reduce overhead corrosion Boost refinery reliability by controlling potential amine recycle loops M. DION, B. PAYNE and D. GROTEWOLD, GE Water & Process Technologies, The Woodlands, Texas S alt fouling and associated corrosion in the crude unit overhead are complex phenomena that impact refin- ery reliability, flexibility and, ultimately, profitability. Establishing an appropriate balance of physical, mechanical and operational parameters, unique to each unit, is critical to minimizing fouling and corrosion throughout the crude unit. Factors such as amine chloride salt points; optimum accumula- tor pH; and overhead water ICP (initial condensation point, also referred to as water dew point) are interrelated and all affect the potential for system fouling and corrosion. Further improvements to refinery reliability can be attained by controlling potential amine recycle loops that can cycle up amine concentrations and move the salt point upstream or within the atmospheric tower itself. Crude unit overhead corrosion control. The first line of defense against overhead fouling and corrosion is the desalter. The desalter is designed to remove the majority of water extractable chlorides that contribute to the formation of highly corrosive hydrochloric acid (HCl) in atmospheric over- head systems. Depending on the desalter design and operation, it typically extracts 9098% of the water extractable species. To protect the system from extractable chlorides that are not removed in the desalter and non-extractable, hydrolysable chlorides (such as organic amine chlorides), filmers, neutral- izers and an overhead water wash are commonly utilized. The first area of concern for overhead corrosion protection is at the initial condensation point (ICP). As the first drop of water condenses (Fig. 1), acids in the vapor phase will transi- tion to the water droplet, creating a low pH, highly corrosive liquid. The neutralizing amine (N) must be present at the ICP to neutralize the hydrochloric acid. Amines can also associate with chlorides in the vapor phase under certain partial pressures, creating amine chloride salt. Once formed, it can migrate from the vapor phase either as a liquid or a solid and is typically extremely corrosive. The tem- perature at which the amine chloride salt exits the vapor phase is commonly referred to as the salt point. The salt point is dependent upon several factors, including the partial pressure of the neutralizing amine, the partial pressure of HCl, and the partial pressure of tramp amines. Tramp amines are generally defined as those other than neu- tralizer amines. They can come from several sources including being present in the crude naturally; from upstream additives such as corrosion inhibitors or hydrogen sulfide scavengers; from another processing unit; or from compounds that may decompose into amines in the crude unit furnace. Control. Overhead pH control is, perhaps, the most impor- tant aspect of overhead corrosion control. The pH in the over- head receiver is generally at least 0.51.5 points higher than the pH at the ICP. The ICP should be maintained in a range between 5.5 and 6.5 by use of an appropriate neutralizing amine. As illustrated in Fig. 2, operating at a pH level outside this range can have a deleterious impact in both directions. For example, if the accumulator pH is 5.5, the ICP pH will typically be between 4 and 5. When the ICP pH is 4.5 or less, acidic corrosion becomes very aggressive. Conversely, when the ICP pH exceeds 6.5, a region exists where the deposition of liquid or solid amine chloride salts can increase the likelihood of salt fouling and under deposit corrosion. H 2 S and other weak acids will increase partitioning from the vapor to the liquid phase as the pH increases. The additional sulfides and weak acids in the condensed water will act as a buffer requiring significantly more amounts of neutralizer for minor movements in pH. The additional neutralizer concentration increases the partial pres- sure of the neutralizing amine, thereby increasing its salt point First water drop at ICP Acids and bases at dew point Electrolytic chemistry Henry partitioning CI H H+ N N N N N N H+ H+ H+ CI H CI CI- CI- CI- H CI H CI H Water chemistry for the initial condensation point. FIG. 1 Originally appeared in: March 2012, pgs 45-47. Used with permission. HYDROCARBON PROCESSING MARCH 2012 CORROSION CONTROL SPECIALREPORT and the associated risk for under deposit corrosion. Additionally, the destruction of metal passivating iron sul- fide scales also becomes a factor under these conditions. In a slightly acidic environment, sulfides will react with the iron, forming a protective iron sulfide film. This protective film is weakened as pH increases, inhibiting the effectiveness of the naturally occurring protective iron sulfide film. Therefore, both the upper and lower levels should be con- sidered hard limits not to be exceeded. Having a pH excursion beyond these limits is generally an indication that there is a significant imbalance in the system from either an incidental or a systematic situation. Most refiners employ an overhead water wash to force the condensation of water vapor and dilute the acids that condense with the water. However, this may not protect against amine chloride salt fouling if the amine salt forms above the overhead temperature at the water wash injection point. The potential corrosion risk can also be compounded if the high salting amines reenter the atmospheric column in the reflux, which can induce an amine recycle loop. Amine recycle. As discussed previously, amines can be pres- ent as either tramp amines or introduced into the overhead as neutralizing amines. When exposed to a liquid-liquid system, aminessuch as monoethanolamine (MEA), diethanolamine (DEA), methyl diethanolamine (MDEA) and ethylenediamine (EDA)will partition to each phase. For instance, in the over- head accumulator, a portion of the MEA will partition to the naphtha reflux and another portion will partition to the con- densed water. If the condensate is used as desalter wash water, it will again partition, with a portion of the amine exiting the desalter in the desalted crude. This creates amine recycle loops (Fig. 3) in the naphtha overhead and desalted crude. These recycle loops can con- centrate the amine within the system. The additional amine loading to the overhead will add to the partial pressure of that particular amine, which will, in turn, increase the salt point of the amine chloride salt. If left unchecked, this amine recycle loop may, in severe cases, foul the top distillation trays. Amine partitioning. The partitioning of amines between the hydrocarbon and water phase is dependent on many factors including the type of amine, the hydrocarbon polarity and the pH of the water. Low pH water can protonate (add protons to) an amine and drive the ionic compound into the water phase. Conversely, alkaline water will deprotonate an amine and drive the partitioning of the non-ionic compound into the hydrocarbon phase. Amine partitioning is dependent on the type of amine (Fig. 4). As more carbons are added to an amine compound, its partitioning will be less pronounced with pH. Ammonia is easily partitioned to the water phase; MEA partitions to a lesser extent; and so on. In a crude unit overhead, operating the overhead accumu- lator water at a slightly acidic pH will assist in breaking the reflux amine salt recycle loop. The use of a low salting amine Amine sources include: Overhead neutralizers Crude oil Slop oil Alkanolamine unit Sour water strippers H 2 S scavengers Cold wet reux Amine Wash water Amine recycle Amine recycle Stripping steam Fractionation column Desalter Tank farm Neutralizer Water wash Tower top reux Accumulator Typical amine recycle loop diagram. FIG. 3 Ammonia: NH 3 NH 4 + MEA: HO CH 2 CH 2 NH 2 HO CH 2 CH 2 NH 3 + Acid Base Acid Base Amine partitioning is dependent on the type of amine. FIG. 4 20 40 60 80 1/7/2011 2/26/2011 4/17/2011 6/6/2011 7/26/2011 9/14/2011 p s i
d P
HDS efuent exchanger dP (indication of exchanger plugging) Eff dP actual Eff dP model Untreated baseline to 3/2008 Unit shutdown for cleaning Untreated Desalted pH modication treatment Detailed rendering of the diesel hydrotreater effluent exchanger pressure drop. FIG. 5 C o r r o s i o n
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m p y 0 100 200 300 400 500 600 700 800 900 1,000 1 2 3 4 5 6 7 8 9 10 pH Iron sulde scale weakens and H 2 S/CO 2 partitioning to liquid phase is enhanced pH at which saltpoint exceeds water dewpoint Salt deposition; under-deposit corrosion (NOTE: This saltpoint curve will shift with varying amine and chloride concentrations) (NOTE: The corrosion rate at pH >7 is equivalent to the rate at pH 4) Optimal control range pH 5.5 6.5 The impact of pH at the initial condensation point. FIG. 2 HYDROCARBON PROCESSING MARCH 2012 CORROSION CONTROL to control pH at the initial condensation point and not salt above the water dew point is critical to an effective overhead corrosion control program. At the desalter, reducing the effluent brine pH will also drive more amines into the effluent brine, thereby minimiz- ing the potential harmful impact from amine recycle loops. It should be noted that the effluent brine pH is the equilibrium pH after the crude oil and wash water mix. Consequently, the effluent brine pH is the control parameter to amine partition- ing within the desalter. Out at the refinery. A US refiner was experiencing throughput reductions and frequent slowdowns as a result of fouling in the effluent side of the diesel hydrotreater feed efflu- ent exchangers. Rather than treat the symptom with an amine halide salt dispersant, the desalter effluent brine pH was low- ered by injecting a product containing citric acid and a scale inhibitor. This partitioned more amines to the effluent brine, reducing the amines in the crude unit overhead, the diesel stream and, consequently, the fouling in the hydrotreater unit. The effluent exchanger pressure drop history was used to generate a multiple regression linear model to normalize the pressure drop for effluent flow and stream properties. The actual exchanger pressure drop and the model estimate are shown in Fig. 5. When the actual pressure drop increases above the models predicted value, it is due to the amine halide salt fouling at an advanced rate. The time periods in Fig. 5 (during treatment) show that the actual pressure drop was lower than the historical observations and, in fact, there was no increase in pressure drop. Wrapping it up. In some systems, amines may recycle back into the tower with the reflux or may reenter the desalter from the overhead condensate. At the desalter, the amines may parti- tion back into the desalted crude and reenter the atmospheric tower. These amine recycle loops may cycle up amine con- centrations and increase the risk of corrosion from amine salt deposits if they occur above the water dew point. The authors believe a model can be used to assist in predicting amine salt points. If the salt point occurs above the water dew point, operating the desalter with an acidic effluent brine can parti- tion a portion of these amines into the effluent brine, thereby reducing the detrimental impact from recycling amines. Using nonvolatile acid products is a good way to assist in reducing the desalter effluent brine pH. The acid decom- poses to inert substances in the crude unit furnace. As refiners have recently reduced atmospheric tower top temperatures to maximize diesel production, a thorough understanding of the ICP, salt point and control of amine recycle loops is critical to maintaining plant reliability in changing plant operational conditions. HP Michael Dion is a phase separation senior product applica- tions specialist for GE Water & Process Technologies. He is respon- sible for technical support and marketing of a refining separation product line. Mr. Dion has seven years of oil field experience and 21 years of refining experience. He has co-authored two patents and numerous articles. Brandon J. H. Payne is a product applications specialist for GE Water & Process Technologies Refinery Corrosion Center of Excellence. He is responsible for global support of GE refinery corrosion treatment programs and has over 14 years of refinery engineering and process treatment experience. Delbert R. Grotewold is a senior regional engineer for GE Water & Process Technologies in the Western US region. He is responsible for process chemical treatment programs, refinery process troubleshooting and process optimization of refinery operations. Mr. Grotewold has over 27 years of refinery engi- neering and process treatment experience. He has authored or co-authored five patents in refinery technology. Article copyright 2012 by Gulf Publishing Company. All rights reserved. Printed in U.S.A. Not to be distributed in electronic or printed form, or posted on a website, without express written permission of copyright holder.