Refining high acid crudes Assessing crude oil corrosivity based on sulphidic and naphthenic acid corrosion. A revised. procedure includes analysis, testing and a corrosion model that takes into account critical parameters for the evaluation of operational risk, unit upgrading and maintenance planning Brian D Chambers Honeywell Process Solutions jonventional rules fer the ( assessment of naphthente acid ‘and sulphidic corrosion and. operating isk have evolved over the past 40 years, primarily based on experience at individual plants processing certain crude streams, This is the basts for the commonly uscd rules of thumb for conditions that generally produce clevaled conosion rates in feaetfonation systems, Currently, the API RP $81 Base Resource Document” provides guidelines that are based on process conditions of total acid number (TAN), sulphur, emperatureandalloy content, Llowever, It has been found that these guidelines are, in many cases, avery conservative, Teading $0 excessive alloy requirements Studies are being mitiated under joint industry sponsorship to improve the ‘ukdelines found in the API RP S81. Corrosion in crude oil 4 wt sulphur are shown graphically in Cia ‘Temperature, F Imalg) 750 2 bese iieatdetes aes Sere aueeiesieiee gute 8 0 1 15 2 2 5% 2m w 2 1% 2 30 Sire ateeeeegreeeee gutta 4 5 7 8 Ww Ss 8 8 0 w ie eeeeroreeeiuoteaetiattitttg w 0 2 1 5 ee isseatterar teat gttea0, 5 8 0 Ww 1 5 1 0 aS wo wt ss wo 15 1520 eiaeaete HaeHioeEaHiOsedEya! Bese i7a eee oeiris tetas! eee eeeea teers ete a0) 8 0 6 20 2m 2 % mM ww 2% 5 7 0 1515 6 8 mM % 4S 8 1 ss rn ne re % 2 0 eieteieeitthoteiistttigs 8 1 sO 2 1 m0 mM 2s 1% 20 0 o 6 © 8 0 current understanding of the relationships discussed previously, which Include: severe conditions for naphthenic acid corrosion at very low aaa© 077A | worss || A i625 8 240 B40 © 50 451-500 507-880 561-800 GDI-650 651-700 TOT-760 3750 Tomperatur, 0 750 Figure 8 Corrosivity assessment charts for 9Cr-1Mo Steet (a) <0.2% 5, (b) 0.21 0.696 5; (c) >396 5; per API RP S81 (Conversion: 40 mpy = 1 mmfy; 600 F = 316 C) with nominal sulphur levels (0.2-0.6 also includes provistons for velocity. As ‘wt86); increasing corrosion rates at previously shown in Figure 6, once the ‘higher sulphur levels; and increasing baseline cortosion rate is determined cottosion rate with increasing for the appropriate streaim conditions TAN levels and matetial, the flow chart describes, 4s previously mentioned, the APIRP the application of a velocity factor (5x) 581 methodology for the assessment of for flow rates of 100 ft/s (32 m/s) or sulphidicandnaphthenicacid corrosion greater. Figure 9 shows the impact of this factor for 9Cr-1Mo steel at 0.2-0.6, wi%6 sulphur, These are much higher conosion rates that would apply to certain vacuum column heat tube and transfer line applications, where velocities can be in the range of 100- 300 fs (32-979), ‘While the corrosion model in API RP S81 is simplistic, it Is based on a significant database of sulphidie corrosion from the modified MeConomy ‘curves. While some data exist on the influence of naphthenic acid on corrosion rate, the base cosrasion data for naphthenic acid corrosion ate less wellestablished. However, the simplicity and structure of the methodology provide an effective and easily applied ‘method for corrosion prediction and a Sate-of-the att basis for RBI in crude oil distillation units and piping. In addition, many oll companies. have gone further by generating corrosion data for specific crude oils, blends and fractions used in their refining operations. However, the extent oft data is currently Timited and has not been applied across the Industry. Further work to develop an expanded crude corrosivity database and corrosivity model incorporating flow ‘modelling Is under way, sponsored by a joint industry programme. Specific crude oil properties influence corrosivity One ares of growing interest 1 the understanding of conditions that either ‘promote or help minimise naphthenic acidcorrosion, Aspreviouslymentioned, most major factors are taken into account in the APL RP S81 method for the assessment of sulphidic and »aphthenteacid corrosion. This method provides guidance for RMI procedures and matelals selection, As experience With this methodology progresses, it hhas been noted that the methodology, ‘while Beneficial, has a tendency to be ‘overly conservative with respect to certain naphthenic acid conditions. ‘Naphthenic acid type One of the key findings from a major research study was that the acidic components commonly found in crude ols, which contripute tothe TAN value, can vary substantially and have a major impact on the resulting corrosivty. As shown in Figure 10, the acidic components present in crude oils Consist of both straight chain molecules (fatty acids that have no sing structures Characteristic of naphthenic acids) and fue naphthenic acids (with one or ‘multiple ring structures)" The fatty acids, while contributing to the total ‘TAN value, ae typically less thermally stable and may decompose quickly during process heating in the refining pbmeipichia ieee eee ceecontribute ttle to. the resultant conosivity. Second, those acidic components that do have naphthenic 250) : acid character have chemical structures I I involving @ R value of 1, 2, 3, 4 or * 07 aN possibly more in the | formule zoo|-| w 071-45 R(CH),COOH, where R is the number a i624 © 2340 fof eyClopentane or cyclohexane sings get and the value of Nis = 0. ‘To futher intespret this type of Information, Table 2 shows data obtained using the FAB-MS technique for thice "naphthenic acids” obtained from crude oils characterised by their 50% off boiling point as low, mediven ape and high boiling point acids?. These data are also compared to. those obtained fora reagent-grade naphthenic ° acid of known corroslvity. The data in (0450 481-800 601-880 §57-600 GUi-660 651-700 701-760 —=750 ‘Table 2 are generally similar to those Temporature, shown in Figure 10 for commercial crude oils with varying amounts of straight chain and tlag strictures Figure 9 Corrosvity assessinent chart for 9Cr-1 Mo Steel at >396 § and >100 ft/s per a a CCorosion rate. may tn the present case, wo pieces of AP/RP 587 (Conversion: 40 mpy =I mmf; 100 is = 32 my 600 = 316 ©) information were comteated. Data frome this study. showed that the higher oiling point acids have. greater percentages of higher ring structures, bad thereas the low boiling point See, naphthenic acid ad. a, Higher ERaman a percentage of the single ring SS pace enone) fomponents, similar to that found! in 8 Gerad tore, FR) the reagentgrade naphthenic acid. | 4 Ferthermore. the results from the comostontetiagprograrn showed that | : inthe range” of typical process temperatures, where naphthenic acid corrosion is commonly observed, the | 29 ‘most corrosive acids wore the reagent: gride acid and the low boiling point | acid. The reagent-yrade naphthenic acid and Jow boiling point samples had a similarly high percentage of single o Ting structure naphthenic acid, In Ofeg Tig 2Aings — SAings 4 Ringe summary, it was determined that the | overall aggressivity of the acids in a Inydrocarbon fraction (at a constant Figure 10 Variations in organic cing structures in selected crude ois!” ‘TAN value) was proportional to the percentage of their single ring structure Acidiecomponents. Therefore it appears "Naphthenic acid structures from crude ail and reagent ‘that FAB-MS data indicating the nsture naphthenic acid using FAB-MS of the aide structures can be used as a method to qualify the corrosivity of Oilsample Straight chain Tring ring 3 ring ring’ Other acid-containing fractions. Reagentnap acké 12, ascetic Saeee) ‘These data also help to explain, to High BPnapacd 9 3% m4 9% wow some degiee, the eason forthe potential ® 0) 8) a1) conservatisin in the AVI RP S81 method Medium BP aap acid 7 oneee es ar esesedlaesnsee Huts fornaphthenic acid carosion incertain LO" BPnapacid 20 aaa ey applications. The cause of this effect Is the inability of the TAN value alone to {ake into account the distribution of naphthenic and non-naphthenic acid Table 2 ‘components in the process stream, “Double values nate repeat PALMS rng on sa spl, ‘mix with low sulphur and low TAN. To illustrate the importance and use Sulphidic versus naphithentc acid Laboratory tests were conducted tof laboratory test data, consideration ‘domination assess corrosivity in various fractions‘of was given to the HVGO stream in the Ina recent study, a particular souice of this new feedstock for comparison with $00-675"P temperature range. The ‘tude oil was evaluated for addition to the corrosion rates obtained with the steam conditions consisted of 3.4 W% 4 feedstock mix. t was characterised as APL RP S81 methoclology and in an sulphur and 4.0 TAN, Based on this having high TAN and sulphur, but it effort to develop less conservative condition, the APLRP 581 methodology ‘was to be blended with a sweet crade guidelines. Sica crip cui amae aeti i 20day Bo \ 5 2 § —| on ° 5 2 18 Cr eomont Figure 11 Corrasion rates versus time for exposure on commonly used alloys in silphur-dominated hot oil environment (9Cr Steel values interpolated from those of ‘SCrand 12Cr steels? Structures of naphthenic acids from base oll and HVGO vs reagent naphthenic acid using FAB-MS Olt sample Straight chain ing 2ring 3ring 4ing Other Reagent nap acid (corrosive) 2 ne lecteeaet aaa Refinery base ollsample 9 % 2 OM Refinery HVGO sample 8 2 m » W 0 Table 3 steel of 20 mpy (0.5 mum/y) at SS0°P values were observed to be low, (288°C) and 30 mpy (0.7 mmJy) at indicating domination by sulphidic 675°F (357°C). These corrosion rate corrosion. Therefore, sulphide scaling values are in excess of the design cut-off would be expected, which tends 10 Jue of 5.0 mpy for piping and would reduce eotsosion rates with time require upgrading to a higher alloy A post-test analysis procedure can be material applied to laboratory-derived corrosion Corrosion autoclave tests were rates for use in refinery materials conducted in the RVGO stream for the seluction decisions. The protocol for assessment of corrosion rates at these this procedure is provided below: ‘wo temperatures. The methodology — Sulphur-dominated conditions: A for the corrosion test vas to run the reduction factor for cases of low NACL HIVGO sample at minimal pressure so value, where sulphide scale would be the autoclave included the use of a pop expected to lower long-term corrosion valve to release the pressure from off- rates. This is based on short and gassing of the HVGO sample during long-term corrosion rates conducted the test under sulphur-deminated conditions ‘The data from these tests were further (Figure 11)” evaluated to obtain representative. — Naphthenic acid-dominated corrosion rates for use inthe design of conditions: Where high NACI values plant piping, This analysts consisted of are obtained from laboratory tests, no fiest consideration of the baseline reduction factor is applied for conosion rates for 9Cr-IMo ste nthe tests along with naphthenic acid corrosion index (NACD valuesproduced sing carbon steel oe Under the ‘A post-test analysis same conditions. The NACI is procedure can be applied ‘determined from the cortosion rate ot oaee carbon steel (in mpy) divided by the to laboratory-derived scale weight (in mg/cm. High values rosion use in (oat) of NACL indleate naphthenic COrFOSION rates for use ‘dominated comrosion conditions, refinery materials selection whereas low values (<10) of NACI isions” indicate suiphurdominated corrosion €¢1Sions ‘omditions In this case, the NACI ‘haphthentc acid corrosion, because this form of corrosion does not usually involve filming or a reduction in the corrosion rate with time of exposure, as ‘exhibited by sulphidie corrosion — High wall shear stress conditions: Where high velocity, multiphase flow conditions result in high wall shear slzess, a correction factors incorporated Into fest cesults conducted at low flow conditions, which effectively increases the expected corrosion rate. This factor varies, depending on the NACI index, and allows for’ velocity-accelerated sulphidie corrosion at low NACI, and velocity-accelerated naphthenic acid corrosion at high NACI values, as well as. intermediate conditions (see Figure 5) — Safety factor: After the previously mentioned adjustments are made to the laboratory corrosion rates, a safety factor can be added, depending on the confidence in the test data and the plant operating conditions. This factor Isusually (2x) for most cases, but can be adjusted higher, if necessary for specific cases. Due to the low NACI values in the present case, a reducing factor was applied to the 9Cr-IMo conesion rates based on Figure 11, to account for the sulphide scaling effect expected in the HVGO stream. In addition, a safety factor of 2x) was applied to the adjusted cotrosion rate data, No additional factor was used for high wall shear stress conditions, since the application involved liguld-Blled pipe flow with wall shear stress levels generally less than 100 Pa. The adjusted coctosion rates for 9Cr-IMo steel were 2 mpy at SS0°F 88°C) and 5.3 mpy at 675" (257°C). As canbe seen, these values are substantially lower than those predicted by the API'RP 581 metho. dology for an HVGO stream with 34 ‘wi¥6 sulphur and 4.0 TAN. The results were actually closer to those predicted by the APL RP S81 proceduee assuming no contribution fom the naphthenic acid at all. For this case, the corrosion rates predicted by API RP S81 were § ‘py at $50°F and 10 mpy at 675°E “The reason for the lack of naphthenic acid effect in the corrosion rate appears to be related to the type of acidic structures in the base oil and concentrated in the HVGO for the present case. The results of the FAB-MS analyses on the base oil and the HVGO are shown in Table 3. The unexpected lack of naphthenic acid character in tls case is caused by the predominance of acidic components that are not highly corrosive over the temperature range used in the crude oil refining unit. Furthermore, the presence of enough sulphur in this stteam to provide @ protective corrosive scale would be expected to impart furthercorrosion protection over _ time. ‘Therefore, this study shows that the API RP $81 methodology provided a sound but very conservative basis for assessment of corrosivity. However, when this method is combined with Taboratory test data simulating process conditions, it can provide a more ‘effective tool for implementing RBI ln ‘crude oil refining units as well as for terial selection in the design and revamping of these units as the feedstock changes over time. Path forward ‘The prediction and evaluation of erude oll cottosivity for refinery operations continues to be an evolving feld. Major strides have been made to separate and understand the roles of the corrosive ‘components commonly found in erude oll, As discussed, laboratory testing (with high temperature autoclave and flow loop systems) augmented by analytical methods such a5 FAB-MS has provided new insight and direction for Iunproved assessment and predictive capabilities. A joint industry-sponsored research effort is under way by Honeywell Process Solutions involving ‘major oil companics to further extend technology in this area The technical emphasis of this programme is the integration of an experimental corrosion test progzam, with supporting analytical data on naphthenic acid and sulphur species. ‘This information will be uscd to define improved, quicker test methods, and better define the safe operating envelopes and conditions that pose @ tisk of accelerated corrosion 10 commonly used alloys. The zesults wil be integrated with a new software tool to aid in the prediction and assessment of refinery hot oll corrosivity. The software tool will utilise the new test data to provide an Improved corrosion prediction and sk assessment than currently avallable with the API RP S81 RBI Resource Document using similar methodologies as highlighted in ‘his article. An accelerated test method for conosiity assessment will be valuable to quickly evaluate limited quantities of actual hydrocarbon. fractions and benchmark ther against other fractions of known conosivity. This procedure will also help to characterise if the comosion was dominated by sulpbidlc for naphthenic acid attack, whieh will ald In better predictive capabilities for Tong-term corrosion rates, as discussed. Additionally, a corrosivity database will be developed, based on levels and types Of sulphidic ane! naphthenic corrosive constituents and flow conditions, ‘quantifiod in teems of wall sheae steess for proper linkage to actual plant ‘operating conditions. Pinay, the data fiom this latter portion of the study will be assembled in a softwace tool to accommodate Dow modelling and rapid interrogation of the conosivity database and rclationships developed From this data Conclusions Hased on the information provided, the following conclusions were made: — Sulphur and naphthenic acs are conrodants in refinery crude oll listllation units that can act separately oor in combination with each other to fine the severity of corrosion in patticitla process streams ~ It's important to evaluate corrosion Jn these units based on conditions specific to the process stream of interest and not use witole crude properties The presence of sulphur-containing compounds in hydrocarbon fractions sn Inhibit naphthenic acid coxeosion. ‘This understanding has come from both experientist information and, ‘more recently, experimental data on hgh TAN fractions that are also high ia sulphur species — High TAN in combination with low sulphur (20.5 w054) can be particularly conosive. This effect predominates ‘when the fraction does nothaveenough reactive sulphur to counteract the highly corrosive naphthenic ackls Explosi Detaclad® Pie is the Reliat Applications for All * Reactors * Columns * Separators * Shell & Tube’ * Coke Drums: wit Phone +33 (0) 4 68 64 56 56/57 + Fox 433 0) 4 68 645658 nobelelad@dynamicmaterials.com— Some sources of crude oll and refined fractions have been found that have high TAN values, but appear not to be as highly corrosive as one might expect based solely on their ‘TAN value. These crucles appear to have a very beneficial combination of conditions: the presence of sufficient sulphur in the fractions, the presence of certain naphthenic acids with particular steuctures that aze less corasive FAB-MS techniques are useful in characterising acidic constituents in refinery crade oil feedstocks — The APL RP 581 methodology provided a sound but very ‘conservative basis for the assessment of comosivity The AFI RF $81 methodology can be augmented with the use of laboratory testing and a protacol for evaluating the test data for usc in materials selection based om certain conditions indicated below: = Sulphur-dominated conditions: A reduction factor {or cases of low NACI value, where sulphide scale would be expected to lower long-term corrosion rates ~_Naphthenie acid-dominated conditions: Where high NACI values are obtained from laboratory tests, no reduction factor is applied High. wall shear stress conditions: Where high velocity, multiphase flow conditions result In high wall shiear stress, a cosrection factor is incorporated to test results conducted at low flow conditions that effectively Increases the expected corrosion rate ~ Safety factor: Afterall diese adjustments are made to the laboratory corrosion rates, a safety factor is added, ‘depending on the confidence in the test data and the plant ‘operating conditions, This attice is based on a presentation from EUROCORK 2008, The "gptan Compson Congres, aatnbugh Uk, ising gh acd sgdes: when is an opportunity not ah portunity September S008 References ‘IRD-SS sk Based inspection, ase Resource Document, American Petroleum Insitute, Washimtem, DX, 2003, 2 Hatch Lf Matar, Hyocrbon Proceting ne 1977, p 189. 3 Coupes W'S, Canarian 96, 19, pp 396-401 Yenc 0, i, 2005, #4, pp 97 1B 5 Kn 8’, "asin ft pele rein and et operations,” Covesions" Envucranents and notes Metals Handbook Vol 15C, ASM Handbook, ASM Totemations, 2006, pp oerstoit 6 Piehl & 1, "Nupnthenic acid coresion in crude oi dstilation units, Corronon/87, Paper "No. 196, "NaC® tutemational Houstin, 7X, 1987, ‘TKane ID, Cajard MS, “a comprehensive study on naphthenic acid ‘oreson Carosion/2002, Paper No, 02888, NACE Intemational, Houston, 1x, 2002. 8 Kane 8 B,"predicing crude of corrosnty: influence of veloc inaction oot composition, fepentie and aly final report, Honeywell Process Solutions (acquired ate Internationa, Houston, 7%, february 2000, 9 Messer Tile 8, Beaton Mt Prulips , *mewe theory for iaphthenic aed. eocrosety of Athabasca oil sands crides”, Corrosion/2004, Paper No. 04634, NACE Intemational, Houston, ‘Tx, 2001 10 Behar Fi, Albeeche P, Organic Geachomisty, 1981, 6, » $97 II Kane RD Madoal Peormance, july 1999, pp 48-54 sntcal Brian D Chambers is with Honeywell Process Solutions, Houston, Texas, Era brian charnbers@honeywellcom Russell D Kane is President of Corrosion LLC In Houston, He is also a consultant tothe AP! Refining Committee, Subcommittee ‘00 Corrosion & Materials Research, for Ethane SCC, Kane received BS, MS and PhD degrees in metalargy and materials science from Case Western Reserve University in Cleveland, ‘Ohio. Ema uss kane@icorrnet - Choose ABB as your Partner for Refinery Process FTIR Solutions FTIR Analysis Solutions Addressing the Needs of the Modern Gomplex Refinery The Best Solutions 1 Gasoline & Diesel Blending wi 1 Hycrotreating il 8 HF Allation eu 5 Catalytic Reforming i ae Heavy Oil Upgrading Guide Distiltion 8 Naphuha Cracking 8 Downsieam Perochemi he Best Services 1M Pull Analyser Engineering and System Integration 1 Startup, Commissioning and lifetime Support Analytical Method Development and Calibration ‘Modelling Services On-going Support, Validation and Performance Audit Services ‘Analytica! Business Us {trea abb.com www. abb.convanebtios vr. ma000 23m