Introduction to Oxidation

and
Mass & Energy Balances
Michael Mannuzza
IT3/HWC
OBG
Baltimore
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2016
 Combustion
• Combustion is an oxidation reaction:
Fuel + O2 ---> Products of Combustion + Heat Energy

• In addition to traditional burner fuels,

incinerator fuel can include solid, gaseous and
liquid waste.
IT3/HWC • The Products of Combustion (POC) are the
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primary concern from an Air Pollution Control
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2016 (APC) perspective.
 Air Pollutants and Regulatory Drivers
• The type of APC system required for an incinerator will be decided
based on the system’s POCs and the regulatory limits mandated
for specific pollutants.
• Emissions of the following pollutants are typically regulated for
most incinerator applications:

IT3/HWC • Dioxin/Furans • NOx

• Mercury (Hg) • Particulate Matter
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• Carbon Monoxide
• Low-Volatility Metals (As, Be, Cr) • HCl & Cl2
• SOx • Others
 Identifying APC Requirements
Three Steps:
1. Quantify anticipated POCs
2. Identify Regulatory Emission
Constraints (establish abatement
requirements)
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3. Quantify the discharge flow rate of
the system.
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 Waste Feed Properties
I. Begin by identifying the properties of the waste feed and
quantifying the constituency of the waste:
1. Material Take-Offs
2. Proximate, Ultimate, and Ash Analysis
3. Sample & Analyze for Specific Compounds
4. Employ Other Empirical Methods
PROXIMATE ANALYSIS ULTIMATE ANALYSIS ASH ANALYSIS
Category wt % Category wt % Category wt %
IT3/HWC Moisture 3.3 Carbon (C) 61.1 Silicon Dioxide (SiO2) 74.1
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2016 Volatile Matter 27.3 Nitrogen (N) 1.35 Iron Oxide (Fe2O3) 3.25
Fixed Carbon 47.3 Sulfur (S) 0.4 Calcium Oxide (CaO) 0.68
Gross Calorific Value 24.73 Oxygen (O) 8.8 Magnesium Oxide (MgO) 0.48
Other 25.25 Other 1.49
*Ash Fusion Point = 1104 ⁰C
 Waste Feed Properties
•If possible, identifying specific compounds in the waste is the
best approach.

GASEOUS WASTE STREAMS LIQUID WASTE STREAMS

COMPOUND NAME % VOLUME COMPOUND NAME Wt. %
Methane 56.33 - 66.40 Toluene 8.4 -11.0
Ethane 1.27 - 3.8 Xylene 1.2 – 3.1
Propane 0.75 -1.2 Propanol 1.9 -17.1
Butane 0.05 -1.0 Isopropylbenzene 0.08 – 9.3
IT3/HWC Acetic Acid 0.5 – 0.9
Octane 0.02 -.08
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2016 Carbon Monoxide 17.40 -21.0 Methyl Bromide 0.9 -1.5
Benzene 0.00 -0.21 Formaldehyde 1.1 -6.7
Toluene 0.00 – 0.46 Sodium Fluoride 1.0 – 1.5
Methylene Chloride 0.01 – 0.8 Hydrogen Chloride 4.5 – 9.5
Water (g) 2.95-23.93 Water (L) 21.3 – 78.42
 Waste Feed Properties
I. Waste feed rates and constituencies are rarely constant. It is
important to establish a realistic waste feed design basis. The
waste feed design basis must address the following:
I. Worst case feed rate
II. Highest heating value condition (kJ/kg of waste)
III. Lowest heating value condition (kJ/kg of waste)
IV. Worst case sulfur condition, chlorine condition,NOx condition, metals
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condition, particulate condition, etc.
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V. Any other critical regulatory or production related criteria associated
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 Stoichiometry of Combustion
I. As a starting point, it is necessary to make some Initial
assumptions. If adequate Oxygen will be made available for
complete combustion, assume the following:
I. All Carbon converts toCO2
II. All halogens convert to acids (e.g., Cl  HCl, Br  HBr)
III. All alkali metals convert to hydroxides (e.g., Na  NaOH)
IV. All remaining hydrogen converts to H2O
IT3/HWC V. All non-alkali metals convert to metal oxides in their most common
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VII. All Sulfur converts to SO2
VIII. Non-combustible constituents pass through unchanged or thermally
decompose to known compounds
 Stoichiometry of Combustion
I. In reality, it is possible that additional products or congeners can
be formed.
I. SO3
II. Diatomic Halogens (Cl2, Br2 )
III. N2, NO, N2O
IV. CO
V. Dioxin/Furans
VI. Others
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II. Formation of these tertiary compounds can be a function of:
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II. Contaminant Concentrations
III. O2 and H2O Concentrations
IV. Catalysts
V. Other factors
 Stoichiometry of Combustion
I. The initial assumptions outlined usually provide a reasonable
estimate of the products of combustion that are generated.
I. Allows the elemental contaminants to be quantified.
II. Provides a mechanism for identifying combustion air requirements and
exhaust flow rates

II. The resulting POCs can then be refined if necessary by applying:

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I. Empirical Data
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II. Advanced Methods
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 Stoichiometry of Combustion
• Example: Dichlorobenzene, C6H4Cl2
C6H4Cl2 + ?O2  ?CO2 + ?H2O + ?HCl

C6H4Cl2 + 6.5O2  6CO2 + 1H2O + 2HCl

1. Balance Carbon atoms first

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2. Balance halogens, metals, Nitrogen & Sulfur next.
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4. Balance Oxygen atoms last
 Stoichiometry of Combustion
1. Balance Carbon & CO2 first:
C6H4Cl2 + ?O2  ?CO2 + ?H2O + ?HCl
How many moles of CO2?
Answer: 6
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C6H4Cl2 + ?O2  6CO2 + ?H2O + ?HCl
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 Stoichiometry of Combustion
2. Balance halogens, metals, Nitrogen & Sulfur next:
C6H4Cl2 + ?O2  6CO2 + ?H2O + ?HCl
How many moles of HCl?
Answer: 2
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C6H4Cl2 + ?O2  6CO2 + ?H2O + 2HCl
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 Stoichiometry of Combustion
3. Balance Hydrogen atoms:
C6H4Cl2 + ?O2  6CO2 + ?H2O + 2HCl
How many moles of H2O?
Answer: 1
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C6H4Cl2 + ?O2  6CO2 + 1H2O + 2HCl
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 Stoichiometry of Combustion
4. Balance Oxygen atoms last:
C6H4Cl2 + ?O2  6CO2 + 1H2O + 2HCl
How many moles of O2?
Answer: 6.5
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C6H4Cl2 + 6.5O2  6CO2 + 1H2O + 2HCl
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 Stoichiometry of Combustion – Mass Balance
C6H4Cl2 + 6.5O2  6CO2 + 1H2O + 2HCl
Compound: C6H4Cl2 O2 CO2 H2O HCl
Molecular Wt. (g/mol): 147.004 32.00 44.011 18.0158 36.461
No. of Moles: 1 6.5 6 1 2
1Total Wt. (g): 147.004 208.00 264.066 18.0158 72.9218
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2Normalized Ratio: 1 1.415 1.796 0.123 0.496
1Total Wt. =
(Molecular Wt.) * (No. of Moles)
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6 4 2
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Thus: 1kg C6H4Cl2 + 1.415kg O2  1.796kg CO2 + 0.123kg H2O + 0.496 kg HCl
Same applies for grams, pounds or any unit other unit of mass.
 Stoichiometry Calculations
This approach can be applied to each constituent identified in a waste stream:
STEP 1: Balance the moles

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STEP 2: Balance the mass
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 Stoichiometry Calculations
• Each constituent can be factored by its mass ratio and then summed to
generate a representative compound that reflects the properties of the
overall waste stream.
• Similarly, a weighted calculation can be performed to determine the net
heat of combustion of the waste stream.

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 Heat of Combustion
Definitions:
• Heat of Combustion: The heat released by combustion of a unit
quantity of fuel with its stoichiometrically correct amount of
combustion air, measured either in calories or Btu.
• Gross Heating Value:The heat released by combustion of a unit
quantity of fuel with both the combustion air and fuel at a known
reference temperature prior to combustion (e.g. 60 ⁰F) after the
IT3/HWC products of combustion are allowed to cool to the initial
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temperature. Also known as Higher Heating Value (HHV).
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• Net Heating Value: The heat release measured prior to the
products of combustion being allowed to cool. Also known as
Lower Heating Value (LHV).
 Heat of Combustion
• For most incinerator applications, we are concerned only with the
LHV of the fuel/waste.
• Numerous data sources are available (reference books, internet,
etc.).
• Can be estimated or obtained through testing.
• Heat of formation
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• Dulong’s Approximation (Btu/lb = 14,544C+62,028(H2-0.125O2)+4,050S)
• Empirical formula based on coal.
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• Can be applied to other carbonaceous waste, but accuracy is questionable.
2016 • 410 Btu (103.3 kcal) per Mole of O 2 Consumed
• Good approximation for hydrocarbons.
• Accuracy diminishes if Oxygen, Nitrogen, Halogens and other elements are present.
 • Mass of exhaust stream
Mass & Energy Balance constituents (solid, gas)
• Heat content of constituents
Mass in = Mass out
Energy in = Energy out

Thermal losses

Control volume • Mass of burner fuel and

IT3/HWC combustion air
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2016 burner fuel
• Mass of waste stream
constituents (solid, liquid, gas)
• Heat content of constituents
• Net heat of combustion of
combustibles
 Mass & Energy Balance
Conservation of Mass & Energy
mstream1 + mstream2 + mstream3 =mstream4
Qstream1+Qstream2+Qstream3 =Qstream4 + Thermal Losses

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 Mass & Energy Balance –Key Points
I. Mass in must equal mass out (m in – mout = 0).
II. Energy in must equal energy out (Q in – Qout = 0).
III. Combustion air volume will generally be a direct function of the
fuel input, however, additional air may be needed to maintain
O2 levels or control temperature.
IV. Adjust the mass of the fuel input until the system energy is
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balanced.
I. Cannot solve directly - must be an iteration.
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II. The Goalseek function in Excel is useful for this approach (modulate
2016 fuel input until Qin – Qout = 0
III. Determine energy of waste gas streams by applying specific
heats.
 Mass & Energy Balance
Conservation of Mass & Energy
mstream1 + mstream2 + mstream3 =mstream4
Qstream1+Qstream2+Qstream3 =Qstream4 + Thermal Losses

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 Applying Specific Heats
• Q=m* Cp*DT
• Q = Heat flow (Btu/hr, MJ/hr, Watts, etc.)
• m = mass flow (lb/hr, kg/hr, etc.)
• Cp = Constant pressure specific heat (Btu/lb-⁰F, J/kg-⁰K, etc.)
• DT = Temperature difference between actual temperature and reference
temperature (T-Tref) (⁰F, ⁰C, etc.)
• Specific heat varies based on temperature and is tabulated for
commonly encountered gases in many reference books. It is also
IT3/HWC frequently presented as a polynomial function of temperature.
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• A very accurate mean Cp can be obtained by integrating this
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polynomial across the temperature range.
Cpmean = ∫[a + bT +cT2]/(T-Tref)  [a(T-Tref)+(1/2)b(T2-Tref2)+(1/3)c(T3-Tref3)]/(T-Tref)
 Radiation Losses
Shell losses are a function of Furnace Radiation Losses1
numerous variables: Furnace Rate (MBtu/hr) Radiation Losses (%)
• Shell temperature <10 3
15 2.75
• Wind velocity 20 2.5
• Shell color 25 2

• Shell area 30 1.75

IT3/HWC >35 1.5
• Emissivity 1 Handbook of Incineration Systems, Brunner, C.
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 Mass & Energy Balance
Conservation of Mass & Energy
mstream1 + mstream2 + mstream3 =mstream4
Qstream1+Qstream2+Qstream3 =Qstream4 + Thermal Losses

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 Converting Mass to Volume
• When calculating process emissions, we routinely need to convert
between mass & volume.
• Avogadro’s Law: Equal volumes of all gases under the same
conditions of temperature and pressure contain the same number
of molecules.
• Definitions & Conversions:
• lb-mol = mass (lbs) ÷ MW
IT3/HWC • 1 lb-mol = 386.728 ft3 @ 70 ⁰F and 14.6959 psi
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• 1 g-mol = 22.414 L @ 0 ⁰C and 760 mm Hg

• ppmv = 106 * Volume of Component ÷ Overall Volume

 Converting Mass to Volume
• Volume is temperature & pressure dependent. It is common to
normalize volume to a standard temperature, to facilitate mass/volume
conversions
• Nm3/hr & m3/hr
• m3/hr = Nm3/hr * (273 + T)/(273 +Tref)
• T = Process Temp. (⁰C)
• Tref = Reference Temp. (⁰C) usually 0 ⁰C

• SCFM & ACFM

IT3/HWC • ACFM = SCFM *(460+ T)/(460 +Tref)
• T = Process Temp. (⁰F)
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• Tref = Reference Temp. (⁰F)
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• Be aware, different reference temps are used for SCFM
• 60 ⁰F, 68 ⁰F, 70⁰F

• Nm3/hr * 0.6341 = SCFM (@ 70 ⁰F)

 Converting Mass to Volume
I. Volume is also effected by pressure, including pressure
due to elevation changes:
I. SCFM is referenced to standard atmospheric pressure at sea -
level = 14.6959 psi (406.8 inches H2O)
II. Nm3/hr is referenced to 760 mm Hg.
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III. When pressure effects must be accounted for:
I. ACFM =SCFM *(406.8/ Pactual)*(460+T)/530
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 Combustion Air
Composition of Dry Atmospheric Air Typical C.A. Constituency (Assumed)
Gas Volume % Weight % Volume
Nitrogen 78.084% Nitrogen 76.85 79.1
Oxygen 20.946% Oxygen 23.15 20.9
Argon 0.9340%
Carbon Dioxide 0.0397%
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Neon 0.001818%
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Methane 0.000179%
 Excess Air
• Excess Air: The air remaining after a fuel has been completely
burned or that air supplied in addition to the amount required for
stoichiometric combustion.
• Increased O 2 content can enhance combustion, or it can lead to
the formation of problematic compounds (i.e., SO3, CO2, NO2)
• Excess air may be required to control exothermic temperature rise
or flammability levels.
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• Regulatory emission limits are typically referenced to a specific O2
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level and a correction factor must frequently be applied to actual
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ppmvcorrected = ppmvtest * [21-%O2base]/[21-O2test]
 Particulate Matter
• Particulate Matter (PM) can be solid, or liquid aerosol.
• Can include condensables
• Particle Size Distribution (PSD) is important.
• Will drive APC Technology Selection
• Determined by source testing.
• Units for PM
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• Micrograms per dry cubic meter (μg/m3)
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• 7,000 gr = 1 lb
• Measurements are dry basis
 QUESTIONS?
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