WO1996033296A1 - Procede pour inhiber une corrosion microbienne - Google Patents

Procede pour inhiber une corrosion microbienne Download PDF

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Publication number
WO1996033296A1
WO1996033296A1 PCT/US1995/009131 US9509131W WO9633296A1 WO 1996033296 A1 WO1996033296 A1 WO 1996033296A1 US 9509131 W US9509131 W US 9509131W WO 9633296 A1 WO9633296 A1 WO 9633296A1
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Prior art keywords
anthraquinone
biofilm
sulfate
anthraquinone compound
corrosion
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PCT/US1995/009131
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English (en)
Inventor
Edward Daniel Burger
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Bio-Technical Resources Lp
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Publication date
Application filed by Bio-Technical Resources Lp filed Critical Bio-Technical Resources Lp
Priority to AU31023/95A priority Critical patent/AU3102395A/en
Publication of WO1996033296A1 publication Critical patent/WO1996033296A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
    • E21B41/02—Equipment or details not covered by groups E21B15/00 - E21B40/00 in situ inhibition of corrosion in boreholes or wells
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/20—Displacing by water

Definitions

  • the invention is directed to a method for inhibiting microbially influenced corrosion.
  • it is directed to a method for inhibiting microbially influenced corrosion of susceptible metals in contact with aqueous liquid systems.
  • microorganisms primarily responsible for corrosion in an anaerobic environment within the oil industry are sulfate-reducing bacteria.
  • Requirements for sulfate-reducing bacteria activity and growth include an anaerobic (oxygen-free) aqueous solution containing adequate nutrients, an electron donor, and electron acceptor.
  • a typical electron acceptor is sulfate, which produces H 2 S upon reduction.
  • a typical electron donor is a volatile fatty acid (e.g., lactic, acetic, or propionic acids), although hydrogen can also function as the electron donor.
  • Conditions in an oil reservoir subject to seawater flooding are excellent for establishing sulfate-reducing bacteria activity. Seawater contains a significant concentration of sulfate, while connate, or indigenous formation, water contains volatile fatty acids and other required trace nutrients (e.g., nitrogen and phosphorus).
  • Hydrogen sulfide is corrosive and reacts with metal surfaces to form insoluble iron sulfide corrosion products.
  • H 2 S partitions into the water, oil, and natural gas phases of produced fluids and creates a number of problems. For instance, oil and gas which contain high levels of H 2 S have a lower commercial value than low sulfide oil and gas. Removing biogenic H 2 S from sour oil and gas increases the cost of these products.
  • Hydrogen sulfide is an extremely toxic gas and is immediately lethal to humans at even small concentrations. Thus, its presence in the oil field poses a threat to worker safety. The discharge of produced waters containing high levels of H 2 S into aquatic or marine environments is hazardous because H 2 S reacts with oxygen and lowers the dissolved oxygen levels in the water.
  • Waters produced from a reservoir in association with oil production, especially those resulting from a seawater flood, will typically contain sulfate-reducing bacteria and required nutrients.
  • Conditions in surface facilities e.g., pipelines, vessels, tanks
  • sulfate-reducing bacteria activity are usually quite favorable for sulfate-reducing bacteria activity.
  • they are capable of activity and growth in a wide range of temperatures found in the oil field.
  • Reduced temperatures in surface facilities many times enhance microbial growth as compared to elevated temperatures within the reservoir.
  • Oil production operations favor the growth of anaerobic sulfate-reducing bacteria since those environments are usually kept oxygen-free to avoid oxidation corrosion of steel vessels, pipelines, and tanks.
  • systems are aerobic, localized anaerobic conditions are maintained on the metallic surface (the substratum) beneath the biofilm due to oxygen consumption by aerobic bacteria.
  • Bacterial corrosion is actually caused by sessile anaerobic bacteria living under a thick biofilm composed of aerobic and facultative bacteria enmeshed in a fibrous anionic ion exchange resin that severely limits the penetration of charged molecules.
  • a fibrous anionic ion exchange resin that severely limits the penetration of charged molecules.
  • Sulfate-reducing bacteria activity in surface facilities is a source of H 2 S production, which causes corrosion, and results in the production of solid corrosion products which may cause operational problems such as plugging of water-injection perforations in injection wells. (Produced waters are frequently reinjected into the formation for secondary oil recovery purposes or may be disposed of by injection into a different portion of the reservoir.) Inhibition of sulfate-reducing bacteria activity will reduce H 2 S production and will halt anaerobic corrosion of the steel surfaces, thereby reducing solids formation.
  • Potential methods for mitigating sulfate-reducing bacteria activity include: temperature control, metabolite removal, pH control, Eh control, radiation, filtration, salinity control, chemical control (e.g., oxidizers, biocides, acids, alkalis), solids control (e.g., pigging or scraping the internal pipeline), and bacteriological controls (e.g., bacteria phages, enzymes, parasitic bacteria, monoclonal antibodies, competitive microflora). Some of these methods will kill the sulfate-reducing bacteria, while others stress or disturb them sufficiently to inhibit their activity.
  • chemical control e.g., oxidizers, biocides, acids, alkalis
  • solids control e.g., pigging or scraping the internal pipeline
  • bacteriological controls e.g., bacteria phages, enzymes, parasitic bacteria, monoclonal antibodies, competitive microflora.
  • Pigging is required to remove or disrupt the biofilm on the pipe surface. Pigging can also remove many of the iron sulfide deposits which may be acting as cathodes to the corroding anodic areas. While pigging will be substantially effective where thick biofilms are present, thin biofilms and thin iron sulfide deposits are not appreciably affected by the scraping action of pigs. Subsequently, biocides and surfactant-biocide treatments are used extensively to control bacterial activity in oil field systems. Combination treatments in conjunction with pigging are more effective than the chemical treatments alone.
  • the invention is directed to a non-biocidal method for inhibiting microbially influenced corrosion of microbially influenced corrosion-susceptible metal surfaces having an anaerobic biofilm containing active sulfate-reducing bacteria comprising contacting the biofilm with a liquid dispersion of anthraquinone compound by which the anthraquinone passes through the pores of the biofilm and is diffused within the biofilm to effect contact with the sulfate-reducing bacteria.
  • the invention is directed to a method for inhibiting microbially influenced corrosion of susceptible metal surfaces by coating the metal surface with a solid organic polymer in which are dispersed finely divided particles of anthraquinone compound, the coating thereby forming a barrier between the metal surface and any anaerobic biofilm formed thereon.
  • the invention is directed to a method for inhibiting microbially influenced corrosion of pipelines constructed from susceptible metals through which liquids are transported in turbulent flow comprising introducing a liquid dispersion of anthraquinone compound into the flowing liquid as a plug the volume of which is sufficient to provide contact with a given point within the pipe for at least one minute.
  • Figure 1 is a schematic representation of a typical biofilm
  • Figure 2 is a schematic representation of the valving involved in the use of pipeline scrapers (pigging).
  • a biofilm is a heterogeneous accumulation of bacterial colonies attached to a substratum. Though characterized as a "biofilm” it is neither completely biological, nor is it continuous in the conventional sense of the word "film.”
  • biofilm consists of discrete bacterial microcolonies immobilized on a substratum immersed in an aqueous medium, the microcolonies being separated by water channels though which convective flow can take place.
  • the microbial cells are held together and to the substratum surface by extra cellular polymeric substances.
  • the medium also called “the substrate”
  • the biofilm can contain other co-existing bacterial species.
  • the biofilm can contain extraneous material such as exoenzymes, solutes and inorganic inclusions such as corrosion products, silt and clay particles.
  • FIG. 1 is a schematic representation of a biofilm which is attached to a metal substratum 1.
  • a continuous thin layer of bacteria 3 are directly attached to the substratum 1.
  • this layer 3 is not always continuous and its continuity does not enter into the efficacy of the invention in this environment.
  • Attached to the thin bacterial layer 3, and/ or directly to the substratum 1, as the case may be, are a series of bacterial cell clusters 5 having channels between them through which the aqueous medium 7 can flow. Because of the porosity of the bacterial cell clusters 5, the aqueous medium 7 and materials dispersed therein are able to enter the structure and contact bacteria within the structure.
  • anthraquinones inhibit their activity. Studies have shown that anthraquinone blocks the production of adenosine triphosphate by sulfate-reducing bacteria, thereby removing the bacteria's ability to respire via sulfate reduction.
  • H 2 S is not produced by the bacteria.
  • Biocides are very reactive, a property which is likely responsible for their limited effectiveness in penetrating into biofilms at low dosages.
  • the extraordinary effectiveness of various forms of anthraquinone lies in their non- reactivity. These products are transported into the biofilm, diffuse through the biofilm voids, and then diffuse or are randomly transported by Brownian motion into the bacterial microcolonies without reduction in concentration as a consequence of a reaction with biofilm constituents.
  • These anthraquinone materials are unaffected by other bacteria or the exopolysaccharide matrix present in the biofilm. Even though solid particles of anthraquinone are required to inhibit the sulfate-reducing bacteria activity, the anthraquinone can be introduced into the microbial environment in several physical forms.
  • the anthraquinone can be introduced as a dispersion of these solid particles while an ionic (sodium salt) form of anthraquinone will allow the anthraquinone to be solubilized in an anaerobic caustic solution with pH greater than 12 and preferably greater than 13.
  • the salt stays soluble if the pH of the solution remains above about 12, with precipitation of solid anthraquinone taking place as the pH is reduced below this value.
  • anthraquinone is in molecular form or consists as extremely small (submicron- sized) particles.
  • the anthraquinone molecules or colloidal particles will then be able to move freely in the biofilm, contacting sulfate-reducing bacteria cells easily.
  • Contact of anthraquinone with the sulfate-reducing bacteria, and partitioning of the anthraquinone into the cell membrane blocks the organism's adinosine triphosphate production.
  • decreases in pH in the biofilm due to acid production from other bacteria in the biofilm or due to a sweeping of lower pH fluid through the pipe
  • the NaOH solution also adds to the effectiveness of the treatment by functioning as a surfactant.
  • the caustic solution helps to disrupt the biofilm and increases the tendency for the biofilm to slough from the pipe wall.
  • the high pH solution also shocks all of the bacteria within the biofilm, reducing all activity even in the absence of the anthraquinone.
  • Field studies in a wastewater treatment system have shown that biogenic sulfide production was mitigated with both caustic and soluble anthraquinone treatments, but the maximum degree of inhibition was higher with the soluble anthraquinone treatment and the restoration of the sulfide production to the original level occurred quicker with the caustic treatment.
  • the protocol for implementation of a treatment with soluble anthraquinone salt is relatively simple.
  • the solution typically contains active anthraquinone at a concentration of about 10%.
  • the solution is pumped from a storage tank into the pipeline transporting the water to be treated.
  • a slug dosage of solution is injected.
  • Enough solution is injected to yield a slug in the pipeline at a concentration of about 250 ppm by wt. active anthraquinone for a contact time of about 10 minutes.
  • the slug may only need to be 50 ppm for 1 minute, while other more difficult systems to treat might require 1000 ppm for 30 minutes to control corrosion adequately.
  • the slug dosage requirement is a function of biofilm composition, thickness, and tenacity and the presence of hydrocarbon constituents associated with the biofilm. Velocity of the flowing water, pipe diameter and length, and the pH and buffering capacity of the water will also affect the soluble anthraquinone requirements. Dispersion of the slug as it travels down the pipeline tends to reduce the pH of the slug ahead of and behind the slug. Dispersion is a function of the pipe diameter, number of bends in the pipe, and distance the slug has traveled. (Perkins, T. K. and J. A. Euchner, "Safe purging of natural gas pipelines," SPE Production Engineering, p.
  • the slug is injected so that dispersion is minimized and the high pH length (i.e., the bulk slug) is sufficient to give at least one minute of contact time at that high pH.
  • High anthraquinone concentrations for short contact times are typically more effective than low concentrations for long times, but circumstances may dictate that the concentration of the injected slug be limited.
  • One such circumstance is when the water being treated contains soluble metals (especially calcium) and sufficient bicarbonate ion such that increasing the pH of the water to above about 9.5 will cause scale formation. If too high an amount of the soluble anthraquinone salt is introduced into this water, then this will occur.
  • the scale formation process will buffer the pH at a level which will cause anthraquinone to precipitate from solution.
  • the combined precipitate of scale and anthraquinone will decrease the overall treatment effectiveness. Limiting the amount of soluble high pH solution injected into this water so that the final water pH is below about 9.5 will minimize the amount of scale formation while still maintaining adequate anthraquinone solubility. If the pH is less than about 9.0, then no scale will form. However, significant anthraquinone will precipitate due to the low pH, thereby reducing the overall effectiveness of the treatment.
  • the frequency of the anthraquinone slug injection is based on corrosion monitoring results. Injection needs to be only frequent enough to maintain the corrosion below a predetermined level. Typically, injection is at a one-week interval, although the frequency might be as often as every other day or as infrequent as once per month.
  • the efficacy of the treatment is increased by maintaining a pipeline pigging program. Pigging the line prior to anthraquinone treatments significantly increases the anthraquinone effectiveness by disturbing the biofilm, reducing its thickness, and removing solid iron sulfide deposits.
  • Treatments with aqueous dispersions of solid anthraquinone are made comparably to those for soluble anthraquinone. Control of pH is not important in these treatments. As with soluble materials, treatments with insoluble anthraquinone should be such that a high anthraquinone concentration is maintained for an adequate contact time as the slug travels down the pipeline.
  • anthraquinone-water slug In long pipelines with numerous bends and/ or in pipelines in which the flow is laminar, dispersion of the anthraquinone-water slug may become significant. This will cause anthraquinone concentration in the slug to be reduced below intended levels as the leading and trailing edges of the slug mix with the flowing water. In the case of salt solution usage, the lower pH of the mixed anthraquinone-water in these "tails" will result in anthraquinone precipitation and possibly reduced treatment effectiveness.
  • the leading edge "tail” can be eliminated by launching a pig into the pipeline immediately prior to beginning anthraquinone injection.
  • the pig will act as a barrier for mixing of the anthraquinone-water slug with water even with low Reynolds Number flow and/ or numerous bends in the pipeline.
  • the pig helps to reduce the thickness of the biofilm with its scraping action and will remove many of the iron sulfide and other solid deposits which contribute to corrosion. All of these factors will help increase the effectiveness of the anthraquinone treatment.
  • a pig trailing the anthraquinone-water slug is detrimental to the treatment since it would remove anthraquinone which has penetrated into the biofilm.
  • Anthraquinone can also be introduced into the system indirectly by passing the aqueous fluid (water) containing planktonic sulfate-reducing bacteria through a vessel containing anthraquinone.
  • the anthraquinone in the vessel can be impregnated or deposited onto a support material.
  • the anthraquinone as a solid can be deposited on plastic or ceramic packing material such as Raschig Rings within a vessel or upon a porous membrane or other support in the flow path.
  • the solubility of anthraquinone in water is extremely low.
  • the water containing the sulfate-reducing bacteria will dissolve a small amount of anthraquinone from the packing and consequently treat the sulfate-reducing bacteria to inhibit their activity.
  • an additive may have to be injected into the water to regulate the solubility of the anthraquinone. Inhibiting the activity of planktonic sulfate- reducing bacteria prior to their colonization on downstream pipe surfaces or capture by existing biofilm will minimize buildup of biofilm and thus inhibit subsequent microbially influenced corrosion.
  • cleaning the surfaces of the pipe by pigging or other methods prior to implementing anthraquinone treatment is extremely beneficial for increasing the effectiveness of the treatment.
  • Enhancement effectiveness of the anthraquinone treatment for some applications can result from the combined utilization of anthraquinone and a biocide or oxidizer.
  • the biocide/ oxidizer might be needed to reduce the amount of biofouling on a surface, while the anthraquinone is responsible for long-duration inhibition of the sulfate-reducing bacteria activity. This is especially true for applications in which a biofouling problem or thick biofilm has been established prior to anthraquinone treatment.
  • Anthraquinone alone will penetrate the biofilm, leaving the sulfate-reducing bacteria inactive, but other bacteria and their resultant biotic and abiotic products (especially iron sulfides) will still be present at the wall and possibly will contribute to additional corrosion.
  • a combined anthraquinone-biocide application such as alternating materials or periodically treating with a biocide in place of an anthraquinone treatment, is more effective than the use of either material separately.
  • External corrosion of buried pipelines and vessels is typically mitigated by use of tapes, coatings, paints, and/ or cathodic protection. If disbondment of the tape/ coating occurs (due to poor application or other circumstances), then corrosion can initiate even in the presence of previously adequate cathodic protection. This corrosion may be microbially-influenced, especially during the initiation phase. Incorporating anthraquinone into the formulation of the solid organic polymer (e.g., tape, coating, or paint) will allow these systems to continue to provide corrosion protection against microbially influenced corrosion even if they are damaged and/ or disbond from the metal surface.
  • the solid organic polymer e.g., tape, coating, or paint
  • Incorporation techniques include: 1) fine dispersed anthraquinone powder; 2) an extremely thin bonded sheet; and 3) a soluble ionic salt formulation.
  • the last has the further advantage that alkali solutions naturally inhibit corrosion.
  • the anthraquinone incorporated in the tape, coating, or paint is available to inhibit sulfate-reducing bacteria in encroaching water that might come into contact with the metal surface due to failure of the protection system.
  • the anthraquinone can also be applied to the pipe or vessel surface as a separate thin coating prior to application of the tape, coating or paint.
  • anthraquinone compound refers to compounds comprising the basic tricyclic structure shown below, including derivatives thereof substituted with up to four simple halogen, carboxyl, hydroxyl or amino substituents.
  • both water-insoluble and water-soluble forms can be used.
  • the non-ionic compounds are largely insoluble in aqueous systems, while ionic derivatives are largely soluble in water.
  • Typical insoluble anthraquinone compounds include 1,8- dihydroxyl anthraquinone, 1-amino anthraquinone, 1-chloro-anthraquinone, 2-chloro-anthraquinone, 2-chloro-3-carboxyl-anthraquinone, 1-hydroxyl- anthraquinone and unsubstituted anthraquinone.
  • Various ionic derivatives of these materials can be prepared by catalytic reduction in aqueous alkali.
  • One such ionic derivative is the reduction product of anthraquinone itself which is the disodium salt of l,4-dihydro-9,10-dihydroxyanthracene.
  • anthraquinone compounds used in the invention do not kill the sulfate- reducing bacteria, but merely inhibit the corrosion activity.
  • the active species of anthraquinone compound is believed to be water-insoluble compounds which apparently deactivate the corrosive action of the sulfate-reducing bacteria. In order for the water-insoluble compounds to be effective, they must be very finely divided to an extent that they can be dispersed into the biofilm.
  • anthraquinone Notwithstanding the fact that the active species seems to be the insoluble form of anthraquinone, it is nevertheless preferred to use the ionic (water-soluble) anthraquinone form because it diffuses into the biofilm and thus contacts the sulfate-reducing bacteria more readily.
  • the activity of the ionic form of anthraquinone seems to be derived from its conversion from the ionic form to the non-ionic form by which it is precipitated as very fine particles which attach to the sulfate-reducing bacteria.
  • the invention is a method to inhibit corrosion caused by sulfate- reducing bacteria comprising adding finely divided anthraquinones to an aqueous medium containing the sulfate-reducing bacteria.
  • finely divided means that the anthraquinone has an average particle size of less than 2.5 micrometers and preferably less than 2.0 micrometers. As a practical matter the minimum particle size is about 0.1 micrometer. As the average particle size is decreased within this range, the activity of the anthraquinone increases.
  • the activity of the anthraquinone is a function of particle size and not available surface area.
  • An anthraquinone particle having an average particle size of 2.0 micrometers used at a concentration of 5 ppm provides satisfactory inhibition of growth of sulfate-reducing bacteria.
  • Particles of the same anthraquinone that have an average particle size of 3.7 micrometers used at a concentration of 30 ppm do not provide satisfactory inhibition of growth of sulfate reducing bacteria. This difference in effectiveness due to particle size is readily apparent upon initial application of the anthraquinone but is even more pronounced a short time after application of the anthraquinone when the effectiveness of the larger particle size anthraquinones is effectively completely lost.
  • compositions are added to the medium containing the sulfate- reducing bacteria in a quantity sufficient to inhibit sulfide production. As little as 1 ppm by weight in the aqueous medium gives significant inhibition for many uses.
  • concentration of active anthraquinone in the medium is at least 5 ppm, preferably 5-50 ppm. Greater concentrations, such as up to 1000 ppm, of course can be used, but in most cases with little advantage so long as the "finely divided" particle size requirement is met.
  • the preferred compositions also contain a surfactant, or wetting agent.
  • the surfactant can be applied by any of a variety of techniques. In the case of a normally solid surfactant, the surfactant and the anthraquinone can be dry blended, preferably prior to the milling step. In the case of a normally liquid surfactant, the surfactant can be sprayed onto the anthraquinone followed by mixing such as rumbling to ensure that an intimate well dispersed mixture is obtained. Alternatively, a liquid solution of the surfactant can be sprayed on the anthraquinone and the anthraquinone further mixed.
  • surfactant is not critical. Any of the commercially available surfactants that are inert to the anthraquinone and other composition ingredients and are compatible with the use environment are suitable. Such surfactants can therefore be nonionic, cationic or anionic with the nonionic surfactants being preferred.
  • Triton® X-100 a nonionic octylphenoxypoly (ethoxyethanol), available from Rohm & Haas
  • Poly-Tergent ® SLF18 poly(oxyethylene)-poly(oxypropylene)-rnonohexylether; mono- octylether; mono-decylether, available from Olin Corp.
  • Morwet® D-425 an anionic sodium salt of condensed naphthalene sulfonate, available from Witco Chemical Co.
  • Stepsperse® DF-500 an anionic blend of lignin sulfonates, available from Stephan Co.
  • Stepwet® DF-90 an anionic linear alkylbenzene sulfonate, available from Stephan Co.
  • Stepsperse® DF-100 an anionic/nonionic blend including lignin sulfonate, available from Stephan Co.
  • Stepflow® 41 an anionic lignin
  • the surfactant is present in the dry compositions in an amount to enable the anthraquinone particles to be quickly wetted and thoroughly dispersed in the aqueous bacteria use locus. Quantities in the range of 2-15%, based on the weight of anthraquinone, are generally preferred.
  • the bulk anthraquinones are normally obtained as particles or granules of comparatively large average particle size, as dry powders or slurries.
  • the finely divided anthraquinone is used in the form of an aqueous suspension containing 10-60 wt % of an anthraquinone.
  • FIG. 2 is a schematic representation of a typical pipeline for transportation of liquids which has facilities for pigging (or scraping) operations.
  • Liquid flow through the line is directed through the main pipeline 1 through upstream valve B and downstream valve G, both of which are open during normal pipeline operation.
  • Valve C in starter line 3 and valve A in scraper outlet line 7 are closed and valve D in pressurization line 9 is open during normal pipeline operation.
  • valve C which connects the main pipeline 1 with outgoing scraper barrel 5 via line 3
  • valve D in pressurization line 9 is closed and scraper outlet valve A in scraper outline line 7 is opened.
  • valve B by pinching down slowly on valve B, the differential pressure within the launch barrel rises and overcomes the friction between the scraper and the launching barrel.
  • the scraper passes slowly through scraper outlet valve A and scraper outlet line 7 into the full flow of the main pipeline 1.
  • valve B is fully opened and valves A and C are closed.
  • scraper return line valve F, main pipeline valve G and scraper receiver line valve H are opened. The scraper then proceeds through the pipeline 1, scraper return line 11 and valve F into receiving barrel 13.
  • inhibitor feed valve E is opened to inject anthraquinone compound into the main pipeline.
  • Valve E is then closed as soon as the chosen quantity of anthraquinone compound has been injected into the main pipeline 1.
  • main pipeline valve G remains fully open and valves F and H are closed. Upon venting the pressure within receiver barrel 13, it can be opened to remove the scraper.
  • Steel pipelines are used to transport seawater from treatment and pumping facilities to oil field water injection wells.
  • the water is injected into specific regions of an oil-producing reservoir to provide secondary oil recovery. This provides additional oil recovery over that which results from primary, or natural, production due to the initial pressurization of the reservoir.
  • the treatment process includes chlorination, filtration, deaeration, and processed-anthraquinone addition.
  • the chlorination kills, via oxidation, the majority of the bacteria and algae entering the system with the water from the sea.
  • the filtration removes most of the sea sediments, large particles, and biomass.
  • Deaeration of the water is critical to remove oxygen, a key element involved in the corrosion process. Deaeration of the seawater to less than about 20 ppb oxygen essentially eliminates the potential for common oxygen-induced corrosion.
  • Treatment of the seawater with soluble anthraquinone is performed downstream of all other processes in the seawater treatment plant.
  • the anthraquinone solution is stored in a nitrogen-inerted (oxygen-free) feed tank connected to the suction-side of a variable-rate injection pump.
  • This pump is connected to the pipeline with standard connecting lines and valves, on the discharge-side of the mainline seawater pumps.
  • a flow meter indicates the volumetric rate of injection of the soluble anthraquinone.
  • a check valve is located between the anthraquinone-pump and the pipeline to prevent seawater from flowing back into the soluble anthraquinone feed tank.
  • a ten-mile long, 60-inch internal diameter pipeline transports 1 million barrels of water per day from the treatment plant to an intermediate injection facility.
  • the average seawater velocity is 3.3 ft/ sec, and the flow is clearly turbulent with the Reynolds Number being 1.5x10°-
  • Corrosion rate and presence of corrosion in the pipeline is determined by internal flush-mounted corrosion coupons, by thru-wall ultrasonic and radiographic inspections, and by various types of internally-transported 'smart' pigs. Inspection of corrosion coupons removed from the pipeline after four-months of contact with the flowing water without processed- anthraquinone treatments indicate an average corrosion rate of 5 mils per year (0.127 mm/yr.). In addition, small pits are present.
  • the total measurable iron represents a loss of 120,000 pounds of iron per year removed from the steel pipeline, or a corrosion rate of 3.6 mils per year (0.093 mm/yr.).
  • the total sulfide associated with the solid iron sulfide in the effluent water represents 19,000 pounds of hydrogen sulfide produced per year.
  • a pH 13.5 anthraquinone solution contains 9.5 wt. % active anthraquinone and has a density of 9.2 pounds per gallon.
  • the active anthraquinone is solubilized in an ionic form in the processed-anthraquinone solution to help increase the effectiveness of transport of the active anthraquinone down the pipeline and into the biofilm on the pipe wall.
  • Soluble anthraquinone solution is injected as a slug into the pipeline twice per month for thirty minutes at a rate of 42 gallons per minute, yielding a concentration of 150 ppm by weight of active anthraquinone in the thirty- minute slug of flowing seawater.
  • the injected anthraquinone increases the seawater pH from 7.8 to 9.4 within the slug.
  • the corrosion coupons indicate that the corrosion rate is reduced to less than 1 mil per year and that pitting is minimal. Radiographic inspections of heavily corroded sites indicate that minimal corrosion has occurred since the last inspection four months previously.
  • Total iron concentrations (solid and insoluble) in water effluent samples taken 48 hours following a treatment are 120 ppb, indicating at least a 95% reduction in iron loss from the pipe.
  • the sulfide associated with the effluent iron sulfide particles is reduced comparably.
  • the concentrations of both the iron and the sulfide in effluent water increases slowly with time during the semi-monthly treatment periods such that the total iron concentration at the end of the period averages about
  • Coupons removed for microbial analyses indicate that the sulfate- reducing bacteria density is 4X10 4 cell/cm 2 and that other bacteria are present at a level of 3x10 4 cells/ cm 2 . All of these monitoring techniques confirm that injections of soluble anthraquinone into the flowing seawater effectively mitigate anaerobic microbially influenced corrosion of the steel pipeline and maintain minimal iron sulfide solids formation.

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Abstract

Un procédé non biocide pour inhiber la corrosion microbienne sur des surfaces métalliques ayant un film biologique anaérobie contenant des bactéries actives réduisant les sulfates, consiste à mettre le film biologique en contact avec une dispersion liquide contenant un composé d'anthraquinone.
PCT/US1995/009131 1995-04-17 1995-07-19 Procede pour inhiber une corrosion microbienne WO1996033296A1 (fr)

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AU31023/95A AU3102395A (en) 1995-04-17 1995-07-19 Method for inhibiting microbially influenced corrosion

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999006326A1 (fr) * 1997-07-29 1999-02-11 Dcv, Inc. Procede permettant d'inhiber la production de sulfure biogene
WO1999031295A1 (fr) * 1996-08-09 1999-06-24 Bio-Technical Resources L.P. Procede pour empecher la corrosion d'origine microbienne
WO2000008235A1 (fr) * 1998-08-07 2000-02-17 Hahn-Meitner-Institut Berlin Gmbh Utilisation du ditertiobutylsulfure (tbds) et/ou du tertiobutylmercaptan (tbm) comme inhibiteurs de la corrosion mircrobienne des metaux
WO2015160487A1 (fr) 2014-04-14 2015-10-22 Ecolab Usa Inc. Biocide pour boues
NO20161136A1 (en) * 2016-07-08 2018-01-09 Inhibio As Compounds and compositions for biofilm prevention
CN110475941A (zh) * 2017-03-24 2019-11-19 沙特阿拉伯石油公司 缓解油田应用中的碳素钢管腐蚀和表面结垢沉积
CN115028591A (zh) * 2022-06-17 2022-09-09 内江金鸿曲轴有限公司 一种蒽醌类化合物及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4561981A (en) * 1984-01-27 1985-12-31 Characklis William G Treatment of fouling with microcapsules
US4911923A (en) * 1985-06-27 1990-03-27 Conoco Inc. Biocide for petroleum operations
WO1991015954A1 (fr) * 1990-04-18 1991-10-31 E.I. Du Pont De Nemours And Company Anthraquinones inhibant la production de sulfure par des bacteries de reduction de sulfate
GB2257428A (en) * 1991-07-12 1993-01-13 Environ Limited Chemical formulation for control of odour emission from sewage etc.
EP0591000A1 (fr) * 1992-10-02 1994-04-06 Bio Technical Resources Limited Partnership Formulations d'anthraquinon finement divisée inhibant la production de sulfure par des bactéries de réduction de sulfate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4561981A (en) * 1984-01-27 1985-12-31 Characklis William G Treatment of fouling with microcapsules
US4911923A (en) * 1985-06-27 1990-03-27 Conoco Inc. Biocide for petroleum operations
WO1991015954A1 (fr) * 1990-04-18 1991-10-31 E.I. Du Pont De Nemours And Company Anthraquinones inhibant la production de sulfure par des bacteries de reduction de sulfate
GB2257428A (en) * 1991-07-12 1993-01-13 Environ Limited Chemical formulation for control of odour emission from sewage etc.
EP0591000A1 (fr) * 1992-10-02 1994-04-06 Bio Technical Resources Limited Partnership Formulations d'anthraquinon finement divisée inhibant la production de sulfure par des bactéries de réduction de sulfate

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999031295A1 (fr) * 1996-08-09 1999-06-24 Bio-Technical Resources L.P. Procede pour empecher la corrosion d'origine microbienne
WO1999006326A1 (fr) * 1997-07-29 1999-02-11 Dcv, Inc. Procede permettant d'inhiber la production de sulfure biogene
AU729284B2 (en) * 1997-07-29 2001-02-01 Arkion Life Sciences Llc Method for inhibiting biogenic sulfide generation
CN100360435C (zh) * 1997-07-29 2008-01-09 Dcv公司 用于抑制生物硫化物产生的方法
WO2000008235A1 (fr) * 1998-08-07 2000-02-17 Hahn-Meitner-Institut Berlin Gmbh Utilisation du ditertiobutylsulfure (tbds) et/ou du tertiobutylmercaptan (tbm) comme inhibiteurs de la corrosion mircrobienne des metaux
WO2015160487A1 (fr) 2014-04-14 2015-10-22 Ecolab Usa Inc. Biocide pour boues
US9909219B2 (en) 2014-04-14 2018-03-06 Ecolab Usa Inc. Slurry biocide
NO20161136A1 (en) * 2016-07-08 2018-01-09 Inhibio As Compounds and compositions for biofilm prevention
NO342374B1 (en) * 2016-07-08 2018-05-14 Inhibio As Compounds and compositions for biofilm prevention
CN110475941A (zh) * 2017-03-24 2019-11-19 沙特阿拉伯石油公司 缓解油田应用中的碳素钢管腐蚀和表面结垢沉积
CN115028591A (zh) * 2022-06-17 2022-09-09 内江金鸿曲轴有限公司 一种蒽醌类化合物及其应用
CN115028591B (zh) * 2022-06-17 2024-05-28 内江金鸿曲轴有限公司 一种蒽醌类化合物及其应用

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