1) ADIABATIC FLAME TEMPERATURE OF CH4COMBUSTION WITH EXCESS AIR (EXAMPLE

AFT)

Calculation of the adiabatic flame temperature for CH4combustion vs. amount of excess air used.
See text, Problem 6.7.

Example Description:

The combustion of hydrocarbon fuels is the most common way to provide heat for materials
processing needs. One of the ways to rank fuels is by their adiabatic flame temperature (AFT),
using either stoichiometric air or O2 for the oxidant. The stoichiometric amount of oxidant is
calculated by assuming complete combustion of the hydrocarbon to CO2 and H2O. (If the fuel
contains S, combustion is to SO2). This example will show how the AFT is calculated for various
amounts of air in excess of stoichiometric amounts (called XSA combustion). Air is assumed to be
79% N2and 21% O2. The units used in this example are °C and kJ.

Data:

Equation [1] shows the standard reaction for the combustion of methane for the formation of
water vapor as the product. The stoichiometric amount of air is 9.524 moles. For reactants
entering at 25°C, the heat content of the product gases plus ΔH°rx at 25°C must equal 0 for
adiabatic conditions. Taking data from FREED’s Reaction tool:

[1]

Calculations and Results:

There are at least two different ways to calculate the AFT. One way is to pick an AFT, and calculate
the % excess oxidant amount. The other is to select the oxidant amount and calculate the AFT. This
example uses the latter approach. Since we are solving for the AFT, we need an explicit equation
for the heat content as a function of temperature, where the lowercase t indicates °C. An
examination of the data indicates that Cp is very close to a linear function of t above about 1200°C,
so the functional equation for Ht-H25 is a quadratic:

Ht-H25= A (t) + B (t²) + C [2]

Excel’s Graphics tool was used to determine values of A, B, and C for each product species
between 1200 and 2000°C. Figure 1 shows the results. The value of R² =1, thus indicating that the
quadratic equation gives an extremely good fit to the data. The H t-H25 equation parameters were
converted from J to kJ, and copied to rows 40 and 44. The mass balance relationships for various
amounts of % excess air are shown in Table I. A heat balance for combustion was written by taking
the sum of all heat effect parameter terms in cells C33:H35; the term for C includes the ΔH°rx for
Equation [1]. A heat balance equation was written in cells D48:I48, using an initial estimate of the
AFT of 1700 in row 47. Super Goal Seek was used to calculate the value of t for each value of %
excess air, and plotted in Figure 2. The AFT varied from about 2050°C at stoichiometric air, to
1200°C at double the stoichiometric air. Excel’s Trend line tool was used to fit a quadratic formula
to the data line in Figure 3. The equation is shown in a text box on the Figure. The value of R² is
0.9995, which indicates an acceptable fit for a heat balance problem. Care should be taken in
making AFT calculations above 2000°C using the stoichiometry written in Equation [1]. This is
because even with excess air, some CO and H2will be present in the gas, and even small amounts
of O, H, and N. If the air is enriched with O2, the calculated AFT may be well above 2500°C, but
the actual AFT will be significantly less.

Another way to calculate adiabatic reaction temperatures is to use FREED’s Reaction option. For
example, 26% XSA has 12 moles of air to one mole of CH4and produces 0.52 moles of O2and 9.48
moles of N2 (in addition to two moles of H2O and one mole of CO2). The column labeled Heat in
Table II is the sum of the heat of reaction plus the heat content of the reaction products, and will
equal zero at the AFT. Figure 3 shows a chart of the results; the heat equals zero about 1740°C.
Excel’s Trend line tool gives the following equation (units are J):

Heat = 0.01752t2 + 463.117t – 854,840 [3]

The equation was solved for Heat = 0 by Goal Seek to find the AFT = 1732°C. This procedure can
be repeated for each value of %XSA of interest, which generates a family of lines on the chart. You
should check this using the textbox equation in Figure 2. FREED’s Reaction tool has an even easier
way to calculate the AFT—use the Calculate feature from the floating toolbar. Enter 0 for the
value, and check the Overall Heat box, and FREED will calculate the temperature where the overall
heat is zero. You can repeat this several times, and use the set of results to create a chart like
Figure 3.

Assignment

Calculate the AFT for the burning of C with air to give a product gas that contains 8% CO2 when
using less than, and more than, the stoichiometric air Note that when using less than
stoichiometric air, the product gas will contain a considerable amount of CO, so the material
balance here takes more arithmetic than for excess air. Try using FREED’s Reaction tool for this
assignment. It will also tell you if your reaction is not balanced correctly.

2) HEAT BALANCE FOR CALCINATION FURNACE WITH HEAT EXCHANGER (EXAMPLE CHX)

Calculation of the heat balance on a process for calcination of MgCO3, including a heat exchanger
to preheat the combustion air. See text, Chapter 6.

Example Description:

Calcination is a process whereby a complex compound (usually a carbonate, hydroxide or sulfate)

is heated to a temperature such that the complex compound decomposes to the oxide. In this
case, MgCO3is heated in a fluidized-bed furnace heated by combustion of CH4to produce MgO.
The MgCO3and CH4enter at 25°C, and the MgO and furnace gases leave at 650°C. The furnace
gases pass through a heat exchanger to preheat the combustion air, thus increasing the efficiency
of the process (in terms of fuel consumption per amount of MgCO3calcined). A sketch of the
process is shown below. The objective of this example is to calculate the effect of air preheat
temperature on amount of MgCO3 calcined, and the temperature of the furnace gases leaving the
heat exchanger. The basis is 1 mole of CH4burned with 11 moles of air (15.5% excess air), and heat
losses of 60,000 J in the calcination furnace and 40,000 J in the heat exchanger,
Data:

The first step is to obtain information about the heat content of the various reactions and streams
involved in the process. FREED’s Reaction tool is the best way to obtain information on the
amount of heat produced by burning CH4with 11 moles of air and by calcining MgCO3 and heating
the products to 650°C. The combustion reaction is:

CH4(g) + (11)N1.58O42(g) →CO2(g) + 2H2O(g) + (8.69)N2(g) + (0.31)O2(g) [1]

The reaction tool found that the sum of combustion heat plus the sensible heat of the product
gases at 650°C was –556,100 J. (Note we have rounded off the heat value to 4 significant figures,
which is quite adequate considering the uncertainties associated with heat losses.) A similar
calculation for MgCO3calcination plus heating the products to 650°C gave an overall heat effect of
176,400 J/mol. The use of FREED’s Reaction tool is not shown on the worksheet because it was
shown before, and it is a rather straightforward FREED application.

Next, we need an equation for the heat content of air and CO2. FREED’s Graphics tool and
Trendline was used to obtain a quadratic heat content equation for air, as shown in Figure 1 of the
worksheet:

Ht-H25 for air = 28.44t + 0.00338t2– 700 (J/mol) [2]

Ht-H25for CO2= 38.43t + 0.01289t2– 1050 (J/mol) [3]

Finally, we need a heat content equation for the products of combustion from Equation [1].
FREED’s Reaction tool is used by putting the reaction products on both sides of the reaction
equation. ΔH°rx is zero because there is no chemical change, so the Heat column simply reflects
the heat content of the products. Figure 2 on the worksheet displays the results for 12 moles of
combustion gas. A linear heat content equation appeared satisfactory for this situation:

Ht-H25 for 12 moles of combustion gas = 404.42t – 17820 (J) [4]

Calculations and Results:

We start with a heat balance around the calcinerby assuming various air preheat temperatures,
and calculate the amount of MgCO3calcined. Table I shows the results on worksheet CHX. Row 35
expresses the results in practical terms of the volume of natural gas required to produce one
tonne of MgO. Heating the combustion air to 600°C cuts the natural gas consumption to about
72% of the requirement for no air preheat.

Next, we look at the heat exchanger, which operates in a counter-current mode. If the heat
exchanger operated at 100% efficiency and no heat loss, the maximum air preheat temperature
would be 650°C. However, we do have heat loss, and no exchanger is 100%efficient in transferring
heat, so the highest air preheat temperature will probably be<600°C. Table II shows the heat
balance calculations for the heat exchanger. The heat available for transfer to the air is shown in
row 41.The heat balance around the heat exchanger is written in row 43 such that when the
correct warm furnace gas temperature (in row 42) is entered, the sum of heat effects = 0. An initial
estimate of 500 for the warm furnace gas temperature was inserted in row 42, and Super Goal
Seekused to calculate the value that closed the heat balance. Figure 3 shows a summary of the
results. Equations relating two of the process parameters were derived from Figure 3 as a function
of the air preheat temperature (apht).

Warm furnace gas temperature = –0.551(apht) + 592 [5]

Volume of CH4 (STP m3) per tonne of MgO produced = 4.45 × 10-5(apht) 2– 0.124(apht) + 201 [6]

Assignment:

What is the effect of cutting the combustion air to 10% XSA? What is the effect of cutting the heat
losses in half for the calcination furnace?

3) THE CALCINATION OF DOLOMITE (EXAMPLE DOL)

Example Objective: Calculate the products formed by the stepwise thermal decomposition of
dolomite and mixtures of dolomite with calcite and magnesite. Concepts: gas-solid equilibria,
the Phase Rule, and thermal decomposition. See text, Chapter 12 and 13.

Example Description:

Calcination is the decomposition of complex compounds into simpler ones, plus the evolution of a
gas. This occurs when the compound is heated to a point where the decomposition products are
more stable than the original compound. The simplest case is the calcination of a carbonate to
form an oxide and CO2. Another name for calcination is thermal decomposition, because thermal
energy is the only driving force for the reaction (i.e., no reactant is necessary, just heat). The
thermal decomposition temperature is defined as the temperature where the sum of the partial
pressures of the gaseous decomposition products is 1 atm. The calcination of MgCO 3 is discussed in
Section 12.2 of the text. This example will show the procedure for calculating the decomposition
temperature for mixtures of carbonates in the CaO–MgO–CO 2 system

Data:

Magnesite and calcite decompose to their respective oxides and CO2according to Equation [1]
and [2]. The calcination of dolomite could produce a mixture of CaO + MgCO3, or a mixture of
MgO + CaCO3as shown in Equations [3] and [4]. FREED’s Reaction tool was used to obtain
thermodynamic data for Equations [1] and [2] as shown in Table I. Note that an alternative form of
CaCO3, aragonite, is not as stable as calcite.

CaCO3 (calcite) →CaO (lime) + CO2 (g) [1]

MgCO3 (magnesite) →MgO (magnesia) + CO2 (g) [2]

CaMg (CO3)2 (dolomite) →CaO(c) + MgCO3 (magnesite) + CO2 (g) [3]

CaMg(CO3)2(dolomite) →CaCO3(calcite) + MgO(magnesia) + CO2(g) [4]

Calculations and Results:

The calcination of dolomite CaMg (CO 3)2 is more complex than for a single carbonate. The CaO–
MgO–CO2system is effectively a 3-component system because the gas phase can be considered as
containing only CO2.*Thermal decomposition of dolomite could produce a mixture of CaO +
MgCO3, or a mixture of MgO + CaCO3. The correct situation can be determined by comparing the
ΔG°rx for Equations [3] and [4] from Table II of worksheet DOL. Alternatively, a comparison of
log(pCO2) can be made; log(pCO2) is identical to logKeq when both the carbonate and the oxide
are present. Equation [4] has a much lower ΔG° and hence is the first reaction to take place when
dolomite is heated to the calcination temperature. Figure 1 shows a plot of ΔG°rx for Equations
[1], [2], and [4]. The temperature where these lines cross the ΔG°rx= 0 line indicates a thermal
decomposition temperature for dolomite of about 690 K. The thermal decomposition
temperatures for magnesite and calcite alone are about 680 and 1160 K. A more accurate
decomposition temperature can be obtained from FREED’s Reaction tool by setting logKr = 0 and
calculating T. Table III shows the results for the decomposition of dolomite; the decomposition
temperature is 419°C. A similar calculation was made for the decomposition temperatures of
MgCO3and CaCO3, and the temperatures are shown on the ternary phase diagram.

The above results now permit the construction of the phase diagram for the CaO–MgO–
CO2system as shown below. The 3-condensed-phase fields are labeled with the temperature at
which the pCO2= 1 atm. The dashed lines emanate from the CO2apex.

Calcination of an initial mixture of magnesite and dolomite occurs along line x–x′″. First the
magnesite decomposes at 407°C (from x to x′), then the dolomite decomposes according to
Equation [4] at 419°C (from x′ to x″), and then the calcite decomposes at 891°C (from x″ to x′″). A
mixture of dolomite and calcite decomposes along line y–y″, first by decomposition of dolomite at
419°C, then calcite at 891°C. Dolomite itself decomposes in the same sequence as a mixture of
dolomite and calcite.
Assignment:

Dolomite is heated in a gas produced by the combustion of 1 mole of CH4and 10 moles of air. At
what temperature will the dolomite start to decompose?