Keijo J. Kinnari

Study of the deactivation mechanism of Al2O3-supported cobalt Fischer-Tropsch catalysts

The influence of water on alumina-supported cobalt catalysts has been studied. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing different concentrations of water vapour. Supporting model studies were carried out using H2O/H2 feeds in conjunction with XPS and gravimetry. Rapid deactivation occurs on Re-promoted CO/Al2O3 catalysts when H2/CO/H2O feeds are used, whereas unpromoted CO/Al2O3 shows more stable activity. The results from the gravimetric studies suggest that only a small fraction of the bulk cobalt metal initially present reoxidizes to cobalt oxide during reaction. However, the XPS results indicate significant reoxidation of surface cobalt atoms or highly dispersed cobalt phases, which is likely to be the cause of the observed deactivation. Rhenium is shown to have a marked effect on the extent of reoxidation of alumina-supported cobalt catalysts.

HYDRATE PLUGGING POTENTIAL IN UNDERINHIBITED SYSTEMS

An underinhibited system is defined as a system where an insufficient amount of thermodynamic inhibitor is present to prevent hydrate formation. Underinhibition might occur due to malfunctioning of equipment, temporary limitations in the inhibitor supplies or operational limitations or errors. Understanding the plugging risk of such systems is important in order to take the correct precautions to avoid blocked flowlines. In this paper we summarize the experimental efforts for the last decade within StatoilHydro on the hydrate plugging risk in underinhibited systems. The flow simulator has been used as the main experimental equipment. The overall results for systems underinhibited with ethylene glycol or methanol show that the plugging potential increases up to a maximum at concentrations around 10-15 wt%. At higher concentrations the plugging potential reduces compared to the uninhibited system. The results can be explained as follows: As water is converted to hydrates in a system containing a thermodynamic inhibitor, the inhibitor concentration will increase until the remaining aqueous phase is inhibited. This self-inhibited aqueous phase will wet the hydrate particles, giving raise to the characteristic term of “sticky” hydrate particles. The aqueous layer surrounding the hydrate particles will form liquid bridges, by capillary attractive forces, upon contact with other hydrate particles or the pipe wall. During the hydrate formation period, there is also a possibility that some of the liquid bridges are converted to solid ones, strengthening the agglomerates. Depending on the oil-water interfacial tension, the phase ratio between the aqueous phase and the solid hydrates and the conversion of liquid bridges to solid ones, this leads to increased plugging risk at lower concentrations of inhibitor (< 20 wt%) and reduced risk at higher concentrations as compared to the uninhibited system.

Optimisation of Fischer-Tropsch Reactor Design and Operation in GTL Plants

Abstract By using examples from fixed-bed and slurry bubble column reactors using supported cobalt Fischer-Tropsch catalysts, the influence of key process parameters on reactor performance is illustrated. It is shown that there is a strong coupling between reaction kinetics, intraparticle / interphase mass-transfer and reactor characteristics which, together with other process parameters, will determine the overall reactor performance.

HYDRATE PLUG FORMATION PREDICTION TOOL – AN INCREASING NEED FOR FLOW ASSURANCE IN THE OIL INDUSTRY

Hydrate plugging of hydrocarbon production conduits can cause large operational problems resulting in considerable economical losses. Modeling capabilities to predict hydrate plugging occurrences would help to improve facility design and operation in order to reduce the extent of such events. It would also contribute to a more effective and safer remediation process. This paper systematically describes different operational scenarios where hydrate plugging might occur and how a hydrate plug formation prediction tool would be beneficial. The current understanding of the mechanisms for hydrate formation, agglomeration and plugging of a pipeline are also presented. The results from this survey combined with the identified industrial needs are then used as a basis for the assessment of the capabilities of an existing hydrate plug formation model, called CSMHyK (The Colorado School of Mines Hydrate Kinetic Model). This has recently been implemented in the transient multiphase flow simulator OLGA as a separate module. Finally, examples using the current model in several operational scenarios are shown to illustrate some of its important capabilities. The results from these examples and the operational scenarios analysis are then used to discuss the future development needs of the CSMHyK model.