Intemational ural of Greenhouse Cas Control 3 (2014) 48-60 Contents lists available at ScienceDirect fects Prati) International Journal of Greenhouse Gas Control journal homepage: www.elsevier.com/locatelligac Effect of temperature on the critical water content for general and localised corrosion of X65 carbon steel in the transport of supercritical CO2 ( Yong Hua’, Richard Barker, Anne Neville Insite funcional surfaces, Sol of Mechanical Eginerng, Unversity of Leeds, ends LS 9, Utd Kingdom ARTICLE INFO ABSTRACT ‘rice ison Received January 2014 Received in reve form ToSeptembsr 2014 Accepted 12 September 2014 ‘Availabe online 15 October 2014 ‘An assessment of both the general and localised corrosion behaviour of X65 carbon steel in water~ containing CO) environments representative of CO> transport in Carbon Capture and Storage (CCS) applications is presented. Autoclave experiments were conducted ata pressure of bar and tempera tures of 35°C and 50°C in environments where the COs phase was ether saturated or under-saturated ‘with water. Such an approach enabled identification ofthe minimum water content for each system, below which no general or localised attack was observed [At 50°C in the water-saturated envionment, material diseoltion was localised, with approximately irene ont ofthe sree sawing sigs osteo ster immersion waste es 38-0 Pa ae insets wer tho able bon cartons (ecb es ahowmesprecpat ono hee rae wees tothe tomato as mores yer Inuner-sturated tests at 50, no corrosion was observed at water content below 1600 ppm, whilst smal evel of corosion were recorded with 300 ppm of water present at 35°C. The cesuts reflect that emperature drops within the system can promote corrosion at lower water concentrations (ona molar basis) and that localised corrosion sa fundamental consideration in such systems. (© 2014 Elsevier Lt, Al rights reserve. 1. Introduction ‘The capture and storage of carbon dioxide (CO2) as a super- Critical uid in geological formations represents one of the most ‘economic considerations which will afford time for the contin= led use of fossil fuels while new technologies are developed and deployed (McGrail et al, 2009). The Carbon Capture and Storage (CCS) process involves tree stages; capture of the CO» from the power plant or industrial process, transmission of the CO, and its Subsequent storage into a geological reservoir (Gale ancl Davison, 2004). Inorderto develop CCS technology, there ae extensive research, efforts worldwide. These efforts largely concentrate on the devel- ‘opment of capture technology to reduce cost (a key barrier to the successful implementation of CCS), and on assessing the feasibility responding author. Tel: -44 07923350018; fx: 44 01132424611 mal adres: mrybleds acu (Y-Hua) ipso or} 102016 gge-201409026 1730-5836/0 2014 Elsevier Lid, Al eights reserved of injecting and monitoring the CO» within reservoirs themselves. Very little focus has been directed towards CO> transmission and to date, theres imited knowledge regarding the corrosion behaviour ‘of steel pipelines in the presence of CO in conditions that are typical of CCS (Sim et al, 2014). This is partially attributed to the difference in operating conditions and stream compositions in CCS pipelines which differ trom CO,-containing fluid transportation in the oil and gas industry (Ayello et al, 2010). ‘with regard to the transport of CO» overlong distances, carbon steel is the most common material of choice based on its relatively low cost and favourable mechanical properties (Choi etal, 2010). However, carbon steel is susceptible fo cotrosion in flue gas envi ronments because ofthe presence of COz, HzO. 02, $0s, NOs. HS and variousother constituents that are capable of forming corrosive products (Choi etal, 2010). ‘Among these impurities, the water content is potentially one ff the most critical considerations and, as such, is the focus of this study. It is well known that dry CO; does nat corrode carbon, steels (Ayello et al, 2010), therefore sufficiently drying CO, can prevent excessive corrosion rates. However, such a process can be‘suse al ermal ural of Greembouse Gos Cont 3 (2014) 8-60 ° economically impractical and liquid water “breakout can_ be ‘expected, When free water exists, it becomes saturated with CO2, creating carbonic acid, posing a threat to pipeline integrity. Addi tionally, the presence of other impurities (such a8 SOs. NOs, HS, etc.) will pose a risk o the durability ofstee! pipelines during trans= port, specifically when the system is contaminated by free water (Sim et al, 2014: de Visser et al, 2008), Currently. the water content for CO pipelines used for enhanced oil recovery (EOR) in the United States is set at 2 maximum of between 500 and 650 ppm (Ayello et al. 2010; Choi et al, 2010; «le Visser etal. 2008), Putting this into context, the solubility limit, ff water in COp over the range of conditions expected for CCS (15-85°C and 73-300 ban, is around 2000 ppm before tree Water precipitation occurs (Cho! and Nesic, 2011). These calculations are based on the assumption that there are no other additional impuri- ties in the system, Which Would inevitably influence the solubility limi, Although a considerable amount of research has been directed ‘towards predicting and understanding the susceptibility of carbon, steel to COp corrosion in the oil and gas industry, the operating pressures (<20 bar CO, )are farless than that required for CO, trans- Portation in CCS (Cho! etal, 2010)-Regardless, some recent studies have focused on the corrosion processes occurting in the liquid fr supercritical COp phase when water is present (McGrail et al, 2000). These publications are reviewed here, with a focus being directed towards tests Which contain water and 02 as an impurity Tor comparative purposes Table | provides a summary of numerous authors’ results ‘who have conducted tests in high pressure water-saturated o uunder-saturated (below the solubility limit) CO, environments. The ‘overall consensus from the corrosion rate data suggests that general corrosion rates are very low when waters below the solubility limit (ie <0.08 mmjyear). When the CO» phase becomes saturated with ‘water, the level of attack becomes noticeably larger, particularly in the presence of O2, according to research by Choi etal. (2010) Their experiments produced corrosion rates of ~1.0Smmjyear for X65 over 24n in the presence of water-saturated super- critical COz at 8Obar and 50°C with the addition of 5.1 bar 0 ‘A review of literature suggests that a significant proportion fof the general corrosion rates determined from mass loss mea- surements in the water-containing CO, environments are low. However, a small numberof publications (sim etal, 2014: Dugstad et al, 2011) strongly suggest that the main mode of damage con- sists of localised pitting corrosion as opposed to general corrosion In some instances, authors have noticed that only 10% ofthe steel surface suffers from material dissolution (Dugstad et al, 2013a), posing the question as to whether general corrosion rates are rep- resentative in such circumstances. Consequently it is advised that studies concentrating on corrosion in CO» transport need to direct attention towards the extent of localised corrosion in the systern, Furthermore, iis important to have in place a procedure to accu- rately and systematically quantify the extent of localised attack to censure that the extent of pitting recorded is indicative ofthe entire system, It is worth noting that the review provided in Table 1 directs, its attention towards systems where water (and in some instances 02) are the only contaminants ie. no consideration is afforded {0 corrosion studies in the presence of S02 and NOs, as this is ‘beyond the scope ofthis particular review in light of the fact the results are not directly comparable with the research presented here, For information on the influence of impurities such as SO and NO, on the corrosion of carbon steel in water-containing Supercritical CO, systems, the reader is directed to the articles by Dugstad et al. (2011, 2013a,b), Choi et al. (2010), Farelas etal. (2012), Ruhl and Kranzmann (2012, 2013) and Xiang et al. (2011, 2012ab). ‘The focus of this paper is directed towards understanding the extent of both genetal and localised corrosion of X65 steel in water-containing CO environments representative of those encountered in CO, transport in CCS. The work contributes to lit- erature by providing a detailed comparison between the levels of localised corrosion and general corrosion for CO transport sys- tems, highlighting the importance of accurate localised corrosion ‘measurements. The study also focuses on the role of temperature and how this parameter influences the critical water content in the system ie. the water content below which no appreciable levels of corrosion are observed, The overallaimof the workis tounderstand Table Comparison of cocosion rates in erature fom experiment in superrtal CO both water-saturated superercal CO, and with water below te solubility ii, CDi pressure Or pressure _Temp(©) Testperiod_Watereantenr(ppm inmole) Corrosion ae (mien) Choi a (2010) 0 ° 0 2h ‘Water saturated Os 1s (aa ppm) = 108 water 33 edt utoctave to ease Corandnesie gon) 40 0 ” 240 Warersarurated 0, (400ml ~02 0 water ade to ately) “02 0 “oa ChotandNesie(2011) 80 33 so 2m 530ppm at the conditions tested within this paper (ie. pressure of 80 bar and tem= peratures of 35 and 30°C), The CO properties are accompanied by the mutual solubility of both COp in water and water in CO, using the model provided by Spycher ef al. (2003). tt can be seen that the density of CO reduces by half as a result of an increase in temperature from 35 to 50°C. Considering that the solubility of water in CO. at both 35 and, ‘50°C is very similar on a molar basis (2437 and 2400 ppm, respec- tively), i€ can be inferred that because of the difference in CO2 density. over double the mass of water can be dissolved into the (COz phase per unit volume of the fuid at 35°C relative to 50°C. Fig 2 shows the average corrosion rates determined from mass Joss measurements for tests conducted in the water-saturated CO environment at a pressure of 80 bar and at temperatures of 35 and 50°C as.a function of immersion time, Experiments conducted at ‘both temperatures exhibited corrosion rates ofaround.1 mm/year 036 ou 022 ore one 004 om ° Corrosion Rate (m/v) 4 2 “8 Immersion time (hours) 1 50°¢,sobar 135°C, Sobor Fig. 2. Corrosion ates of earbom stein the water saturated COz phase at SODar 2a emperatures of 35 and 50" Cor imersion tes of 14,24 and 4h Water neat i the CO, phase approximately 3437 and 3400p at 35°C and 50:C, respectively2 taal ternational our of Greenhouse Gas Control 31 (2014) 48-60 Table Mutual slaty f water and COs inthe superrtieal phase Temperature (O Pressure (ba) ( densiy sla?) acer in 60s (opm) Corin water own) lover the first 14h. As the test duration is increased, the average corrosion rate in the system at 50°C noticeably drops, whilst at 35°C corrosion continues at a similar rate to that abserved after 14h, showing no significant indication of a change in the rate of material dissolution over 48, Comparing the results of these tests with literature, Choi d 11) recorded a corrasion rate of approximately (0.4mmjyear for 24h tests at 80 bar and $0°C in water-saturated CO, The test results in Fig. 2 indicate a much lower corrosion rate of 0.03mm/year over 24n in the same conditions. In con- trast, Sim et al. (2014) performed experiments on X65 steel in ‘water-saturated CO, at 80 bar and 40°C for 168). They obtained a ‘corrosion rate of 0.08 mm/year at 40°C which les directly between, the corrosion rates recorded in Fig, 2 after 48h of 0.03 mmlyear (at 50°C) and 0.10mmiyear (at 35°C), showing strong agreement and helping to validate the results observed here. Ie is important to note is that the lower temperature experi- ‘ment produces the highest corrosion rate over the 48 h test. uch a feature may beat least partially attributed tothe increased quantity cof water in the system as a result of the increased comptessibil~ ity of CO, atthe lower temperature. As stated previously, there is approximately double the mass of water in the COz phase within theautoclave at 35°C in comparison tothetest at 50°C, despite both, environments containing similar molar concentrations (Table 4) of water i COp, Fig. 3 shows the SEM images of the carbon steel surface after different exposure times at 50°C. After 14h of exposure, traces ‘of FeCO, can already be identified on the surface of the sample (Fig. 3(a)), The presence of the crystalline product is verified by the XRD measurements provided in Fig. 4. In other regions of the sample surface crystals were visibly much smaller and appeared (0 nucleate along the polishing lines of the sample surface (Fig. 2(b)). Throughout the duration ofthe test, the size of the crystals and the level of coverage becomes more significant. After 48 (Fig. (@), in areas where precipitation has occurted, the corrosion product becomes much more compact, with a high degree of coverage and © q@) ‘ig. 3. SEM inages of the covtoded samples exposed to water-saturated CO, at 50‘C and SO bar for (a) 14h Region A:(b)14h— Region B; e)24h- Regon A and) 48 — Region¥. uae a /ncernaonl ours ef Geemouse Gas Control 31 (2014) 48-80, 2 2400 [a hours x-Fe 1600 0-Feco, sol 9 0 2400 +600 800 Intensity (lobs{cts]) 2400 1600 800 a 0 4 9 6 7 Position ["2Theta] (Copper(Cu)) Fig. 4. XRD parm of amples exposed 0 water-saturated COs phase at 50°C and ba for 14,24 an 8 ‘an increase in grain size. The nucleation and growth of the crys- tals, along with their increase in surface coverage coincides with the reduction in corrosion rate throughout the duration of the test, as observed in Fig. 2. As the erystalline FeCOs on the surface becomes more extensive the ratio ofthe FeCO peaks detected on ‘the XRD pattern tothe Fe peak begins to increase and become more dominant, Corrosion is initiated by the condensation of water onto the steel surface as a result of small variations in pressure and tem erature within the system (Choi and NeSic, 2011). Once the water ‘condenses onto the steel surface, it becomes quickly saturated with both CO» and Fe" from the dissolution ofthe steel, enabling FeCOs ‘to precipitate onto the steel surface and further reduce the corro- sion reaction occurring (observed in Fig. 2) (Choi and NeSi¢, 2011) Ic is believed that the presence of FeCOs, is capable of blocking active sites on the surface of the sample and acting as a diffusion barrier to species involved in the cathodic reaction (Zhang ¢t a, 2012). Fig. 5 shows the SEM images and photographs of the sample ‘exposed to the water-saturated CO. phase for different immersion timesat 35 °Cand 80 bar. Unlike tests performed atthe higher tem= perature of 50°C, the sample removed from the 35°C environment ‘showed signs of discolouration over the entire sample surface. The level of attack appeated visibly greater at 357°C. Again, the nature ‘of this corrosion product was confirmed by the XRD measurements as crystalline FeCO3, as shown in Fig. 6 ‘he formation of FeCOs crystals was visible under the SEM after 14h (Fig 5a))-At tis stage, very litte discolouration ofthe sample ‘was evident and except for areas where precipitation has occurred the remaining surface was relatively clean. Although the majority (of the surface appeared uncorroded after 14h, closer inspection using the SEM revealed that small deposits of corrosion products ‘were visible on the material surface (Fig. 5(b)} As the test progresses to 24, the FeCOs corrosion product ‘becomes more extensive in localised areas (Fig. 5(¢)) and the entire surface hecomes discoloured. When focusing on the regions of discolouration on the SEM (Fig. 5(@)), it was apparent that the small corrosion product deposits which were randomly distributed lover the surface had become more extensive, The deposits in these areas were identified as FeCO3 based on the XRD pattern taken from these specific tarnished areas. After 48h, the level of corrosion visibly increased as the surface became even more discoloured. The SEM images indicated that in regions where si nificant FeCO precipitation nad occurred (Fig, 5(e)) the film failed to show the level of compactness observed at 50°C. In other regions of the sample i, discoloured areas (Fig. (0), small, ran- ‘dom deposits of FeCO; were again visible and had become more extensive, explaining the increased level of discolouration with time, It is clear that two very different corrosion mechanisms are ‘occurring at the two different supercritical conditions of 35°C and 50°C, AC 50°C, the level attack is very localised, with approxi- ‘mately 90% of the surface showing no signs of discolouration or localised attack after 48 (see photographs in Fig. 3). Furthermore. in the regions where localised attack was observed, precipitation appears to occur very quickly, producing a compact film covering the area being corroded and reducing dissolution of the mate- rial significantly. in contrast, at 35°C after 48), the entire carbon steel surface becomes discoloured and regions of more significant localised attack can also be easily identified (Fig. 5). The entire discolouration of the sample indicates that corrosion is accurting lover a significant proportion of the surface and is not confined to solely a small surface area as observed at 50°C. Consequently, the precipitation of the corrosion product over localised areas has ‘much less impact on the total degradation rate of the material and as such, the corrasion rate fails to change noticeably through- out the 48 test. Furthermore, in areas where precipitation was ‘observed, the crystals were not as compact as those seen at 50°C, suggesting that the precipitation rate of the crystals is slower as a result of the lower temperature in the system. These fea- tures of the FeCO3 layer and its slower rate of formation could be related tothe lack of significant protection offered against material dissolution. 32, Corrosion fests in under-saturated CO phase at 50°C Tests. in water-saturated CO, phase described previously revealed that corrosion of carbon steel can take place at the steel surface at both 35 and 50°C, However, considering the real con- ditions during the transport of CO» in the pipelines, water content {ends tobe below the solubility limit. Therefore itis also important to study the behaviour of carbon steels when exposed to under- saturated conditions in the supercritical CO phase. Fig. 7 shows the measured corrosion rates of samples exposed to the water-saturated CO phase in comparison to the under- saturated conditions at 50°C and 80 bar for immersion times of 48h, They consist of tests at water contents of 2650, 1600 and 700 ppm. No corrosion was observed at a water content below 1600ppm. This measurement is supported by the SEM image in Fig. 8(a) which shows the carbon steel sample after 48h exposure {to supercritical COp in the presence of 1600 ppm water. The surface ‘was visibly clean and no indication of carresion was present from, observations using the SEM. {As the water content was increased t0 2650 ppm, the average general corrosion rate reached 0.014 mmjyear. SEM images of the sample surface provided in Fig. 8(b) and (c) indicate that corrosion products were detected on the surface of the sample, confirming,o taal ternational our of Greenhouse Gas Control 31 (2014) 48-60 ) () ig. 5. St0 image ofthe coroded samples expose to water-saturated CO; at 35°C and Oba for (a) 14h gion A; (b) 14 ~ Reon B; () 24h — Region A: (8) 248 — Regon B(e) 48h Region Aad (0) 48 - Region B that corrosion had taken place. At the saturation limit (3400 ppm), corrosion rate increased further to above 0.02mmiyear over 48, (of exposure as stated previously and as shown in Fi ‘Te important point to note from this set of tests are that corro- sion can take place in conditions where the water content is below the solubility limit ie. when there is no free water in the system, However, the results also suggest that the current requirement for ‘water content £0 be below 650 ppm in the COs pipeline ( 1 2008) would be sufficient forthe prevention of corrosion in the supercritical CO environment at an operating temperature of‘suse al ermal ural of Greembouse Gos Cont 3 (2014) 8-60 48 hours, HW oe 0- FeCo, ‘80000 Intensity (lobs|cts}) ‘0000 . a a a a) Position ("2Theta] (Copper(Cu)) Fig. 6. XRD paern of samples exposed to water-saturated CO phase at 35°C and bs for 14,24 and 50°C and that a much higher water content could be tolerated at this specific temperature and reduce the relative cost for 650 ppm should be much higher than 1500 ppm, 3.3. Corrosion tests in under-saturated CO» phase at 35°C Fig 9 shows the measured corrosion rates of samples exposed to the water-saturated CO, phase in comparison to the under- saturated conditions at 35°C and 80bar for immersion times of 0035 03 002s Corrosion Rate (mm/year) 0.005 > 1000 1500 48h, From Fig. 0, it is clear that corrosion is observed at every con- centration of water considered at 35°C, whereas no corrosion was ‘measured below a water content of 1600 ppm at 50°C. From this, perspective, the molar concentration limit of 650 ppm would not bbe sufficient to completely prevent corrosion inthe system at 35°C, although general corrosion rates would be very small in such ci ‘cumstances (ie. below 0,02 mm|year). Sim etal. (2014) performed similar tests to those performed here at a pressure of 80bar and temperature of 40°C for 168h, They introduced water to the sys- ‘em at concentrations of 900-3500 ppm and found that corrosion rates averaged between 0,06 and 0.08 mm/year over this range, showing similarity with the results presented in Fig 9, which were conducted at a temperature only 5°C lower. Despite a mass loss being measured for the coupon exposed to 300ppm water in supercritical CO> at 35°C, no indication of corrosion could be detected on the SEM over the regions scanned (Fig. 10(a)), As the quantity of water in the system was increased ‘upto 1770 ppm, signs of corrosion became more apparent as corro- sion products became more visible on the surface (Fig. 10(a)-(@) Based on the mass loss results in Fig. 9, water content of 2800 ppm _marks the transition point in erms of general corrosion behaviour from a low corrosion rate of 0.03 mm{year (at 1770 ppm) to arela- tively higher corrosion rate of over 0.1 mmyear in water-saturated (COp phase. The regions of localised attack observed on the sample surface shawed clear signs of FeCOs precipitation in the presence of 2800 ppm water (Fig. 10(e)) and the water-saturated environment (Fig. 10(f) as a result of the increased level of material dissolution in this area where the water has condensed. 4. Discussion 4.1, Localised corrosion vs. generat corrosion behaviour From analysing photographs of the samples in the water saturated CO phase and the under-saturated conditions it is evident that the corrosion in the system, particularly in higher ‘water content environments can be very localised, There is a ug gestion that the ‘general’ corrosion rates calculated from mass loss ‘measurements may not be an accurate reflection of the detrimen- tal effect the water concentration may be having in terms of metal penetration. Therefore, in addition to the mass loss measurements, surface profilometry was conducted to review the extent of surface pitting in comparison to the genetal corrosion rate, All samples analysed using profilometry were first cleaned thoroughly with 200 250030003500 Water Content (ppm) Fig. 7. average comosion fates of carbon ste! n water-saturated supercitcal COs and under saturated supercrial CO 2 50°C and 80ba or 48h,6 taal ternational our of Greenhouse Gas Control 31 (2014) 48-60 (©) (d) Fig. 8. SEMimagesof samples enosed tO» phe containing (2 1600 ppm water (b) 2680 ppm water.(<) 2550 ppm water at closer magieation and (@) water-saturated (0; 3150" Cand s0bse afer 4h Clarke's solutions to remove any traces of corrosion product that that an average of the 10 deepest pits and the maximum pit depth may prevent the pits from being detected and accurately quanti- should be used for pit damage characterisation of the sample area. fied. The pit depth analysis was conducted in alignment with ASTM In terms of the samples removed from the water-saturated Standard 645-94 ( ). The standard stipulates and under-saturated COp environment, the regions of localised : e° 7 900? | a ig. 9. average corrosion fates of carbon sel in water-saturated supercritical Oy and unde saturated supeteritical CO; a 35°C and 8Obar or a8,‘uo a ermainal furs of reenouse Cas Control (2014) 48-60 s © (C) Fi. 10 SEM images of sample exposed 0 COs phase containing (2) 300 ppm swatersatrate CO» 995: and shar ater attack could generally easily be focused on by the profilometer. In these instances, each region of localised attack was systemati- cally scanned and the most aggressively attacked areas were used to determine the extent of localised corrosion through cansider- ation ofthe top 10 deepest pits When the regions of greatest attack. ‘were more ambiguous to identify three 3 mm x 3mm areas were randomly scanned on the surface, The most severe ofthese images (b) et; (0) 700.ppm water () 1200 ppm wate, (4) 177Oppm wate. (€) 2800 9M and (1 in terms of attack where then used to assess the extent of pitting corrosion Fig, 11 provides examples of the profilometry measurements, taken ofthe samples subjected ta the water-containing supercriti- «al COp at 50°Cand 80 bar. The profilometty images ate provided in conjunction with the general corrosion rates (from mass loss mea- surements) and the localised corrosion rates calculated from these taal ternational our of Greenhouse Gas Control 31 (2014) 48-60 10 \ z a $1 : i I r a g Nomeasureable | No measureable 8 corrosion corrosion ee] 0.01 socio, 700 11600 2650 water-saturated ‘Water Content (ppm) ‘General Corrosion Rate m Average Pitting Rate Fig. 11. average covtosion ats of carbon steel fom water-saturated supercritical C0» and uader-satuated superctical CO a 50-C and SObar for 48h pesented ia conjuction with proflometry images ofthe samples andthe maximum and average iting aes. top 10 deepest pits measured. Fig. 11 indicates thatthe level of pit- tingattack on the steel surface is over an order of magnitude greater than the general corrosion rate, showing that localised corrosion represents a real threat to the integrity of carbon steel pipelines involved in transporting water-containing supercritical CO, if the ‘water content is substantial enough. The results show that ifthe ‘water content at 50°C is 1600 ppm oF below, then no corrosion (general or localised) will be observed. However, ifthe water con- tent is increased 102650 ppm, then the average pitting rate reaches ‘0.2 mmjyear (maximum of 0.4mmiyear). despite the water con- tent being below the solubility limit of 3400 ppm, When the CO is, ‘completely saturated with water at 50°C, the average pitting rate ‘was 1.4mmyear, in comparison to the general corrosion rate of (0.02 mm/year. The results highlight the importance of understand ing and quantifying the localised corrosion rates in these systems to ensure pipeline integrity. Fig. 12 provides examples of the proflometry measurements, taken of the samples subjected (0 the water-containing CO at 35°C and 8Obar along with the general and localised corrosion rates, The reduction in temperature from 50 to 35°C resulted in corrosion being detected at 2 much lower water concentration of 300 ppm, but no localised attack was detected on the surface. At the water content increased from 700 ppm up to water-saturated conditions, the pit growth rate trends to increases with water con- tent from 0.3 mmyeat fo 0.9 mm|year. When localised corrosion ‘was recorded, the rates of attack were over an order of magni tude greater than the general corrosion rates, just as with tests at 50°C. Again, these results illustrate that localised corrosion is, 4 concern in supercritical CO, transport when the system is con- taminated with Water, Additionally, the fests at 35°C show that ‘when the water content is close to the maximum set in the US ‘of between 500 and 650ppm (ie. at 700ppm), pitting rates can reach 0.3 mm/yeat with only water present as the impurity. These ‘observations are in alignment withthe research of Sim et al.(2014) ‘who performed focalised corrosion rate measurements on X65 steel in supercritical COp over a range of water contents from 900 ppm. to water-saturated, At 40°C and 8Obar, they recorded maximum, pitting rates of between ~0.5 and 0Smmiyear over the entire range of water contents considered, which bears a close resem- blance tothe pitting rates determined in this study. Given that the‘suse al ermal ural of Greembouse Gos Cont 3 (2014) 8-60 ” SSEEScE 10 \ ' 8 Gorrosion Rate (mm/year) 700 1200 4770 2800 water-saturated Water Content (ppm) General Corrosion Rate Average Pitting Rate Fig. 12. Average comosion ates of carbon steel rom water-saturated supercritical CO, and under-saturateé supercritical Cy a 35°C and 8Obar for 48h presented in conjuction with proflomery images ofthe samples an the maximum ad average iting ates. experiments performed by Sim et al (2014) were only at a tem= perature of 5°C greater, the two aspects of independent research support one another very well, 5. Conclusions ‘The research presented in this papers focused towards under- standing the extent of both general and localised corrosion in ‘water-containing Cp environments representative af CO» trans- Port in CCS. Tests were conducted at a pressure of 8Obar and ‘temperatures of 35°C and 50°C in both the under-saturated and saturated CO, phase for 48h to understand the effect of tempera ture changes on the critical water content required for corrosion to initiate. The main conclusions which can be drawn from this study are: « Inthe water-saturated CO, environment, two very different types ‘of corrosion behaviour were observed at temperatures of 35, and 50°C, At50°C, the level attack was localised, with approx- imately 90% of the surface showing no signs of corrosion after 48. In localised regions where corrosion occurred, precipitation of crystalline FeCO; occurred quickly, producing a compact film covering the corroded areas and reducing the rate of dissolution ‘ofthe materialover the exposuie time. The average corrosion rate lover 48h was recorded at just over 0.02 mmyear. + Incontrast, for water-saturated tests at 35°Cafter 48h the entire carbon steel surface was corroded and regions of more significant localised attack were visible. The precipitated crystals were less ‘compact, offering less protection to the surface and resulting in an average corrosion rate of 0.1 mmjyear over 48h, five times higher than that recorded at 50°C.@ taal ternational our of Greenhouse Gas Control 31 (2014) 48-60 ‘In under-saturated tests at 50°C, no corrosion was observed at water content of 1600 ppm and below, whilst a measurable corrosion rate was recorded for 300 ppm Water addition at 35°C (0.005 mmyeat). In all tests performed, the level of localised attack was over an trder of magnitude higher than the general corrosion rate cal- culated. The rate of pitting became more severe with increasing Water content for both temperatures '» Average pitting rates of 0.2 and 1.4mmjyear were recorded for Water contents of 2650 and 3400 ppm (water-saturated) at 50°C whilst average pitting rates between 0.3 and 0.9 mmiyear were determined between 700 and 3437 ppm (water-saturated) at 35°C, ‘The results reflect that the temperature drop from 50 to 35°C within the system can promote corrosion at lower water concen- trations on a molar basis} and that the level oflocalised corrosion can be over an order of magnitude greater than that determined as an average corrosion rate from mass loss measurements. References AT Standard G1-03, 2003 Sanda atice for Preparing Cleaning and Evalo- “tg Corosoh Test Specimens, ASTM Iterational West Constohacken. 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