Biocide injection as a means of internal microbiologically induced corrosion (MIC)2. Hydrogen
corrosion control of oil pipelines sulphide is soluble in water at pressures and temperatures common in oil field operations and when D F Aloko1 & A D Mohammed2* dissolved, behaves as a weak acid and usually causes Department of Chemical Engineering, Federal University of pitting in a process termed as sour corrosion. Hydrogen Technology, P. M. B 65, Minna, Niger State, Nigeria sulphide can be generated by sulphide reducing Email: alokoduncan@yahoo.com1; abduldyamoh@yahoo.com2 bacteria (SRB). These bacteria contribute to corrosion Received 15 January 2007; revised received 1 May 2007; due to their ability to flourish in the absence of oxygen accepted 17 July 2007 and their ability to change sulphide ions into hydrogen sulphide3. This research work is aimed at investigating the effect of Microbiologically induced corrosion (MIC) has biocide injection in the treatment of internal corrosion of oil been identified as one of the major causes of pipelines. In this research, carefully formulated laboratory experiments are performed on a sample of sump tank discharge corrosion of oil pipelines4. from Mobil Producing Nigeria (MPN) offshore facilities using Technically, biocide is any substance that is formaldehyde (methanol) as the biocide. This is to assess its effect poisonous to organisms and can inhibit their on bacterial proliferation as well as hydrogen sulphide (H2S) metabolism or annihilate them. According to Mobil formation, under both aerobic and anaerobic conditions. The result from the turbidity observed in untreated cultures showed Producing Nigeria, biocide refers to a preparation of that bacterial growth had occurred in them and such growth must formaldehyde that betters biocide physical properties have been hindered by the formaldehyde in the treated aerobic and but maintains its chemical property and fungicidal anaerobic cultures. A blackening of lead acetate paper observed capacity5. with emanating rotten egg smell gas is an indication for the The objective of this work seeks to investigate the formation of hydrogen sulphide gas. Biocide (formaldehyde) has proved to be efficient at combating bacterial growth and hydrogen efficacy of biocide in the treatment of internal sulphide production by the bacteria. These results show that corrosion of oil pipeline by laboratory experiments biocide can be used to prevent internal corrosion of oil pipeline using sump sample obtained from MPN offshore since it inhibits hydrogen sulphide formation from metabolism of facilities alongside formaldehyde which happens to be the bacteria. the major constituent of biocide used in almost all oil Keywords: Corrosion, Biocide, Hydrogen sulphide, Aerobic companies. condition, Anaerobic condition IPC Code (s): F16L57/00, A01N25/00 Experimental Procedure Sample collection The sample to be tested was collected from the Today, severe corrosion of critical oil pipelines is sump tank discharge system of production platform of causing a major concern in the worlds oil industries. Mobil Producing Nigeria Unlimited. The sample was Corrosion audit has been carried out by many collected in clean, transparent plastic container and consulting firms in order to investigate the root cause was covered properly until ready for test in the of the corrosion and recommend a suitable solution laboratory. for corrosion control, to ensure asset integrity and maintain flow assurance1. Preparation of lead acetate papers Corrosion in its broadest sense may be defined as Filter paper was cut into strips of 50 – 60 mm the deterioration of a substance or its properties length and 8 – 10 mm width. The cent – o- gram because of a reaction with environment. Primarily in balance was used to weigh 0.25 g of lead acetate the oil field, it refers to the destruction of metal by a crystals. The crystals were then dissolved in 10 mL of chemical reaction with a given environment, caused water. Cut strips of filter paper were dipped into the by existence of an electrochemical mechanism2. lead acetate solution and allowed to soak for about Many forms of corrosion of metals are known, 3 min before they were removed, placed in a flat glass based on the principal causative substance: oxygen, plate and allowed to dry in the oven before being used water, carbon dioxide, hydrogen sulphide and as lead acetate paper. NOTES 537
Preparation and sterilization of nutrient medium (broth) Incubation of sub – cultures
2.5 g of nutrient powder was measured and taken Out of the two sets of four inoculated test tubes into a glass beaker. 100 mL of distilled water taken in (the one further treated with formaldehyde and the a glass beaker into which the nutrient powder was one with no formaldehyde), a test tube was taken dispensed. The powder was allowed to soak for about from each set and carefully placed in the anaerobic 10 min before being swirled to ensure a proper mix. jar. A candle was lit and placed in the same jar, the lid Afterwards, 10 mL of the solution was measured out was then carefully replaced and the edge lined with and dispensed into each of the 10 clean test tubes and grease. The flame from the candle reduced in glow their openings were sealed off with aluminium foil. until it finally extinguished, that is an indication that The test tubes were secured in the metal gauze stand all the oxygen within the anaerobic jar had burned and placed in the autoclave for wet sterilization for out. Carefully, the jar with its contents was placed in about 15 min at 125oC and 15 Ibf/in2 (1.09 kgf/cm2). the incubator alongside the other two subs - cultures. The media in different test tubes were then The incubator was adjusted to 32oC and the refrigerated. experimental set–up was left in it for 12 days.
Preparation and incubation of primary culture Collection of cultures
Two of the test tubes containing nutrient broth At the expiration of 12 days, the incubated cultures were used in this stage. The aluminum foil was were carefully removed from the incubator. The smell removed from the brim of one test tube while which each culture exuded, the appearance of each holding it very close to the flame of a spirit lamp to lead acetate paper collected, and the turbidity of each ward off every bacterium or micro – organism that culture were carefully noted. The lead acetate papers might enter the medium. The wire loop was held in were collected in separate sterilized bottles. The the flame until it turned red hot, then it was dipped bottles were then labeled appropriately: Untreated in the sump sample to remove a loopful of it. The anaerobic culture, treated anaerobic culture, untreated loopful of sump sample was dispensed into the open aerobic culture, treated aerobic culture, lead acetate test tube. Again, aluminum foil was used to seal off papers – aerobic and lead acetate papers - anaerobic. the test tube opening. This procedure was repeated for a second medium and both inoculated test tubes, Results were put in the incubator which was left at about The results obtained have been summarized in 32°C. The set–up was left for 36 h to allow for Table 1. Following observations can be made from proper bacterial growth, if any. The following day, the results obtained. the media were ready for inocula to be drawn from Appearance of lead acetate papers them. • lead acetate paper withdrawn from the Preparation of sub – cultures and biocide injection untreated anaerobic cultivation had blackened Four fresh media in four different test tubes were at the tip hanging close to the culture, inoculated by the same procedure as in case of • lead acetate paper from treated anaerobic incubation of primary culture. cultivation remained white even at the end of Two out of the four freshly inoculated media were 12-day incubation just like it was at the further treated with formaldehyde. A strip of lead beginning, acetate paper was hung up on the inside of the brim • lead acetate paper withdrawn from untreated of each of the four test tubes with the aid of aerobic cultivation blackened at the tip just aluminum foil which also served as lid for each test like the one withdrawn from the untreated tube. anaerobic cultivation, and Table 1⎯Appearance of lead acetate papers, smell and turbidity of cultures Cultivation Formaldehyde treatment Lead acetate papers Turbidity Smell Initial Final Initial Final Initial Final Aerobic Yes White White Negligible Negligible No No No White Blackened Negligible High No Yes Anaerobic Yes White White Negligible Negligible No No No White Blackened Negligible High No Yes 538 INDIAN J CHEM. TECHNOL., SEPTEMBER 2007
• lead acetate paper withdrawn from the Conclusion
formaldehyde- treated aerobic cultivation was Formaldehyde has proved to be efficient at observed to have remained white at the end of combating bacterial growth, bacterial metabolism and the incubation period like it was in the by extension, hydrogen sulphide production by beginning. bacteria as well as pipeline internal corrosion as caused by H2S, other factors remaining the same. The Turbidity of cultures efficiency is irrespective of whether or not the • primary culture in two test tubes was condition is anaerobic. observed to be very turbid after a day of Furthermore, growth in the untreated aerobic incubation, culture implies that, though sulphate - reducing • formaldehyde- treated culture incubated in the bacteria do exist under anaerobic environments anaerobic jar was observed to have remained such as that obtainable inside pipelines, they may clear after 12-days of incubation, also be able to thrive in aerobic environments-an • culture which was not treated with ability that would make them facultative and not formaldehyde and incubated in the anaerobic full anaerobic. Another possibility is the existence jar was observed to have turned very turbid of other bacteria than SRB in the sump tank after 12-days of incubation, discharge. Ultimately, it has been shown that • formaldehyde-treated aerobic culture was biocide can be used to combat pipeline internal observed to have remained clear optically as corrosion since it inhibits H2S formation from observed in the treated anaerobic culture, and metabolism of the bacteria. • intense turbidity was observed in the It is recommended that other factors within the untreated aerobic cultivation. pipelines such as viscosity, flow of oil and pressure within the pipeline should be investigated to ascertain Smell from cultures their influence on the biocide injection program. A A very disagreeable smell, of rotten egg was observed mathematical formula to define the amount of biocide from both anaerobic and aerobic cultivations but not to be injected in each pipeline and other methods of from the sample treated with formaldehyde. This was combating internal corrosion are attractive areas for observed at the end of the 12-day incubation period future research. taking off the aluminium foil seal. Acknowledgement Discussion The authors would like to acknowledge the time, Turbidity of the primary culture after incubation effort of Mobil Producing Nigeria Unlimited, Ibeno, showed that bacteria within some samples were still Akwa-Ibon State, Nigeria and also dedication of alive and were infact, capable of growth. This was a Mr. Ogo Nwaoche Godfrey during the research work. necessary step to ensure non-wastage of experimental material in subsequent stages. The turbidity observed References in untreated cultures showed that bacterial growth had 1 NALCO/Exxon Energy Chemicals, L.P., 2001, Corrosion occurred in them, such growth must have been Audit for Exxon Mobil Empire fields at Eket, Nigeria. hindered by formaldehyde in the treated anaerobic 2 Corrosion types overview web page, http: // and aerobic cultures. In short, increased turbidity httd.njuct.edu.cn/mat web/ corrosie/c.htmhttp://www. bd.com/ds/technical Center/inserts/Nutrient_Gelatin.pdf. indicates bacterial growth. 3 Sulphur bacteria web page, http://www.reef.educ/asp pages/ For this research however, the non-growth of seeb.asp. bacteria in the treated cultures is attributable to the 4 NACE, 1999, Biologically Induced Corrosion. formaldehyde because the control set–ups were 5 Mobil producing Nigeria unlimited, 1999, Corrosion similarly handled at every stage, other than the Principles OIMS – PR – 1.0. 6 Mobil producing Nigeria unlimited, 2001, Joint Venture injection of formaldehyde. A blackened lead acetate Operations Overview. paper observed along with emanating rotten egg smell 7 Richard M B, “Black powder” in the gas industry sources, in the experimental results can, be an indication for characteristics and treatment, gas machinery Research the formation of hydrogen sulphide gas. council, 1998, 3 – 1, 3-2.