REDUCING MEASUREMENT UNCERTAINTY IN PROCESS GAS QUALITY MEASUREMENTS Class # 5330 Darin L.

George Senior Research Engineer Southwest Research Institute 6220 Culebra Road San Antonio, Texas USA Introduction The general term gas quality is used to refer to many different measures of the content of a natural gas stream. Common measures of gas quality include heating value, water vapor content, hydrogen sulfide or total sulfur content, levels of inert gases such as CO2, and hydrocarbon and water vapor dew points. These values determine how the gas stream must be handled, whether it can be used efficiently by customers, and whether the potential exists for damage to end-user equipment or pipelines that carry the gas stream. The presence of water and hydrogen sulfide in a gas stream, for instance, can create sulfuric acid and pit the walls of a pipeline. Shifts in heating value and specific gravity of the gas can lead to poor furnace performance, or require adjustments of gas-fired industrial equipment. High levels of non-hydrocarbon gases will reduce the heating value and make transportation of the gas less economically efficient. To determine whether natural gas meets gas quality standards in their transportation tariffs, producers and transmission companies must accurately measure all contents of the stream that affect gas quality. Accurate gas quality data will also be crucial to the effective introduction of liquefied natural gas (LNG) and marginal gas supplies into the natural gas transmission network in the near future. Accurate gas quality measurements depend not only on the instruments used to make measurements, but on the methods and equipment used to carry samples to the instruments. This paper will discuss several causes of measurement errors in gas quality analysis. These errors can be either bias errors that lead to consistently high or low gas quality measurements different from the actual value of the gas stream, or precision errors that lead to random shifts in the measurement from the actual value. The paper will identify several ways to reduce quality measurement errors of a gas sample as it makes its way from the pipeline sample point to the point of analysis. Several references are listed at the end of the paper to provide the reader with further guidance. In particular, the reader is referred to the latest editions of API MPMS Chapter 14.1 (Reference 1) and GPA 2166 (Reference 2) for guidance on sampling methods, which will not be discussed here. Causes of Sample Distortion and Measurement Errors As noted by Behring (Reference 3), there are generally three causes of natural gas sample distortion that lead to errors in gas quality assessment. 1. The gas composition is not distributed uniformly in the pipeline, and the probe is not located at the appropriate location to collect an average or representative sample of the stream. In some cases, the pipeline itself may contain condensed liquids, either hydrocarbon liquids or condensed water, and a sample of the gas phase alone may not indicate that liquids are also present. 2. The gas sample is exposed to temperature and pressure conditions that cause condensation and change the composition of the gas sample before analysis. 3. Molecules of the sample gas adsorb (stick) to the walls of materials used to transport and contain the sample, and do not travel to the analysis instrument. The first two causes of distortion primarily affect measurements of heating value and water vapor content, and can be avoided with proper knowledge of the hydrocarbon and water dew points of the stream. The third cause of distortion can also cause errors and uncertainty in other measures of gas quality such as H2S measurement. These three causes are key points that should be remembered by the reader, as designing equipment to avoid them will greatly minimize uncertainties and errors in gas quality analysis.

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Hydrocarbon and Water Vapor Dew Points A necessary step before gathering a sample of a gas stream is to use any available information to determine conditions within the pipeline. The dew points of a gas stream are often used as measures of gas quality, but they are also needed to minimize uncertainties and errors in measurements of other gas quality parameters. The hydrocarbon dew point is defined as the pressure and temperature at which hydrocarbon constituents in a natural gas mixture begin to change phase from gas to liquid. For instance, if the temperature of a natural gas mixture is reduced while the pressure remains constant, the temperature at which hydrocarbon condensation begins to occur is the hydrocarbon dew point temperature. The water vapor dew point of a natural gas is the pressure and temperature at which water vapor contained in the gas mixture begins to condense. While the water vapor dew point depends mainly on the amount of moisture in the stream, the hydrocarbon dew point depends in a complex manner on the amounts and distribution of the heavy hydrocarbons, particularly hexane and heavier. The water vapor and hydrocarbon dew points of a given gas stream will almost always be different, and will both vary with the pressure of the stream. If a gas sample is cooled at one pressure, the water dew point may be reached well before the hydrocarbon dew point, while at another pressure, the hydrocarbon dew point may be reached first for the same gas. Figure 1 gives an example of the hydrocarbon and water dew point curves for a 1,050 Btu/scf gas containing 5 lb/MMscf of water vapor, showing this behavior. Knowledge of the dew points of a gas stream, either by measurement or by analysis of an existing sample, will allow sampling hardware and methods to be properly selected and applied to minimize errors and uncertainties. It is recommended that both dew points be determined before sampling begins. Equipment used to collect or transport samples for gas quality analysis should be above the higher of these two dew point temperatures at the maximum expected line pressure.
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Figure 1. Coexisting hydrocarbon and water vapor dew points for a typical transmission gas. Guidance for measuring dew points using a chilled mirror are given later in this paper. Guidance for determining hydrocarbon dew points using previous gas analyses and calculations can be found in Reference 4. The Sample Point The first point where errors in a gas stream analysis can be reduced is the location where a sample is taken from the pipeline. A common industry guideline is that a sample probe should extend into the center one-third of the pipeline. By keeping the probe inlet away from the pipeline walls, the sample drawn into the probe is more likely to be from a well-mixed region of the stream and representative of the overall gas stream composition. Placing the probe at the center of the pipeline also minimizes the chances of ingesting liquids. The presence of liquids in the gas pipeline usually indicates a gas quality problem, however, and where probes are installed to avoid sampling liquids that may be flowing along the bottom of the pipeline, gas samples should be analyzed carefully.

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If the operating pipeline temperature and pressure are not well beyond either the hydrocarbon or water vapor dew point, it may be prudent to assume that liquids are present in the pipeline. The 6th edition of API Chapter 14.1 (Reference 1) has recently clarified its guidelines on sample probe location. Where streams are near the hydrocarbon or water dew point, probes should be placed at least 5D downstream of any element that creates a disturbance in the flow, where D is the maximum diameter of the disturbance. For major disturbances that change the flow profile in the stream, such as orifice plates, elbows, flow conditioners, valves, etc., D should be taken as the inside pipe diameter at the disturbance. The reason for this precaution is that eddies or vortices formed by the disturbance may create regions of low pressure where condensation would occur within the stream itself. Placing the probe far enough from the disturbance will avoid sampling of these gasliquid regions, which may not be representative of the stream as a whole. When gas streams are at flowing conditions well above the hydrocarbon or water dew point, many different probe designs may be used successfully. More attention should be given when the pipeline is operating near or at either of these dew points. Consideration should be given to applying heat to the sampling apparatus to move the temperature away from the dew point, or using a special probe designed to avoid cooling and condensation of the sample. If a regulating probe is needed to reduce the pressure of a sample before collection or analysis, applying heat or using a specially designed probe that avoids condensation should be considered here as well. If it is believed that liquids are present in the pipeline, and only a sample of the gas phase is desired, filters on the probe may be useful in keeping liquids from the gas-phase sample, as long as the filters do not alter the composition of the gas and distort other measures of gas quality in the sample. Cleaning and Passivation of Sample Containers and Sample Lines Surface effects that draw components out of a gas stream must be avoided to keep sample compositions stable. Even clean, solid surfaces are subject to adsorption and desorption of molecules. However, porous surfaces can preferentially trap certain molecules, and liquid coatings on walls can dissolve gas molecules or release them as pressure and temperature of the equipment change. For this reason, stainless steel is recommended for sample cylinders (both constant-volume and floating piston) so that components are not lost from or added to the sample before it is delivered to an analyzer in the laboratory. Elastomers used in valve seats or o-rings should also be selected based on their ability to resist adsorption and desorption, and to withstand high temperatures if necessary. If the gas stream is known to be high in H2S or sulfur content, sample cylinders should be lined or coated with non-reactive epoxy or passivated on the inside surface to avoid corrosion problems. Reference 1 recommends that H2S be analyzed on site using an on-line analyzer where practical, to eliminate any possibility of adsorption or reaction with the sample cylinders. The same guidelines should be applied to sample lines, filters, regulators and other equipment used to transport samples to a cylinder or a field analyzer. Research (References 5 and 6) has evaluated several methods of cleaning sampling surfaces in sample containers and lines. Flowing saturated steam proved to be the most robust method for ridding sampling surfaces of residues that may distort the next sample collected. In particular, the flowing steam removed oily liquidhydrocarbon residues that were demonstrated to dissolve heavy hydrocarbons out of the gas phase. For floatingpiston sample cylinders, it is recommended that the cylinder be disassembled, the metal parts be steam cleaned, and old contaminated soft seals be replaced with new seals. These practices should be followed when putting equipment into service, or each time before a sample container is used. Analysis Equipment and Other Devices Once the gas sample has been transported to the analyzer, either through a sample line to an on-site device or via sample container to a laboratory, the accuracy of the analysis device itself becomes important. Different devices are used to assess the different aspects of gas quality. Common devices include: Length-of-stain tubes. Automated and manual chilled mirror devices, used in the field to measure water vapor content as well as water vapor and hydrocarbon dew points. Gas chromatographs (GCs) in the laboratory or in the field for analyzing hydrocarbon and inert gas content of the stream and computing heating value.

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Dedicated on-line moisture analyzers, which can use a variety of measurement principles to determine water vapor content and dew point. Dedicated field instruments for H2S and total sulfur analysis.

This section will briefly discuss the first four categories of analyzers and ways to reduce their uncertainties and measurement errors. Length-of-stain tubes. As Reference 7 notes, length-of-stain tubes are commonly used in the industry as go/no-go indicators, detecting merely whether a certain contaminant such as CO2, water vapor, or hydrogen sulfide is present in the gas stream. These are glass tubes packed with a granular material, coated with a chemical reagent that changes color when it reacts with a particular contaminant in the gas sample. The length of stationary packing in the tube that changes color is proportional to the concentration of the contaminant and the volume of the gas sample drawn through the tube. Length-of-stain tubes have several disadvantages, one being that tubes treated to detect one component in the gas may give false readings when other components are present. Water vapor tubes, for example, may give false readings in the presence of alcohol or glycol. Another disadvantage is that the accuracy of measurements depends on the operator; uncertainties in measured water vapor content can be as high as 25%. While length-of-stain tubes have an advantage of simplicity and a large body of experience surrounding their use, many operators prefer to use the tubes simply to detect the presence or absence of a contaminant in a gas sample, and use appropriate analyzers to quantify the contaminant or judge gas quality. Chilled mirror devices. Reference 7 also presents a review of steps that can be taken to improve the accuracy of measurements made with manual chilled mirror devices. The original purpose of the Bureau of Mines chilled mirror device was to measure the water vapor dew point of the stream, so that its water vapor content could be determined using a published correlation (Reference 8). The device has since been adapted to hydrocarbon dew point measurement as well, and the recommendations of Reference 7 apply to both applications. Conditions within the pipeline should be accurately reflected in dew point measurements; that is, the chilled mirror device should measure the dew point at pipeline pressure. If the pipeline pressure and temperature are believed to be near the hydrocarbon or water dew point, precautions should be taken to avoid condensation of water or hydrocarbons in the line transporting the sample to the chilled mirror. A typical approach would be to heat the sample line to a safe temperature above the pipeline temperature. One disadvantage of the Bureau of Mines chilled mirror dew point tester is its subjectivity. Dew point temperature measurements depend on the operators skill at controlling the refrigerant flow, and on the operators ability to identify and interpret the condensation seen on the mirror. Improved measurement accuracy can be obtained by checking and calibrating pressure and temperature instruments used with the dew point tester on a regular basis. However, certain sources of bias uncertainty cannot be eliminated by calibration, and should be considered when assessing measurement accuracy. For instance, a recent study (Reference 9) discussed how very thin films of condensation on the chilled mirror will not be visible to an operator until the depth of the liquid film is comparable to a single wavelength of visible light. By estimating the minimum film thickness that would be visible on a typical chilled mirror, then determining the amount of cooling required for the condensation to become visible, the authors determined that a typical dew point temperature measurement could underestimate the point at which liquids first condense by 0.4F to 2.7F (0.2C to 1.5C). In the field, this measurement bias would depend mainly upon the properties of the gas being analyzed, with richer gas streams having smaller undermeasurement biases. A round-robin study (Reference 10) estimated the reproducibility of hydrocarbon dew point temperatures among different operators on the same gas stream to be 2.3F (1.3C) at the one-sigma confidence level. This value depended mainly upon differences between the operators, but did not include the bias due to the limit of visibility discussed above. Reference 8 specifies a cooling rate of 1F per minute for the mirror during dew point measurements. If the mirror is chilled faster than the recommended cooling rate, the device measuring the mirror temperature may lag the temperature of the mirror surface, causing the measured dew point temperature to be biased high. Faster cooling rates will lead to larger time lags and larger bias. While an operator can cool the mirror as rapidly as possible in a preliminary measurement of dew points, the 1F/minute guideline should be followed for better accuracy and repeatability. Flow rates through the device should follow manufacturers specifications, typically 5 scfh, but if valves in the apparatus (used to control flow rate) cause large pressure drops and create the potential for condensation before the gas flow reaches the chilled mirror, lower flow rates may be applied to minimize this potential for bias.

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One cause of measurement error by new operators is confusion of one type of condensation for another. Examples of hydrocarbon, water, and alcohol condensation are shown in Figure 2 to help users avoid errors in identifying them. Hydrocarbon dew points are often preceded by an iridescent ring, and at the dew point, small droplets will form on the mirror within the ring. Water vapor condensation is marked by distinct, opaque gray spots with sharp edges, while alcohol forms indistinct white spots on the mirror. The ability of the operator to differentiate between these will help to avoid errors in gas quality assessment.

Figure 2. Examples of various types of dew formation on a chilled mirror surface. From left to right, hydrocarbon condensation, water vapor condensation, and alcohol condensation. Biased measurements can also be caused by improper cleaning of the mirror (Figure 3). Deposits on the mirror surface can act as nucleation sites that will cause condensation to form early and lead to measured dew point temperatures that are biased high. Soft materials such as cotton, along with a fast-evaporating cleaner such as ethanol or rubbing alcohol, should be used to clean the polished metal mirror without scratching. Scratches can also provide nucleation sites for condensation.

Figure 3. Examples of improper cleaning of a dew scope mirror leading to nucleation sites that bias measurements (Reference 7). Left, a poorly cleaned mirror with small deposits remaining; right, deep scratches left by improper cleaning. As stated earlier, because the Bureau of Mines chilled mirror device requires an operator to identify the dew point visually, measurements are considered subjective. As of 2006, automated chilled mirror devices were available to the global natural gas industry and just being introduced to the U.S. natural gas industry. These devices, similar to the manual chilled mirror device, detect condensation by a change in light intensity reflected off the mirror to an optical sensor. No independent research has been performed to evaluate these devices at this time, so no recommendations can yet be made on their accuracy compared to the subjective manual chilled mirror or on their ability to distinguish different types of condensation. Gas chromatographs. Because of the wide variety of gas chromatographs available for field and laboratory use, no attempt will be made here to discuss their maintenance. The reader should consult the manufacturer(s) of their devices in this regard. However, some common methods to avoid calibration errors are common to all devices. Reference 1 requires that when a calibration gas is first obtained, its composition should be used with equations of state to compute its hydrocarbon dew point. Before the calibration standard is first used, the delivery

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cylinder for the standard must be heated to a temperature of 30F (17C) above the computed hydrocarbon dew point. The cylinder must be kept at this temperature for at least four hours before the cylinder is opened, to ensure that all components in the cylinder have vaporized. Similar guidelines apply to the sample lines from the calibration standard to the chromatograph, and any regulators in the system. Where a gas chromatograph is used to analyze a gas stream composition, a useful method for detecting problems with the delivery of samples to the GC is the use of a response factor plot (Reference 5). This relies on the known composition of the calibration gas and the response of the GC detector to specific hydrocarbons. An example is shown in Figure 4, where response factors for a thermal conductivity detector (TCD) are plotted versus molecular weight of normal paraffin hydrocarbons. This plot should produce a straight line for the first few hydrocarbons, due to the physical mechanism by which a TCD measures the amount of molecules present. A similar plot would be produced using response factors from a GC with a flame ionization detector.

Figure 4. Example plot of TCD response factors versus molecular weight, showing the linear response for undistorted calibration samples and the non-linear response for a distorted sample (Reference 5). When a known gas composition is used to calibrate a GC, and one or more component response factors fall below the straight line, this indicates that those components have been lost somewhere between the calibration gas supply and the GC. Unless the calibration gas can be shown to have an incorrect certified composition, the user should suspect that sample distortion has occurred and work to correct it. Of course, natural gas calibration standards can themselves be distorted while samples are delivered to the GC. Reasons for distortion may include storage in a pressure cylinder contaminated with oil on the inside walls, or failure to maintain the calibration gas cylinder at a temperature above its hydrocarbon dew point. If this distortion of a calibration gas is not caught and corrected, errors will occur in the heating value and hydrocarbon dew point obtained from GC analysis of the pipeline stream. Errors in calculated hydrocarbon dew point can, in turn, lead to the choice of incorrect sampling methods for later analyses. Automated moisture analyzers. Like the hydrocarbon dew point analyzers, no third-party studies evaluating their performance are available to the natural gas industry. Unlike hydrocarbon dew point analyzers, however, several models of moisture analyzers are available to monitor moisture content and water vapor dew point, using a variety of technologies (Reference 7). Techniques to ensure accurate analysis depend on the strengths and weaknesses of each technology and their need for calibration, as discussed below. Electrolytic devices use a voltage potential to split (electrolyze) the water molecules in a gas sample and produce a current proportional to the moisture level in the sample. In this way, such devices can provide an absolute measurement of water vapor content that does not require calibration. Electrolytic devices tend to have linear responses down to moisture levels of hundreds of parts per million, but they are sensitive to the flow rate and

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require a clean gas sample free of liquids and alkalis to function correctly. On the other hand, capacitance sensors are relative measurement devices and must be calibrated against known moisture standards. These devices use a dielectric, hygroscopic material sandwiched between a pair of electrodes to form a capacitance cell. The hygroscopic material absorbs water vapor from the gas stream until equilibrium is reached. When an AC voltage is applied to the electrodes, the return signal is proportional to the capacitance of the cell, which in turn is proportional to the moisture level in the cell. Sensors can be mounted directly in the pipeline, but they are subject to contamination and false readings from glycol and other contaminants in the flowing stream. Many users prefer to mount the sensor in an independent sample loop with filters to remove contaminants detrimental to the sensors operation. Laser-based analyzers operate on the principle that every molecule has a unique fingerprint for the absorption of light at specific wavelengths. By tuning a laser to a specific frequency, a sensor can be created in which light energy is selectively absorbed by the molecules of interest in a gas sample. Since absorption is directly proportional to the concentration of the absorbing molecules, a properly tuned device can provide a direct measurement of moisture concentration, CO2 concentration, or the concentration of other gaseous components for which a laser diode of the appropriate frequency is available. One manufacturer notes that these devices have an extremely fast response time compared to other sensors due to the use of light absorption instead of chemical equilibrium to determine moisture content. Filtering of the sample may be needed for accurate measurements, and as with many compounds of interest, other components may absorb light at the wavelength tuned for H2O absorption, so that care must be taken to avoid false values. Finally, piezoelectric sensors, or vibrating crystal sensors, are relative measurement devices that require periodic calibration. The crystal is coated with a hygroscopic material that adsorbs water vapor from a flowing gas sample. As the coating adsorbs water from the sample, the total mass of the crystal increases and its vibration frequency changes. This frequency is read and compared to a reference, such as the oscillation frequency of a reference crystal sealed in a controlled environment. By comparing this oscillation frequency to the crystal frequency after all moisture has been removed from the same sample, the water vapor content by mass of the original sample can be determined. Temperature, pressure, and flow rate can affect the frequency response of piezoelectric sensors, so that control or compensation of these parameters may be necessary for accuracy. To their credit, these moisture sensors are accurate in the presence of contaminants, particularly H2S. Conclusion This paper has highlighted some, but not all, of the ways in which measurement errors related to gas quality can be reduced. Much of the paper has reviewed approaches specific to the devices used to measure hydrocarbon dew points, water vapor dew points, moisture content, and heating value. Regardless of the composition and level of contaminants in each companys pipeline, however, all users of sampling and analysis equipment will benefit the most by seeking and eliminating the three causes of sample distortion and measurement error listed at the start of the paper. By designing sampling equipment that avoids these causes, the samples delivered to gas quality measurement devices will be representative of conditions in the pipeline. By then applying insight on the performance of specific devices, uncertainties and errors in gas quality measurements will be minimized. References 1. API Manual of Petroleum Measurement Standards, Chapter 14 Natural Gas Fluids Measurement, Section 1 Collecting and Handling of Natural Gas Samples for Custody Transfer, Sixth Edition, American Petroleum Institute, Washington D.C., February 2006. 2. GPA Standard 2166, Obtaining Natural Gas Samples for Analysis by Gas Chromatography, Gas Processors Association, Tulsa, Oklahoma, 2005. 3. Metering Research Facility Program: Interim Research Results for Collecting and Handling Natural Gas Samples, Behring, K.A., GRI Topical Report No. GRI-98/0034, Gas Technology Institute, Des Plaines, Illinois, April 1998. 4. George, Darin L., and Kelner, E., Additions and Changes to the Latest Revision of API Chapter 14.1, Proceedings of the Eighty-First International School of Hydrocarbon Measurement, Oklahoma City, Oklahoma, May 2006, Class #5255. 5. Metering Research Facility Program: Natural Gas Sample Collection and Handling-Phase I, Behring, K.A. III and Kelner, E., GRI Topical Report No. GRI-99/0194, Gas Technology Institute, Des Plaines, Illinois, August 1999.

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6. Metering Research Facility Program: Natural Gas Sample Collection and Handling-Phase III, Kelner, E., Sparks, C. R., and Behring, K.A. III, GRI Topical Report No. GRI-01/0070, Gas Technology Institute, Des Plaines, Illinois, August 2002. 7. Metering Research Facility Program: Natural Gas Sample Collection and Handling-Phase IV, George, D. L., Barajas, A. M., Kelner, E., and Nored, M., GRI Topical Report No. GRI-03/0049, Gas Technology Institute, Des Plaines, Illinois, January 2005. 8. ASTM Standard D 1142, Standard Test Method for Water Vapor Content of Gaseous Fuels by Measurement of Dew Point Temperature, ASTM International, West Conshohocken, Pennsylvania, USA, 1995. 9. Cowper, C. J., Natural Gas Hydrocarbon Dewpoint: Comparison of Measurement and Calculation Methods, presented at the Second Gas Analysis Symposium and Exhibition, January 2002, Masstricht, the Netherlands. 10. Warner, H. R., Leamer, E. E., Spence, A. P., Bone, R. L., Hubbard, R. A., Bernos, J., and Kriel, W. A., Hydrocarbon Dewpoint Determination of Lean Natural Gases, Proceedings of the Eightieth GPA Annual Convention, San Antonio, Texas, USA, March 2001.

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