

present in the fuel gas system include dehydration sys- TABLE 4.4
tems (as discussed in Section 4.2.1) and steam/electric Typical Composition of Steam Reforming/PSA Tail Gas
tracing of refinery fuel gas lines.10
Fuel Gas Component PSA Tail Gas Composition (vol%)
CH4 17
4.1.5  Combustible Waste Gas Streams H2O <1
H2 28
The quantity and variety of combustible waste gas
CO2 44
streams in the hydrocarbon and petrochemical indus-
CO 10
tries is virtually unlimited. Many of these waste gas
N2 <1
streams are relatively high in inert concentration,
with large amounts of nitrogen and carbon diox- Total 100
ide often present. As a result, these waste fuels are Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook,
often low in heat content, with lower heating values CRC Press, Boca Raton, FL, 2001.
(LHVs) in the range of 400–800 Btu/scf (0.42–0.84 MJ/
PSA is a cyclic process that uses beds of solid adsor-
Nm3). For these reasons, waste fuels are not usually
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bent to remove impurities such as carbon dioxide, carbon

compressed into the main refinery fuel gas system.
monoxide, methane, and nitrogen from the hydrogen
Two of the most widely used combustible waste gas
production stream. A simplified process flow diagram
fuels, pressure swing adsorption (PSA) tail gas and
of a typical steam reforming hydrogen production unit
Flexicoking gas, are discussed in detail in the follow-
using PSA is shown in Figure 4.1.
ing sections.
The steam reforming process is conducted in four
stages8,9,12,13:
4.1.5.1  PSA Tail Gas
1. Feedstock preparation: Feedstock (light hydro-
PSA tail gas is a low-pressure, low-Btu fuel gas produced carbons such as methane, propane, butane, and
as a by-product of a PSA process, a key purification com- light liquid naphtha) at approximately 450 psig
ponent in the steam reforming hydrogen production (31 barg) is preheated and purified to remove
process. Table 4.4 contains the approximate composition reformer catalyst poisons such as halogens and
of a typical PSA tail gas fuel stream. sulfur-containing compounds.

Feed

Steam Steam
generation

Reforming
Purification

Shift

Steam
generation
Cooling

99.9% Vol. H2
PSA

FIGURE 4.1
Simplified process flow diagram for hydrogen reforming/PSA. (Adapted from Meyers, R.A., Handbook of Petroleum Refining Processes, 2nd edn.,
McGraw-Hill, New York, Chapter 6.2, 1997.)
 76
2. Reforming: The purified feedstock is reacted with
steam to form carbon monoxide and hydrogen:
° F and Ni Catalyst  m
C nH m + nH 2O 1500
→  n +  H 2 + nCO Fuel Gas
 2
(4.1)
The reaction is endothermic and occurs within the
process tubes of a reformer furnace in the presence
of nickel catalyst at approximately 1500°F (815°C).
3. Shift conversion: The water–gas shift reaction
is employed to convert the carbon monoxide
produced in the reforming step into additional
hydrogen and carbon dioxide:
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CO + H 2O → H 2 + CO 2 (4.2)
The shift conversion step is exothermic and is
conducted at approximately 650°F (343°C) in the
presence of a chromium/iron oxide catalyst.
4.
Hydrogen purification/PSA: Following the
shift conversion step, the hydrogen production
stream enters the PSA portion of the process.
Adsorbent beds remove the impurities (carbon
dioxide, carbon monoxide, methane, and nitro-
gen) and a small portion of the product. Typical
hydrogen recovery is 80% or greater, with prod-
uct purity of approximately 99.9 vol%.
The PSA unit must be frequently regenerated via
depressurization of the adsorbent beds. When depres-
surization occurs, PSA tail gas (sometimes referred to as
PSA waste gas) is produced at a pressure of about 5 psig
(0.35  kg/cm2g) or less. The PSA tail gas consists of the
impurities removed by the adsorbent beds, as well as
the hydrogen that is not recovered in the product stream.
The tail gas serves as the primary fuel for the reformer
furnace burners. Due to flame stability problems associ-
ated with firing the low-pressure, high-inert-concentra-
tion (carbon dioxide and nitrogen) PSA tail gas alone,
the PSA tail gas is typically supplemented by a light
refinery fuel gas. The PSA and refinery fuel gases are
fired in a dual-fuel burner specifically designed for the
steam reforming/PSA process. In this arrangement, the
PSA and refinery fuel gases enter the combustion zone
through separate fuel connections and burner nozzles.
The dual-fuel burners are capable of firing the two fuel
mixtures separately or simultaneously, with PSA gas never
providing more than 85 vol% of the total reformer fuel.
4.1.6  Flexicoking Waste Gas
Flexicoking waste gas is a low-pressure, low-energy
fuel gas produced by petroleum refiners as a by-prod-
uct of the Exxon Flexicoking process. Flexicoking is a
The Coen & Hamworthy Combustion Handbook
TABLE 4.5
Typical Composition of Flexicoking Waste Gas
Flexicoking Waste Gas
Composition (by Volume)
Component Sample 1 Sample 2
CH4 1.0% 0.8%
H2 20.0% 21.0%
CO2 10.0% 10.5%
CO 20.0% 18.6%
N2 45.0% 45.6%
H2O 4.0% 3.5%
H2S 150 ppm 0
COS 120 ppm 120 ppm
Total 100% 100%
Source: Adapted from Meyers, R.A., Handbook of Petroleum
Refining Processes, 2nd edn., McGraw-Hill, New
York, 1997.
continuous fluidized-bed thermal cracking process
used in the conversion of heavy hydrocarbon feedstocks
(typically heavy gas-oils from atmospheric and vacuum
distillation) to various gaseous and liquid hydrocarbon
products. Table 4.5 contains the approximate composi-
tion of two sample Flexicoking waste gas fuel streams.14
A simplified process flow diagram of the Flexicoking
process is shown in Figure 4.2. In the Flexicoking process,
hot (500°F–700°F or 260°C–370°C) gas-oil is injected into
the reactor vessel containing hot, fluidized coke particles.
Thermal cracking reactions inside the reactor vessel pro-
duce fresh petroleum coke that is deposited as a thin film
on the surface of existing coke particles inside the reactor
bed. Cracked vapor products exit the Flexicoking process
through the reactor vessel overhead stream for additional
downstream processing. Coke from the reactor vessel is
continuously injected into the top of a second fluidized
vessel, the coke heater, where it is heated and recycled
to maintain a reactor-bed temperature of 950°F–1000°F
(510°C–540°C). A portion of the coke fed into the top
section of the coke heater is injected into the bottom of
a third fluidized vessel, the gasifier. Inside the gasifier,
the coke is reacted with air and steam at approximately
1500°F–1800°F (820°C–980°C), producing a low-energy
fuel gas, or Flexicoking gas, consisting primarily of nitro-
gen, hydrogen, carbon monoxide, and carbon dioxide.
The Flexicoking gas flows from the top of the gasifier
to the bottom of the heater, where it provides the heat
necessary to maintain the reactor-bed temperature and
helps fluidize the coke heater bed. The high-­temperature
Flexicoking gas leaving the coke heater is used for high-
pressure steam generation before entrained coke fines are
removed in a cyclone/venturi scrubber system. Because
the low-energy gas stream leaving the Flexicoking pro-
cess contains substantial concentrations of H2S (~150 ppm
 Fuels 77

Tertiary Low Btu gas

cyclones to cleanup
To fractionator

Steam
generation

Scrubber

Start
Slurry
Dry fines Venturi
scrubber
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Gasifier
Reactor

Heater

Steam

Air
blower

FIGURE 4.2
Simplified process flow diagram for flexicoking. (From Meyers, R.A., Handbook of Petroleum Refining Processes, 2nd edn., McGraw-Hill,
New York, Chapter 12.1, 1997.)

by volume), the gas must first be sent through a hydrogen Having assembled this information, the following for-
sulfide removal system before it can be burned as fuel.9,13 mulae are used to calculate molecular weight:

∑ MW × y =
4.1.7  Physical Properties of Gaseous Fuels 1
MW = (4.3)
∑ x /MW
i i
i i
Tables 4.6 through 4.8 provide physical and combustion
property data for a large variety of common fuel gas
mixtures and their chemical components. where
MW is the molecular weight of the mixture
MWi is the molecular weight of component i
yi is the mole fraction of component i
xi is the mass fraction of component i
4.2  Gas Property Calculations
4.2.1  Molecular Weight Example 4.1

Molecular weight is the mass in grams of 1 g-mol of a
chemical compound. Avogadro’s number defines the
number of molecules in a gram-mole to be 6.02252 ×
1023, a fundamental constant. To determine the molecu-
lar weight of a mixture of gases, it is necessary to know
the molecular weight of each compound and the com-
position of the gases in terms of mole or mass fractions.
Given the mass percentages of 10% H2O, 25% CO2,
and 65% N2. Convert the mass percent to a vol-
ume percent basis.
Taking the mass percentage composition of each
gas and molecular weight will give the moles of
each gas per gram. The number of moles of H2O
in 1 g of mix gas will be 0.1 (gramH2O/gramMix) ×
(1 mol/18 g) = 0.0055 mol/g.
 78
TABLE 4.6
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Volumetric Analysis of Typical Gaseous Fuel Mixtures

Natural Gas (%) LPG (%) Refinery Gases (Dry) (%) Waste Gases (%)
Refinery Refinery
Fuel Gas Cracked Coking Reforming FCC Gas Gas PSA Flexicoking
Component Tulsa Alaska Netherlands Algeria Propane Butane Gas Gas Gas Gas Sample 1 Sample 2 Gas Gas
CH4 93.4 99 81 87 — — 65 40 28 32 36 53 17 1
C2H4 — — — — — — 3 3 7 7 5 2 — —
C2H6 2.7 — 3 9 — — 16 21 28 9 18 19 — —
C3H6 — — — — — — 2 1 3 15 8 6 — —
C3H8 0.6 — 0.4 2.7 100 — 7 24 22 25 20 14 — —
C4H8 — — — — — 100 1 — — — — — — —
C4H10 0.2 — 0.1 1.1 — — 3 7 7 0 2 1 — —
C5 and — — — — — — 1 — — — — — — —
higher
H2 — — — — — — 3 4 5 6 3 3 28 21

The Coen & Hamworthy Combustion Handbook

CO — — — — — — — — — — — — 10 20
CO2 0.7 — 0.9 — — — — — — — — — 44 10
N2 2.4 1 14 0 — — — — — 7 8 3 <1 45
H2O — — — — — — — — — — — — <1 3
O2 — — — — — — — — — — — — — —
H2S — — — — — — — — — — — — — —
Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC Press, Boca Raton, FL, 2001.
 Fuels
TABLE 4.7
Physical Constants of Typical Gaseous Fuel Mixtures
Natural Gas LPG Refinery Gases (Dry) Waste Gases
Refinery Refinery
Cracked Coking Reforming FCC Gas Gas PSA Flexicoking
Fuel Gas Component Tulsa Alaska Netherlands Algeria Propane Butane Gas Gas Gas Gas Sample 1 Sample 2 Gas Gas
Molecular weight 17.16 16.1 18.51 18.49 44.1 58.12 22.76 28.62 30.21 29.18 28.02 24.61 25.68 23.73
LHV (Btu/SCF) 913 905 799 1,025 2,316 3,010 1,247 1,542 1,622 1,459 1,389 1,297 263 131
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HHV (Btu/SCF) 1,012 1,005 886 1,133 2,517 3,262 1,369 1,686 1,769 1,587 1,515 1,421 294 142
Specific gravity 0.59 0.56 0.64 0.64 1.53 1.1 0.79 0.99 1.05 1.01 0.97 0.85 0.89 0.82
(14.696 psia/60°F,
Air = 1.0)
Wobbe number, 1,318 1,343 1,108 1,416 2,035 3,110 1,540 1,694 1,726 1,579 1,538 1,541 312 157
HHV/(SG1/2)
Isentropic coefficient 1.30 1.31 1.31 1.28 1.13 1.10 1.24 1.19 1.19 1.20 1.21 1.23 1.33 1.38
(Cp/Cv)
Stoichiometric air 10,554 10,567 10,554 10,525 10,369 10,371 10,402 10,379 10,322 10,234 10,311 10,375 9,667 8,265
required
(SCF/MMBtu)
Stoichiometric air 805 806 805 803 791 791 794 792 787 781 787 792 738 630
required
(lbm/MMBtu)
Air required for 15% 12,138 12,152 12,138 12,104 11,925 11,926 11,962 11,936 11,870 11,769 11,858 11,931 11,117 9,505
excess air
(SCF/MMBtu)
Air required for 923 924 923 920 907 907 910 908 903 895 902 907 845 723
15% excess air
(lbm/MMBtu)
Volume of dry 10,983 10,956 11,141 10,953 10,962 10,996 10,890 10,909 10,871 10,847 10,911 10,904 11,722 13,517
combustion products
(SCF/MMBtu)
Weight of dry 865 862 876 863 870 874 861 864 862 860 864 862 985 1,103
combustion products
(lbm/MMBtu)
Volume of wet 13,257 13,258 13,415 13,163 12,788 12,757 12,935 12,862 12,771 12,689 12,821 12,902 14,198 15,585
combustion products
(SCF/MMBtu)
Weight of wet 973 971 984 968 957 958 958 957 952 948 864 957 1,102 1,201
combustion products
(lbm/MMBtu)
AFT (°F) 3,306 3,308 3,284 3,317 3,351 3,351 3,342 3,348 3,359 3,371 3,353 3,345 3,001 2,856
Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC Press, Boca Raton, FL, 2001.
Note: All values calculated using 60°F fuel gas and 60°F, 50% relative humidity combustion air.

79
 80 The Coen & Hamworthy Combustion Handbook

TABLE 4.8
Physical Constants of Typical Gaseous Fuel Mixture Components
Gas Density Ideal Gas, 14.696
Specific Heat Latent Heat of psia, 60°F Btu/scf Heating Value
Boiling Vapor Capacity, Cp Vaporization
Btu/ft
3 Btu/lbm
Point Pressure 60°F and 14.696 psia and Specific Gas Specific
Fuel Gas Chemical Molecular 14.696 100°F 14.696 psia Boiling Point Gravity Density Volume LHV HHV LHV HHV
No. Component Formula Weight psia (°F) (psia) (Btu/lbm/°F) (Btu/lbm) (Air = 1) (lbm/ft3) (ft3/lbm) (Net) (Gross) (Net) (Gross)

Paraffin (alkane) series (CnH2n+2)

1 Methane CH4 16.04 −258.69 — 0.5266 219.22 0.554 0.042 23.651 909 1010 21,495 23,875
2 Ethane C2H6 30.07 −127.48 — 0.4097 210.41 1.038 0.079 12.618 1619 1770 20,418 22,323
3 Propane C3H8 44.10 −43.67 190 0.3881 183.05 1.522 0.116 8.604 2315 2516 19,937 21,669
4 n-Butane C4H10 58.12 31.10 51.6 0.3867 165.65 2.007 0.153 6.528 3011 3262 19,679 21,321
5 Isobutane C4H10 58.12 10.90 72.2 0.3872 157.53 2.007 0.153 6.528 3000 3252 19,629 21,271
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6 n-Pentane C5H12 72.15 96.92 15.57 0.3883 153.59 2.491 0.190 5.259 3707 4009 19,507 21,095
7 Isopentane C5H12 72.15 82.12 20.44 0.3827 147.13 2.491 0.190 5.259 3699 4001 19,459 21,047
8 Neopentane C5H12 72.15 49.10 35.9 0.3866 135.58 2.491 0.190 5.259 3683 3985 19,390 20,978
9 n-Hexane C6H14 86.18 155.72 4.956 0.3864 143.95 2.975 0.227 4.403 4404 4756 19,415 20,966

Napthene (cycloalkane) series (CnH2n)

10 Cyclopentane C5H10 70.13 120.60 9.917 0.2712 137.35 2.420 0.180 5.556 3513 3765 19,005 20,368
11 Cyclohexane C6H12 84.16 177.40 3.267 0.2901 153.25 2.910 0.220 5.545 4180 4482 18,849 20,211

Olefin series (CnH2n)

12 Ethene C2H4 28.05 −154.62 — — 207.57 0.969 0.074 13.525 1499 1600 20,275 21,636
(Ethylene)
13 Propene C3H6 42.08 −53.90 226.4 0.3541 188.18 1.453 0.111 9.017 2182 2333 19,687 21,048
(Propylene)
14 1-Butene C4H8 56.11 20.75 63.05 0.3548 167.94 1.937 0.148 6.762 2879 3080 19,493 20,854
(Butylene)
15 Isobutene C4H8 56.11 19.59 63.4 0.3701 169.48 1.937 0.148 6.762 2860 3068 19,376 20,737
16 1-Pentene C5H10 70.13 85.93 19.115 0.3635 154.46 2.421 0.185 5.410 3575 3827 19,359 20,720

Aromatic series (C0H2n-6)

17 Benzene C6H8 78.11 176.17 3.224 0.2429 169.31 2.697 0.206 4.857 3591 3742 17,451 18,184
18 Toluene C7H8 92.14 231.13 1.032 0.2598 154.84 3.181 0.243 4.118 4274 4475 17,672 18,501
19 o-Xylene C8H10 106.17 291.97 0.264 0.2914 149.1 3.665 0.280 3.574 4958 5210 17,734 18,633
20 m-Xylene C8H10 106.17 282.41 0.326 0.2782 147.2 3.665 0.280 3.574 4956 5208 17,734 18,633
21 p-Xylene C8H10 106.17 281.05 0.342 0.2769 144.52 3.665 0.280 3.574 4957 5209 17,734 18,633

Additional fuel gas components

22 Acetylene C2H2 26.04 −119 — 0.3966 — 0.899 0.069 14.572 1424 1474 20,769 21,502
23 Methyl CH3OH 32.04 148.1 4.63 0.3231 473 1.106 0.084 11.841 766 867 9,066 10,258
alcohol
24 Ethyl alcohol C2H5OH 46.07 172.92 2.3 0.3323 367 1.590 0.121 8.236 1448 1599 11,918 13,161
25 Ammonia NH3 17.03 −28.2 212 0.5002 587.2 0.588 0.045 22.279 359 434 7,966 9,667
26 Hydrogen H2 2.02 −423.0 — 3.4080 193.9 0.070 0.005 188.217 274 324 51,625 61,095
27 Oxygen O2 32.00 −297.4 — 0.2186 91.6 1.105 0.084 11.858 — — — —
28 Nitrogen N2 29.16 −320.4 — 0.2482 87.8 0.972 0.074 13.472 — — — —
29 Carbon CO 28.01 −313.6 — 0.2484 92.7 0.967 0.074 13.546 321 321 4,347 4,347
monoxide
30 Carbon CO2 44.01 −109.3 — 0.1991 238.2 1.519 0.116 8.621 — — — —
dioxide
31 Hydrogen H2S 34.08 −76.6 394.0 0.2380 235.6 1.177 0.090 11.133 587 637 6,537 7,097
sulfide
32 Sulfur dioxide SO2 64.06 14.0 88 0.1450 166.7 2.212 0.169 5.923 — — — —
33 Water vapor H2O 18.02 212.0 0.9492 0.4446 970.3 0.622 0.047 21.061 — — — —
34 Air — 28.96 −317.6 — 0.2400 92 1.000 0.076 13.099 — — — —
 Fuels 81

TABLE 4.8 (continued)

Physical Constants of Typical Gaseous Fuel Mixture Components
Unit Volume per Unit Volume of Combustible Unit Mass per Unit Mass of Combustible

Required for Required for Flammability

Stoichiometric Stoichiometric Stoichiometric Stoichiometric Limits (vol.%
Combustion Flue Gas Products Combustion Flue Gas Products in Air Mixture)
Fuel Gas
No. Component O2 N2 Air CO2 H2O N2 SO2 O2 N2 Air CO2 H2O N2 SO2 Lower Upper No.

Paraffin (alkane) series (CnH2n+2)

1 Methane 2.0 7.547 9.547 1.0 2.0 7.547 — 3.989 13.246 17.235 2.743 2.246 13.246 — 5.0 15.0 1
2 Ethane 3.5 13.206 16.706 2.0 3.0 13.206 — 3.724 12.367 16.092 2.927 1.797 12.367 — 2.9 13.0 2
3 Propane 5.0 18.866 23.866 3.0 4.0 18.866 — 3.628 12.047 15.676 2.994 1.624 12.047 — 2.0 9.5 3
4 n-Butane 6.5 24.526 31.026 4.0 5.0 24.526 — 3.578 11.882 15.460 3.029 1.550 11.882 — 1.5 9.0 4
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5 Isobutane 6.5 24.526 31.026 4.0 5.0 24.526 — 3.578 11.882 15.460 3.029 1.550 11.882 — 1.8 8.5 5
6 n-Pentane 8.0 30.186 38.186 5.0 6.0 30.186 — 3.548 11.781 15.329 3.050 1.498 11.781 — 1.4 8.3 6
7 Isopentane 8.0 30.186 38.186 5.0 6.0 30.186 — 3.548 11.781 15.329 3.050 1.498 11.781 — 1.3 8.3 7
8 Neopentane 8.0 30.186 38.186 5.0 6.0 30.186 — 3.548 11.781 15.329 3.050 1.498 11.781 — 1.3 8.3 8
9 n-Hexane 9.5 35.846 45.346 6.0 7.0 35.846 — 3.527 11.713 15.240 3.064 1.463 11.713 — 1.1 7.7 9

Naphthene (cycloalkane) series (CnH2n)

10 Cyclopentane 7.5 27.939 35.81 5.0 5.0 28.939 — 3.850 11.155 14.793 3.146 1.283 11.155 — — — 10
11 Cyclohexane 9.0 33.528 42.970 6.0 6.0 33.528 — 4.620 13.386 17.750 3.146 1.283 11.155 — 1.2 8.4 11

Olefin series (CnH2n)

12 Ethene 3.0 11.320 14.320 2.0 2.0 11.320 — 3.422 11.362 14.784 3.138 1.284 11.362 — 2.7 36 12
(Ethylene)
13 Propene 4.5 16.980 21.480 3.0 3.0 16.980 — 3.422 11.362 14.784 3.138 1.284 11.362 — 2.0 11.7 13
(Propylene)
14 1-Butene 6.0 22.640 28.640 4.0 4.0 22.640 — 3.422 11.362 14.784 3.138 1.284 11.362 — 1.6 10 14
(Butylene)
15 Isobutene 6.0 22.640 28.640 4.0 4.0 22.640 — 3.422 11.362 14.784 3.138 1.284 11.362 — 1.6 10 15
16 1-Pentene 7.5 28.300 35.800 5.0 5.0 28.300 — 3.422 11.362 14.784 3.138 1.284 11.362 — 1.3 10 16

Aromatic series (C0H2n-6)

17 Benzene 7.5 28.300 35.800 6.0 3.0 28.300 — 3.072 10.201 13.274 3.380 0.692 10.201 — 1.2 8.0 17
18 Toluene 9.0 33.959 42.959 7.0 4.0 33.959 — 3.125 10.378 13.504 3.343 0.782 10.378 — 1.2 7.1 18
19 o-Xylene 10.5 39.619 50.129 8.0 5.0 39.619 — 3.164 10.508 13.673 3.316 0.848 10.508 — 1.0 7.6 19
20 m-Xylene 10.5 39.619 50.129 8.0 5.0 39.619 — 3.164 10.508 13.673 3.316 0.848 10.508 — 1.0 7.0 20
21 p-Xylene 10.5 39.619 50.129 8.0 5.0 39.619 — 3.164 10.508 13.673 3.316 0.848 10.508 — 1.0 7.0 21

Additional fuel gas components

22 Acetylene 2.5 9.433 11.933 2.0 1.0 9.433 — 3.072 10.201 13.274 3.380 0.692 10.201 — 2.5 80 22
23 Methyl 1.5 5.660 7.160 1.0 2.0 5.660 — 4.498 4.974 6.482 1.373 1.124 4.974 — 5.5 44 23
alcohol
24 Ethyl alcohol 3.0 11.320 14.320 2.0 3.0 11.320 — 2.084 6.919 9.003 1.911 1.173 6.919 — 3.3 19 24
25 Ammonia 0.75 2.830 3.582 — 1.5 3.330 — 1.409 4.679 6.008 1.587 5.502 — 15.5 27 25
26 Hydrogen 0.5 1.887 2.387 — 1.0 1.887 — 7.936 26.323 34.290 8.937 26.353 — 4.0 74.2 26
27 Oxygen — — — — — — — — — — — — — — — — 27
28 Nitrogen — — — — — — — — — — — — — — — — 28
29 Carbon 0.5 1.877 2.387 1.0 — 1.887 — 1.410 1.897 2.468 1.571 — 1.870 — 12.5 74.2 29
monoxide
30 Carbon — — — — — — — — — — — — — — — — 30
dioxide
31 Hydrogen 1.5 5.660 7.160 — 1.0 5.660 1.0 4.682 6.093 0.529 4.682 1.880 4.3 45.5 31
sulfide
32 Sulfur dioxide — — — — — — — — — — — — — — — — 32
33 Water vapor — — — — — — — — — — — — — — — — 33
34 Air — — — — — — — — — — — — — — — — 34

Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC Press, Boca Raton, FL, 2001.
 82 The Coen & Hamworthy Combustion Handbook

The table presented here gives the number of compound and the composition of the gases in terms of
moles/gram of each gas and their normalized vol- mole or mass fractions. Having assembled this informa-
ume, calculated from the mole fraction of each gas tion, the following formulae are used to calculate heat-
to the total moles of mix gas. ing values:

Gas Mass Percent (%) mol/g

Normalized
Volume Basis (%)
HVv = ∑ HV
v,i × yi (4.4)

H2O 10 0.00555 16.11

CO2
N2
25
65
0.00568
0.0232
16.49
67.36
HVm = ∑ HV
m ,i × xi (4.5)

where
Example 4.2 HVv is the heating value of mixture, volume basis
HVv,i is the heating value of component i, volume basis
Find the density of flue gas at 350°F (180°C) and HVm is the heating value of mixture, mass basis
2 atm. The composition of the flue gas by volume
HVm,i is the heating value of component i, mass basis
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is 17% H2O, 6% CO2, and 77% N2.

To calculate the density of flue gas, one should
take the density of air at standard temperature Example 4.3
and pressure and molecular weights of flue gas
and dry air. The molecular weight of flue gas can Determine the HHV of a gas mixture comprised
be found by taking the volume percentages and of 60% natural gas and 40% H2 in Btu/ft3.
molecular weights of each gas. For the gas mixture, one should take 1 ft3 of
the gas mix coupled with the HHV of each indi-
vidual gas.
mole H 2 O g mole CO 2 g
MWFG = 0.17 × 18 + 0.06 × 44 The HHVs are presented as follows:
mole FG mol mole FG mol
CH4 = 1012 Btu/ft3
mole N 2 g g H2 = 325 Btu/ft3
+ 0.77 × 28 = 27.26
mole FG mol mol

For the molecular weight of air, it will be com- ft 3 CH 4 Btu ft 3 H 2 Btu Btu
0.6 3
× 1012 3 + 0.4 × 325 3 = 737.2 3
posed of 21% dry O2 and 79% N2, thus resulting in ft mix ft ft3 ft ft

 g   g  g Example 4.4
MWAir = 0.21  32 + 0.79  28 = 28.84
 mol   mol  mol
Determine the HHV of a gas mixture comprised
of 30% natural gas, 50% H2, and 20% N2. Calculate
Using the temperature of air at STP, one can solve heating values based on the mass of gases.
for the density of flue gas at the given tempera- Similar to the earlier example, one should take
ture and pressure: 1 lbm of mix gas with the heating values to get the
mixture HHV. The HHV of each gas based on
mass will be
 2   27.26   288  kg
ρFG = 1.2    = 1.46 3
 1   28.84   273 + 176  m CH4: 23,875 Btu/lbm
H2: 61,095 Btu/lbm

4.2.2  Lower and Higher Heating Values lbm CH 4 Btu lb H Btu

0.3 × 23, 875 + 0.5 m 2 × 61, 095
lbm mix lbm lbm mix lbm
The LHV of a gas is the heat released by combustion of
a specific quantity of that gas with the products of com- Btu
= 37 , 710
bustion remaining as vapor. The higher heating value lbm
(HHV) adds to the LHV the latent heat of any steam pro-
duced as a combustion product. It represents the total
4.2.3  Specific Heat Capacity
heat obtained by first burning a fuel and then cooling
the products to standard temperature. Heating values The specific heat capacity of a gas is the energy that must
may be provided on a volume basis, typically Btu/scf be added to a specific amount of the gas to raise its tem-
(kJ/m3), or a mass basis such as Btu/lbm (kJ/kg). perature by 1°. If the gas is maintained at constant pres-
To determine the heating value of a mixture of sure during this heating process, the value is referred
gases, it is necessary to know the heating value of each to as cp. If the gas is maintained at constant volume, the
 Fuels 83

value is referred to as cv. Specific heat is not a constant
for a given gas; it is a function of temperature. Specific
heat can be defined on a volume basis, typically Btu/
lbmol-°F (kJ/kgmol-°C); or on a mass basis such as Btu/
lbm-°F (kJ/kg-°C).
To determine the specific heat of a mixture of gases, it
is necessary to know the specific heat of each compound
at the mixture temperature and the composition of the
gases in terms of mole or mass fractions. Having assem-
bled this information, the following formulae are used to
calculate specific heat (cp and cv formulae are analogous,
only cp formulae are shown):
cp ( vol) = ∑c p,i ( vol) × yi (4.6)
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The specific heat of the gas mix coupled with the
molecular weight can be used to solve for the spe-
cific heat on a mass basis:
Btu 1 lbmol Btu
7.24 × = 0.265
lbmol °F 27.26 lbm lbm °F
4.2.4  Flammability Limits
Flammability limits define the range of fuel concentrations
in air that will sustain a flame without additional air or
fuel. The upper flammability limit (UFL) is the maximum
fuel concentration that can sustain a flame and the lower
flammability limit (LFL) is the minimum. These limits are
often tabulated for fuels at some standard temperature,
typically 60°F (16°C). Flammability limits are not constants

for a given gas; they are functions of the air/fuel mixture

cp (mass) = ∑c p,i (mass) × xi (4.7) temperature. An extensive discussion of this subject can be
found in the work of Coward and Jones.15
Wierzba and Karim16 present a method for estimating
where
the flammability limits as a function of mixture temper-
cp (vol) is the specific heat of mixture, volume basis
ature by calculating adiabatic flame temperature (AFT).
cp,i (vol) is the specific heat of component i, volume
First, the AFT for the standard temperature mixture is
basis
determined. Next, the mixture temperature is set to the
cp (mass) is the specific heat of mixture, mass basis
desired level and the fuel concentration is varied until
cp,i (mass) is the specific heat of component i, mass
the calculated AFT for the nonstandard temperature
basis
matches the AFT for the standard temperature. They
provide an approximating method for calculating AFT
Example 4.5 for sub-stoichiometric mixtures.
Both Coward and Jones and Wierzba and Karim indi-
Calculate the specific heat of a gas mixture on a
mole basis or mass fraction. The mixture consists
cate that a form of Le Chatelier’s rule can be used to
of 17% H2O, 6% CO2, and 77% N2. calculate LFL and UFL for many combinations of fuels
and inerts. Both references also mention that this rule
fails to accurately predict for a few important situa-
Btu/ Btu/ cal/ cal/ tions. One notable example is a mixture of ethylene and
Gas MW lbmol° F lbm · °F g · °C g · mole · °C carbon dioxide that differs substantially from normal
N2 28 6.94 0.248 0.248 6.94 calculated LFL and UFL. Another example is any mix-
H2O 18 8.02 0.445 0.445 8.02 ture of chemicals that is prone to react with another at
CO2 44 8.80 0.200 0.200 8.80 temperatures below the ignition point, such as ethylene
and hydrogen. Mixtures involving significant amounts
of inert compounds (e.g., H2O, N2, and CO2) require
The mix gas-specific heat, based on percentage special treatment either by the AFT method described
values, is calculated to be earlier or by grouping the inerts with fuel components
in known proportions matching conditions for which
moleH 2 O Btu mole CO 2 Btu LFL and UFL have been measured. This latter method
0.17 × 8.02 + 0.06 × 8.80
moleMix mole °F moleMix mole °F is described in detail by Coward and Jones.14
With these exceptions in mind, the following mixing
mole N 2 Btu Btu
+ 0.77 × 6.94 = 7.24 rules can be used to calculate LFL and UFL for most
moleMix mole °F lbmol °F
common gas mixtures:
100
Taking the molecular weight of the gas mixture LFL = (4.8)
will yield

∑ yi/LFLi

100
lbm UFL = (4.9)
∑ y /UFL
MWmix = 0.17(18) + 0.06 ( 44) + 0.77(28) = 27.26
lbmol i i
 84 The Coen & Hamworthy Combustion Handbook

4.2.5  Burning Velocity 4.2.6 Viscosity

Flame speed and burning velocity are terms that are Viscosity is discussed in detail in Chapter 8. A useful
often used for the rate of propagation of a flame through mixing rule is also provided.
a flammable mixture. The burning velocity is depen-
dent not only on the fuel gas composition, gas/air mix-
ture ratio and temperature of the mixture, but also on 4.2.7  Derived Quantities
the physical dimensions of the combustion device and
In addition to the specific properties described earlier,
the interaction of the flame with heat absorbing sur-
there are a number of useful derived parameters that
faces. Burning velocity is thus not an absolute value, but
may be of interest when studying combustion systems.
is measurement device dependent. Quoted values for
flame speed or burning velocity should include infor-
mation regarding the method of measurement. Since
4.2.7.1  Partial Pressure
the measured burning velocity is not an absolute value,
comparisons of burning velocities for various fuels Partial pressure is the pressure exerted by a single
must be made on the basis of data collected on identical component of a mixture when that component alone
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test instruments. occupies the entire volume at the mixture temperature.

Figure 4.3 shows burning velocity data for a variety Dalton’s law states that the total pressure of a mixture
of fuel gases. Note that the maximum velocity generally is the sum of the partial pressures of the components.
occurs in a fuel-rich mixture with less than 100% theo- While this law has been demonstrated to be somewhat
retical combustion air in the fuel/air mixture.8 in error, especially at high pressures, it is often useful

Blue water gas

3.6 9.0

Hydrogen
3.2 8.0
Burning velocity, ft/s (except hydrogen and acetylene)

Burning velocity, ft/s (hydrogen and acetylene only)

2.8 7.0

2.4 6.0
Ethylene
Acetylene

2.0 Carbureted 5.0

water gas

1.6 4.0
Coke oven gas
Carbon Illuminants
Butane
1.2 monoxide 3.0
Ethane

0.8 2.0
Producer
gas

0.4 Natural gas

Methane 1.0

Propane
0 0
0 20 40 60 80 100 120 140
Primary air, % of theoretical

FIGURE 4.3
Burning velocity for various gaseous fuels.
 Fuels 85

for estimating purposes to determine whether a more
detailed analysis is justified. The basic relationship is
pi = yi ↔ TP (4.10)
Partial pressures are of interest when estimating the
probability of forming condensate in a gas mixture.
When the partial pressure of a component exceeds the
vapor pressure of that component at the mixture tem-
perature, condensation is likely.
mixtures that also require enrichment and supplemen-
tal fuel firing to maintain ignition. Fertilizer plants and
other chemical plants produce ammonia, which may
be sent to a flare in an emergency. Waste gases that are
sent to flares in these facilities may be pure ammonia or
diluted with nitrogen or water vapor.
The variety of gases and the hazards associated with
each requires careful review of all aspects of system
design to ensure that these fuels are safely handled,
whether in a flare, a furnace, or an incinerator.

4.2.7.2  Adiabatic Flame Temperature

The AFT is the temperature at which the enthalpy of the
products of combustion equals the sum of the enthalpy
4.3  Liquid Fuels
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of the reactants plus the heat released by the combus-

tion process. Heat loss due to radiation, convection, or 4.3.1  Production, Refining, and Chemistry
conduction is not included; hence the reference to adia-
The primary concern for a typical refinery is to convert
batic. Accounting for dissociation of combustion prod-
a barrel of crude oil (42 U.S. gallons) into usable prod-
ucts is important. Customarily, the AFT is determined
ucts. A barrel of crude oil can typically be refined to
for a stoichiometric fuel/air mixture, although other
provide 11 gal of gasoline, 5.3 gal of kerosene, 20.4 gal of
mixtures such as LFL and UFL are sometimes studied
gas-oil and distillates, and 5.3 gal of heavier distillates.9
for special purposes, as discussed in Section 4.3.2.
The end products derived from crude oil number in the
thousands. Table 4.9 provides a listing of many of these
4.2.7.3  Other Special Cases products. The processes that produce these different
products are vast and complicated. Figure 4.4 provides a
Landfills and digester facilities produce an off-gas that
general refinery flow diagram.
must be disposed to prevent odor problems in the com-
munity. The gas is generally a mixture of CO2 and CH4. TABLE 4.9
Landfills are rarely above 30%–40% methane, while
Quantitative Listing of Products Made by the U.S.
digesters may be as high as 60%–70% methane. In some Petroleum Industry
landfills, perimeter wells are used to draw air into the
edges of the landfill, which prevents the spread of anaer- Product Classification Number of Individual Products
obic bacteria and methane. In these cases, the methane Lubricating oils 1156
content is even lower and some air is also sent to the flare. Chemicals, solvents, misc. 300
Marine and truck loading facilities burn the vapor Greases 271
displaced from the tankers or trucks during the loading Asphalts 209
operation. In many cases, the displaced vapor is mostly air Waxes 113
with some amount of evaporated gasoline or diesel fuel. White oils 100
Depending on the ambient temperature, the resulting mix- Rust preventatives 65
ture could be very rich in hydrocarbon vapor, or very lean. Diesel and light fuel oils 27
Medical equipment, such as bandages or hypodermic Motor gasolines 19
needles, is often sterilized by contact with ethylene oxide Residual fuel oil 16
(ETO) vapors. ETO sterilizer flares are designed to receive Liquified gases 13
the ETO vapor after the sterilization process is complete. Other gasolines 12
The composition coming to these flares generally con- Transformer and cable oils 12
sists of a mixture of ETO and either air or nitrogen. It Kerosenes 10
Aviation gasolines 9
should be noted that ETO has a flammability range from
Jet fuels 5
3% to 100% and a very low ignition temperature.
Carbon blacks 5
Flares are often used as backup equipment for inciner-
Cokes 4
ators during maintenance or malfunctions. In this type
Fuel gas 1
of service, the waste gas is usually enriched with a sub-
stantial amount of clean fuel gas to ensure reliable burn- Total 2347
ing. Steel mills produce off-gases that consist mainly of Source: Gary, J.H. and Handwerk, G.E., Petroleum Refining, 3rd edn.,
H2, H2O, CO, CO2, and air. These are generally low LHV Marcel Dekker, New York, 1994.
 86 The Coen & Hamworthy Combustion Handbook

Crude

Typical refinery
products

LPG and gas Vapor Refinery fuel

Crude
recovery gas
unit

Stabilizer Straight run gasoline

section LPG

Regular
gasoline
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Naphtha Hydro Reformate

Crude Reforming Premium
treating
unit gasoline

ATMOS
TWR Middle distillates Hydro Solvents
section treating
Aviation fuels

HVY atmos gas oil Catalytic Gasoline

cracking Diesels
VAC gas oil

Crude Heating oils

Fraction bottoms
unit

Treatingandblending
Lube oils
Vacuum Solvent
section extraction
Greases
Gasoline, naphtha,
Lube base stocks
Hydro and middle distillates
Asphalts
cracking

Lube oils Industrial

Solvent fuels
Propane dewaxing Waxes
deasphalter

Refinery
fuel oil
Gasoline, naphtha, and middle distillates
Visbreaker
Fuel oil

Asphalt

Delayed Gasoline, naphtha, and middle distillates

coker
Coke

FIGURE 4.4
Refinery flow diagram. (Adapted from Gary, J.H. and Handwerk, G.E., Petroleum Refining, 3rd edn., Marcel Dekker, New York, 1994.)
 Fuels
The primary chemical components of crude oil are
carbon, hydrogen, sulfur, oxygen, and nitrogen. The
percentages of these elements found in a crude oil are
most frequently used to characterize the oil. Two terms
frequently used when referring to crude oil are “sweet”
crude and “sour” crude. Sweet crude is oil that contains
less than 0.5 wt% sulfur, while sour crude contains greater
than 0.5 wt% sulfur. Sulfur content is of importance and
concern, due to the sulfur oxides that are produced during
combustion. SO2, for example, is a gas that has been shown
to contribute significantly to several different environ-
mental problems—namely, in acid rain formation and in
its ready conversion to sulfuric acid, H2SO4. The nitrogen
content of crude oil is of special interest to the combustion
industry due to the high levels of nitrogen oxides or NOx
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(see Chapter 10) produced during combustion of these
fuels (e.g., approximately 0.2 lb/MMBtu NOx or 142 ppm
can be attributed to “Fuel NOx” for an oil that contains
0.47 wt% nitrogen). Like SOx, NOx is an environmentally
damaging group of gases. Any time a fuel is burned in
air with a hot flame, NOx gases are produced. The greater
the flame temperature of the combustion, the greater the
amount of NO that will be produced. NO is then oxidized
to form NO2 (over a period of minutes or hours), which is a
major contributor to photochemical smog. In general, the
fate of SO2 and NO are intertwined, as can be seen by the
following reaction sequence17:
SO2 + OH− → HSO 3−
HSO 3− + O 2 → SO 3 + HOO −
SO 3 + H 2O → H 2SO 4 (g )
H 2SO 4 (g ) H
2O
→ H 2SO 4 (aq )
The following is a parallel reaction that takes place
between nitrogen oxide and the hydroperoxy radical,
thus producing more of the hydroxyl radical to feed the
aforementioned initial reaction:
HOO − + NO − → OH − + NO 2−
The overall reaction is then
SO 2 + NO − + O 2 H
2O
→ NO −2 + H 2SO 4 (aq)
Crude oil compositions are relatively constant.
However, slight deviations in composition can result in
vastly different refining methods. Crude oils also con-
tain inorganic elements such as vanadium, nickel, and
sodium, and usually contain some amount of water and
ash (noncombustible material). The main hydrocarbon
87
constituents of crude oils are alkanes (paraffins), cyclo-
alkanes (naphthenes), and aromatics.
Alkanes (also called paraffins after the Latin parum
affinis, “little affinity”) are those chemical structures
that are based on carbon atoms having only single bonds
and that are completely saturated with hydrogen atoms.
Some of the alkane hydrocarbons are listed in Table 4.8.
The basic chemical formula for an alkane is CxH2x+2,
where “x” is the number of carbon atoms present. Crude
oils can contain structures with up to 70 carbon atoms.9
However, the vast majority of the compounds contain
40 carbon atoms or less. When the number of different
constitutional isomers (different chemical connectivity
and different physical properties, yet identical chemi-
cal formulae) is considered (tetracontane [C40H82] has
over 62 trillion possible isomers18), it is evident that the
compositional diversity between differing crude oils is
almost limitless.
Cycloalkanes (cylcoparaffins or naphthenes) are
alkanes in which all or some of the carbon atoms are
arranged in a ring. When a cycloalkane contains only
one ring, the general formula is CxH2x. The most sta-
ble cycloalkane is cyclohexane, while cyclobutane and
cyclopropane are the least stable. The properties of
cycloalkanes are very similar to those of alkanes, as
shown in Table 4.8.
Aromatic compounds are those compounds that con-
tain at least one benzene-like ring. Benzene, discovered
in 1825, has a chemical formula of C6H6, and is stable
and nonreactive relative to alkanes and cycloalkanes.
Aromatics, such as the heterocyclic compounds pyridine
and furan, are composed of rings that contain elements
other than carbon. For example, the benzene ring contains
six carbon atoms, whereas the pyridine ring contains five
carbon atoms and one nitrogen atom. Properties of some
of the aromatic compounds are contained in Table 4.8.
It is worth mentioning the group of compounds called
alkenes (olefins). Alkene compounds do not occur natu-
rally in crude oil, but are produced by reaction during
the refining process. Therefore, it should be expected
that a refined end product will have some percentage of
ethylene, propylene, or butylene, for example. Alkenes
have the general formula of CxH2x and contain a carbon–
carbon double bond. Properties of some of the alkenes
are contained in Table 4.8.
When a crude oil is refined, the first step is, invariably,
distillation. The purpose of distillation is to separate
lighter components from heavier ones, based on their
respective volatility. The target of distillation is to sepa-
rate the crude oil into different fractions. Each fraction
consists of a boiling point range that will yield a mixture
of hydrocarbons; see Table 4.10. Some of these mixtures
can then be used as product (fuels, solvents, etc.) or fur-
ther refined into gasoline or other desirable mixtures.
Catalytic cracking is a typical process used to break
 88 The Coen & Hamworthy Combustion Handbook

TABLE 4.10 to gas flames, while heavier oils require a more compli-
General Fraction Boiling Points cated process and produce flames that are quite radiant
and more highly dependent on atomization techniques
Distillation Fraction Temperature Range
than the light oils. Oils are fired in burners by them-
Butanes and lighter <90°F selves, or in combination with fuel gas, waste gas, or
Gasoline 90°F–220°F both. Naphtha is frequently fired in combination with a
Naphtha 220°F–315°F PSA or other waste gas, and requires good vaporization
Kerosene 315°F–450°F to provide a quality flame.
Fuel oils 450°F–800°F
Residue >800°F 4.3.2 Oils
Source: Leffler, W.L., Petroleum Refining for the Non- According to the American Standard Testing Methods
Technical Person, Penn Well Publishing, Tulsa,
OK, 1985. With permission.
(ASTM) D-396, fuel oils are divided into grades, based
on the types of burners for which they are suitable.20 The
grades are determined by those values determined to be
down and rearrange alkane mixtures produced via dis-
most significant in figuring performance characteristics.
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tillation into smaller, highly branched alkanes by heat-

ing the mixtures to high temperatures in the presence of
a variety of catalysts. Figure 4.5 shows a fluid catalytic
cracking process.19 Due to the reactions that take place
during catalytic cracking, the product streams are gen-
erally heavier than the feed streams. Alkanes that are
more highly branched are desirable because they have
a higher octane rating than their unbranched cousins.
Of particular interest are the liquid fuels produced
during the various refining processes that are used
by the hydrocarbon and petrochemical industries.
Refineries frequently burn these liquid fuels in process
heaters so that the heat liberated during combustion can
be used to drive a more profitable process. Light fuel oils
are relatively easy to burn and produce flames similar
The two classifications that separate these fuel oils are “dis-
tillates” and “residuals,” where distillates indicate a distil-
lation overhead product (lighter oils) and residuals indicate
a distillation bottom product (heavier oils). Table 4.11 helps
in differentiating between these various classifications, and
Table 4.12 reveals typical analyses for these oils.
4.3.2.1  Light Oils
Grade 1 and 2 oils are light distillate (fuel) oils used
primarily in applications that do not require significant
atomization by air or steam in order to reduce droplet
size for proper burning. No. 1 oil will typically vapor-
ize when it comes into contact with a hot surface or gas.
No. 2 oil is significantly easier to burn than residual oil

Gas-
concentration
unit

Fuel gas
To C3C4 to treating
flue gas
system
Debutanized gasoline
Reactor

Naphtha
Main column
Regenerator

Light cycle oil

Heavy cycle oil

Main-column bottoms

Heavy recycle
(optional)

Air Fresh feed

FIGURE 4.5
Flow diagram of UOP fluid catalytic cracking complex. (From Meyers, R.A., Handbook of Petroleum Refining Processes, 2nd edn., McGraw-Hill,
New York, Chapter 3.3, 1997.)
 Fuels 89

TABLE 4.11
Requirements for Fuel Oils (per ASTM D 396)
No. 4 Distillate
Classification No. 1 Distillate No. 2 Distillate (Heavy) No. 6 Residual
Density (kg/m ) @ 60°F (15°C), max
3 850 876 — —
Viscosity @ 104°F (40°C) mm/s2
Min 1.3 1.9 >5.5 —
Max 2.1 3.4 24 —
Viscosity @ 212°F (100°C) mm/s2
Min — — — 15
Max — — — 50
Flash point °F (°C), min 100 (38) 100 (38) 131 (55) 140 (60)
Pour point °F (°C), max −0.4 (−18) 21 (−6) 21 (−6) —
Ash, % mass, max — — 0.1 —
Sulfur, % mass, max 0.5 0.5 — —
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Water and sediment, % vol., max 0.05 0.05 0.5 2.0

Distillation temperature °F (°C)
10% volume recovered, max 419 (215) — — —
90% volume recovered, min — 540 (282) — —
90% volume recovered, max 550 (288) 640 (338) — —
Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC Press, Boca Raton, FL, 2001.

TABLE 4.12
Typical Analysis of Different Fuel Oils
No. 1 No. 2 No. 4 No. 6 Fuel
Fuel Oil Fuel Oil Fuel Oil Oil (Sour)
Ash (%) <0.01 <0.01 0.02 0.05
Hydrogen (%) 13.6 13.6 11.7 11.2
Nitrogen (%) 0.003 0.007 0.24 0.37
Sulfur (%) 0.09 0.1 1.35 2.1
Carbon (%) 86.4 86.6 86.5 85.7
Heat of combustion 20,187 19,639 19,382 18,343
(HHV), Btu/lb
Specific gravity 0.825 0.84 0.898 0.97
60°F/60°F
Density (lb/U.S. 6.877 6.96 7.488 8.08
gal)

Source: Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC
Press, Boca Raton, FL, 2001.

due to the reduced amount of atomization and preheat-

ing requirements. Atomization is the breaking apart of a
liquid into tiny, more easily combustible, droplets using
steam, air, fuel gas, or mechanical means. These light
distillate oils will typically distill out between 450°F
and 800°F (230°C and 430°C).
4.3.2.2  Heavy Oils
No. 4 oil is a heavy distillate oil typically blended from,
and thus having characteristics of, both light distillates
and residual oils. These oils do not readily combust and
therefore require some type of atomization, but still fall
into a viscosity range that does not require preheating
prior to burning (Figures 4.6 and 4.7).
FIGURE 4.6
Burner firing heavy oil no. 1. (From Baukal, C.E. (ed.), The John Zink
Combustion Handbook, CRC Press, Boca Raton, FL, 2001.)
4.3.2.3  Residual Oils
No. 6 oil is a heavy residual oil sometimes referred to as
Bunker C oil. This oil requires significant atomization for
proper combustion. Due to its high viscosity, No. 6 oil
requires heating during handling and further heating prior
to combustion chamber injection. No. 6 oil is usually pre-
heated to 150°F–200°F (66°C–93°C), to decrease its viscos-
ity, before being atomized and injected into the burner.
 90 The Coen & Hamworthy Combustion Handbook

TABLE 4.13
Naphtha Elemental Analysis
Component Vol%
n-Heptane 1.610
Methylcyclohexane 2.433
2-Methylheptane 5.618
4-Methylheptane 1.824
3-Methylheptane 4.841
1c,3-Dimethylcyclohexane 3.252
1t,4-Dimethylcyclohexane 1.040
1t,2-Dimethylcyclohexane 1.169
n-Octane 16.334
1c,2-Dimethylcyclohexane 1.674
1,1,4-Trimethylcyclohexane 3.500
2,6-Dimethylheptane 2.094
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1c,3c,5-Trimethylcyclohexane 2.638
m-Xylene 2.426
p-Xylene 0.797
2,3-Dimethylheptane 1.475
4-Methyloctane 3.417
2-Methyloctane 4.491
3-Methyloctane 4.576
o-Xylene 1.137
n-Nonane 10.120
Other 23.534
Total 100.000

320
FIGURE 4.7
Burner firing heavy oil no. 2. (From Baukal, C.E. (ed.), The John Zink 310
Combustion Handbook, CRC Press, Boca Raton, FL, 2001.)
300
Temperature,°F

4.3.3  Liquid Naphtha 290

Liquid naphtha is similar in its characteristics to kerosene 280

(Table 4.13). Figure 4.8 shows a typical naphtha distilla-
tion curve. In general, naphtha will boil out of a mixture
between 220°F and 320°F (100°C and 160°C). Naphtha is
categorized, based on its volatility, into light, intermedi-
ate, and heavy naphtha. Naphtha is a major constituent
of gasoline; however, it generally requires further refin-
ing to make suitable quality gasoline. Prior to firing naph-
tha in a burner, care must be taken to vaporize it so that
the combustion will be more complete and uniform.
4.3.4  Physical Properties of Liquid Fuels
When liquid fuels are encountered, there are certain
properties that determine into which category they are
divided, and for what processes they are suitable.
4.3.4.1  Flash Point
The flash point of a liquid is the lowest temperature at
which enough vapors are given off to form a mixture
270
260
250
240
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Cumulative percent volume
FIGURE 4.8
Naphtha distillation curve. (From Baukal, C.E. (ed.), The John Zink
Combustion Handbook, CRC Press, Boca Raton, FL, 2001.)
that will ignite when exposed to an ignition source.
The standard method for determining flash point is
ASTM D-93. Under certain conditions, ASTM D-56 can
be used for light distillate oils. Some flash point values
are provided in Table 4.11. The flash point is an impor-
tant property for indication of volatility and for storage
requirements.
 Fuels 91

4.3.4.2  Pour Point When the Reynolds number is less than 2100, the flow
is typically streamlined and smooth, and called lami-
The pour point of a liquid is determined by ASTM D-99
nar. However, when the Reynolds number increases
and indicates the lowest temperature at which an oil
above 2100, internal agitation takes place, and the flow
will flow at a controlled rate. If the fluid temperature
is considered turbulent. As seen in the Equation 4.11, as
goes below this point, flow will be inhibited.
the viscosity increases, the flow becomes more laminar,
assuming the other properties stay constant. Viscosity is
4.3.4.3 Distillation divided into two different categories: kinematic viscos-
ity and absolute viscosity.
The distillation of a liquid gives an indication of its vola-
Kinematic viscosity (ν) is dependent on fluid den-
tility, as well as the ease with which it can be vapor-
sity, and has units of length 2/time. Typical units for
ized. The test evaluates the vaporization range of a fuel
kinematic viscosity are stokes (0.001 m 2/s), centistokes
between its end point (the point at which 100% of the
(stoke/100), Seconds Saybolt Universal (SSU), and
volume has vaporized) and the initial boiling point (the
Seconds Saybolt Furol (SSF). Because the density of
point at which the liquid begins to vaporize). Figure 4.9
a fluid is dependent on temperature, the viscosity of a
shows a typical crude oil distillation curve.
Downloaded by [RMIT University Library] at 22:20 30 October 2017

fluid is likewise dependent on temperature. As the

temperature increases, the viscosity of a fluid will
4.3.4.4 Viscosity decrease (become more fluid or less viscous), and vice
versa.
In layman’s terms, the viscosity is a fluid’s resistance to
Absolute viscosity (μ) can be calculated by multi-
flow. Technically, the viscosity is the ratio of shear stress
plying the kinematic viscosity by the density of the
to shear rate of a fluid in motion. Most fluids under con-
fluid. The most common units for absolute viscosity
sideration in this chapter (gases, fuel oils) are Newtonian
are the poise (1 Pa s) and the centipoise (cp), which is
fluids because the ratio given earlier is constant with
poise/100.
respect to time, at a given temperature and pressure.
The viscosity of oil is a very important consideration
A  very important factor in the determination of fluid
in proper burner design. As previously mentioned, the
flow is the dimensionless quantity called the Reynolds
more viscous the fluid, the more preheating required
number. The Reynolds number is calculated as
prior to burning. Several useful conversions are listed
DVρ DV as follows:
Re = or Re = (4.11)
µ ν
1 lbm/ft h = 0.00413 g/cm · s
where
D is the pipe diameter 0.000413 kg/m · s
V is the fluid velocity 1 cP = 0.01 P
ρ is the fluid density 0.01 g/cm · s
μ is the fluid absolute viscosity 0.001 kg/m · s
ν is the fluid kinematic viscosity
6.72 × 10−4 lbm/ft s
1000
900 Residue
1 St = 0.0001 m2/s = 100 cSt
800 centistokes = (0.266 × SSU) − (195/SSU) for SSU 32–100
Boiling temperature, °F

700 (0.220 × SSU) − (135/SSU) for SSU > 100

Gas-oil
600
See also Table 4.11 and Figure 4.10.
500
400 Kerosene
300 4.3.4.5 Density, Gravity, Specific Volume,
Naphtha
200 and Specific Weight
Gasoline
100 Density is a fluid’s mass per unit volume, and is impor-
Butanes and lighter
0 tant due to its effect on other properties, such as viscos-
0 10 20 30 40 50 60 70 80 90 100
ity. Additionally, the density is used to calculate the heat
Cumulative percent volume
capacity of an oil. The densities of liquids are frequently
FIGURE 4.9
given as the American Petroleum Institute (API) gravity
Crude oil distillation curve. (From Baukal, C.E. (ed.), The John Zink or the specific gravity (SG). Density and specific gravity
Combustion Handbook, CRC Press, Boca Raton, FL, 2001.) are related in that a liquid with a specific gravity of 1 has
 92 The Coen & Hamworthy Combustion Handbook

–30 –20 –10 0 10 20 30 40 50 60 70 80 90 100 120 140 160 180 200

200,000
500,000
50,000
20,000 100,000
10,000 50,000
5,000 20,000
2,000 10,000
5,000
1,000
3,000
400 2,000

200 1,000
600

N
o.
100

6
400
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75
300
Kinematic viscosity, centistokes

50
No
40 200
.5
he
No

30
av 100
.4

y
No

20

Viscosity, SSU
.5

15 80
lig
ht

10 60

8
50
No

6
.2

5
40
4

3
35

2
32

0.5
–20 0 20 40 60 80 100 120 140 160 180 200 240 280 320 360 400

Temperature, °F

FIGURE 4.10
Viscosity of fuel oils. (From Baukal, C.E. (ed.), The John Zink Combustion Handbook, CRC Press, Boca Raton, FL, 2001.)

a density of 1 kg/m3 (62.4 lb/ft3). The specific gravity of a Water is frequently used as a reference substance
liquid can be calculated by the formula and, at 60°F (16°C), has a specific gravity of 1.0 and a
ρ density of 1.94 slugs/ft3 (999 kg/m3), where 1 slug =
SG = (4.12) 1  lbf ft/s2. Specific gravity for gases requires an addi-
ρref
tional assumption relating to pressure and tempera-
where ture. Gas-specific gravity is defined relative to air as the
ρ is the density of the substance in question at specific reference substance and is generally determined at a
conditions standard temperature and pressure. Under those condi-
ρref is the density of a reference substance at a specific tions, gas-specific gravity can be calculated as the ratio
condition of molecular weights.
 Fuels 93

Example 4.6
In a typical combustion situation, determine
the  molecular weight of flue gas at 15% excess
air, the wet O2 percent, and dry O2 percent pres-
ent in the flue gas. Assume natural gas as the
working fluid.
Following the general combustion equation, the
balanced stoichiometric equation will be
CH 4 + 2φ [ O2 + 3.76 N2 ]
The specific volume (volume per unit mass) is the
reciprocal of the density, and is commonly used in ther-
modynamic calculations.
The specific weight of a fluid (γ) is defined as its weight
per unit volume. The relationship that relates specific
weight to the density is γ = ρ × g, where ρ is the density,
and g is the local acceleration (32.174 ft/s2 or 9.81 m/s2).
The specific weight of water at 60°F (16°C) is 62.4 lbm/ft3
(9.80 kN/m3).

→ CO 2 + 2H 2 O + 2φ  O 2 + 3.76 N 2  − 2O 2 4.3.4.6  Heat Capacity (Specific Heat)

The heat capacity, or specific heat, of a fluid is defined as
where ϕ = 1 + EA%. the amount of heat that is required per unit mass to raise
The following table provides the calculated the temperature by 1°. Typical units of heat capacity are
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byproducts per mole of CH4 Btu/(lbm · °R) or kJ/(kg · K) in SI units. Heat capacity is

temperature dependent, and is defined in terms of con-
stant volume or constant pressure, as can be calculated
Moles/ by the following equations:
Mole CH4
Moles/Mole CH4 @ 15% EA Grams/Mole CH4
 δh 
Cp =  (4.14)
CO2 1 1 1 × 44 = 44  δT  p
H2O 2 2 2 × 18 = 36
O2 2ϕ−2 0.3 0.3 × 32 = 9.6
 δh 
Cv =  (4.15)
 δT  v
N2 7.52ϕ 8.648 8.648 × 28 = 242.1

The molecular weight of flue gas will be the total where

mass of resultant products divided by the
total moles produced, as can be seen here:
g FG
MWFG = ( 44 + 36 + 9.6 + 242.1)
mole CH 4
1 mole CH 4
× = 27.66
(1 + 2 + 0 .3 + 8 .648 ) mol
l e FG
The wet and dry O2 products formed will be
the moles of O2 produced divided by the total
moles including and excluding moles of H2O,
respectively:
Cp is the heat capacity at constant pressure
Cv is the heat capacity at constant volume
δh is the change in enthalpy
δT is the change in temperature
To calculate the heat capacity of a petroleum liquid, to
g within 2%–4% accuracy, the following equations can be
mol employed:
0.388 + (0.00045 × °F )
C= for units of Btu/(lbm -°R )
SG
(4.16)

1.685 + (0.039 × °C )
0.3 C= for units of kJ/(kg-K ) (4.17)
O 2 wet = × 100 = 2.51% SG
11.948

0.3 where
O 2dry = × 100 = 3.0%
11.948 − 2 C is the heat capacity
SG is the specific gravity (relative density), so long as
°API is inversely proportional to specific gravity; the liquid temperature is between 32°F and 400°F
therefore, as °API increases, the density decreases. (0°C and 205°C) and the specific gravity is between
When a fluid and water are compared at 60°F (16°C), the 0.75 and 0.96 at 60°F (16°C)8
°API can be calculated as
Further information about gaseous and liquid fuels
141.5 and their properties can be obtained from the references
°API = − 131.5 (4.13)
SG listed at the end of this chapter.21–24
 94
References
1. U.S. Energy Information Administration, Natural Gas
Data Report, Natural Gas Reserves Summary as of
December 31, December 30, 2010.
2. U.S. Energy Information Administration, Total Energy
Data Report, Annual Energy Review, October 19, 2011.
3. Reed, R.J., North American Combustion Handbook, Vol. I,
North American Mfg. Co., Cleveland, OH, 1986.
4. Gas Processors and Suppliers Association, GPSA
Engineering Data Book, Vol. I, 10th edn., GPSA, Tulsa, OK,
1987.
5. Austin, G.T., Shreve’s Chemical Process Industries, 5th edn.,
McGraw-Hill, New York, 1984.
6. Gas Processors and Suppliers Association, GPSA
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Engineering Data Book, Vol. II, 10th edn., GPSA, Tulsa,
OK, 1987.
7. McCabe, W.L., Smith, J.C., and Harriot, P., Unit
Operations of Chemical Engineering, 5th edn., McGraw-
Hill, New York, 1993.
8. Perry, R.H., Green, D.W., and Maloney, J.O., Eds., Perry’s
Chemical Engineers’ Handbook, 7th edn., McGraw-Hill,
New York, 1997, Chapter 27.
9. Leffler, W.L., Petroleum Refining for the Non-Technical
Person, PennWell Publishing, Tulsa, OK, 1985.
10. Gary, J.H. and Handwerk, G.E., Petroleum Refining, 3rd
edn., Marcel Dekker, New York, 1994.
11. Reed, R.D., Furnace Operations, 3rd edn., Gulf Publishing,
Houston, TX, 1981.
The Coen & Hamworthy Combustion Handbook
12. Nelson, W.L., Petroleum Refining Engineering, 3rd edn.,
McGraw-Hill, New York, 1949.
13. Meyers, R.A., Handbook of Petroleum Refining Processes,
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