Enhancing Desalter Performance to Successfully Process High Metal Crudes Jeffrey A.

Zurlo Senior Refinery Application Specialist GE Power & Water Water & Process Technologies Introduction Contaminants in crude oil feed stocks can be an impediment to processing discoun ted crude oil supplies in a reliable, safe, and profitable fashion. Specificall y, metals contamination poses a threat to a wide array of refinery operations in cluding crude unit fouling, catalyst contamination, and finished product quality . Almost all crude oils contain detectable metal levels, and their solubility a nd concentrations can vary widely. While some forms of metal contamination can be effectively removed via the normal desalting process, other types do not rea dily transfer to the water phase and therefore require additional means to remov e them. , A number of approaches have been used to remove metal contaminants i n the past, including filter adsorption, precipitation, and treatment with inorg anic acids among many others. Work over the past 20 years has shown the most e ffective method to maximize metal removal in the desalting process is to effect a transfer of the metals from the hydrocarbon phase to the water phase utilizing water soluble hydroxyacids. An additional benefit to this method is the remova l of amine and ammonia compounds from the crude oil, which will reduce crude tow er fouling and overhead system salt-induced corrosion. Care must be exercised when selecting a Metal Removal (MR) Aid treatment program . Many hydroxyacid compounds will introduce unwanted side effects, including lo w boiling point compounds that will increase fractionator overhead issues by par titioning to the overhead system, compounds that degrade at crude preheat temper atures to low boiling point compounds mentioned above, autopolymerization in the crude preheat that result in fouling, and scaling tendencies in the brine syste m. Due to these known issues, Metal Removal (MR) Aid technology has evolved fro m commodity acids, through the addition of scale inhibitors to prevent scale adh erence, to the most recent proprietary blends that include solution modifiers to prevent scale formation. The recent product evolution successfully removes met als and amine compounds without introducing harmful side effects, resulting in a robust and commercially viable technology that can allow increased volumes of d iscounted, high metal crude oils to be processed. Iron Removal Capabilities Betz Laboratories initiated work in the 1980 s to remove iron from various oil strea ms to minimize the impact on finished products. Additionally, it is widely kno wn that metal contamination of catalysts used in production of hydrocarbon fuels results in undesirable conditions that increase hydrogen and coke production an d ultimately limit fuels production. For example, a number of indices have been developed for FCC catalysts to relate metal contamination on the equilibrium ca talyst to hydrogen and coke production, including: Jersey Nickel Equivalent Index = 1,000 * (Ni + 0.2V +0.1 Fe), and Shell Contamination Index = 1,000 * (14Ni + 14Cu + 4V + Fe). As can be seen above, iron plays a marked role in metal contamination of FCC cat alyst, albeit lower than nickel and vanadium. At an independent Midwestern refinery, a reduction in iron was desired to reduce impact of this contaminant on their FCC catalyst. A study was undertaken to id entify the nature of the metals contamination for the crudes processed at this f acility, and treatment methods for iron removal were identified. Raw crude samples were homogenized and filtered. The raw crude and filtrate wer

e then analyzed for metal contaminants. It was determined that most, but not al l, of the iron could be filtered out of solution only 17% of the iron in the feed was not removed via filtration. This indicates that iron exists in this crude i n both particulate and soluble forms, likely iron oxides, irons sulfides, and ir on naphthenates. Figure 1 shows the level of metal contaminants removed via fil tration. Figure 1 - Metal Species Removed from Crude by Filtration Although much of the iron in the raw crude was filterable, desalting using tradi tional primary demulsifiers only removed about 15% of the total iron content of the crude oil. A screening test was performed with several commercially availab le solids wetting agents used in desalters to measure the potential improvement in particulate iron removal. While there was notable improvement over desalting alone, iron removal still did not approach the level removed via filtration Figur e 2 shows the results of the solids wetter screening added to samples also treat ed with primary demulsifier. Figure 2 - Solids Wetter Iron Removal The final phase of the study involved applying various chemical treatments desig ned for metal removal in the desalting process and measuring iron levels in the desalted crude to gauge removal capability. A traditional primary demulsifier was applied throughout the test in addition to the listed treatment categories. As Figure 3 clearly shows, iron removal was greatly enhanced by treatment with a Metal Removal Aid iron removal of 80% was achieved at 40 ppm treatment. This pe rformance approaches that achieved by filtration, and was almost double the remo val when a solids wetter was applied. Figure 3 - Iron Removal by Various Chemicals Calcium Removal Capabilities More recently, calcium content in crude oils has been on the rise, with the most troublesome being in the form of hydrocarbon soluble naphthenates. In particul ar, crude oils extracted from North Sea, West African, and Asian sources, such a s Harding, Heidrun, Gryphon, Doba, and Bohai Bay crudes have shown to contain wa ter insoluble calcium, with some levels up to 400 ppm. Attempts to process thes e crude oils without sufficient calcium removal capabilities results in rapid fo uling in the crude preheat exchanger train, crude heater, crude tower internals, and product quality issues. Metal Removal Aids have proven to be effective solutions for removing calcium na phthenate contamination. A European refinery was attempting to increase the lev el of high calcium North Sea Crude into its blend. Doing so resulted in an unac ceptable increase in calcium in the anode grade coke that was being produced, fo rcing the refiner to either reduce the quantities of high calcium crude, take a severe economic penalty to downgrade the coke quality, or remove the calcium fro m the coker feed stream. A Metal Removal Aid treatment program was initiated at the crude unit desalters in addition to the demulsifier technology. Figure 4 s hows the resultant calcium levels in the coke product before and after the Metal Removal Aid treatment was initiated. After an initial period to adjust all tre atment program parameters, calcium levels were reduced by 70-80% and the coke pr oduct consistently met the specification for anode grade coke. This treatment p rogram has been in place for more than four years. Figure 4 - Calcium in Coke Product

Amine Removal Capabilities Amine contamination can be introduced into the crude unit through the crude supp ly, slop oil recycle streams, or recycled from overhead neutralizer programs in the desalter wash water. These amines can build up in a system over time and ca use amine chloride salt related issues above the water dew point in the crude fr actionator tower and/or the overhead systems. Advancements in neutralizer techn ologies has reduced the impact of above water dew point salt fouling, and amine contamination/recycle through the desalter can reduce or eliminate the benefit o f using advanced neutralizer treatment programs. As amines typically partition both into the oil and water phases, the crude oil desalting process does not effectively remove amine contamination, introduced by the crude feed, poor quality wash water, or slop oil sources. Tramp amine cont amination has been shown to contribute to crude fractionator and overhead system salt fouling and subsequent under salt deposit corrosion. , A Gulf Coast refinery was experiencing fouling and corrosion issues in their cru de unit fractionator overhead system. Root cause analysis indicated that the ca use was amine contamination in the crude supply due to injection of H2S scavenge r prior to shipment. The amines remaining in the desalted crude were increasing the salt point of overhead stream above the water dew point, resulting in above dew point amine chloride salt formation. A program was developed using Metal R emoval Aids to remove the amine contamination in the desalter. Figure 5 - Amine Gain in Desalter Water Due to the ease of analysis, it was decided to analyze the desalter wash water b oth into and out of the desalter and determine the amount of amine extracted int o the wash water (amine gain ). By balance, amine gained in the wash water will be los t in the crude supply. Figure 5 shows the results of applying the Metal Removal Aid to the desalter amine gain in the wash water increased from about 15% to abov e 65%. A change in crude slates due to supply demands reduced the amount of ami ne-contaminated crude charged to the unit. Even with this change, the Metal Rem oval Aid more than doubled the amount of amine extracted from the crude oil as c ompared to baseline. Figure 6 shows the impact on amines in the crude fractionator overhead accumulat or water. As this chart clearly indicates, amine levels were reduced by over 70 %. Neutralizer feed to this system is controlled via pH measurement, and pH was held between 5.6 and 6.5 during the evaluation. Salt point calculations indica te that the reduced amine concentration in the overhead stream reduced the salt point by 12F and moved the potential for above dew point salt formation out of the crude unit fractionator tower and into the overhead condenser system. Figure 6 - Amine Concentration in Overhead Water Conclusions Metal Removal Aids have been successfully applied in a growing number of applica tions. While exact goals differ, all are geared toward removing contaminants fr om the crude oil supply that will have harmful effects downstream of the desalte r, including fouling, heat transfer loss, impact on catalytic processes and fini shed fuel quality issues. The examples cited show iron removal of 80%, calcium removal in excess of 80%, and 70% amine removal from the crude stream. The tech nology continues to evolve, and the last generation of products can achieve thes e goals without incurring harmful side effects to the refining process. Every application of Metal Removal Aid is unique, and offers its own set of chal lenges that can influence ultimate performance. As the volume of experience gro ws, the information obtained helps to deepen the understanding of how to success fully apply Metal Removal Aids to an ever-broader set of operating conditions an d feed stocks. Operating parameters such as dewatering efficiency, pH control,

operating temperature, desalter type, slop oil and wash water quality, and other potential process limitations all must be considered when selecting and evaluat ing a treatment program.