CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY UNDERDEPOSIT CO,/H,S CORROSION ON A MULTIPHASE OIL PRODUCTION PIPELINE. G. Hoxha’, N. Buongiorno™, M. Cabrini’, F. Bolzoni’* Internal corrosion failure occurred on an 8-inch line after 18 years of service, The production fluid flow is multiphase and associated gas contains CO; (ca. 0.5 mol.%) and HyS (ca. 35 ppm). Failure analysis revealed the presence of a film of carbonates and sulfides on the metal surface immediately near the corroded area. CO; corrosion on the bottom of the line was accelerated by a galvanic effect between the bare metal surface under deposit and the scale of carbonates and sulfides. The actual corrosion rates were in good accordance with those calculated using the De Waard and Milliams model. INTRODUCTION The oil field of Cavone is located in the north of Italy. Crude production started in 1980. Production remained almost costant during the first 10 years of the life, about 2 500 - 3 000 bbl/d of heavy oil of 25 degree API. Production of water was low (W.C. < 10%). No corrosion was observed during this period and this created the erroneous conviction that corrosion would not be a problem in this field. No corrosion inhibitor treatment was considered for the pipeline network and corrosion monitoring was not carried out correctly. From 1990 crude production has decreased costantly with time and, in the same time, water production has increased. Now, water cut is about 70% and water salinity is about 30 g/l. Associated gas contains 0.3 - 0.6 mol.% CO, and ca. 35 ppm of H,S. Gas production has also decreased with total GOR remaining almost constant at 20 - 26 Sm*/m’. ENI - AGIP diy., Corrosion & Materials Dept., Milan ITALY ENI - AGIP div., District of Crema, Crema ITALY Faculty of Engineering, University of Bergamo, Dalmine ITALY. '' Appl. Phys. Chem. Dpt., Polytechnic of Milan, Milano ITALY 413CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY The first corrosion problems were observed in 1991-1992 as water production increased. Attack was found on the crude side of the heat exchangers and on the first stage separators. Corrosivity of production fluid was pointed out as cause of the attack, Nevertheless, a deeper study of the problem was not considered. The items were repaired and for a certain period corrosion inhibitor was injected at the arrival manifold. In 1998, over a very short period of time (few days) two corrosion failures occurred on a 8-inches, 7 km long pipeline. The line gathers more than 60% of the total production of the field. Pipeline data and operating conditions are shown in TABLE.1 Production was trasferred on a 4-inches pipe with consequent substantial reduction of produced volumes. However, considering that the field area is highly inhabited, particular care was dedicated to safety and environmental problems. The first hypothesis was that corrosion attack could be extented along the pipe. The failures were repaired and an extended control of the state of the pipeline was decided before putting it back in production. Intelligent pig was selected as the best alternative for this purpose Two other failures occurred during the cleaning operations preparing the line for the pig launch. High quantities of sludge and corrosion products were dragged- out by cleaning water. This confirmed the hypothesis that the line was highly damaged. Two sections of the line were cut-off for further corrosion failure analysis, FAILURE ANALYSIS Visual Inspection. Fig.2 shows the longitudinal section of the damaged tube. Three areas with different morphology are visible on the internal surface. Wall thickness is heavily reduced at the bottom of the pipe (6 o'clock position). Different perforating attacks occluded by corrosion products are present. The area is completely covered by a thick layer of deposit of corrosion products, solid high-weight hydrocarbons and inorganic precipitates. There is only slight corrosion on the adjacent area (8 o'clock). A tight layer of corrosion products covers the surface, which is notably thinner than that observed on the bottom of the pipe. The other part of the tube is not corroded. No corrosion product and/or other layers are present on the surface which results covered just by crude oil. 414CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY, The specific morphology of the corrosion attack and deposits seems to be indicative of stratified flow over the line. Low flow velocities and the geometry of the line (almost horizontal), are further indications that confirm this. The bottom part was always water wetted and hence corroded. The totally absence of corrosion on the upper part of the line confirmed that this part was in contact with the oil which has protected the metal against corrosion. Chemical sampling. The treatment with acid and with sodium arsenite reveals the presence of sulphides on the lateral walls of the tube, outside the thick layer of corrosion products (fig.3). Neither sulphides nor the characteristic effervescence of dicarbonates are revealed on the massive deposit, which occludes the perforating attacks. Spectrometr EDS a1 X-ray spectrometry results and SEM - EDS observations are shown on the figs.4, and 5. The morphology and the composition of the deposits on the corroded area at the bottom of the line and on the area adjacent to it are completely different. Corrosion products at the bottom of the line consists mainly in iron hydroxide (Fe ID) (fig.Sa). Large quantities of chlorine and only small quantities of sulphur are also present (fig.4a), while at the adjacent area the quantity of sulphur is distinctly greater than the quantity of chlorides (fig.4b). X-ray spectrometry shows the presence of iron oxides and iron carbonates (magnetite and siderite) (fig. 5.b) Some calcium is also present probably in form of carbonate. Bacteriological Sampling. Samples from different parts of tube are also submitted to bacteriological exams. A small presence of sulphate reducing bacteria (SRB) is revealed on the area corresponding to 8 o'clock position, while the SRB are not present under the deposit of corrosion products on the highly corroded area on the bottom of the pipe. Therefore, it is supposed that their presence does not influence the attack. ISCUSSION The line is 18 years old and pipe wall nominal thickness is ca. 7mm. Considering that corrosion took place over all the lifetime of the line the corrosion rate on the perforated attacks should be at least ca. 0.4 mm/year aisCASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY, It is very important to note that during the first period of service crude and gas production was high and the water cut of production fluid was low. The flow was probably turbulent and water wetting on the bottom was too difficult to occur. Thus, it is reasonable to suppose that oil wetting protected the line during this period. Begining from 1988, higher water quantities and lower flow rates caused the stratification of water at the bottom of the line and, probably, corrosion phenomena to start. This means that corrosion took place over a shorter period than the total lifetime and, correspondingly, the actual corrosion rate was almost, ca. 0.7 mnv/year. Theoretical corrosion rates were calculated with the De Waard ¢ Milliams model (1) and NORSOK M506 model. Corrosion rate, considering the worst operating conditions, results in 0.15 + 0.5 mm/year. Another model, based on a probabilistic approach, gives low probabilities for having considerable thickness loss (2). Taking into account that usually the models are considered conservative, it is clear that the only CO, corrosion effect can not justify the observed attack. Moreover the corrosion occurred under the deposit in a totally different condition from that of "clean" metallic surface usually considered by the theoretical models. Presence of H,S, even in small concentration, must be considered too. Several authors have asserted that small quantities of H»S have a beneficial effect on the CO, uniform corrosion at ambient temperatures. Iron sulphide which precipitate during corrosion helps the formation and the stability of the protective layer of iron carbonate (siderite)(3). In some other cases the risk of localised pitting corrosion has been underlined. The penetration rate was shown to be several times higher than that foreseen by the CO, corrosion models. Published laboratory work has not been conclusive and further study is needed to clarify the mechanism(4). Presence of iron sulphide in the bulk of the siderite layer renders it electrically conductive and cathodic with respect to the bare steel. Thus, in case of layer damage, a galvanic cell is established with the bare steel acting as anode. The exposed steel corrodes at high rates due to unfavourable rapport between the usually small surface of the pit and the large surface of the surrounding area covered with corrosion product layer of cathodic nature, We think that the same mechanism (fig.1) was the cause of the corrosion altack observed on the pipeline, In a horizontal pipe, in low flow velocity conditions, there are three different separated fluids: the gas on the top, the crude oil in the middle and the water on the bottom of the line, The upper part of the line remains in contact with gas and oil during all the time, thus, does not corrode. With time, at the bottom of the line, a deposit of corrosion products, high- weight hydrocarbons and mud is formed favoured by the low flow velocity. 46CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY Corrosion conditions created under and above the deposit are completely different. The metallic surface above the deposit is in contact with moving formation water which contains dissolved CO, and HS. Some corrosion occurs on this area and iron carbonate and iron sulphide film precipitates. Otherwise, the water under deposit is almost stagnant and the concentration of CO, and H,S is very low because they have to diffuse through the deposit before reaching the metallic surface. The precipitation of carbonates and sulphides under deposit is very difficult. A galvanic macrocell is established between the area covered by carbonates and sulphides and the bare steel under deposit. The cathodic reaction occurs on the covered area and the consequent alkalinization of the ambient near the surface increases the stability of the protective film of corrosion products. The anodic reaction takes place under deposit and creates acidic conditions which increases further corrosion. The reaction product in this case is iron hydroxide which precipitates but does not form protective film. Corrosion rate is proportional to the ratio of the surfaces of the anodic and cathodic areas. By visual inspection a value of 1:1 to 1:2 seems to be reasonable. Assuming that the cathodic reaction rate, which occurs on a "clean" metallic surface, is similar to that foreseen by the De Waard ¢ Milliams model and considering the multiplying factor, the theoretical corrosion rates result in good accordance with those actually observed. REMEDIAL ACTIONS Production life for Cavone field is foreseen for other 20-25 years. The localisation of the failures along the line and failure analysis clearly confirmed the worst hypothesis that the corrosion attack was present over all the length of the line. Partial replacement was thougth to be insufficient thus the construction of a new pipeline was considered. The new line is a 6-inches nominal diameter. This assures higher flow rates and some turbulence in order to avoid deposition on the bottom of the line. The material of the new line is API 5L X52 and the thickness 7.11 mm. The line is completed with launch and receiving traps for periodical cleaning pig. The pigging program will be established following field experience. Continuos corrosion inhibitor treatment is foreseen and now activity is undertaken for the choice of the inhibitor product through field tests. Corrosion coupons will be installed in water traps at the start and at the end of the line. 417CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY CONCLUSIONS AND RECOMMENDATIOS 1. The analysis shows that the most probable cause of the failure on the pipeline was CO,/H,S underdeposit corrosion. The stratification of the water on the bottom of the pipe and the formation of a thick deposit consisting in corrosion products, high-weight hydrocarbons and mud were the conditions for attack to set off. 2. The mechanism of the observed phenomenon is of galvanic corrosion form. The area under the deposit behaved as anode, while the adjacent area covered with protective corrosion products film behaved as cathode. Calculated corrosion rates, considering the anode/cathode ratio, were in good accordance with the actual ones. 3. To avoid formation of deposits and to assure some oil wetting on the bottom of the line the flow should be turbulent. So flow velocities higher than 1 m/s have been recommended. Periodical cleaning pigs will be used for removal of deposits. 4. Inhibitor treatment and corrosion monitoring are indispensable and will be implemented for corrosion control over the next 25 years of foreseen production life REFERENCES, (1) C. de Waard, U. Lotz “Prediction of CO; corrosion of carbon steel”. NACE Corrosion’93, New Orleans, paper 69. (2) D-Condanni, P.Fassina, L.Lazzari, R.Galvagni “Corrosion related risk evaluation for well tubing and pipelines”. NACE Corrosion’97, Dove, paper 323. (3) A.lkeda, M.Ueda, S.Mukai, “Influence of environmental factors on corrosion in CO, source well”. NACE Corrosion’85, Houston, paper 29. (4) M.B.Kermani, L.M.Smith “CO, corrosion control in oil and gas production”. E.F.C. Publications Nr.23, The Institute of Materials, 1997. 418CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY. TABLE 1. Pipeline operating data and operating conditions Length Nominal diameter Thickness Oil Flow Rate Gas Flow Rate Water Flow Rate Pressure ‘Temperature C02 in gas 12S in gas Water Salinity Mud Anodic ar 7km 8 inches 7mm 120 mid 3.000 Smid 250 mid 15 +4,5 bara 45 +55°C 0.4 - 0.6 mol.% ca. 35 ppm ca. 30 gil Cathodic area : FeCO, / FeS Fe FeOOH Fig, |. Flow Conditions and Corrosion Mechanism. 419CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY, Fig. 3. Pipe view after assay with sodium arsenite. Yellow areas confirm the presence of sulphides near the corroded area. 420CASE HISTORIES ON INTEGRITY AND FAILURES IN INDUSTRY Fig. 4. EDS - analysis: (a) 6 o’clock position, (b) 8 o’clock position. (b) Fig. 5. X - Ray Difractometry: (a) 6 o’clock position, (b) 8 o’clock position. (A- akaganeite, FeOOH; M = magnetite, FeO,; $ = siderite, FeCO; ) 421 z ra ] ina ro apis prestSt (200s Remaininst 0s) ives aude presehe ova Remasningt 05) 17 nad feats B23 57 oc 1, Tt T | ‘ | | | | qT | hy } | ae | Te 2b)