Integration of Total Sulfur and Wobbe Index Analysis Using Uv Spectroscopy and TDL Oxygen Measurement

INTEGRATION OF TOTAL SULFUR AND WOBBE
INDEX ANALYSIS USING UV SPECTROSCOPY AND

TDL OXYGEN MEASUREMENT
David Greaves, Samuel Rolley, Andy Burgess, and Daniel Murphy

Applied Analytics, Inc.
29 Domino Drive, Concord, MA 01742
KEYWORDS
Natural Gas, Total Sulfur, Wobbe Index, VCSEL, SO2, Spectroscopy
ABSTRACT
In natural gas applications it is often desirable to know the total sulfur content of the gas to verify
environmental regulation compliance, and also the Wobbe index of the gas to characterize its
energy content. Currently this is achieved using multiple analyzers. However, by integrating a
UV absorbance spectrophotometer and a Vertical-Cavity Surface Emitting Laser (VCSEL) based
tunable diode laser into a system using conventional measurement techniques, both analyzers can
be consolidated into a single unit while improving overall accuracy and dynamic range. This
combination not only allows for improved performance and reduction in the initial investment
but also lessens the aggregate cost of ownership over the use of separate analyzers. The
advantages of the resulting apparatus and analytical method as well as the cost-benefit analysis
of this configuration are discussed in detail.
INTRODUCTION
In 2009 the United States alone, the total consumption of natural gas was over twenty-two
trillion cubic feet [17]. Such a staggering number casts little doubt on the importance of natural
gas for the economy and our daily lives. However, not all natural gas is created equal. Two
major factors influence the quality of natural gas: sulfur and energy content.
Natural gas with low energy content generally means that more gas must be burned in the same
amount of time as a high energy content gas to produce the same amount of heat. Therefore,
burning gas with low energy content leads to higher flow rates in transport piping and a higher
Session 5.2: – Page 1 –

© Copyright 2011, International Society of Automation. All rights reserved.
ISA 56th Analysis Division Symposium 2011, League City, TX.
volume of gas being burned per unit time, which in turn increases the rate at which pollutants are
sent into the atmosphere. The energy content of natural gas is measured using the Wobbe index.
Sulfur content is another major factor in determining natural gas quality. Sulfur content in
natural gas is converted to sulfur dioxide when combusted. Sulfur dioxide (SO2) is a major
cause of acid rain. The EPA requires that the sulfur content of natural gas be monitored and
reported using a continuous emissions monitoring (CEM) analyzer as part of the acid rain
program [6]. Ideally, natural gas should have high energy content while having low total sulfur
content.
Analytical methods and apparatus have existed for a long time to measure total sulfur and
Wobbe index separately, but it is the goal of this paper to show to that there is not only a major
economical benefit from combining the two, but also analytical benefit as well.
BACKGROUND
TOTAL SULFUR
Due to the fact that all fossil fuels were derived from organic matter they contain varying
amounts of sulfur compounds. Generally, as the density of the fuel increases (i.e., from natural
gas to oil to coal) the amount, variety and complexity of the entrained sulfur compounds grow.
Also, because fossil fuels originally developed under different conditions around the world, the
location from which the fuel was extracted also plays a role in determining its sulfur content. In
a world with an ever expanding global economy paired with a steadily growing energy demand,
a variety of fuels from domestic and foreign sources must be utilized to satisfy the need for
energy [14].
Such an intermingling of diverse fuel sources leads to a wide range of sulfur content across the
board. Juxtaposed with ever more stringent SO2 emissions reporting guidelines, the need for a
reliable total sulfur analysis method to provide continuous and accurate total sulfur readings is
apparent [7].
The challenge of a total sulfur measurement is that sulfur is present in such a wide variety of
compounds as well as in its elemental form. Trying to measure each individual compound
separately and performing a summation would be impractical.
One reason for this is the shear number of potential sulfur compounds. Each potential sulfur
compound would need to be speciated and measured separately. This would require an analyzer
that uses a variety of physical and analytical methods to separate and differentiate each
compound. Such an analyzer would necessitate a calibration for each individual component
while being prone to countless interfering compounds. Additionally, each measured compound
would be accompanied by some degree of error, which when all compounds were subsequently
summated their combined error would be enormous.

Instead of measuring each sulfur compound individually, it would be better to convert all sulfur
containing compounds to a single species which would be representative of the total sulfur
content. This can be accomplished by oxidizing the fuel through combustion. When the fuel is
burned, any entrained sulfur compounds combine with oxygen to form sulfur dioxide (SO2). The
amount of SO2 produced is directly proportional to the amount of sulfur in the fuel and can
therefore be correlated to the total sulfur content.
WOBBE INDEX
When a fuel is burned, the primary objective is to generate energy in the form of heat. This heat
could be used for heating commercial and residential buildings, electrical generation, or control a
myriad of industrial processes. In all cases it is vital to know how much energy can be produced
from burning a given amount of fuel. On the surface, this seems as simple as dividing the BTU
output of the fuel by its volume, but the measurement is complicated by the inherent properties
of burner design.
A burner operates by first allowing fuel to mix with air in a controlled fashion and then pass
through a small orifice to regulate its flow rate. The flow rate of a flammable gas mixture
through a constant orifice size, however, is dependent on its density. A denser gas mixture will
flow more slowly due to a larger mass trying to push through the orifice at any given time; while
conversely, a thinner gas mixture will flow more freely through the same orifice.
The Wobbe index is a method of expressing the energy content of a fuel by taking into account
its density with respect to the density of air, which is better known as its specific gravity. The
equation for calculating Wobbe index is as follows:
WI = (HHV) / SG1/2 (1)
Where WI = Wobbe Index (BTU/ft3)

HHV = High Heating Value (BTU/ft3)
SG = Specific Gravity (dimensionless)
Therefore, in the case of two gases with the same high heating value flowing through an identical
orifice, the mixture with the lower specific gravity will have the higher Wobbe number. This
makes sense as the gas with the lower specific gravity will have a higher flow rate and thus
deliver more energy per unit time.
The Wobbe index is of particular importance for two reasons. The first is that for a burner
orifice of constant size any two fuel gases with the same Wobbe number will produce the same
amount of heat per unit time regardless of composition, and are therefore interchangeable. The
second is that for two fuel gases with disparate Wobbe numbers, the size of the orifice can be
continuously controlled (e.g. through use of a proportional valve) such that both gases will
produce the same amount of heat per unit time [12].

APPLICATIONS
PROCESSING
As natural gas production expands to meet growing demand the industry is turning to more, and
increasingly diverse, sources to bolster supply. This reality is leading to natural gas being
extracted from new sources or from existing sources using new technology to reach gas that was
once considered unobtainable. Because of this, the sulfur and energy content of these new
sources is different than the gas obtained from traditional sources. This has lead to an increase in
the need for processing of natural gas before it can be sent to market. In order to know what gas
needs to be processed, and how much processing is required, it is important to measure the total
sulfur and Wobbe index of gas as it is extracted [9].
The gas must then be processed until it meets the EPA definition for “pipeline natural gas”
according to 40 CFR 72.2:
Pipeline natural gas contains 0.5 grains or less of total sulfur per 100 standard
cubic feet. Additionally, pipeline natural gas must either be composed of at least
70 percent methane by volume or have a gross calorific value between 950 and
1100 Btu per standard cubic foot. [1]
In order to certify that natural gas meets these requirements before entering the pipeline system,
it is necessary to measure both the total sulfur content and the Wobbe index number.
DISTRIBUTION
After natural gas is extracted and processed, it enters a transmission phase where is transported
over long distances through a pipeline system. Although gas must be certified before entering
the pipeline system, it is still common for out of spec gas to make its way in. Gas with high
sulfur content can accelerate corrosion of the pipeline infrastructure leading to costly
maintenance and repair. Also, natural gas is ultimately billed based on its heating value, and
various state and local governments require that the heating value of natural gas is routinely
reported and falls within an acceptable range. Therefore, the total sulfur and Wobbe index
number of natural gas must be measured as it enters and exits the transmission pipeline system
[14].
GAS BLENDING
When natural gas is found to be out of spec and does not meet the criteria to be considered
pipeline quality, it does not necessarily mean that it cannot be used. Currently, there is little
infrastructure in place to adequately blend natural gas streams together to optimize sulfur and
energy content. There are two concerning trends arising in the natural gas industry. The first is
the increasing amount of liquefied natural gas (LNG) entering pipelines from foreign sources.
LNG inherently has a higher heating value than traditional natural gas sources due to the

liquefaction process. The second is natural gas with a high sulfur content obtained from new
sources by new methods (e.g., hydrofracking) [14].
Measuring the total sulfur content as well as the Wobbe index number of the gas, however,
would allow gas streams to be blended together to reduce sulfur and/or energy content. By
having sources of natural gas with high Wobbe index, high sulfur content, and a source of inert
gas (e.g. nitrogen), it would be possible to precisely mix the three sources together to create a
stream that meets pipeline quality specifications.
PETROCHEMICAL
FLARE STACK MONITORING
A preeminent concern in petrochemical facilities is flare stack monitoring for both sulfur and
energy content. The Environmental Protection Agency (EPA) limits SO2 emissions as part of the
acid rain program of the Clean Air Act. The EPA, as part of 40 CFR 60.18, also regulates the
minimum energy content of gas to be burned in a flare stack [2]. In order to comply with these
regulations, it is imperative for petrochemical facilities to have continuous accurate data of the
total sulfur as well as Wobbe index number for gas in their flare lines.
There is a major economic benefit for monitoring sulfur and energy levels. Primarily, SO2
emissions are currently controlled by a cap and trade program. If a petrochemical facility emits
more SO2 than they hold allowances for, then they are required to purchase additional
allowances from a facility that has reduced their emissions and has extra allowances. Therefore,
by understanding the flow of sulfur through a plant, emission reduction strategies can be
formulated to target the highest sulfur contributing processes for maximum effectiveness.
The EPA requires that flare stacks be operated with a flame present at all times. In order to meet
this requirement, costly assist gas must be used to ensure the energy content of the gas stays
above a minimum value. By properly monitoring the Wobbe index of their flare gas,
petrochemical facilities can use feed forward control to reduce their use of assist gas when the
energy content of the flare gas itself is high enough [6].
PROCESS CONTROL
Many petrochemical processes require the addition of heat to sustain various chemical and
physical processes. Part of this demand is met by utilizing the waste gas from one or more
processes as the fuel gas for another. This allows the plant to maximize energy efficiency and
cut back on emissions, however it poses the additional challenge of varying the sulfur and energy
content of the gas at the inlet of some processes.
By continuously measuring the Wobbe index number of the fuel gas coming into a given
process, a feed forward control signal may be generated to open or close a proportional valve
before the burner. In this way the flow of energy into the process can be controlled, allowing the
heat input to stay constant despite the changing inlet conditions.
CATALYST PROTECTION
Several petrochemical processes require combustion to take place in the presence of expensive
catalysts to lower activation energy requirements and optimize energy efficiency. Many
catalysts, however, can be poisoned and rendered ineffective if they are exposed to sulfur
containing compounds. Therefore it becomes critical to monitor the sulfur content of gas that
will be exposed to these catalysts to ensure that the sulfur content is below an acceptable limit.
In cases where sulfur content is determined to be too high, a feed forward control signal can be
generated to divert flow from the process and allow the process to run off of a separate
acceptable fuel gas (e.g., natural gas) until the sulfur content of the original fuel gas stream
becomes acceptable again. Also, when the gas meets specification the Wobbe number can be
used to optimize the flow rate of the gas in the reaction to maximize efficiency of the process.
TECHNOLOGY
TOTAL SULFUR MEASUREMENT
Many methods have been developed to measure total sulfur. A sample of the most common
measurement techniques are outlined below.
LEAD ACETATE
The lead acetate analyzer is different from all other analysis techniques in that instead of
oxidizing entrained sulfur in fuel into SO2 it reduces it to hydrogen sulfide (H2S). The fuel is
hydrolyzed in a pyrolyzer furnace and the effluent is ejected onto the surface of lead acetate tape.
When exposed to H2S lead acetate reacts to form lead sulfide, which manifests itself as a dark
stain on the otherwise white tape. By measuring the rate of darkening of the tape it is possible to
calculate the H2S concentration.
FLAME PHOTOMETRIC DETECTION
Gas chromatography can be used to measure total sulfur when coupled with a flame photometric
detector. This process employs a pyrolyzer furnace to combust a fuel sample such that entrained
sulfur compounds are oxidized to SO2. The combusted gas is then passed through a primary
separation column and into a slider valve which removes the bulk of the SO2 from the
background of the combusted gas. This SO2 rich gas is then passed through a secondary
separation column the effluent of which is then passed through a hydrogen rich flame in a flame
photometric detector. The SO2 luminesces as it passes through the flame, and the intensity of the
emitted light is measured by a photomultiplier tube, which can then be correlated back to the
total sulfur concentration [13].

CHEMILUMINESCENCE
Chemiluminescence is a chemical process in which light is emitted as a byproduct of a chemical

reaction. This process is most notably used to light glow sticks, but the same phenomenon can
be utilized to measure total sulfur.
By mixing the fuel gas with hydrogen and passing it through a pyrolyzer furnace the entrained
sulfur compounds will react to produce SO2 and sulfur monoxide (SO). The effluent of the
pyrolyzer is then mixed with ozone (O3) which has the effect of oxidizing the SO portion of the
effluent into SO2 at an excited electrical state. As this excited SO2 relaxes to its ground state it
luminesces its extra energy in the form of photons. The intensity of the luminesced light, which
is proportional to the SO concentration, can then be measured with a photomultiplier tube and
correlated with the total sulfur concentration [5].
X-RAY FLUORESCENCE
X-ray fluorescence can be used to determine the total sulfur content of a fuel. Instead of
oxidizing or reducing the fuel to SO2 or H2S respectively, x-rays can be employed to measure
individual sulfur atoms regardless of the compounds. Because x-rays are high energy waves,
they have extremely short wavelengths. The wavelengths are short enough that they can be used
to ionize individual sulfur atoms by exciting their low energy electrons to higher energy orbitals.
The ionized sulfur atoms then relax back to their ground state and fluoresce the extra energy as
photons with a wavelength equal to the energy difference between the two orbitals. The
fluoresced light can be measured with an x-ray detector and correlated with the total sulfur
concentration.
UV SPECTROSCOPY
UV spectroscopy can take advantage of absorbance and/or fluorescence to measure the total
sulfur concentration of a fuel. For either method, the fuel must first be properly mixed with air
and combusted in a pyrolyzer furnace to convert all entrained sulfur into SO2.
In relatively high sulfur content applications it is possible to use the absorbance spectrum of SO2
to measure the total sulfur content of the fuel. The combusted gas from the pyrolyzer can be
flown through a flow cell of a predetermined length where it is exposed to UV light. Any SO2 in
the flow cell will absorb some of the incident light and the difference between the intensity of the
incident light to that of the measured light can be correlated to the total sulfur concentration [8].
In low sulfur content applications it is possible to use UV fluorescence to measure the total sulfur
concentration. After combustion in the pyrolyzer, the effluent containing SO2 is passed into a
flowcell. A UV light source is shown through a monochromator to selectively shine UV light
near 214nm into the flow cell. The light near this wavelength will be absorbed by the SO2 in the
flowcell and then re-emitted from the SO2 as fluoresced light near 330 nm. A photomultiplier
tube can be used to measure the intensity of the fluoresced light which may then be correlated
with the total sulfur concentration [3].

COMPARISION
As shown in table I, out of these total sulfur measurement technologies UV spectroscopy is the
most beneficial. Aside from air and nitrogen, UV spectroscopy requires no additional gases as
utilities. UV spectroscopy is also completely solid state which greatly reduces maintenance
frequency and cost. However, it is the fact that UV spectroscopy requires complete combustion
of the process gas which makes it ideal for integration with a Wobbe index analyzer.
TABLE I. TOTAL SULFUR MEASUREMENT COMPARISION
Solid No Complete No No
State Consumable Oxidation Hydrogen Ozone
UV Spectroscopy X X X X X
Lead Acetate X
Flame Photometric
X X X X
Detector
Chemilluminescence X X X
X-Ray Fluorescence X X X X
WOBBE INDEX MEASUREMENT
As discussed previously Wobbe index is a measure of not only the heat capacity of a fuel but
also the density. Therefore a Wobbe index analyzer is itself an integration of two analyzers,
namely one for measuring heat capacity and another for measuring density. Each of these values
has many methods that have been developed for their measurement, however for the purposes of
this paper the density of the fuel may be assumed to be a known value given by a density sensor
and a focus will be put on the measurement of heat capacity. A number of heat capacity
measurement methods are discussed below.
CALORIMETER
The most direct method for determining the energy density of a fuel is the calorimeter. Many
different types of calorimeters have been devised but they all operate on generally the same
principal. The fundamental premise of the calorimeter is that an amount of fuel is burned in such
a way that the heat generated is transferred into a mass, and the change of some physical
property of that mass is measured and the heat required to generate a change of that magnitude is
calculated to find the energy density.
Some examples of this would be transferring the heat into a sealed volume of a gas (e.g., air) and
measuring the increase in pressure as heat is added. Another example would be transferring the
heat into a block of metal and measuring the strain on the surface as the material expands with
the addition of heat. However, this is generally accomplished by transferring the heat into a

known volume of liquid (e.g., water) and monitoring the corresponding increase in temperature
[11].
It is possible to use a calorimeter in an online process, but its accuracy and stability are greatly
affected by changes in ambient conditions. It is also inherently impossible to achieve one-
hundred percent heat transfer efficiency and therefore correction factors must be calculated
during calibration to account for these losses. As a result, any subsequent deviations in the
process conditions will nullify the results and mandate a recalibration of the system. Finally, the
use of a calorimeter requires a constant flame while burning the fuel which requires additional
instrumentation and complexity as well as requiring a loss of data and downtime in the event of a
flameout.
RESIDUAL OXYGEN MEASUREMENT
In order to completely burn a specific amount fuel there must be a minimum amount of oxygen
to satisfy the stoichiometric requirement for combustion. For any hydrocarbon following the
CnH2n+2 structure, the general balanced combustion equation in air is as follows [12]:
CnH2n+2+(n+([2n+2]/4))[O2+3.785 N2]-> nCO2+(n+2)/2H2O+3.785(n+([2n+2]/4))N2 (2)
Therefore:
AR = (n + [2n+2]/4)[1mol O2 + 3.785mol N2] (3)
Where AR = Combustion Air Requirement (mol air/mol fuel)
Similarly to the calculation of the Wobbe index number discussed earlier in this paper, the
volumetric flow of a fuel gas is proportional to its specific gravity. The denser the gas the slower
it will flow through an identical orifice compared to that of a less dense gas. Due to this fact, a
correction factor needs to be applied to the combustion air supply based on density. This
correction value is known as the CARI index and can be calculated by the following equation:
CI = (AR) / SG1/2 (4)
Where CI = CARI Index (mol air/mol fuel)

SG = Specific Gravity (dimensionless)
The following table shows the pertinent data for calculating CARI index as well as Wobbe index
for all linear alkanes from methane through octane [12]:
As is clearly visible from Figure 1, there is a direct linear relationship between CARI index and
Wobbe index. Therefore, instead of measuring the high heating value of a fuel directly using a
calorimeter, it is possible to determine the air requirement to calculate the CARI index number
and then correlate that to the Wobbe index.

The combustion air requirement can be calculated by measuring the difference in oxygen
concentration before and after combustion. The amount of oxygen after combustion will be less
than the initial amount because the difference will be used to make CO2 and H2O during the
combustion reaction.
TABLE II. CARI & WOBBE INDEX OF LINEAR ALKANES
Component Formula n AR SG CI HHV WI

Methane CH4 1 9.570 0.55392 12.86 909 1221.35
Ethane C2H6 2 16.748 1.03820 16.44 1619 1588.94
Propane C3H8 3 23.925 1.52260 19.39 2315 1876.11
n-Butane C4H10 4 31.103 2.00680 21.96 3011 2125.49
i-Butane C4H10 4 31.103 2.00680 21.96 3000 2117.72
Pentane C5H12 5 38.280 2.49120 24.25 3707 2348.65
i-Pentane C5H12 5 38.280 2.49120 24.25 3699 2343.58
Hexane C6H14 6 45.458 2.97550 26.35 4404 2553.10
Heptane C7H16 7 52.635 3.45980 28.30 5100 2741.86
Octane C8H18 8 59.813 3.94410 30.12 5796 2918.46
The following plot shows the relationship between CARI and Wobbe index [12]:
3500.00
3000.00
y = 97.942x - 28.692
2
R = 0.9999
2500.00
Wobbe Index
2000.00
1500.00
1000.00
500.00
0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
CARI Index
FIGURE 1. CORRELATION BETWEEN CARI AND WOBBE INDEX

When air is used as the source of oxygen, the initial oxygen concentration can be assumed to be
20.9%, the amount of oxygen after combustion will vary based on the fuel composition and is
referred to as the residual oxygen. By using an oxygen sensor to monitor the residual oxygen
concentration, the combustion air requirement may be continuously monitored which allows for
continuous online measurement of the Wobbe index of the fuel via the CARI index.
The following are existing methods for measuring the oxygen concentration of a gas stream.
ZIRCONIUM OXIDE
The most common oxygen sensor for measuring combustion efficiency is the zirconium oxide
sensor. The sensor element is primarily made of zirconium oxide doped with calcium, which is
held at an elevated temperature around 1200°C. Either side of the element is layered with
platinum which acts as an anode and cathode across which a voltage is measured. At the
elevated temperature of the sensor, the platinum layers become porous enough to allow oxygen
ions to pass through. The element forms a lattice structure that regulates the rate at which oxygen
ions pass from the anode to the cathode with respect to the partial pressure of oxygen on either
side of the element. By exposing one side of the element to a reference gas with a known
oxygen concentration (e.g. air) and the other side to the sample gas, the voltage measured across
the anode and cathode will be proportional to oxygen content of the sample gas and the oxygen
concentration may be calculated.
Although the zirconium oxide oxygen sensor is simple and has fairly good response
characteristics, it also has two drawbacks that make it undesirable for use in an analytical
application. Foremost, the zirconium oxide element is expensive and breaks down over time
which requires routine maintenance and adds to the overall cost of ownership of the system it is
used in. Also, the sensor only works at elevated temperature which can cause the residual
oxygen to react with other components of the sample stream, thus lowering the oxygen
concentration and artificially increasing the combustion efficiency reading.
PARAMAGNETIC
It is also possible to take advantage of the paramagnetic properties of oxygen to measure oxygen
concentration. It is an inherent property of oxygen that when it is exposed to a magnetic field it
has the effect of strengthening it. This behavior is known as paramagnetism. Some gases, such
as nitrogen, have the opposite effect of weakening an electric field, which is known as
diamagnetism.
A mechanical system has been devised to exploit this discrepancy that comprises a dumbbell
shaped container filled with nitrogen placed in a magnetic field. As sample gas containing
oxygen is passed outside of the dumbbell, it creates an imbalance in the magnetic field that
exerts a rotational force on the dumbbell. The higher the oxygen concentration of the sample
gas, the stronger the rotational force on the dumbbell becomes. An electromagnet is used to keep
the dumbbell from spinning. The current that must be supplied to the electromagnet is directly

related to the rotational force and therefore the oxygen concentration. By measuring this current
it may be correlated to the oxygen content and the oxygen concentration may be calculated.
THERMAL CONDUCTIVITY
Gas chromatography can be used to measure oxygen content when paired with a thermal
conductivity detector (TCD). The TCD houses a Wheatstone bridge circuit that contains a
thermistor on each leg. The Wheatstone bridge is balanced with each leg being exposed to an
equal flow of a common reference gas (e.g., hydrogen, helium) such that the voltage across the
bridge is zero. One leg of the Wheatstone bridge is exposed to a sample gas while the other
remains constantly exposed to the reference gas. If the sample gas has a different thermal
conductivity then the reference gas it will cause the thermistor on the sample leg to change its
resistance and create a voltage across the bridge. A gas chromatograph is used before the TCD
to physically separate the components of the sample stream using a packed column. This way
each component of the sample stream will manifest itself as a discrete peak in the voltage trend
of the TCD. The area of the corresponding oxygen peak can be used to calculate the oxygen
concentration.
TUNABLE DIODE LASER
The oxygen concentration of a sample gas can be determined spectroscopically by using a

VCSEL tunable diode laser. Oxygen has a unique and extremely distinct absorption line at
763.43nm. By precisely controlling the current and temperature of a VCSEL, light can be
produced at exactly this wavelength. The sample gas containing oxygen can be passed through a
flow cell where it is exposed to the laser light. When measuring the difference in light intensity
between the sample and a zero gas (e.g., nitrogen), the drop in intensity is proportional to the
oxygen content of the sample gas, thus the oxygen concentration can be calculated.
COMPARISION
As shown in table III, out of these residual oxygen measurement technologies the tunable diode
laser is the most beneficial.
TABLE III. RESIDUAL OXYGEN MEASUREMENT COMPARISION
Solid No Residual
State Consumable Oxygen
Tunable Diode Laser X X X
Calorimeter X X
Zirconium Oxide X X
Paramagnetic X X
Thermal Conductivity X

The tunable diode laser is completely solid state and requires no consumables, which greatly
reduces maintenance frequency and cost. The tunable diode laser also measures residual oxygen
from combustion which lends itself to integration with a UV spectroscopy based total sulfur
analyzer.
APPROACH
FIGURE 3. INTEGRATED TOTAL SULFUR & WOBBE INDEX ANALYZER
PYROLYSIS
Both total sulfur and Wobbe index measurements require that the process stream be combusted
prior to analysis. As shown in figure 3 a process gas enters a sample conditioning system through
the process inlet. The majority of the gas is passed through a fast loop and immediately returned
to the process line to ensure minimal lag time. A mass flow controller (MFC) is used to allow a
small amount of process gas through the sample loop for analysis. A second MFC is installed on
an air line which permits precise control over the amount of air added the process. Both MFCs
communicate with a computer and may be independently controlled to produce a continuous
range of air to fuel ratios. The air-fuel mix is then sent through a pyrolyzer furnace maintained
at 1100°C to ensure complete combustion of the process gas. After passing through the
pyrolyzer, any entrained sulfur from the process gas will exist in the form of SO2. The oxygen
level of the gas stream will have reached its lowest level after all of the fuel has been combusted
to CO2 and H2O. The sample stream has now been properly conditioned to allow total sulfur and
Wobbe index measurements.
UV SPECTROSCOPY
The combusted gas passes from the outlet of the pyrolyzer to a series of flow cells. Figure 4
shows an example of four flow cells connected in series to increase the path length of the
measurement.
FIGURE 4. MULTIPLE FLOW CELLS IN SERIES
Path length is important because absorbance spectroscopy is built on two equations of Beer-
Lambert’s law [3]. The first is:
A = log (I0/I) (5)
Where A = Absorbance
I0 = Light In
I = Light Out

By measuring the intensity of light received at a detector, this equation allows for the calculation
of absorbance. This value is essential for the application of the second equation:
A = εbc (6)
Where A = Absorbance
ε = Molar absorptivity
b = Path Length
c = Concentration
In this equation molar absorptivity is a physical constant at each wavelength for the particular
compound being measured. Therefore, if the concentration of the process gas is held constant
the absorbance will be higher for a longer path length and lower with a shorter path length. For a
low concentration process gas it becomes imperative to increase the path length to achieve a
measureable increase in absorbance.
Based on equation 2, for ideal stoichiometric combustion 2 moles of air are required to burn 1
mole of CH4, producing a 3:1 dilution factor between the process and the combusted gas
measured in the flow cells (e.g. 2ppm SO2 in the flow cell represents 6ppm total sulfur in the
process). The detection limit of total sulfur in the process gas may be lessened by reducing the
amount of dilution by using a cylinder of compressed oxygen, or a commercially available
oxygen generator, to remove the nitrogen from the equation. UV fluorescence may be used in
rare cases where detection limits lower than 1ppm are required; however UV absorbance is
sufficient for the majority of gas phase applications.
VCSEL
After passing through the flow cells the combusted process gas enters the housing of the VCSEL
tunable diode laser, as illustrated in figure 5. The VCSEL is a semiconductor device that
converts electrical current into coherent, monochromatic light. The light emitted from the diode
is all of one specific wavelength, and all the waves are in phase with one another. The
spectroscopic value of using a laser as a light source lies in the coherence and wavelength
precision of the signal, which enables the system to monitor sample absorbance at an extremely
well-defined spectral region. For a component such as oxygen, the capacity for isolating these
high-absorbance lines is critical for measuring concentration.
As shown in figure 6, the laser diode is tuned between its natural emission frequency (pt. A) and
a sharp peak in oxygen’s absorbance spectrum (pt. B) using electrical current. The level of light
transmittance at the monitored peak will vary with the concentration of oxygen in the process
stream, such that a higher oxygen concentration yields a more prominent dip at point B. The
VCSEL also monitors transmittance at its natural frequency, (pt. A) where oxygen is known to
absorb no light. This spectral baseline provides a constant reference for calculating how much
absorbance is due strictly to oxygen in the process.

FIGURE 5. VCSEL TUNABLE DIODE LASER ILLUSTRATION
FIGURE 6. VCSEL SPECTROSCOPY ILLUSTRATION

BENEFITS
ANALYTICAL
As discussed previously in this paper the VCSEL tunable diode laser is measuring the residual
oxygen leftover from combustion which is then used to calculate the CARI index number
according to equation 4. In an ideal stoichiometric combustion reaction 100% of the fuel is
combined with 100% of the available oxygen leaving only CO2 and H2O. Nevertheless, in
reality ideal stoichiometric combustion on a macroscopic scale cannot be achieved. In order to
ensure complete combustion of a fuel it must exist in an excess of oxygen such that the fuel
becomes the limiting component in the combustion reaction.
Overestimation of the oxygen required for combustion has the negative consequence of
increasing the dilution of the combusted process gas, which increases the lower detection limit of
the total sulfur measurement. By integrating a VCSEL tunable diode laser, however, the residual
oxygen content of the combusted gas is continuously measured. This allows the analyzer to
transmit a feedback control signal to the mass flow controllers, automatically adjusting the air to
fuel ratio if a rise or fall in residual oxygen concentration is detected. By doing so the dilution
factor can be continuously minimized and this allows for the greatest possible absorbance by the
SO2. This has the effect of increasing the accuracy, stability, and sensitivity of the total sulfur
measurement for overall greater performance.
ECONOMIC
In addition to the analytical benefit of combining a total sulfur and Wobbe index analyzer using
UV spectroscopy and a VCSEL tunable diode laser, there are a multitude of economic benefits as
well. By eliminating redundancies in the two systems a single unit containing both detection
systems requires a lower initial investment. Running only one pyrolyzer instead of two reduces
the total energy consumption and cuts the amount of product that is burned in half. Using fewer
analyzers minimizes maintenance and spare parts inventory. Also, both detection methods (i.e.
UV spectroscopy and VCSEL laser) are entirely solid state and require no consumables, thereby
further reducing total cost of ownership.
CONCLUSION
In many applications throughout the natural gas and petrochemical industries it is necessary to
monitor the total sulfur as well as the energy content of a gas stream. Whether that gas is being
pulled from the ground, fueling a chemical process, being flared as waste, transported across the
country, or being sold to a consumer, it is imperative to measure these values. By utilizing UV
as well as VCSEL spectroscopy to measure the effluent from a single pyrolyzer, both of these
quantities can be characterized by a single analyzer simultaneously. Additionally, the process of
measuring the Wobbe index allows for feedback control that improves the performance of the
total sulfur detection. In a time where constraints and regulations of the emission of sulfur

compounds are growing tighter and tighter the importance of such measurement capabilities is
ever growing.
REFERENCES
1. “40 CFR 72.2”, Code of Federal Regulations, U.S. Government Printing Office,
Washington D.C., 1995.
2. “40 CFR 60.18”, Code of Federal Regulations, U.S. Government Printing Office,
Washington D.C., 1995.
3. Barshad Y, UV-VIS Spectrometer - On-Line Diode-Array UV/VIS Fiber Optic

Spectrometer for Composition Monitoring, Measurements & Control, June 1992.
4. Barshad, Y., Burgess, A., “Process Analyzers for Clean Coal Applications,” Proceedings
of Instrumentation, Systems, and Automation Society, 54th Analysis Division
Symposium, 2009.
5. Benner, Richard L., Stedman, Donald H., “Chemical Mechanism and Efficiency of the
Sulfur Chemiluminescence Detector”, Applied Spectroscopy, Vol. 48, Number 7, 1994.
6. Environmental Protection Agency, “The Plain English Guide to the Clean Air Act”,
(http://www.epa.gov/air/caa/peg/), 2011.
7. Foss, Michelle M., “Interstate Natural Gas – Quality Specifications &

Interchangeability”, Center for Energy Economics, Sugar Land, TX, Decemeber, 2004.
8. Greaves, D., Burgess, A., Murphy, D., Brown, M., "Analyze This", Hydrocarbon
Engineering, Farnham, Surrey, England, Vol. 15, Issue 2, February, 2010, Page 50-54.
9. Halchuk-Harrington, Rosemarie, Wilson, Robert D., “AGA Bulletin #36 and Weaver
Interchangeability methods: Yesterday’s Research and Today’s Challenges”.
10. Hailey, David, “Flare Gas Measurement and Recovery of Fuel Feed Gas with Residual
Oxygen Calorimetry”.
11. Hall, James L., Headlee, A. J. W., “Heating value of Natural Gas Determination of Total
and Net Values with a Water-Flow Gas Calorimeter”, Industrial and Engineering
Chemistry, October, 1944, Pg. 953-955.
12. Hawkins, Jim, McGowan, Ann, “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”.

13. Melda, Kenneth J., “Total Sulfur in Fuels: A Proven Process Gas Chromatographic
Technique to Measure the Reduced Limits”.
14. Naturalgas.org, “Natural Gas - From Wellhead to Burner Tip”,

(http://www.naturalgas.org/naturalgas/naturalgas.asp), 2011.
15. Pasquale, Alberto, Spitler, Rodney W., “Taking ASTM D5453 On-Line Determination of
Total Sulfur in Gasoline and Diesel”.
16. Perry, Green, Perry’s Chemical Engineers’ Handbook, Seventh Edition, McGraw-Hill,
United States of America, 1997.
17. U.S. Energy Information Administration, “Natural Gas”,

(http://www.eia.gov/naturalgas/), 2011.
18. Zumdahl, Steven S., Zumdahl, Susan A., Chemistry – 6th Edition¸ Houghton Mifflin,
Boston, Massachusetts, 2006.


Integration of Total Sulfur and Wobbe Index Analysis Using Uv Spectroscopy and TDL Oxygen Measurement

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Integration of Total Sulfur and Wobbe Index Analysis Using Uv Spectroscopy and TDL Oxygen Measurement

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INTEGRATION OF TOTAL SULFUR AND WOBBE

INDEX ANALYSIS USING UV SPECTROSCOPY AND

David Greaves, Samuel Rolley, Andy Burgess, and Daniel Murphy

Natural Gas, Total Sulfur, Wobbe Index, VCSEL, SO2, Spectroscopy

Session 5.2: – Page 1 –

Session 5.2: – Page 2 –

WI = (HHV) / SG1/2 (1)

Where WI = Wobbe Index (BTU/ft3)

Session 5.2: – Page 3 –

Session 5.2: – Page 4 –

FLARE STACK MONITORING

TOTAL SULFUR MEASUREMENT

FLAME PHOTOMETRIC DETECTION

Session 5.2: – Page 6 –

Chemiluminescence is a chemical process in which light is emitted as a byproduct of a chemical

Session 5.2: – Page 7 –

TABLE I. TOTAL SULFUR MEASUREMENT COMPARISION

WOBBE INDEX MEASUREMENT

Session 5.2: – Page 8 –

RESIDUAL OXYGEN MEASUREMENT

CnH2n+2+(n+([2n+2]/4))[O2+3.785 N2]-> nCO2+(n+2)/2H2O+3.785(n+([2n+2]/4))N2 (2)

AR = (n + [2n+2]/4)[1mol O2 + 3.785mol N2] (3)

Where AR = Combustion Air Requirement (mol air/mol fuel)

CI = (AR) / SG1/2 (4)

Where CI = CARI Index (mol air/mol fuel)

Session 5.2: – Page 9 –

TABLE II. CARI & WOBBE INDEX OF LINEAR ALKANES

Component Formula n AR SG CI HHV WI

FIGURE 1. CORRELATION BETWEEN CARI AND WOBBE INDEX

Session 5.2: – Page 10 –

Session 5.2: – Page 11 –

TUNABLE DIODE LASER

The oxygen concentration of a sample gas can be determined spectroscopically by using a

TABLE III. RESIDUAL OXYGEN MEASUREMENT COMPARISION

Session 5.2: – Page 12 –

FIGURE 3. INTEGRATED TOTAL SULFUR & WOBBE INDEX ANALYZER

FIGURE 4. MULTIPLE FLOW CELLS IN SERIES

A = log (I0/I) (5)

Session 5.2: – Page 14 –

Session 5.2: – Page 15 –

FIGURE 6. VCSEL SPECTROSCOPY ILLUSTRATION

Session 5.2: – Page 16 –

Session 5.2: – Page 17 –

3. Barshad Y, UV-VIS Spectrometer - On-Line Diode-Array UV/VIS Fiber Optic

7. Foss, Michelle M., “Interstate Natural Gas – Quality Specifications &

Session 5.2: – Page 18 –

14. Naturalgas.org, “Natural Gas - From Wellhead to Burner Tip”,

17. U.S. Energy Information Administration, “Natural Gas”,

Session 5.2: – Page 19 –

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