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(2010) Question 58: In your experience has a non-phosphorous corrosion inhibitor been successfully used to mitigate naphthenic acid corrosion? In what circumstances and under what conditions are non-phosphorous corrosion inhibitors used?

Phosphorus-based naphthenic acid corrosion inhibitors have been successfully used in the refining industry since the early 1980’s. Phosphorus provides its protection to steel by corroding it and forming a passive layer that, under SEM/EDS, proves to be an Iron/Phosphorus/Sulfur blend.
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(2010) Question 59: What are refiners using to define the corrosivity of high acid crude oils and how is this data obtained?

In line with industry rules of thumb, Marathon considers a crude to be high acid with a whole crude Total Acid Number (TAN) above 0.5% or a side stream above 1.5%. With low sulfur crude slates the maximum TAN may be reduced, as one of our refineries that runs a predominantly sweet slate experienced naphthenic acid corrosion resulting in the TAN limit being reduced to 0.3%. Crudes are blended to the refinery TAN limit with sulfur, metallurgy and specific stream temperatures taken into account.
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(2010) Question 60: Please discuss advanced methods you use to monitor corrosion in operating units. Are any of these used in conjunction with the DCS for continuous on-line monitoring?

Marathon utilizes three methods of corrosion monitoring in the crude/vacuum units: multipoint resistance measurement (iicorr, FSM, GEBetz RCM) systems for naphthenic acid corrosion, ER probes, and corrosion coupons. While the use of coupons may not be considered an ‘advanced method’ for monitoring corrosion, we do continue to utilize them in our refining system.
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(2010) Question 63: Certain crudes are treated with H2S scavenger to meet a 10 ppm or less specification in the vapor space. In your experience, what is the disposition of the reacted and unreacted scavenger additive through the crude unit? Will this product and/or associated byproducts create corrosion or product quality issues in the crude unit or downstream units?

The majority of H2S scavengers used today are water-soluble, cyclic amines which can quickly react with H2S, forming a water-soluble reaction product. However, these amine-based scavengers are not without potential problems. As formulated, these scavengers often contain un-reacted amines.
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(2010) Question 64: Please discuss the latest tray and packing technologies for improved fractionation efficiency in existing crude and vacuum units. In particular, what is the effectiveness in terms of fouling/plugging and resulting run length?

Well designed and installed fractionator tray, packing and liquid/vapor distributor equipment are one important tool in ensuring the crude/vacuum unit is able to reach its targeted runlength. A good understanding of operating parameters along with measures and systems to ensure that operation stays within those parameters are the other tools necessary to meet that targeted runlength.
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(2010) Question 67: Have you experienced coking or other fouling of reboilers in naphtha distillation service (splitter, debutanizer, etc.)? If so, what operational or design changes did you implement to eliminate this problem?

Two types of fouling are common in naphtha reboilers. The first type of fouling is generated as a result of the more reactive cracked stock hydrocarbons and is typically seen only in units like Cokers or FCCUs with a cracking process. The second type of fouling is a more complicated issue related to the presence of sulfides in the naphtha and can be seen in straight run units like the Atmospheric Crude.
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