Energy & Fuels, Vol.18, No.4, 1005-1013, 2004
Bulk stabilization in wax deposition systems
Managing paraffin deposition in crude oil transport pipelines comprises a significant operating expense for petroleum producers. Incipient wax-oil gel deposits age with time via a counter-diffusion mechanism where there exists a critical carbon number (CCN); wax molecules with carbon numbers greater than the CCN diffuse from the bulk fluid into the gel, and vice versa. Paraffin deposit samples were obtained from a real crude oil using a coldfinger wax deposition device and were analyzed by gas chromatography. Comparison of bulk oil and deposit compositions demonstrates that crystallization of n-paraffin components occurs at lower carbon numbers than analogous non-n-paraffin hydrocarbon components. A new concept is introduced of using the depletion of paraffin components from the bulk solution to delineate aging and incipient gelation phenomena. Depletion is defined as the normalized decrease in mass fraction of a paraffin component in the bulk fluid during deposition. Deposition performed using model fluids demonstrates that depletion is dependent upon the bulk fluid temperature. When the bulk fluid temperature is maintained lower than the cloud point, the highest molecular weight components form stable crystals in the bulk fluid, effectively sequestering the components from the liquid phase and reducing molecular diffusion into the gel deposit. At sufficiently low bulk fluid temperature conditions, an "upper CCN" value establishes an upper bound to the molecular weight range of paraffin components which contribute to the aging process. An analysis of a field deposit confirms the aging behavior of paraffin deposits observed on the coldfinger, and indicates that CCN values are in the mid 20's at field conditions.