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Title: Mercury species in natural gas condensate
Author: Shafawi, Azman Bin
ISNI:       0000 0001 3395 129X
Awarding Body: University of Plymouth
Current Institution: University of Plymouth
Date of Award: 1999
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The presence of ultra-trace levels of mercury in industrial gas and condensate streams is a cause of both environmental and production concern. The toxic nature of the element, in all forms, together with its ability to shut-down large processing plants dictates a need for its accurate and precise measurement. The study which investigated the recovery of various mercury species, spiked into synthetic and real condensate samples using conventional and new digestion and/or extraction techniques showed recovery was dependent upon the speciation. Using the most efficient technique, L-cysteine with persulphate, recoveries of over 90 % were obtained for diphenyl mercury, ethyl and phenyl mercury chlorides and mercury chloride. The recovery of 15% for the important dimethyl mercury species limits the use of this technique. A novel technique has been developed for the determination of total mercury in complex liquid hydrocarbons. Samples (up to 1.0 ml) were vaporised (400°C) and swept through a gold-coated silica trap maintained at 200°C, which retained all mercury species and discarded the matrix. The trap when heated to 900°C released the mercury for measurement by atomic fluorescence spectrometry (AFS). The recoveries for eight mercury species spiked (10 to 50 ng ml -1) into toluene and condensate were generally over 90 %. The instrumental limit of detection (LOD) was 11 pg. The total mercury content of gas condensates, gasolines and heavy oils were determined. Gas chromatography coupled, via a pyrolysis interface, with AF detection was able to determine mercury species in gas condensate, at picogram levels (LOD: 2.5 to 7 pg) using a direct sample injection procedure. For a given column system the positive identification and quantification of up to eight mercury species was obtained. A maximum injector temperature of 125 °C was recommended, to avoid the conversion of species. Mass balance calculations show a strong correlation between the total mercury content and the sum of the lower diallcyl mercury species, for all condensate samples studied. Three commercially available mercury removal systems, A, B and C produced a reduction in the mercury content of hydrocarbon streams under pilot plant conditions. The two stage system, 'A', produced a minimum of 30 % conversion from organomercury to elemental mercury after the hydrogenation reaction in stage 1. While elemental mercury was adsorbed by the stage 2 reactor, the organomercury species were not removed. The single stage adsorber 'B' showed 100 % removal efficiency for three dialkyl mercury species in liquid hydrocarbon streams. The removal efficiency for adsorber 'C' was species dependent. Two common condensate species gave values of 50 to 80 % removal efficiency while the third species showed time-dependent bleed-off.
Supervisor: Not available Sponsor: Petroliam Nasional Bhd, Malaysia ; P.S. Analytical Ltd
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Petrochemical processes; Mercury determination