EP0296882A1 - Method of reducing microbial growth in storage systems containing hydrocarbon liquids - Google Patents

Method of reducing microbial growth in storage systems containing hydrocarbon liquids Download PDF

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Publication number
EP0296882A1
EP0296882A1 EP88305791A EP88305791A EP0296882A1 EP 0296882 A1 EP0296882 A1 EP 0296882A1 EP 88305791 A EP88305791 A EP 88305791A EP 88305791 A EP88305791 A EP 88305791A EP 0296882 A1 EP0296882 A1 EP 0296882A1
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EP
European Patent Office
Prior art keywords
water
active ingredient
microbial growth
hydrocarbon liquid
biocide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP88305791A
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German (de)
English (en)
French (fr)
Inventor
Steven Thomas Swift
Larry Mark Stevens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0296882A1 publication Critical patent/EP0296882A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water

Definitions

  • the present invention relates to a method for using biocide treated water to reduce microbial growth in storage systems containing hydrocarbon liquids.
  • Hydrocarbon liquids such as kerosene, jet fuel, gas oils and lubricating oils are often stored in systems such as storage tanks, aircraft fuel tanks and holds of tankers. When so stored, water invariably accumulates in the bottom of the system due to con­densation of water from warm air onto the walls of the system, separation of free-water entering the system with the hydrocarbon liquid or leaks in the system. Frequently, micro-organisms such as bacteria, fungus, yeast and mold are present in the air and water entering the storage system. These contaminants will multiply rapidly because the hydrocarbon liquid at the water/hydrocarbon interface serves as a nutrient for their growth.
  • the result of this microbial growth is (1) corrosion of the metal sub­strate of the system; (2) plugging of equipment such as filters, engine fuel pipes, nozzles, separators, etc.; and (3) contamination of the hydrocarbon liquid with water due to malfunction of equipment such as a filter/­ separator. Items (2) and (3) are particularly critical when the hydrocarbon liquid is a jet fuel since free-water, which forms ice crystals at high altitude, or particulates in the fuel could lead to filter plugging onboard the aircraft.
  • biocides have also been suggested to control microbial growth.
  • the biocide for the biocide to be effective, it must be present in the water phase, either through direct addition or through partition from the hydrocarbon liquid. If added directly to the water phase in the system and allowed to remain for an extended period of time; i.e. typically a week or more (as illustrated in British Patent 1,372,560 and U.S. Patent 3,251,662, the disclosures of which are incorporated herein by reference), the biocide can diffuse from the water into the hydrocarbon liquid, making it unacceptable for use. This is particularly true for jet fuel which must meet stringent specifications, such as ASTM test D-1655 in the United States which does not allow biocide addition. In addition, disposal of the water phase is complicated since it now contains a biocide.
  • the biocide will diffuse into the water phase so as to control microbial growth.
  • this approach has the same deficiencies as the addition of biocide to the water phase in that the biocide will be present in the hydrocarbon liquid, which may not meet required specifications, and thus, is unacceptable for use.
  • this method comprises:
  • the active ingredient in the discharged water may then be neutralized to a non-toxic form to facilitate disposal of the water.
  • the hydrocarbon liquid should also be tested to confirm that it meets appropriate specifications. Further treatment of the hydrocarbon liquid (e.g. by clay filtration) may be performed to ensure removal of any residual active ingredient.
  • the method described herein provides a simple technique for utilizing biocide treated water to effectively reduce or eliminate microbial growth in a storage system containing hydrocarbon liquid without adversely affecting the quality of the liquid remaining in the system during biocide treatment.
  • This method which may conveniently be applied to essentially any type of storage or fuel handling system, also provides for environmentally acceptable water treatment and disposal.
  • Storage system 10 which is partially filled with an upper layer of hydrocarbon liquid 12.
  • the source of the hydrocarbon liquid is not critical and may vary broadly.
  • the liquid will be a petroleum hydrocarbon liquid, such as kerosene, gasoline, jet fuel, diesel fuel, gas oils and the like.
  • Storage system 10 also contains a lower layer of water 14 in contact with the bottom or floor of system 10, said water having one or more micro-organism therein and being separated from the hydrocarbon liquid 12 by a hydrocarbon liquid/water interface 16.
  • water containing a biocide having an active anti-­microbial ingredient is introduced into the lower portion of system 10 through line 18, preferably at a point below the level of hydrocarbon liquid/water interface 16 (e.g., a drain line).
  • the amount or volume of water added is not critical. However, since the micro-organisms will tend to proliferate on the floor of system 10, the amount of water added should be sufficient to cover at least a portion, preferably a major portion of the floor of system 10. Best results will be obtained if the amount of water added will be sufficient to cover essentially the entire floor of system 10.
  • the water may be derived from any suitable source including distilled water, city water or industrial water.
  • biocide used is not critical and may be chosen from a wide variety of compounds available in the marketplace, depending upon the particular micro-organism or organisms contaminating the system.
  • the biocide will contain an active anti-microbial ingredient to react with the microbial growth as well as other materials which could be inerts, carrying solvents and the like.
  • Suitable biocides include those sold under the tradenames DBNPA 7287 (Dow), Omadine TBAO (Olin) and Kathon FP (Rohm and Haas).
  • the concentration of the biocide in the water is not critical and can vary broadly depending upon the concentration of the active ingredient in the particular biocide chosen as well as the period of time said active ingredient is in contact with the microbial growth.
  • the con­centration of active ingredient in the water need only be that sufficient to kill or reduce at least a portion of the microbial growth contacted. If the concentration of active ingredient is too low, very little reduction in microbial growth will be obtained or extended contact time (i.e. in excess of 7 days) will be required to achieve significant reduction in microbial growth. However, very high concentration of active ingredient will promote transfer of the biocide components (including the active ingredient) into the hydrocarbon liquid.
  • the concentration of active ingredient in the water be sufficient to eliminate a major portion, more preferably at least 99% and most preferably essentially all (i.e. at least 99.9%) of the microbial growth contacted within a period of time of five days or less, more preferably within about three days or less.
  • the concentration of active ingredient in the water will be at least about 10 wppm, preferably at least 20 wppm, and will range from about 10 to about 200 wppm or more, preferably from about 20 to about 100 wppm for contact times of 120 hours or less, preferably 100 hours or less and more preferably 75 hours or less.
  • the minimum contact time will vary depending upon the concentration of active ingredient in the water and the desired reduction in microbial growth. Accordingly, the minimum contact time need only be that sufficient to kill at least a portion of the microbial growth contacted. In practice, however, the contact time will be at least 24 hours. As such, the contact time of active ingredient with microbial growth will typically vary from about 24 hours to about 120 hours, preferably from about 24 hours to about 100 hours and more preferably from about 24 to about 75 hours.
  • hydrocarbon liquid 12 and biocide treated water 14 be maintained in a quiescent state to further minimize transfer of the biocide components into liquid 12.
  • the spent biocide treated water may be stored for further use, used to treat microbial growth in other storage systems (with additional biocide being added as make-up) or disposed of in an environmentally acceptable manner.
  • Possible disposal techniques include sending the biocide treated water to a waste treatment plant provided the concentration of active ingredient is sufficiently low (i.e. typically 1 wppm or less) or chemically deactivating the active ingredient.
  • Figure 1 shows that spent biocide treated water is passed through line 20 to a treatment tank 22 in which said water is contacted with a chemical introduced into tank 22 through line 24.
  • the active ingredient (iso­thiazoline) has been found to be effectively neutralized by sodium bisulfite, with from about 18 to about 36 parts of bisulfite being required for each part of isothiazoline. Once the active ingredient is degraded, the water can then be disposed of in a conventional manner through line 26.
  • hydrocarbon liquid 12 will be essentially free of active ingredient; i.e., the concentration of active ingredient in hydrocarbon liquid 12 will be 0.5 wppm or less.
  • liquid 12 could undergo further treatment (e.g., clay treatment) to remove any residual active ingredient.
  • the temperature and pressure at which the above described biocide treatment process is carried out is not critical and could vary broadly. However, ambient conditions are preferred.
  • the contaminated water was then contacted (or treated) with water containing from 20 to 160 wppm Kathon FP (i.e. from 2.4 to 19.2 wppm isothiazoline) and the percent bacteria and fungus killed at each concentration determined by measuring the level of viable organisms in water samples withdrawn immediately prior to biocide addition and at 8 hours, 1 day, 2 days and 3 days thereafter.
  • Microbial levels were determined using the Viable Plate Count Method in which a sample of the water phase is diluted in sterile dilution broth (isotonic saline) and a 1 ml. portion thereof is placed on a Petri dish containing nutrient agar.
  • Each microbial cell will form a colony on the dish in 2-3 days and by counting the number of colonies and taking into account the dilution factor, the original count can be determined (see Stanier, R. Y. et al., The Microbial World, pp. 301-302, Prentice-Hall, New York (1970) for further information on the Viable Plate Count Method).
  • Figures 2 and 3 The percent bacteria and fungus killed using Kathon FP are shown in Figures 2 and 3.
  • Figure 2 shows that about 99.99% reduction in bacteria can be achieved with about 10 wppm of isothiazoline in a 24 hour period. Greater reductions (i.e. 99.999% or more) require about 20 wppm isothiazoline and a 72 hour contact time.
  • Figure 3 shows that at least about 10 wppm of isothiazoline was required to achieve about 99% reduction of fungus in about 48 hours, while about 20 wppm isothiazoline gave 99.9% reduction in the same period.
  • Figures 2-5 also show that contact time of the microbial growth with the active anti-microbial ingredient can be reduced by using higher concentrations of active ingredient.
  • the present invention was field tested in a 40,000 barrel storage tank containing 20,000 barrels of aviation fuel. Two 5,000 gallon batches of clean water, each containing 24 wppm of isothiazoline, were pumped into the tank through a discharge line below the level of the fuel. Two hundred gallons of water bottoms from other storage tanks having bacteria and fungus populations were then pumped into the tank through the discharge line to ensure a measurable biological population is present initially. The water phase in the tank was sampled immediately after addition of the contaminated water and at 16, 40 and 64 hours thereafter. Bacteria and fungal viable counts were determined using the Viable Plate Count Method described in Example 1 and the results summarized in Table 1 below: TABLE 1 Sample Hr.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
EP88305791A 1987-06-23 1988-06-22 Method of reducing microbial growth in storage systems containing hydrocarbon liquids Withdrawn EP0296882A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6582487A 1987-06-23 1987-06-23
US65824 1998-04-23

Publications (1)

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EP0296882A1 true EP0296882A1 (en) 1988-12-28

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EP88305791A Withdrawn EP0296882A1 (en) 1987-06-23 1988-06-22 Method of reducing microbial growth in storage systems containing hydrocarbon liquids

Country Status (4)

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EP (1) EP0296882A1 (pt)
AU (1) AU1826488A (pt)
BR (1) BR8803031A (pt)
NO (1) NO882525L (pt)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2384005A (en) * 2001-10-18 2003-07-16 Chevron Usa Inc Use of deactivatable biocides to prevent microbial growth in hydrocarbons

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372560A (en) * 1970-12-31 1974-10-30 Nippon Oil Co Ltd Procedure for sterilizing oil tanks

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372560A (en) * 1970-12-31 1974-10-30 Nippon Oil Co Ltd Procedure for sterilizing oil tanks

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2384005A (en) * 2001-10-18 2003-07-16 Chevron Usa Inc Use of deactivatable biocides to prevent microbial growth in hydrocarbons
GB2384005B (en) * 2001-10-18 2004-08-18 Chevron Usa Inc Deactivatable biocides for hydrocarbonaceous products
AU2002301454B2 (en) * 2001-10-18 2008-10-23 Chevron U.S.A. Inc. Deactivatable biocides for hydrocarbonaceous products

Also Published As

Publication number Publication date
BR8803031A (pt) 1989-01-10
NO882525L (no) 1988-12-27
NO882525D0 (no) 1988-06-08
AU1826488A (en) 1989-01-05

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