THE CONTROL OF BOILERS 2nd Edition SAM G.

DUKELOW

5-7 Combustion Chemistry and Products of Combustion For all fuels, the actual chemical process is the oxidation of the hydrogen and the oxygen in the fuel by combining them with oxygen from the air. The nitrogen from the air and any other noncombustibles in the fuel pass through the process with essentially no chemical change. A minimal amount of nitrogen in the air combines with oxygen to form nitrous oxides (NOx), which pollute the air. Some fuels contain a small percentage of sulphur, which-when burnedresults in sulphur oxides that pollute the air. These may also corrode the boiler if the flue gas containing them is allowed to cool below the dew point. Figure 5-10 demonstrates the basic chemical process and the chemical elements and compounds involved in complete and incomplete combustion. For any fuel, a precise amount of combustion air is needed to furnish the oxygen for complete combustion of that fuel's carbon and hydrogen.The precise amount of combustion air is called thc theoretical air for that particular fuel.If the fuel analysis is known, the theoretical air requirements can be calculated easily.

The amounts of carbon and oxygen for complete combustion of carbon are represented by the formula:

Weights equivalent to the molecular weight in pounds combine. One molecule of carbon containing one atom of carbon combines with one molecule of oxygen containing two atomsof oxygen to form one molecule of carbon dioxide containing one atom of carbon and two atoms of oxygen.

As with the carbon combustion, weights equivalent to the molecular weights in pounds combine. Two molecules of hydrogen, each containing two atoms of hydrogen, and one molecule of two atoms of oxygen make two molecules of water, with a total of four atoms of hydrogen and two atoms of oxygen. A simple example of the many incomplete combustion reactions resulting in intermediate hydrocarbon compounds is the partial combustion of carbon, resulting in carbon monoxide rather than carbon dioxide.

In this case some of the potential heat energy from the carbon remains in the carbon monoxide.

With the right conditions of time, temperature, and turbulence, and by adding more oxygen to the carbon monoxide, the carbon monoxide will further oxidize to carbon dioxide, releasing the second part of the heat energy from the original carbon.

The common chemical reactions in combustion are shown in Table 57, with the heat energy resulting from the combustion reaction. Figures 5-9 and 5- 10 and Table 5-7 identify those products of combustion that are produced by the oxidation of the hydrogen, carbon, or sulfur present in the fuel. As indicated, the combustion process produces heat, but a low percentage of the heat produced is not useful in transferring heat to the boiler water. As hydrogen combines with oxygen during the combus-tion process to form water, the combustion temperature vaporizes the water into superheated steam. This vaporization absorbs the latent heat for producing the steam from the hot combustion gases. As the gases pass through the boiler and exit from the system, the gases retain the vaporized water in the form of superheated steam, and the latent heat and any remaining sensible heat are lost from the process.

The amount of latent heat loss is determined by the hydrogen content of the fuel. If the fuel is natural gas and thus is higher in % hydrogen, the latent heat loss is greater than if the fuel were coal, which is lower in % hydrogen. The effect on boiler efficiency for different fuels is shown in Figure 5- 1 1 .

Since this latent heat is not useful to a combustion process, the fuel is said to have a gross and a net heating value or a higher (HHV) or a lower (LHV) heating value. It is important to keep in mind that combustion air must be furnished for the total combustion or on the basis of the HHV, while only the LHV has any effect on the heat transfer of the system. Figure 5-12 demonstrates with a coal analysis how the difference between these two heating values can be calculated.

5-8 Theoretical Air Requirements and Relationship to Heat of Combustion Using the combustion chemistry formulas, if the fuel analysis is known, the theoretical amount of oxygen can be calculated. The amount of oxygen can easily be converted to a quantity of combustion air due to the known content of oxygen in air. An example of this calculation using a formula developed from the combustion equations and the known content of oxygen in air is given in Figure 5-13. In this example the amount of air theoretically required to produce 10,000 Btu is also shown. Table 5-8 is a tabulation of combustion constants that is useful in simplifying such calculations. Figure 5-14 demonstrates using the table of combustion constants for a gaseous fuel of 85 percent methane and 15 percent ethane.

Note that the amount of combustion air required to produce 10,000 Btu is nearly the same for coal and natural gas. If the reciprocals are taken, the result is Btu/lb of air. Table 5-9 shows that for coal, oil, or gas the Btu/lb of air is approximately the same evcn though the Btu/lb of the fuels is radically different. The difference between the Btu/lb of air on a net basis for these fuels is smaller than that shown in the table. The fact that combustion air requirements can be closely approximated, based on the heat requirement, is an important concept used in the application of combustion control logic.

5-9 The Requirement of Excess Combustion Air In actual practice gas-, oil-, coal-burning, and other systems do not do a perfcct job of mixing the fuel and air even under the best achievable conditions of turbulence. Additionally, cqmplete mixing may take too much time-so that the gases pass to a lower temperature area not hot enough to complete the combustion-before the process is completed.If only the amount of theoretical air were furnished, some fuel would not burn, the combustion would be incomplete, and the heat in the unburned fuel would be lost. To assurc complete combustion, additional combustion air is furnished so that every molecule of the fuel can easily find the proper number of oxygen molecules to complete the combustion.

This additional amount of combustion air that is furnished to complete the combustion process is called excess air. Excess air plus theoretical air is called total air. Having this necessary excess air means that some of the oxygen will not be used and will leave the boiler in the flue gases, as shown in Figure 3-4, which describes the fuel and air chemicals mass balance. The oxygen portion of the flue gas can be used to determine the percentage of excess air. If the percentage of excess air is increased, flame temperature is reduced and the boiler heat transfer rate is reduced. The usual effect of this change is the increase in the flue gas temperature, as shown in Figure 5-15.

If oxygen in the flue gas is known or can be measured and no table or curve is available, the following empirical formula provides a close approximation of the percentage of excess air. This formula is based on dry basis percentage oxygen. The excess air calculation based on wet basis percentage oxygen is a complex formula based on the wet basis percentageoxygen and the complete fuel analysis by weight basis percentages of its constituents.

Measurements of either percentage of carbon dioxide or the percentage of oxygen in the flue gas or both are used to determine percentage of excess air, but the percentage of oxygen is preferred for the following reasons: (1) Oxygen is part of the air-if oxygen is zero, then excess air is zero. The presence of oxygen always indicates that some percentage of excess air is present. (2) The percent of carbon dioxide rises to a maximum at minimum excess air and then decreases as air is further reduced. It is thus possible, with the same percentage of carbon dioxide, to have two different percentages of total combustion air. For this reason, the per-centage of carbon dioxide cannot be used alone as a flue gas analysis input to a combustion control system.

(3) To determine excess air with the same precision, greater precision of measurement is required for the percentage of carbon dioxide method than for the percentage of oxygen method. (4) The relationship between the percentage of oxygen and the percentage of excess air changes little as fuel analysis or type of fuel changes, while the percentage of carbon dioxideto- excess air relationship varies considerably as the percentage of carbon-to-hydrogen ratio of the fuel changes.

The heat loss in the flue gases essentially depends upon the difference between the temperature of the flue gases and that of the incoming combustion air, the amount of excess air, and the fuel analysis. There is an optimum amount of excess air because less air will mean unburned fuel from incomplete combustion, and more air will mean complete combustion but more heat loss in the flue gas due to the greater mass of the flue gases.

The amount of excess air required depends upon the type of fuel, burner design, fuel characteristics and preparation, furnace design, capacity as a percent of maximum, and other factors. The amount for any installation should be determined by testing that particular unit.An approximate amount of excess air required for full capacity is shown in Table 5-10.

The charts in Figures 5-16, 5-17, and 5-18 show the relationship between the flue gas analysis by volume and the percentage of excess air for natural gas, fuel oil, and coal. While these curves are for fuels with specific fuel analyses, the curves for % oxygen vs. excess air are quite similar, while the % carbon dioxide vs. excess air curves are quite different for the different fuels.

These curves also show the difference between the flue gas analysis depending upon the presence or removal of the water vapor that is formed by the combustion process. This difference is important to note for two reasons. Since approximately 1970, flue gas analyzers for % oxygen using the zirconium oxide fuel cell principle have been marketed. This type of % oxygen analyzer, which analyzes the flue gas on the wet basis, is now the standard method for permanently installed flue gas analysis equipment. On the other hand, 7% oxygen vs. excess air formulas, including the one in the text above, are based on the dry basis, which was universally used until the early 1970s.

In addition, these newer zirconium oxide analyzers normally measure the % oxygen on a net basis. If combustible gases such as CO are present, the high temperature and catalytic action of the measuring cell complete the combustion by subtracting a portion or all of the oxygen passing the analysis cell. It is thus not necessary to subtract C02 from the % oxygen before it is used in the older formulas. Since these formulas are on the dry basis, however, it is necessary to convert the wet basis analyzer readings to dry basis before using them in the older equations for combustion calculations.

In analyzing flue gases to determine % excess air, it is useful to have a check on the accuracy of the analysis. Figure 5-19, which is based on dry basis analysis, can be used for this purpose. By drawing a straight line, as shown, between the % oxygen and the % carbon dioxide values, there is an intersection with the hydrogen-carbon ratio line.

When using a particular fuel of a certain H/C ratio, the intersection should always be at the same point on the line. If it is not, the fuel has changed or the results of the analysis are incorrect. If the fuel analysis is known, the measurement of % oxygen can be used to determine the correct % carbon dioxide, or the % carbon dioxide can be used to determine the correct % oxygen. If boiler tests are being made and the fuel analysis is constant, any data (within limits of measurement accuracy) that doesn't measure up to this kind of examination should be thrown out.