THEORETICAL INTRODUCTION TO THE USE OF A RESIDUAL OXYGEN MEASUREMENT METHOD FOR THE ANALYSIS OF COMBUSTION AIR REQUIREMENT INDEX

(CARI) AND WOBBE INDEX OF FUEL GASES.

Ann McGowan BTU Product Manager COSA INSTRUMENT Corporation Houston, TX 77028 Jim Hawkins Engineering Manager COSA INSTRUMENT Corporation Houston, TX 77028

KEYWORDS
Combustion Air Requirement Index, CARI, Wobbe Index, Fuel Gas, Stoichiometric Air to Fuel Ratio, Requirement Stoichiometric Air Requirement, Air/Fuel Ratio

ABSTRACT
A Residual Oxygen Measurement Method can be used to directly measure the Combustion Air Requirement Index (CARI) of a natural gas and other fuel gases. When the amount of energy supplied to the burners is required, CARI can be directly correlated to the Wobbe Index of the fuel gas. This paper will review how to calculates a fuels Stoichiometric Air to Fuel Ratio requirement, CARI and discuss CARIs relationship to the Wobbe Index.

INTRODUCTION
In the Residual Oxygen Measurement method, a continuous gas sample is mixed with dry air at a precisely maintained constant ratio. This fuel air mixture is then oxidized in a combustion furnace in the presence of a catalyst at 800C. A zirconia oxide cell is used to determine the residual oxygen concentration in the combusted sample. The residual oxygen is a direct measurement of the Combustion Air Requirement Index (CARI), a dimensionless parameter indicating how much air is required for the stoichiometric combustion of a fuel

gas. CARI can be mathematically correlated to the Wobbe Index of the fuel gas for an indication of the amount of energy supplied to the burner. However, to understand the residual oxygen measurement method, one must be familiar the stoichiometric air requirement, the definition of CARI and its relationship to the Wobbe Index. Lastly, the effect of alkenes, hydrogen, and carbon monoxide on the relationship between CARI and the Wobbe Index will be discussed.

STOICHIOMETRIC AIR/FUEL RATIO1

The Stoichiometric Air Requirement of a gas is the amount of dry air required to completely combust one mole of fuel gas. A simplified combustion equation using Methane as the fuel is typically written as: CH4 + O2 CO2 + 2H2O (1)

Equation (1) can be re-written to represent any hydrocarbon fuel whereby the hydrocarbon is represented by CxHy. Balancing the equation you now have: CxHy + (x + y/4) O2 xCO2 + (y/2)H2O (2)

In looking at this combustion equation (2), the stoichiometric requirement for oxygen, s, can be defined as s = (x + y/4),

(3)

However, this equation represents using pure oxygen for combustion. But normally, combustion takes place using air not pure oxygen. Taking into account the use of air as your source of oxygen, equation (2) now becomes CxHy + (x + y/4) (O2 + 3.785N2) xCO2 + (y/2)H2O + 3.785 (x + y/4)N2 (4)

Although there are other components such as Argon and Carbon Dioxide in air, for the equation (4), we assumed that air is made up of 20.9% oxygen and the rest (79.1%) is made up of Nitrogen. Based upon these percentages, for every O2 moles in air you will have 3.785 N2 moles. (79.1/20.9 = 3.785). Note that Nitrogen does not add to the combustion, but it is included to insure the equation is balanced. Since, Air is only 20.9% Oxygen, for complete combustion to occur, for every mole of a hydrocarbon fuel you will require: 4.785s moles of air [moles air] [moles fuel] (5)

Using equation (5) the air requirement for complete combustion can be calculated for any hydrocarbon. Table 1 shows a table of selected hydrocarbons and their corresponding air requirements.2,3 TABLE 1 AIR TO FUEL RATIO REQUIREMENT FOR THE COMBUSTION OF SELECTED ALKANES

COMPONENT
METHANE ETHANE PROPANE n-BUTANE i-BUTANE PENTANE i-PENTANE HEXANE HEPTANE OCTANE

FORMULA
CH4 C2H6 C3H8 C4H10 C4H10 C5H12 C5H12 C6H14 C7H16 C8H18

# C's (x)
1 2 3 4 4 5 5 6 7 8

# H's (y)
4 6 8 10 10 12 12 14 16 18

s
2.0 3.5 5.0 6.5 6.5 8.0 8.0 9.5 11.0 12.5

Air/Fuel Ratio
9.570 16.748 23.925 31.103 31.103 38.280 38.280 45.458 52.635 59.813

COMBUSTION AIR REQUIREMENT INDEX (CARI)

The volumetric flow of a fuel gas through a burner orifice (restriction) is dependent upon the specific gravity of that fuel. Therefore, the amount of air required for complete combustion of a fuel will vary with the density of the fuel gas. The Combustion Air Requirement Index (CARI) is a dimensionless parameter indicating how much air is required for the stoichiometric combustion of a fuel gas. CARI = Air/Fuel Ratio (specific gravity) (6)

For a mixture of gases, the CARI can be calculated by CARI =

(AFRi * Xi)
( (SGi * Xi))

(7)

Where

X = Component Mol % AFR = Air to fuel Ratio for each component SG = specific gravity for each component i = component

Table 2 displays the air/fuel ratios and associated CARI value for selected alkanes. TABLE 2 AIR TO FUEL RATIO AND CARI FOR SELECTED ALKANES

COMPONENT
METHANE ETHANE PROPANE n-BUTANE i-BUTANE PENTANE i-PENTANE HEXANE HEPTANE OCTANE

Relative Density
0.55392 1.03820 1.52260 2.00680 2.00680 2.49120 2.49120 2.97550 3.45980 3.94410

Air/Fuel Ratio
9.57 16.75 23.93 31.10 31.10 38.28 38.28 45.46 52.64 59.81

CARI
12.86 16.44 19.39 21.96 21.96 24.25 24.25 26.35 28.30 30.12

As you can see from the scatter plot in Figure 1, the relationship between the Air/Fuel ratio and CARI is linear with a correlation of R2 = 0.9846.

35
C8H18

30 25 CARI 20 15 10 5 0 10 20 30 40
CH4 C2H6 C3H8 C4H10 C5H12

C6H14 C7H16

y = 0.337x + 10.896 R2 = 0.9846 50 60 70

Air/Fuel Ratio

FIG. 1 RELATIONSHIP BETWEEN AIR/FUEL RATIO AND CARI FOR ALKANES

WOBBE INDEX
If the flow of the fuel across a burner orifice varies then it follows that the energy produced during combustion will also change. The Wobbe Index is defined as the amount of energy introduced to the burners. Wobbe Index = Calorific Value (specific gravity) Table 3 displays the calculated parameters for each of the selected alkanes. (8)

TABLE 3 DATA AND CALCULATED VALUES FOR SELECTED ALKANES Net Wobbe Net Heating Index Ratio Between Value Relative (BTU/SCF) CARI and Wobbe (BTU/SCF) Density CARI COMPONENT
METHANE ETHANE PROPANE n-BUTANE i-BUTANE PENTANE i-PENTANE HEXANE HEPTANE OCTANE 0.55392 1.03820 1.52260 2.00680 2.00680 2.49120 2.49120 2.97550 3.45980 3.94410 12.86 16.44 19.39 21.96 21.96 24.25 24.25 26.35 28.30 30.12 909 1619 2315 3011 3000 3707 3699 4404 5100 5796 1221.35 1588.94 1876.11 2125.49 2117.72 2348.65 2343.58 2553.10 2741.86 2918.46 94.98 96.67 96.76 96.81 96.46 96.84 96.63 96.88 96.89 96.90

The CARI Wobbe relationship is linear, for hydrocarbon fuels with a mix of alkanes (Cx Hx+2). As the scatter plot in Figure 2 illustrates, the Wobbe Index can be mathematically calculated with a correlation of R2 = 0.9999. As both Table 3 and the Figure 2s trend-line indicate, the ratio between CARI and the Wobbe Index is fairly constant. With the line intercept set at 0 the linear relationship between CARI and Wobbe for alkanes becomes: Y = 96.732 X (9)

3500 Net Wobbe Index (BTU/SCF) 3000 2500 2000

C2H6 C6H14 C7H16 C4H10 C5H12 C3H8 CH4 C8H18

1500 1000 500 0 10 15

y = 97.942x - 28.692 R2 = 0.9999 20 CARI 25 30 35

FIG. 2 - RELATIONSHIP BETWEEN CARI AND WOBBE INDEX FOR ALKANES

RESIDUAL OXYGEN MEASURMENT METHOD

In the Residual Oxygen Measurement method, a continuous gas sample is mixed with dry air at a precisely maintained constant ratio. This fuel air mixture is then oxidized in a combustion furnace in the presence of a catalyst at 800C. A zirconia oxide cell is used to determine the residual oxygen concentration in the combusted sample. The Residual Oxygen Measurement Method mimics what takes place in your burner and provides a direct measurement of the Combustion Air Requirement Index (CARI). As the above equations indicate CARI can be mathematically correlated to the Wobbe Index of the fuel gas for an indication of the amount of energy supplied to the burner. GAS MIXING CHAMBER Figure 3 is an illustration of a basic flow diagram of the typical gas inlets and mixing chamber configuration of an analyzer designed for Residual Oxygen Measurement Method. The purpose of the mixing chamber is to combine the air and fuel gas streams into an air/fuel gas mixture for combustion.

The air and fuel gas streams must first be equalized for temperature and pressure o Pre-regulators and dome loaded pressure regulators (booster relays) are used to equalize the pressure of the fuel gas and air streams o A heat exchanger is used to equalize the temperature of the fuel gas stream and air

The two streams then pass through a set of precision orifices operating at supercritical stage into the gas mixing chamber where a air/fuel gas mixture is created o Orifices are sized according to the fuel gas composition and BTU range; the ratio of the diameter of the orifices controls the o The amount of air/oxygen introduced is a constant controlled by the orifice size. This amount will be in excess of what is required for complete combustion of the fuel gas o Changes in ambient conditions affect the air stream and fuel gas stream equally and have no effect on the fuel to air ratio

FIG. 3 SYSTEM FLOW DIAGRAM 4

RESIDUAL OXYGEN MEASUREMENT The air/fuel gas mixture flows out of the mixing chamber into an oven containing a zirconia oxide cell. The zirconia oxide cell, similar to that shown in Figure 4, is held at a temperature of 800C and provides the source of combustion. The amount of oxygen in the air/fuel mixture that is not used during the combustion process, the residual oxygen, is measured by the zirconia oxide cell. The amount of oxygen used during the combustion process is representative of CARI. In theory, knowing the initial amount of oxygen and the residual oxygen in the combusted stream, the amount of oxygen used during the combustion process can be calculate by simple subtraction. CARI = O2 Used for Combustion = Initial O2 Residual O2 (10)

The Wobbe Index can then be calculated from the CARI value, given the linear relationship between the two parameters.

Vent Oven Inlet Air/Gas Mixture

Heating Spiral

Oxygen Sensor Drain

FIG. 4 ZIRCONIA OXIDE CELL4 USING CALIBRATION GASES TO CALCULATE WOBBE INDEX4 Two calibration standards, a High and Low calibration gas mixture representing the range of the Wobbe Index of the process stream, can be used to establish the linear relationship between CARI and the Wobbe Index. By measuring the concentration of Oxygen in the flue gas after calibrating the instrument, the Wobbe index can be calculated by solving the linear equation: Wobbe Index = aO + b Where; a,b = calibration constants O = concentration of residual oxygen in the flue gas Equation (11) can be re-written as: Wobbe Index = WH WL OH OL Where; WH = Wobbe Index, High Calibration gas WL = Wobbe Index, Low Calibration gas OH = concentration of residual oxygen after combusting High Calibration Gas OL = concentration of residual oxygen after combusting Low Calibration Gas O = concentration of residual oxygen in the sample gas * (O OL) + WH (12) (11)

EFFECT OF ALKENES, HYDROGEN AND RELATIONSHIP OF CARI AND WOBBE INDEX

CARBON

MONOXIDE

ON

THE

TABLE 4 DATA AND CALCULATED VALUES FOR SELECTED ALKANES, ALKENES, HYDROGEN AND CARBON MONOXIDE Net Heating Value (BTU/SCF)
274 321 909 1619 1502 2315 2188 3011 3000 2877 3707 3699 3574 4404 5100 5796

COMPONENT
HYDROGEN CARBON MONOXIDE METHANE ETHANE ETHYLENE PROPANE PROPYLENE n-BUTANE i-BUTANE BUTENE PENTANE i-PENTANE PENTENE HEXANE HEPTANE OCTANE

Relative Density
0.06960 0.96707 0.55392 1.03820 0.96858 1.52260 1.45286 2.00680 2.00680 1.93715 2.49120 2.49120 2.42144 2.97550 3.45980 3.94410

CARI
9.07 4.87 12.86 16.44 14.59 19.39 17.86 21.96 21.96 20.63 24.25 24.25 23.06 26.35 28.30 30.12

Net Wobbe Index (BTU/SCF)

1038.59 326.42 1221.35 1588.94 1526.17 1876.11 1815.24 2125.49 2117.72 2067.09 2348.65 2343.58 2296.77 2553.10 2741.86 2918.46

Ratio Between CARI and Wobbe

114.52 67.08 94.98 96.67 104.63 96.76 101.61 96.81 96.46 100.21 96.84 96.63 99.59 96.88 96.89 96.90

As you can see by Table 4, the ratio between CARI and Wobbe Index is not the same across alkanes, alkenes, carbon monoxide and hydrogen. However, for fuel gases containing a mix of these components, a suitable choice of calibration gases can compensate for this error.

CONCLUSION
The Residual Oxygen Measurement Technique provides a direct measurement of the Combustion Air Requirement Index (CARI). CARI is a dimensionless parameter indicating how much air is required for the stoichiometric combustion of a fuel gas. The Wobbe Index, a measure of energy supplied to the burner, can be then readily calculated from the CARI value. The ratio between CARI and the Wobbe Index is a constant for gas mixtures containing alkanes. For fuel gas mixtures containing large amounts of alkenes, hydrogen or carbon monoxide calibration gases can be used to compensate for the non-linearity of the CARI/Wobbe relationship across these components.

REFERENCES
1. 2. 3. 4. Chau, P.C. Class Notes UCSD 2000 http://courses.ucsd.edu/winter2002/ceng100/notes/adiabatic_flame.pdf. GPA Standard 2145 Table of Physical Constants for Hydrocarbons and Other Compounds of Interest to the Natural Gas Industry. Lide, David R., Handbook of Chemistry and Physics, 71st Edition 1990-1991. Hobre Instruments B.V. Wobbe Index Analyzer, Installation, Operation and Maintenance Manual. February 2002.