Jacobus

Yaeger

By John Jacobus, Jacobus and Associates Corp., Atlanta, GA, and Arthur G. (Buddy) Yaeger, Jr., Natural Gas Distribution and Transmission Consulting, Inc., Georgetown, TX

Odorant Loss In New Gas Distribution Steel Pipelines

misnamed, in an early U. S. Bureau of Mines study on warning agents.8 Absorption is a process in which a gas phase molecule such as a mercaptan is physically dissolved into a liquid phase. This process will occur only if condensed liquids exist in a pipeline, i.e., if condensates or additives such as oil are present. One of the shortcomings of oil fogging of new pipe is the deposition of liquids (oil) that have the ability to remove odorant from the gas phase until such time as absorptive saturation of the liquid occurs. The Gas Engineers Handbook9 states, Oil wet mains appear to maintain odorant better than dry mains. Such would be the case only after odorant saturation of the oil occurs. Dead end lines herein refers to distribution lines which are in intermittent service. These lines may experience a non-equilibrium condition in which excessive odorant is adsorbed on the pipeline walls resulting in loss of vapor phase odorant concentration.

ecent and older literature has addressed the phenomenon of odorant loss in new steel natural gas distribution and transmission systems.1, 2, 3, 4, 5,-6 This article summarizes some of the findings and tested solutions to this problem. The diminution of the concentration of natural and/or man-made odorants in natural gas and liquefied petroleum gas (LPG), down to and including total loss of odorant, is referred to in the vernacular as odor fade. There are a number of chemical and physical phenomena that can give rise to depletion of the concentration of odorants, particularly mercaptans, in natural gas or LPG. Some examples are oxidation, adsorption, absorption and dead-end lines. Steel pipe is generally produced from metal sheets by welding the juncture of the formed sheets into a pipe configuration. The original metal sheets possess a coating of metal oxides, also called mill scale. Both the seam welding of the pipe and circumferential welding during subsequent construction of pipelines produce additional deposits of metal oxides, also called rust. The most prevalent odorant utilized in natural gas in the U.S. is tertiary butyl mercaptan (TBM) or blends thereof. Among the constituents of mill scale and rust are metal oxides (active sites) capable of chemically reacting with mercaptans such as TBM to produce products (disulfides) which are less volatile and less odorous than the original mercaptan odorant.7 The following chemical reaction occurs: 2 RSH + 6 FeO(OH) - > RSSR + 2 Fe3O4 + 4 H2O (1)

Odorant Loss Solutions

The various factors which affect odorant removal from gas streams in new iron pipe include temperature, pressure, gas flow rate and iron oxide concentration. In general, the lower the temperature, the greater the odorant loss. This is explicable since the rate of adsorption of gaseous molecules is inversely proportional to temperature.6 Adsorption is directly proportional to pressure at constant temperature. Thus, higher line pressures result in additional adsorption of odorant molecules. At higher flow rates the diffusion of odorant molecules to a pipe surface is less probable, resulting in decreased adsorption and possible subsequent oxidation of the odorant molecules at active sites. The iron oxide concentration is a function of the cleanliness of pipe. In general, the cleaner the pipe the smaller the iron oxide concentration. Of the various factors affecting odorant removal, the most controllable parameters are pressure and gas flow rate. In both of the recent studies cited above 1,2 it was found that pressure reduction of the system (from 5 psi to 2 psi in distribution systems and from 260 psi to 87 psi in transmission systems) resulting in concomitant higher flow rates resulted in faster breakthrough of odorant. The distribution system in reference 1 served a sports facility which had numerous gas fired facilities. Most of those facilities operated only when the sports facility held events. Therefore, service was interrupted between events and during the off season. This resulted in dead-end lines for days or months at a time. Various scenarios were followed to ensure properly odorized gas reached the various gas consumers including the addition of substantial volumes of liquid odorant into the piping system (slugging) which proved to be ineffective. Additionally, this practice led to odor complaints. Line slugging, once a common practice, is now seldom used inasmuch as it generally is ineffective and has the potential to lead to false leak (over-odorization) complaints such as pre-ignition odors. Subsequently, the gas pressure was lowered and liquid odorant was injected into the system or wick odorizers were utilized. During this

where R = (CH3)3C- for TBM. The iron oxide product of this reaction, Fe3O4, is incapable of further reacting with mercaptans and the original active site containing Fe(O)OH is thus passivated. Until such time as all active sites are passivated, oxidation of mercaptan odorants will continue with a resultant reduction of the vapor phase concentration of the odorant. Adsorption is a process in which a molecule such as a TBM molecule is physically attracted to and adheres to a surface. The process of adsorption is reversible and when equilibrium is reached, the adsorption/desorption rates at constant pressure are equal. The amount of adsorption that can occur is a function of the composition of the surface and of the surface area. The surface area of mill scale coating or of rust is greater than that of the underlying native metal (steel) and the thicker the mill scale coating the more adsorption is expected to occur. However, until such time as a surface has achieved equilibrium with the adsorbed species that species concentration in the gas phase above that surface is reduced. In other words, the mercaptan concentration is reduced until such time as adsorptive equilibrium is achieved. Adsorption will also occur on other metal pipe surfaces such as copper utilized in LPG systems. On the other hand, certain plastic surfaces such as polyethylene do not appreciably adsorb odorants.6 The phenomenon of adsorption has been appreciated for more than 70 years. It is addressed, although

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period, the systems appeared to have stabilized in terms of odorant concentration. At the end of the 2005 sports season, the facility was essentially dormant for a period of five months and, upon reopening, it was found that the system was properly odorized utilizing city gas with no odorant augmentation. The transmission system in reference2 utilized three different approaches to condition new steel lines, including slugging, injection of highly odorized gas, and continuous liquid dosing. Slugging was found to be ineffective in passification of new lines. Continuous liquid odorant dosing was used with some success in systems where bypass odorizers could not be employed. The major drawback was the increased amount of odorant required to passify a new line relative to the injection of highly odorized gas, commonly two to three times as much. Introduction of highly odorized gas (ca. 40 ppm mole basis) resulted in relatively rapid passification of pipe (five days for a four-mile section) after which the pressure was raised from 65 psi to 260 psi with no negative effects.

Conclusions
Methodology does exist for safely conditioning new steel pipe relative to odorant loss. When a new gas system (transmission, distribution, consumer) is brought into service, the sense of smell should not be utilized to determine if the system is purged of air and that natural gas is present in the line. Rather, a gas detector (combustible gas indicator) should be utilized. If a new gas system is brought into service and unodorized gas is detected, immediately notify the gas supplier to ensure that the supplier is properly odorizing the gas and, if so, what action(s) need to be taken to rectify the absence of odorant. Neither the National Fuel Gas Code (NFPA 54) nor U.S. Department of Transportation regulations (49 CFR 192) address issues of potential odorant loss in new gas systems. Companies and company employees involved in the construction and utilization of new steel transmission and distribution gas systems requiring odorization should be cognizant of the potential for under-odorized or non-odorized natural gas to exist at the initiation of service of those systems. P&GJ Authors: John Jacobus has a B.S. degree in chemistry from Southwestern at Memphis and a Ph.D. degree in organic chemistry from the University of Tennessee. After a 25-year teaching career (Princeton, Clemson, Tulane), he entered the consulting profession. He provides consulting and expert witness services in a broad range of fuel gas issues involving gas odorants and gas related incidents. Arthur G. (Buddy) Yaeger, Jr. has a B.S. degree in chemical engineering from Tulane University and retired from Entergy Corp. with nearly 37 years experience in operations and engineering management in the natural gas distribution business in New Orleans. He is president of Natural Gas Distribution Consulting, Inc. where he provides consulting and expert witness services in a broad range of gas distribution operations, practices and procedures.

REFERENCES
1 Flynn, E. (Mulcare Pipeline Solutions, Boonton Township, NJ, WWW.Mulcare.com) and M. Cook, Gas Technology Institute (IGT) Symposium, Houston, July 2006. 2 Larcher, A.V (AlintaGas Research Laboratory, Bentley, Western Australia) and J.H. . Bromley, 9th Asian Pacific Confederation of Chemical Engineering Congress, Paper #934, Christchurch, New Zealand, 2002. 3 Suchomel II, F., Odorization, IGT, Chicago, 1980, p. 181. 4 Kniebes, D.V Odorization, IGT, Chicago, 1980, p. 197. ., 5 J.K. Wright, Odorization II, IGT, Chicago, 1990, p. 405. 6 Moran, E.A., P.G. Pai and I. Carducci, Odorization III, IGT, Chicago, 1993, p. 449. 7 Campbell, I.D., N.A. Chambers, and J. Jacobus, IGT Odorization Symposium, Chicago, 1994. 8 Katz, S.H., and E.J. Talbert, U. S. Bureau of Mines Technical Paper 480, Government Printing Office, Washington, DC, 1930, p. 6. 9 Anon., Gas Engineers Handbook, Industrial Press Inc., New York, 1965, p. 9/115.

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