Use of carbon steel ball bearings to determine the effect of biocides and corrosion inhibitors on microbiologically influenced corrosion under flow conditions.

A consortium of sulfate-reducing bacteria consisting mostly of Desulfovibrio, Desulfomicrobium, and Desulfocurvus from oil field produced water was cultivated in a chemostat, receiving medium with 20 mM formate and 10 mM sulfate as the energy and 1 mM acetate as the carbon source. The chemostat effluent, containing 5 mM sulfide and 0.5 mM of residual acetate, was passed through 1-ml syringe columns with 60 carbon steel ball bearings (BBs) of 53.6 ± 0.1 mg each at a flow rate of 0.8 ml/h per column. These were treated every 5 days with 1.6 ml of 300 ppm of glutaraldehyde (Glut), tetrakis(hydroxymethyl)phosphonium sulfate (THPS), benzalkonium chloride (BAC), or Glut/BAC, a mixture of Glut and BAC. Alternatively, BBs were treated with 33% (v/v) of a water-soluble (CR_W) or an oil-soluble (CR_O1 or CR_O3) corrosion inhibitor for 20 s after which the corrosion inhibitor was drained off and BBs were packed into columns. The effluent of untreated control columns had no acetate. Treatment with the chemically reactive biocides Glut and THPS, as well as with Glut/BAC, gave a transient increase of acetate indicating decreased microbial activity. This was not seen with BAC alone indicating it to be the least effective biocide. Relative to untreated BBs (100%), those treated periodically with Glut, THPS, BAC, or Glut/BAC had a general weight loss corrosion rate of 91, 81, 45, and 36% of the untreated rate of 0.104 ± 0.004 mm/year, respectively. Single treatment with corrosion inhibitors decreased corrosion to 48, 2, and 1% of the untreated rate for CR_W, CR_O1 and CR_O3, respectively. Analysis of the distribution of corrosion rates from the weight loss of individual BBs (N = 120) indicated the presence of a more slowly and a more rapidly corroding group. BAC treatment prevented emergence of the latter, and this quaternary ammonium detergent appeared most effective in decreasing corrosion not because of its biocidal properties, but because of its corrosion inhibitory properties.

Biocide-mediated corrosion of coiled tubing.

Coiled tubing corrosion was investigated for 16 field water samples (S5 to S20) from a Canadian shale gas field. Weight loss corrosion rates of carbon steel beads incubated with these field water samples averaged 0.2 mm/yr, but injection water sample S19 had 1.25±0.07 mm/yr. S19 had a most probable number of zero acid-producing bacteria and incubation of S19 with carbon steel beads or coupons did not lead to big changes in microbial community composition. In contrast other field water samples had most probable numbers of APB of 102/mL to 107/mL and incubation of these field water samples with carbon steel beads or coupons often gave large changes in microbial community composition. HPLC analysis indicated that all field water samples had elevated concentrations of bromide (average 1.6 mM), which may be derived from bronopol, which was used as a biocide. S19 had the highest bromide concentration (4.2 mM) and was the only water sample with a high concentration of active bronopol (13.8 mM, 2760 ppm). Corrosion rates increased linearly with bronopol concentration, as determined by weight loss of carbon steel beads, for experiments with S19, with filtered S19 and with bronopol dissolved in defined medium. This indicated that the high corrosion rate found for S19 was due to its high bronopol concentration. The corrosion rate of coiled tubing coupons also increased linearly with bronopol concentration as determined by electrochemical methods. Profilometry measurements also showed formation of multiple pits on the surface of coiled tubing coupon with an average pit depth of 60 µm after 1 week of incubation with 1 mM bronopol. At the recommended dosage of 100 ppm the corrosiveness of bronopol towards carbon steel beads was modest (0.011 mm/yr). Higher concentrations, resulting if biocide is added repeatedly as commonly done in shale gas operations, are more corrosive and should be avoided. Overdosing may be avoided by assaying the presence of residual biocide by HPLC, rather than by assaying the presence of residual surviving bacteria.

Use of Homogeneously-Sized Carbon Steel Ball Bearings to Study Microbially-Influenced Corrosion in Oil Field Samples.

Microbially-influenced corrosion (MIC) contributes to the general corrosion rate (CR), which is typically measured with carbon steel coupons. Here we explore the use of carbon steel ball bearings, referred to as beads (55.0 ± 0.3 mg; Ø = 0.238 cm), for determining CRs. CRs for samples from an oil field in Oceania incubated with beads were determined by the weight loss method, using acid treatment to remove corrosion products. The release of ferrous and ferric iron was also measured and CRs based on weight loss and iron determination were in good agreement. Average CRs were 0.022 mm/yr for eight produced waters with high numbers (10(5)/ml) of acid-producing bacteria (APB), but no sulfate-reducing bacteria (SRB). Average CRs were 0.009 mm/yr for five central processing facility (CPF) waters, which had no APB or SRB due to weekly biocide treatment and 0.036 mm/yr for 2 CPF tank bottom sludges, which had high numbers of APB (10(6)/ml) and SRB (10(8)/ml). Hence, corrosion monitoring with carbon steel beads indicated that biocide treatment of CPF waters decreased the CR, except where biocide did not penetrate. The CR for incubations with 20 ml of a produced water decreased from 0.061 to 0.007 mm/yr when increasing the number of beads from 1 to 40. CRs determined with beads were higher than those with coupons, possibly also due to a higher weight of iron per unit volume used in incubations with coupons. Use of 1 ml syringe columns, containing carbon steel beads, and injected with 10 ml/day of SRB-containing medium for 256 days gave a CR of 0.11 mm/yr under flow conditions. The standard deviation of the distribution of residual bead weights, a measure for the unevenness of the corrosion, increased with increasing CR. The most heavily corroded beads showed significant pitting. Hence the use of uniformly sized carbon steel beads offers new opportunities for screening and monitoring of corrosion including determination of the distribution of corrosion rates, which allows estimation of the probability of high rate events that may lead to failure.