DK164599B - PROCEDURE FOR COMBATING SULPHATE-REDUCING BACTERIA DESTRUCTION OF INDUSTRIAL, ORGANIC OR Aqueous liquids, AND A METAL WORKING CONCENTRATE - Google Patents

Description

DK 164599 B

The present invention relates to a process for combating destruction of industrially used liquid or organic water-containing or aqueous liquids containing organic materials, the destruction of which is caused by obligate anaerobic, sulfate-reducing bacteria and a metalworking concentrate which, at appropriate dilution. with water is suitable for the preparation of metal working fluids and containing oils and / or glycols, emulsifiers and corrosion inhibitors.

Destruction of industrial, liquid, organic materials containing water or industrially used aqueous liquids containing organic materials, where the destruction is caused by the growth of microorganisms that metabolize organic matter while forming harmful metabolites, is a widespread problem in many branches of industry. This growth of microorganisms requires the presence of free water in liquid organic matter, e.g. an oil, the growth and activity of the microorganisms, although they can often enter the organic phase, e.g. an oil phase, largely limited to the water phase. In practice, it is actually impossible to exclude the small initial amount of water required to initiate the growth of microorganisms from liquid organic matter, and in fact water is incorporated in greater or lesser amounts consciously into many liquid organic materials which used in industry. A wide variety of bacteria, molds and yeasts occur in the destruction of liquid organic materials, and it is also virtually impossible to exclude all such microorganisms from the liquid organic materials. Examples of such used, liquid, organic materials and aqueous liquids containing organic materials subject to destruction caused by the growth of microorganisms include petroleum hydrocarbons and vegetable oils and liquids.

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2 products containing them, including fuel oils, lubricating oils and mineral oil-based hydraulic fluids, oil-in-water emulsions, e.g. metalworking fluids; water-in-oil emulsions, e.g. a water-in-oil emulsion of hydraulic fluids, and aqueous solutions and emulsions of glycols used as metal working fluids. Other aqueous liquids containing organic materials that are severely damaged by the growth of microorganisms are water-based paints, sulfite fluids from treatment 10 of paper pulp, and even liquids which are largely inorganic, e.g. water from industrial processes, electroplating solutions, and oil source injection water. Industrial destruction of liquid, organic materials and aqueous liquids containing organic materials, e.g. petroleum carbohydrate hydrocarbons and vegetable oils, where the destruction is caused by the growth of microorganisms, can result in corrosion of metal storage tanks, e.g. in the storage of fuel oils and in the extraction and processing of mineral oils and in the corrosion of metalworking articles, e.g. by machining, drilling, grinding and rolling of metals, if the destruction occurs in metalworking liquids used as lubricants and coolants during metalworking, by the breakdown of additives in lubricating oils, with the consequent deterioration of the lubricating properties of sulfur, and by the reduction of lubricating oil and by reducing by oxidation or reduction of nitrogen-containing emulsifiers and corrosion inhibitors with subsequent deterioration and instability of oil-in-water and water-in-oil emulsions, by reducing the oil-water interface voltage in stored fuel oil with subsequent breakdown of oil. water separation and contamination of the fuel oil with water, and by blocking pipes, filters and openings of microorganism masses.

The oxygen levels in the liquid, organic materials and aqueous liquids containing organic materials used in the industry, e.g. petroleum hydrocarbons and vegetable oils and liquid products containing them are often low

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3 and may be further diminished by the growth of aerobic and optional anaerobic microorganisms, thereby promoting the growth of obligate anaerobic, sulfate-reducing bacteria (by the term "obligate anaerobic, sulfate-reducing bacteria" is meant in the present specification mandatory anaerobic bacteria capable of extracting metabolic oxygen from compounds containing sulfur in a positive oxidation step and leaving it in a reduced state, usually hydrogen sulfide, or metabolically reducing elemental sulfur to hydrogen sulfide). Examples of mandatory anaerobic bacteria that cause destruction in industrially used fluids include Desul-fovibrio desulfuricans, Desulfovibrio gigas and Desulfotoma-culum nigrificans (Clostridium nigrificans or Desulfovibrio orientis). Compulsory anaerobic sulfate-reducing bacteria metabolize sulfates and sulfonates reductively, e.g. sulfate and sulfonate-containing emulsifiers, e.g. alkyl sulfates and alkylarylsulfonate emulsifiers, and sulfur-containing oils and fats and free sulfate ions present in water, with the release of hydrogen sulfide, which results in extremely serious problems with the destruction of liquid organic materials and aqueous liquids containing organic materials, f. eg. petroleum hydrocarbons and vegetable oils, e.g. fuel oils, lubricating oils, mineral oil-based, hydraulic fluids, oil-in-water emulsions, especially metal processing fluids; water-in-oil emulsions, especially a water-in-oil emulsion of hydraulic fluids; aqueous solutions and emulsions of glycols used as metal working fluids, with the development of bad odors and corrosion caused by the released hydrogen sulphide and destruction of emulsifiers, with subsequent deterioration and instability of the emulsions. Similar problems of destruction caused by obligate anaerobic, sulfate-reducing bacteria also occur in sulfite fluids from the treatment of paper pulp, water-based paints, oil source injection water, water from 35 industrial processes, electroplating solutions, sealed water circulation systems, e.g. heat exchangers and

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4 aqueous cooling and heating systems, storage systems and hot water release and gas seals for gas tanks used for hydrocarbon gas storage. destruction caused by obligate anaerobic, sulphate-reducing bacteria is a particularly difficult problem in the water that accumulates at the bottom of fuel oil tanks and in oil source injection water.

01ie-in-water emulsion metal working fluids and aqueous solutions and emulsions of glycols used as metal working fluids, e.g. coolant for machine tools and coolant for metal rolling, which liquids contain mineral or vegetable oils or glycols, emulsifiers, corrosion inhibitors and water with, if desired, fats, soaps and small amounts of special additives to serve as foil softeners and anti-foaming agents. known as high pressure additives, are widely used for cooling and lubrication purposes in metalworking processes. These fluids have a number of functions in metalworking processes, including lubrication and reduction of temperature * at the interface between tool and workpiece, promotion of tool life and removal of flakes and chips from the metalworking area and cooling of sheet metal during rolling and pressing processes. For economic reasons, it is essential that the metal working fluid be kept in a recycling system so that the liquid can be reused repeatedly. Such metalworking fluids usually contain from ca. 1 to approx. 15% by volume of oil and / or glycols and processed at temperatures ranging from just above room temperature to 40-60 ° C. Thus, coolants for machining metal work at temperatures just above room temperature, and their content of oil and / or glycol varies from approx. 1% in abrasive coolants, where heat dissipation to maintain dimensional accuracy is paramount, to approx.

15% in rigorous machine operations where lubrication is an essential necessity, while metal rolling coolants generally have an oil and / or glycol content of 2-5

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5 volume% and works at higher temperatures, often 40-60 ° C. These metalworking liquids are readily susceptible to destruction by the growth of microorganisms and their oxygen levels are often very low, especially if the liquid 5 is not in use. This promotes the growth of obligate anaerobic, sulfate-reducing bacteria, resulting in serious problems of destruction caused by decomposition of alkyl sulfate and alkylarylsulfonate emulsifiers, degradation of the emulsions, release of free oil and corrosion, and bad odors caused by the release of hydrogen sulfide. Consequently, combating destruction caused by the growth of obligate anaerobic, sulfate-reducing bacteria is of paramount importance in the recycling and recycling of oil-in-water emulsion metalworking liquids and aqueous solutions and emulsions and glycols used as metalworking liquids.

Attempts have been made to combat destruction caused by the growth of microorganisms by incorporating many biocides, but the properties required by a satisfactory biocide are extremely severe and relatively few have been found to be commercially successful. Thus, a biocide to be used to control the destruction of the growth of microorganisms, other than being effective in killing or inhibiting the growth of microorganisms, should be desirably non-toxic and non-irritating in use, having satisfactory stability in an appropriate manner. times at the appropriate temperature ranges and pH values, preferably being soluble in water to achieve a suitable concentration in the aqueous phase where the microorganisms grow, and preferably not being soluble in the oil phase or the organic phase, being compatible with the present invention. system, e.g. without adversely affecting the properties and stability of the emulsion, induce foaming or froth formation, or in itself affect the pH of the system and, if used in fuel oils or in metalworking, do not produce undesirable ash by combustion. Various

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6 phenols, e.g. p-chloro-m-cresol and phenol, heavy metals, compounds which release formaldehyde, and other pesticide-active compounds have been used commercially with various degrees of success in combating destruction 5 caused by the growth of microorganisms and the safety has been questioned. of the application of many of them. As a result, there is a continuing need for new methods to control the destruction caused by the growth of microorganisms, particularly destruction caused by the growth of obligate anaerobic, sulfate-reducing bacteria.

It is known that 1- (2-hydroxyethyl) -2-methyl-5-nitro-imidazole (hereinafter referred to as "metronidazole"), 1,2-dimethyl-5-nitroimidazole (hereinafter "dimetridazole"), 1- (2-Hydroxypropyl) -2-methyl-5-nitroimidazole (hereinafter referred to as "secnidazole") and 1-methyl-2-isopropyl-5-nitroimidazole (hereinafter "ipronidazole") are active against protozoa, amoebas and certain anaerobic bacteria that can infect humans and animals. Compulsory anaerobic, sulfate-reducing bacteria are not known to cause infections in humans and animals, and so far it has not been suggested that the above compounds be effective against obligate anaerobic, sulfate-reducing bacteria in human or veterinary medicine, or that they are effective in combating destruction of industrially used liquids caused by the above bacteria. Therefore, metronidazole, dimetridazole, secnidazole, and ipronidazole would not be obvious to those seeking new avenues to combat the destruction caused by such microorganisms, nor would the compounds possess the combination of other properties that are necessary so that they can be successfully used to combat such destruction.

As a result of research and experiments, it has now surprisingly been found that the nitroimidazole compounds dimetridazole, metronidazole, secnidazole and ipronidazole can be used to control the growth of obligate anaerobic, sulfate-reducing bacteria in liquid organic materials.

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7 containing water or aqueous liquids containing organic materials. It is to be understood that the term "nitroimidazole compounds" as used in the present specification means dimetridazole, metronidazole, secnidazole and ipronidazole.

Accordingly, in accordance with the present invention, there is provided a method for combating the destruction of industrially used liquid organic materials or water aqueous liquids containing organic materials, the destruction of which is caused by mandatory anaerobic, sulfate-reducing bacteria.

The process of the present invention is characterized by incorporating in the aqueous phase one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole in an amount sufficient to prevent the growth of obligate anaerobic sulfate-reducing bacteria.

Examples of industrially used liquid organic materials or water used in industry 20 aqueous liquids containing organic materials are fuel oils, lubricants, mineral oil-based, hydraulic fluids, oil-in-water emulsions, especially metalworking liquids; water-in-oil emulsions, especially a water-in-oil emulsion of hydraulic fluids; aqueous solutions and emulsions of 25 glycols used as metal working fluids, sulphite fluids from the treatment of paper pulp, water-based paints, oil source injection water, industrial process water, electroplating solutions, sealed water circulation systems, storage systems and hot water gas dispensing systems; for the storage of hydrocarbon gases.

The concentrations of the nitroimidazole compounds which can be used separately or in combination according to the present invention are generally between 100 and 500 35 ppm, and in particular 100 ppm, of the total volume of the liquid.

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8 organic material containing water, or the aqueous liquid containing organic materials to be protected from destruction caused by the growth of obligate anaerobic, sulfate reducing bacteria, but lower or higher concentrations may be used in accordance with the particular problem of the destruction concerned and can easily be determined by appropriate testing.

Preferably, the nitroimidazole compounds are not soluble in the organic phase of liquid organic materials containing water and aqueous liquids containing organic materials, and are sufficiently soluble in the aqueous phase thereof to provide concentrations effective to inhibit the growth of obligate anaerobes. sulfate-reducing bacteria, they are non-toxic and non-irritating in use, unlike most of the agents heretofore used to control destruction caused by the growth of microorganisms, they are satisfactorily stable over a suitable period of time. suitable temperatures and pH values, they do not adversely affect the properties and stability of oil-in-water and water-in-oil emulsions, they do not induce foaming or froth formation, they do not in themselves affect the pH value, and they do not produce unwanted ash by combustion.

The nitroimidazole compounds used in the process of the present invention can be added as such to the liquid organic materials containing water or to aqueous liquids containing organic materials which it is desirable to protect against destruction caused by the growth of mandatory anaerobic, sulfate reducing 30, but they are preferably added in the form of solutions, suspensions or emulsions in suitable solvents, e.g. water, glycols, e.g. ethylene glycol, ethyloxalate, dimethylformamide, dimethylacetamide, liquid hydrocarbons, e.g. petroleum, and mixtures thereof, which may contain one or more surfactants if necessary. One

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9 illustrative example of a suitable composition is a suspension prepared by blending microfine dimetridazole (25 w / v%), "Texofor 46" (4 w / v%), "Arylan® CA" (6 w / v%), "Attagel 50" (1.0% w / v) and petroleum 5 (odorless) to 100%.

"Texofor M6" is an ethoxylated oleic acid containing 6 moles of ethylene oxide per liter. moles of oleic acid; "Arylan® CA" is calcium dodecylbenzenesulfonate; "Attagel 50" is a swelling attapulgitler.

The present invention further relates to a metal machining concentrate which, at appropriate dilution with water, is suitable for the preparation of metal machining fluids and which contains oils and / or glycols, emulsifiers and corrosion inhibitors, and the metal machining concentrate of this invention is characterized in that additionally contains an amount, preferably from 0.05 to 5% (w / v), of one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole sufficient to give a metal working liquid after dilution with water. concentration of nitroimidazole compounds sufficient to prevent the growth of obligate anaerobic, sulfate-reducing bacteria.

If desired, the nitroimidazole compounds can be used in conjunction with known anti-destructive agents caused by the growth of microorganisms, e.g. phenols, such as p-chloro-m-cresol and phenol, heavy metals and compounds which release formaldehyde in the process of the present invention to combat the destruction of liquid, organic or industrial water used in the industry, aqueous liquids containing organic materials. The nitroimidazole compounds can also combat destruction caused by nitrite and nitrate reducing bacteria in liquid organic materials containing water and aqueous liquids containing organic materials.

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The valuable properties of the nitroimidazole compounds of the present invention in controlling the growth of obligate anaerobic sulfate-reducing bacteria in liquid organic materials containing water and aqueous liquids

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Containing organic materials subject to destruction caused by the growth of obligate anaerobic sulfate reducing bacteria are demonstrated in the following experiments 1 to 4.

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Experiments 1-4 Activity against obligate anaerobic sulfate-reducing bacteria

Inhibition of the growth of obligate anaerobic sulfate-reducing bacteria.

Test procedure (I) for obligate anaerobic sulfate-reducing bacteria

The test compounds are incorporated by adding the appropriate amounts of aqueous solutions containing 5000 ppm dimetridazole or metronidazole to obtain concentrations of 50, 100, 250 and 500 ppm in an oil-in-water-20 emulsion known to be highly contaminated. with obligate anaerobic sulfate-reducing bacteria. Samples of the contaminated oil-in-water emulsion where no test compound is added are retained as control. Samples of the contaminated oil are taken immediately after the addition of the test compounds and after 3, 5 and 24 hours.

Iron sulphite agar (Oxoid Ltd) is prepared and filled into 10 ml test tubes. The tubes are sterilized in an autoclave at a pressure of 1.05 kg / cm for 15 minutes and sealed with Astell caps to ensure an airtight seal and consequently allow anaerobic growth. The tubes are placed in a water bath at 50 ° C to keep the agar flowing. Graft needle eyelets (1/50 ml) of the samples of bacterially contaminated oil-in-water emulsions are then used as inoculum and the tubes are incubated at 37 ° C for 5 days.

The effect of the test compounds on obligate anaerobic sulfate-reducing bacteria present in the contaminated oil-in-water emulsion is stated as follows:

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Assessment +++++ complete black - no inhibition ++++ good growth but not complete black +++ black / gray spots of inhibition and growth ++ gray with black spots 5 + clear except a few black spots 0 clear - complete inhibition.

The following results are obtained:

Experiment 1 (a) Metronidazole

Concentration Contact time with metronidazole of 15 metronidazole Immediately 3 hours 5 hours 24 hours 0 (control) +++++ +++++ +++++ +++++ 50 ppm +++++ +++++ +++ ++ 100 ppm +++++ +++++ ++ + 250 ppm ++++ +++ + 0 20 500 ppm +++ ++ + 0 (b) Dimetridazole

Concentration Contact time with dimetridazole 25 dimetridazole Immediately 3 hours 5 hours 24 hours 0 (control) +++++ +++++ +++++ +++++ 50 ppm +++++ ++++ ++ ++ +++ 100 ppm ++++ +++ ++ + 30 250 ppm ++++ ++ + 0 500 ppm +++ +00 35

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Experiment 2 (a) Metronidazole

Concentration Contact time with metronidazole 5 of metronidazole Immediately 3 hours 5 hours 24 hours 0 (control) ++++ ++++ ++++ ++++ 100 ppm ++++ +++ + + 200 ppm +++ + ++ ++ 10 500 ppm +++ + + 0 (b) Dimetridazole

Concentration Contact time with dimetridazole 15 of dimetridazole Immediately 3 hours 5 hours 24 hours 0 (control) ++++ ++++ ++++ ++++ 100 ppm ++++ +++ ++ 0 200 ppm ++ + +00 20 500 ppm +++ 0 0 0 25 30 35

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Experiment 3 (a) Metronidazole

Concentration Contact time down metronidazole 5 of metronidazole Immediately 3 hours 5 hours 24 hours 25 pom ++++ +++ +++ +++ 50 ppm ++++ +++ +++ +++ 100 ppm ++++ +++ ++ 10 (b) Dimetridazole

Concentration Contact time with dimetridazole of dimetridazole Immediately 3 hours 5 hours 24 hours 15 - - 15 ppm ++++ +++ ++ ++ 50 ppm ++++ +++ ++ ++ 100 ppm ++ - H- + ++ ++ + 20

Experiment 4 Experimental Procedure (II)

Flasks containing 100 ml of aqueous solutions containing 50, 100, 250 or 500 ppm of the test compound are treated with an oil-in-water emulsion of 0.1 ml which is known to be highly contaminated with obligate anaerobic sulfate reducing bacteria. A control flask without test compound is also produced. Samples from the control flask are taken immediately after addition of the oil-in-water emulsion and from all flasks after 3, 5, 24 and 48 hours.

Iron sulphite agar (from Oxoid Ltd) is prepared and filled w in 10 ml test tubes. The tubes are sterilized in an autoclave at a pressure of 1.05 kg / cm for 15 minutes and sealed with Astell caps, which ensure an airtight seal and consequently allow anaerobic growth. The tubes are placed in a water bath at 35 ° C to keep the agar flowing. Grafting Needle Eyes (1 / 5C ml)

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of the samples of bacterially contaminated oil-in-water emulsions are then used as inoculum and the tubes are incubated at 37 ° C for 7 days. The effect of the test compounds on obligate anaerobic sulfate reducing bacteria present in the contaminated oil-in-water emulsion is reported as described above. The following results are obtained: 10 15 20 25 30 35

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"KathoiP ^ MW886", "Grotaii ^ TK2" and "Bodoxin" are commercially available industrial biocides used to control contamination with mandatory anaerobic sulfate-reducing bacteria.

5 The results obtained in experiments 1, 2, 3 and 4 confirm that metronidazole, dimetridazole, ipronidazole and secnidazole inhibit sulfide production of obligate anaerobic sulfate-reducing bacteria, with the effective concentration in these experiments 1-4 being approx. 100 ppm. The effective concentration of "Kathor ^ MW886", which can cause severe skin and eye irritations, is also at approx. 100 ppm. For "Grotan TK2" and "Bodoxin" the effective concentration is higher, approx. 500 ppm.

The compatibility of nitroimidazoles according to the present invention with water-in-oil emulsion metalworking liquids prepared from commercially available metalworking concentrates / one demonstrated in the following experiments 5 to 8 wherein the commercially available metalworking concentrates are: 20

Concentrate A; a generally applicable cutting oil emulsion, used at a concentration of 2 to 3 volume / volume%;

Concentrate B: a generally applicable cutting oil,.

25 - at a concentration of 1 to 4 v / v%;

Concentrate C: an aluminum rolling oil which becomes unstable at the "bite" of the roll and is subsequently recovered, used at a concentration of 5% v / v%; 30

Concentrate D: a semi-synthetic cutting oil formulation, used as a cutting oil at a concentration of 1 to 2 v / v%; 35

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Concentrate E: a generally applicable cutting oil, used at a concentration of 3 to 5 v / v%;

Concentrate F: a cutting oil used for machining of high fineness, used at a concentration of 3 v / v%;

Concentrate G: a non-oil based aqueous synthetic abrasive liquid,. used at a concentration of 2 v / v%.

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Experiment 5 Emulsion stability

Cutting and rolling oils used in the form of oil-in-water emulsions must maintain their emulsion stability during use. This experiment is conceived to assess the stability of such oil-in-water emulsions by recording the tendency of small oil droplets to grow together, which is indicative of instability.

Oil-in-water emulsions containing commercially available oil concentrates are prepared by the following procedure [Institute of Petroleum Standard Test (IP) 263/70]:

Distilled water and the oil concentrate are brought to a temperature of 20 ° C + 4 ° C separately before mixing. An appropriate volume of water is stirred in a 500 ml conical flask, using a magnetic stirrer, at a rate sufficient to create a fluid vortex just deep enough to reach the bottom of the flask. The appropriate volume of oil concentrate and the appropriate volumes of a solution containing 5000 ppm metronidazole, dimetridazole or ipronidazole 30 in water to give 50, 100, 250 and 500 ppm metronidazole, dimetridazole or ipronidazole in the oil-in-water emulsion (total volume) 200 ral), is then quickly added from a medical syringe (without needle) and stirring is continued for 2 minutes after the additions are completed. Oil-in-water emulsions not containing a nitroimidazole compound,

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manufactured in the same way for control. Then, the oil emulsion is allowed to stand at room temperature for 24 hours.

A sample of the oil emulsion thus obtained is diluted to 1: 2000 with "S ter if lex® No. 1 Saline" (from Allan & Han-5 bury1 s Ltd.) and the total size distribution of small oil droplets in a 0, 5 ml sample of this dilution is determined using a Coulter Counter (100 µm opening) (Coulter Electronics Ltd) associated with a P64 Analyzer and Plotter. Then, the oil-in-water emulsions are left for 7 days 10 and the size distribution of small oil droplets is again determined using the same setting of Coulter Counter so that direct blends can be made. As is usually the case with oil-in-water emulsions, which have been undisturbed for some days, a separation between oil, impurities and water has occurred between the two determinations 15 and prior shaking of samples for the other determination the flask for 30 seconds alternatively rotating clockwise and counterclockwise.

The following results are obtained: (a) Oil-in-water emulsion containing 2% v / v

20 of concentrate A

3

Metronidazole: An increase in 2-5 µm drops at 100 ppm of metronidazole after 7 days suggests very little emulsion instability.

Dimetridazole: Emulsion stability after 7 days is improved 25 - slightly, especially at 50 ppm dimetridazole.

Ipronidazole: No significant decrease in emulsion stability after 7 days.

(b) Oil-in-water emulsion containing 1 v / v%

30 of concentrate B

Metronidazole: After 7 days, the emulsion stability is slightly improved.

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Dimetridazole: After 7 days, slight instability in the oil-in-water emulsion containing 250 ppm dimetridazole is detected.

Ipronidazole: No significant change in emulsion stability was observed after 7 days.

(c) Oil-in-water emulsion containing 3% v / v% of concentrate F

Metronidazole: No change in emulsion stability is detected after 7 days.

Dimetridazole: No change in emulsion stability is detected after 7 days.

(d) Oil-in-water emulsion containing 3% v / v% of concentrate E 15 -

Metronidazole: After 7 days, a slight increase in emulsion stability is detected.

Dimetridazole: The emulsion stability after 7 days is within satisfactory limits.

20 Ipronidazole: After 7 days, a very small decrease in emulsion stability is observed.

(e) Oil-in-water emulsion containing 1 v / v% of concentrate D

Metronidazole: No change in emulsion stability is detected after 7 days.

Dimetridazole: After 7 days, a slight increase in emulsion stability is detected.

Ipronidazole: After 7 days, a very small decrease in the stability of the oil-in-water emulsion containing 250 ppm ipronidazole is observed.

35

ISLAND

26

DK 164599 B

(f) Oil-in-water emulsion containing 2% v / v% of concentrate G

Ipronidazole: No significant change in emulsion stability is detected after 7 days.

5

(g) Oil-in-water emulsion containing 2 v / v of concentrate C

Metronidazole: No change in erosion stability is detected.

Dimetridazole: No change in emulsion stability is detected.

Ipronidazole: A very slight decrease in emulsion stability is detected after 7 days.

The results show. the incorporation of metronidazole, dimetridazole and ipronidazole at concentrations of 50, 100, 250 and 500 ppm in the oil-in-water emulsion has no significant adverse effect on emulsion stability.

Experiment 6 Corrosivity

This experiment was conducted (IP 287/74) to assess the ability of oil-in-water emulsions to prevent machinery from rusting and compounds becoming inoperative during manufacturing operations, using the following procedure:

Cast iron turnings. (Herbert Machine Tools Ltd., P.O.

25

Box 30, Edgeweck Works, Coventry, England) is washed in acetone (reagent purity) and dried in a heater at 48 ° C. During washing, the chips are not touched by hand. When dry, the chips are sieved on a 0.67 mm sieve, discarding the metal passing through the sieve. Draw a square of 35 x 35 mm 30 (¾ with pencil in the center of a filter paper. '("Whatman ^' No. 5,

Qualitative, 90 mm), which is then placed at the bottom of a petri dish. Using a spatula and a mold, the marked area of 35 x 35 cm is then covered with a single layer of shavings *

The former is then removed and amounts of 2 ml of oil-in-water emulsions (prepared according to the procedure described in

ISLAND

27

DK 164599 B

Experiment 5) containing a range of oil concentrates is pipetted onto the chips so that the entire area of the petri dish is covered and the chips are thoroughly moistened. Then place a lid over the petri dishes. After 5 hours, the filter paper is removed from the bowl, washed with boiled water and allowed to dry. Next, a transparent grid is placed over a recorded test area of 35 x 35 mm on the dry filter paper and the area of rust staining is evaluated and expressed as a percentage. For ease of assessment, the percentile area of spots should be greater than 10% and less than 60%. The dilution of each oil concentrate, where there is a significant decrease in area of stains (known as the "breaking point"), is determined. For each oil concentrate, a series of oil-in-water emulsions containing the breaking point amount of the oil concentrate and 50, 100, 250 and 500 ppm metronidazole, dimetridazole or ipronidazole are prepared, and each oil-in-water emulsion is tested by the above procedure.

The following results are obtained: 20 25 30 35

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Experiment 7 has an effect on the pH

Oil-in-water emulsions are prepared as described in Experiment 5y and their pH values are measured 1 and 7 days after manufacture using a pH meter equipped with a 5 Ingold electrode.

The following results are obtained: 10 15 20 25 30 35

DK 164599 B

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These results suggest that at the concentrations tested, metronidazole, dimetridazole, and ipronidazole did not significantly affect the pH of the oil-in-water emulsions tested.

5

Experiment 8 Foam and froth formation characteristics

This experiment is devised (IP 312/74) to assess the foam and froth characteristics of the oil-in-water emulsions by the following procedure: 10 -01-in-water emulsions of oil concentrates are prepared by the procedure described in Experiment 5 but the distilled water is replaced by synthetic hard water (a calcium sulfate solution having a total hardness equivalent of 200 + 100 ppm expressed as calcium sulfate, prepared by dissolving 0.344 g of calcium sulfate (Ca SO4.2H2 O per liter of distilled water). A 100 ml portion of oil-in-water emulsion is placed in a 250 ml graduated vial (subdivided according to and in accordance with BS 604: 1952), closed and shaken vigorously for 15 seconds.

After shaking, the measuring glass is placed in a vertical position and the volume of foam and liquid is noted immediately and 1, 5, 10 and 15 minutes after shaking (froth can also form over the foam, but this froth tends to break down leaving air pockets). and the height of the foam in the measuring glass is difficult to determine, the foam which is heavier can be easily seen, and for the sake of convenience the foam level is noted).

Concentrate C forms a precipitate when emulsified using synthetic hard water. This precipitate is not altered by the incorporation of metronidazole, dimetridazole or ipronidazole. The test is repeated using distilled water instead of synthetic hard water, and it is the results of this dilution of concentrate C with distilled water that are set forth below.

The following results are obtained in which "volume" shows the volume of foam and liquid:

DK 164599 B

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These results show; that the incorporation of metronidazole, dimetridazole or ipronidazole at the indicated concentrations makes no significant difference in foam and froth characteristics of the oil-in-water emulsions tested.

The following example illustrates metalworking concentrates which, by appropriate dilution with water, are suitable for preparing metalworking fluids of the present invention.

10

Example

A suspension is prepared by mixing 25% w / v% micro size dimetridazole, 4% w / v% "Texofor M6", 6% w / v% "Arylan" - "CA", 1.0% w / v% "Attagel 50" and petroleum (odorless) · to-100 volume !.

1 liter of this concentrate is mixed with 99 liters of a generally applicable cutting oil concentrate to obtain 100 liters of a cutting oil concentrate containing 2500 ppm dimetridazole. This 100 liter concentrate can be diluted with 2400 liters of water to give 2500 liters of metal working fluid containing 100 ppm dimetridazole.

25 30 35

Claims (11)

A process for combating the destruction of liquid, organic, water-containing or industrially used aqueous liquids containing organic materials, the destruction of which is caused by mandatory anaerobic, sulfate-reducing bacteria, characterized in that in the aqueous phase incorporates one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole in an amount sufficient to prevent the growth of obligate anaerobic, sulfate-reducing bacteria. Process according to claim 1, characterized in that the industry-used liquid organic materials containing water or industrially used aqueous liquids containing organic materials are petroleum hydrocarbons or vegetable oils containing water or aqueous liquids containing petroleum hydrocarbon. there or vegetable oils. Process according to claim 1 or 2, characterized in that the liquid organic materials containing water or aqueous liquids containing organic materials are fuel oils, lubricating oils, mineral oil-based, hydraulic liquids, oil-in-water emulsions. , water-in-oil emulsions, especially a water-in-oil emulsion of hydraulic fluids; aqueous solutions and emulsions of glycols used as metal working fluids, sulphite fluids from the treatment of paper pulp, water-based paints, oil source injection water, industrial process water, electroplating solutions, sealed water circulation systems, 30 gas storage systems and hot water release systems, hydrocarbon gas storage. Process according to any one of claims 1-3, characterized in that a solution, suspension or emulsion containing one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole and water, glycols, ethyl oxalate , dimethylformamide, dimethylacetamide or liquid hydrocarbons or mixtures thereof, and if necessary one or more surfactants, are added to liquid organic materials containing water or aqueous liquids containing organic materials. Process according to any one of claims 1 to 4, characterized in that the amount of one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole is incorporated into the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials are from 100 to 500 ppm of the total volume of the liquid organic materials containing water or the aqueous liquids containing organic materials. Process according to any one of claims 1 to 4, characterized in that the amount of one or more nitroimidazole compounds selected from dimetride-azole, metronidazole, secnidazole and ipronidazole is incorporated into the aqueous phase of liquid organic materials containing water or aqueous liquids containing organic materials, is 100 ppm of the total volume of the liquid organic materials containing water or the aqueous liquids containing organic materials. Process according to any one of claims 1 to 6, characterized in that one or more nitroimidazole compounds selected from dimetridazole, metronidazole, secnidazole and ipronidazole are used together with one or more known agents for controlling bacterial destruction of 30 Liquid organic materials used in the industry used in water or aqueous liquids containing organic materials, preferably together with p-chloro-m-cresol, phenol, heavy metals and / or compounds which release formaldehyde. Method according to any one of claims 35 1 to 7, characterized in that the obligate anaerobic, sulfate-reducing bacteria are one or more of the species DK 164599B Desulfovibrio desulfuricans, Desulfovibrio gigas and Desul-fotomaculuro nigrificans. Process according to any one of claims 1 to 7, characterized in that the nitroimidazole compound is dimetridazole or metronidazole. 10. Metalworking concentrate suitable for dilution with water suitable for the preparation of metalworking liquids containing oils and / or glycols, emulsifiers and corrosion inhibitors, characterized in that it additionally contains an amount, preferably from 0.05 to 5. % (w / v) of one or more nitroimide-azole compounds selected from dimetridazole, metronidazole, secnidazole, and ipronidazole sufficient to provide, in dilute water processing metal, a concentration of nitroimidazole compounds sufficient to prevent removal mandatory anaerobic, sulfate-reducing bacteria. Metalworking concentrate according to claim 10, characterized in that the nitroimidazole compound 20 is dimetridazole or metronidazole.