The majority of natural gas processing plant and pipeline operators will readily identify with the most

commonly reported pipe contamination related problem - that of the so-called black powder.

This black powder is made up of various forms of iron sulphide (FeS), iron oxide (FeO), hydrocarbons and asphalt components. However, more recently, a new form of contamination has been catching operators attention. It too involves sulphur and is commonly referred to as the elemental sulphur formation and deposition process.

Although sulphur is a small part of the overall make-up of the extensively analysed contamination deposits, the term elemental sulphur has been applied due to the general yellowish colour and sulphur smell of the deposits. The elemental sulphur deposition mechanism is quite similar to the black powder phenomenon, however it is less predictable and seems to arise even though elemental sulphur is not identified in the initial composition of the gas to be transported.

As gas transportation proceeds down the network and through a series of chemical reactions eventually catalysed by the presence of other components[1], some of the sulphur bearing molecules release elemental sulphur (S8). This is due to the very complex phase diagram of sulphur that lends itself to pass from gas to solid state when physical conditions of pressure and temperature are met. These conditions, obviously related to the partial pressure of S8, are extremely difficult to predict and give the impression that the process has a random-like occurrence characteristic.

Although rigid quality specifications apply to the composition of the gas to be transported, a series of chemical and physical processes can lead to the formation of undesirable contaminants (for example, carbonyl sulphide (COS), hydrogen sulphide (H2S) and carbon disulphide (CS2)), which will eventually release sulphur in its gas phase. Once the sulphur vapour is in the transported gas and at a specific partial pressure it is likely to undergo a change from gaseous state directly to solid state S8 (desublimation phase change) with pressure and temperature evolving down the pipeline network.

The recorded observations of elemental sulphur detection have been rapidly increasing with the development of large transportation networks operating at high pressures. The phenomenon now appears to be a worldwide problem which not only adversely impacts natural gas supplies but also coal seam gas supplies.

The consequences of the presence of elemental sulphur vary, ranging from a nuisance value to complete disruption of gas supply or failure of equipment. Extensive damage to rotating plant, including fires, has been attributed to the presence of elemental sulphur. The presence of elemental sulphur not only translates to the potential for gas supply interruption, damage to equipment and problems with general reliability of supplies, but also places very significant and costly demands on system maintenance.

Current technology is not able to continuously and accurately determine the level of sulphur vapour within a pipeline system. This is because the level of sulphur vapour is minute, at sub parts per million (ppm) concentrations. Figure 1 illustrates varying sulphur vapour concentrations in a rich natural gas composition for varying pressure and temperature conditions.

Extensive gas chromatograph-mass spectrometer (GC-MS) and inductively coupled plasma-mass spectrometer (ICP-MS) analysis of pipeline elemental sulphur samples, sourced from a number of Australian and overseas natural gas transmission pipelines, have been performed through the Separation Science Laboratory at Murdoch University, Perth. The generated total ion chromatograms have clearly demonstrated the significant presence of simple and complex hydrocarbon components within the deposits. This analysis work has identified compressor oils, greases, gas dehydration fluids, condensate, single hydrocarbon types and a variety of elements, including a number of the transition metals, as being present in the so-called elemental sulphur samples.

Although the samples have common elements and compounds, there are subtleties between samples that can assist in the origin of some of the sample components and in the particle formation and deposition process. Obviously by having the ability to control the entry or creation of these elements and compounds will help reduce the elemental sulphur deposition problem. It is possible that the presence of the particles already in suspension in the gas stream may, together with the nucleated sulphur particles, provide a sufficient number of particles for the coagulation (particle growth) process to occur. This is because the coagulation rate is proportional to the square of the number of particles present. It is therefore possible that there may be circumstances where the number of particles nucleated is not large enough for significant coagulation to take place.

The control of the elemental sulphur deposition process is not within the scope of this article it is an extensive topic and is discussed elsewhere.

As for the more common black powder problem, the elemental sulphur deposition mechanism also has demonstrated that there may be preferential site conditions. For instance, at certain locations along a given transmission pipeline system, a metering or pressure regulation site A may be known to be a location for elemental sulphur deposition, yet a similar facility B on the same pipeline receiving the same natural gas at near identical flowing pressure and temperature conditions will not be impacted, or be minimally impacted, by the elemental sulphur deposition phenomenon.

Single facilities that source their gas supply from a lateral that have a horizontal T connection to the mainline appear to be susceptible to the sulphur deposition process provided the ratio of the gas flow into the lateral is less than approximately one fiftieth of the mainline flow (case studies have confirmed this), although the pipe orientation has a significant influence. This also means that small gas usage equipment located at pipeline facilities, such as gas engine alternators, are more susceptible to sulphur deposition. As a general rule the greater the drop in pressure at the contaminated site, the higher the probability of elemental sulphur deposition.

The research conducted to date has provided an understanding as to why and how the elemental sulphur formation and deposition processes occur. From these findings a number of engineering and general pipeline operational recommendations have been able to be made and successfully tested under field conditions. The main research program results include:

* Determination of the kinetics associated with the sulphur desublimation (vapour state directly to solid state) process. This has provided an insight as to why the deposition process occurs. * Generation of the sulphur vapour map for the prediction of sulphur vapour saturation levels within a gas stream. Demonstrated that sub ppm levels of sulphur vapour only are required for deposition to occur * Demonstration, through computational fluid dynamics studies, of the contribution to elemental sulphur deposition due to the complexities of two-phase flow at pipeline T junctions. Understanding as to why preferential site selection occurs for observed deposits. * The susceptibility of some valve types and cage configurations to elemental sulphur deposition occurrence. * The significant contribution of hydrocarbon compounds to the elemental sulphur formation and deposition process. * The impact of the sulphur transportation process to the formation of elemental sulphur has shown the importance of the interaction of various sulphur compounds during the gas transportation process to the elemental sulphur formation process. * Parallels between the black powder and elemental sulphur contamination processes. * Determination that some of the more unique elements detected appear to have their origins in the soils and/or crustal rock found along the particular pipeline routes.

The so-called elemental sulphur deposition process is extremely complex, however the kinetics involved are now being understood. Foreign particles in the gas stream clearly can significantly contribute to this unwanted process. Further research is required, particularly into the flow dynamics and the design of equipment used at pressure reduction facilities and into why preferential site selection can occur for the deposits. The ongoing support of the APIA and its membership in this research work is gratefully acknowledged.

The consequences of the presence of elemental sulphur vary, ranging from a nuisance value to complete disruption of gas supply or failure of equipment.

References

1. Pack, D. J., 2005. Elemental Sulphur Formation in Natural Gas Pipelines. PhD Thesis. The University of Western Australia. 2. Pack, D. J., 2006. Elemental Sulphur Formation in Natural Gas Transmission Pipelines. APIA Research Program Project Number 2000-09, CRC-WS Project Number 01-301, Phase 2 Investigations.