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CHEMICAL AND PHYSICAL ANALYSIS OF NATURAL GAS PIPELINES CORROSION PRODUCTS (BLACK POWDER)

T. S. Villela; J. M. Silva; E. H. S. Cavalcanti; (National Institute of Technology INT Rio de Janeiro/RJ Brazil); J. C. Cobucci, P. A. Ferreira; G. S. Pimenta, (PETROBRAS/CENPES/DEP/TMEC Rio de Janeiro/RJ Brazil); Fernando Coelho (TBG Transportadora Brasileira Gasoduto Bolvia-Brasil S.A.) Summary
Black powder is usually present in natural gas pipelines and plants and is mainly corrosion products. It tends to accumulate in places which geometry is favorable as dead-end of pipelines. The presence of black powder in natural gas pipelines can lead to high operational costs due to production loss and equipment clogging. Black powder can be sheared to very small sizes, leading to obstruction of valves, compressors and others equipments. Corrosion monitoring consists in accompanying the corrosion process and operational conditions in order to obtain relevant information about pipelines and plants materials that permits to decide preventive actions to minimize corrosion effects. The use of electrical resistance sensors and weight loss coupons are very common in natural gas pipelines and provide important information about corrosion process, but it does not allow to identify the source of corrosion mechanism. In this case, qualitative and quantitative chemical analysis of corrosion products is generally used. This technical work present the results of chemical analysis of black powder samples taken from pipelines from three natural gas Companies at different times of sampling. The range of black powder particles size indicated that in the same pipeline we can find powder with various sizes. For instance, sample A with particles between 210m and 44 m and sample B was thinner, the major fraction was < 37 m. In the other pipeline we found samples with very large size, like sample E (95,45 % with 297 m). In the third pipeline we found solid residues evenly distributed along the measured range, like sample F ( 297 m to < 37 m) and fine ones, like sample C (69,79% < 37 m). Table 1 Size distribution of black powder samples. Sample A Mesh # + 48 -48x65 -65x100 -100x150 -150x 200 -200x 325 -325x400 -400 Size (m) 297 210 149 105 74 44 37 < 37 % 8,10 11,54 20,38 19,24 13,74 17,45 2,47 7,08 Sample B % 3,81 4,37 6,70 8,43 6,46 15,54 6,54 48,15 Sample C % 8,16 1,43 2,35 2,73 1,64 5,89 8,01 69,79 Sample E % 95,45 0,26 2,45 0,81 0,47 0,26 0,07 0,22 Sample F % 19,94 11,57 11,62 9,70 7,57 12,60 9,35 17,65

The organic fraction of the black powder analyzed by gaseous chromatography and infrared spectrometry after the extractions with ethyl ether and n-hexane was basically formed by aliphatic and aromatic hydrocarbons, fatty acids, carboxylic acid and orthorhombic sulfur (S8). This result indicated that the organic fraction presented the characteristics of mineral oil and/or emulsifiers. The sulfur was detected in the organic fraction because it is soluble in ether.

The analysis showed that the major fraction of black powder was the inorganic fraction 88,70 to 99,52%. The qualitative analysis by infrared spectrometry indicated the presence of SiO2 and CO3= ions. The principal elements identified by x-ray fluorescence were O2, Fe, S and Si (see table 2). These results suggest the presence of a corrosive process of the carbon steel with the formation of some oxides (>% of Fe3+, see table 3). The presence of Fe2+, determined by volumetric analysis (balance between Fe/Fe2+/Fe3+, see table3), may be associated with the corrosion by H2S with generation of iron sulfide FeS. The percentage of carbon and sulfur was determined by direct combustion. The presence of silicon oxide, determined by gravimetryc method, could be related to residues formed during pipeline construction. Table 2 - X-Ray Fluorescence of inorganic fraction of black powder samples. SAMPLE A (%) SAMPLE B (%) SAMPLE C (%) 45,94 28,50 27,99 33,67 7,20 1,82 10,48 42,80 51,39 0,33 0,16 1,87 4,80 18,57 15,27 SAMPLE F (%) 37,18 15,29 42,00 0,17 2,93

Oxygen Silicon Iron Sulfur Loss on ignition

Table 3 Quantification of SiO2, Fe3+, Fe2+, C and S to the samples A, B and C. SAMPLE A 75,24 7,92 2,46 2,46 0,11 SAMPLE B 28,44 13,38 18,53 7,29 0,18 SAMPLE C 37,97 16,46 5,36 3,95 0,94

SiO2 Fe+3 Fe+2 C S

We could make some suppositions with the results found by the analysis by x-ray diffraction (see table 4). The presence of lepidocrocite in sample A was associated to corrosion by chloride ions, however the formation of goethite in the same sample was explained by the oxidation of iron in presence of humidity. For sample B the corrosion process of carbon steel produce goethite, amorphous iron and vaterite CaCO3 normally formed by the action of fresh water at elevated temperatures. For sample C maghmite was detected, what suggests a uniform attack by oxygen in the presence of humidity. Siderite FeCO3 was also associated with a uniform attack by carbon dioxide gas present in free water. The alpha quartz residue may be formed during pipeline construction or from well formation water. Table 4 - X-Ray Diffraction of samples A, B and C Sample A traces absent absent traces absent present little Sample B absent absent absent traces present traces intense Sample C absent present present absent absent traces intense

Lepidocrocite Maghemite Siderite Goethite Vaterite Alpha quartz Amorphous FeOx

Acknowledgment
We would like to thank the MCT and FINEP Agreement 65.00.000.17 (resources CTPETRO/ANP).