Inhibiting formation of biogenic sulphide via combination of biocide and metabolic inhibitor

FIELD: chemistry.

SUBSTANCE: method involves treating a water-based medium containing sulphate-reducing bacteria SRB in industrial aqueous systems of chemical production and oil refining. Inhibition of production of biogenic sulphide with SRB takes place as a result of synergetic action of a biocide component in a first concentration and a metabolic inhibitor in a second concentration. The biocide immediately destroys the first portion of SRB. The biocide component is selected from a group comprising aldehydes, amine-type compounds, halogenated compounds, sulphur compounds, salts of quaternary phosphonium and/or combinations thereof. The metabolic inhibitor inhibits growth of a second portion of SRB without its direct destruction. The metabolic inhibitor component is selected from a group comprising nitrite, molybdate, tungstate, selenate, anthraquinone and/or combinations thereof. Contact between the SRB and the biocide and metabolic inhibitor can take place continuously, intermittently or simultaneously.

EFFECT: method ensures efficient inhibition of production of biogenic sulphide with SRB during combined use of components in considerably lower concentrations than if the biocide or metabolic inhibitor was used separately.

25 cl, 2 dwg, 1 ex

 

The present invention relates generally to the regulation of the production of biogenic sulfide. In another aspect of the invention concerns the use of at least one biocide and at least one metabolic inhibitor for synergistic inhibition of the production of sulfide by bacteria, sulfate reducing.

When used in the present description, the phrase "consists essentially of", "consisting essentially of" and similar phrases do not exclude the presence of other steps, elements or materials which are not specifically listed in the description, such as stage, elements or materials do not affect the basic and novel characteristics of the invention; in addition, they do not exclude impurities normally associated with the elements and materials.

The above terms and phrases are intended for use in areas outside of U.S. jurisdiction. Within the jurisdiction of the U.S. the above terms and phrases should be used, because they are considered U.S. courts and the Patent office of the USA.

The presence of sulfides (e.g., H2S, HS-and S2-in liquids creates serious problems due to the toxicity, odor and Korroziya nature. It is well known that the presence of sulphides in many liquids is a consequence of the recovery of sulphate to sulphide, postanal is that sulfate bacteria (SRB). SRB are usually found in water-related devices for the production of oil, and they can be found in virtually all industrial water processes, including, for example, device a water cooling device manufacturing pulp and paper, chemical manufacturing and oil refining.

Requirements for activity and growth of SRB include essentially anaerobic aqueous medium containing the appropriate nutrients, electron donor and electron acceptor. Typical electron acceptor is a sulfate, which when restoring produces H2S. Typical electron donor is a volatile fatty acid (e.g. acetic or propionic acid), although hydrogen can also function as an electron donor. Conditions of staying in the oil tank, washed by the sea water in the submerged condition, excellent to determine the activity of SRB. Sea water contains significant concentrations of sulfate, while relict water or local water formation, contains volatile fatty acids and other necessary micronutrients (e.g., nitrogen and phosphorus). Conditions within industrial water systems, such as flowing streams from manufacturing operations or flows of cooling water, also contribute to the activity of SRB because of anaerobe is th a biological film which is formed on the pipeline or vessel wall. The same is true for the internal surfaces of sewer pipes and other piping and equipment associated with the processing systems municipal wastewater.

The hydrogen sulfide (H2S) is corrosive and interacts with metal surfaces with the formation of insoluble products of iron sulfide. When working on the oil fields H2S is allocated to water, oil and natural gas phase developed fields and creates a number of problems. For example, oil and gas, which contain high levels of H2S have a lower commercial value than oil and gas with low sulfide content. Removal of biogenic H2S from containing mercaptans of oil and gas increases the cost of these products. In addition, H2S is a highly toxic gas, and it can be fatal to humans even in small concentrations. His presence in wastewater systems is a threat to the safety of workers. Discharge of produced water containing high levels of H2S, in water or marine environment, harmful, because H2S reacts with oxygen and reduces the levels of dissolved oxygen in the water.

Corrosion caused by H2S produced by SRB, often leads to extensive is the damaged. Pipelines, tank bottoms and other parts of the equipment can quickly be destroyed if there are areas where microbial corrosion. If there is a destruction of the pipeline or the bottom of the storage tank leaking fluid can have severe environmental consequences. If destruction occurs in water or gas mains, working under high pressure, the consequences can be injury or death of workers. Any such destruction is associated with significant costs for repair or replacement.

In the past, there were two main approaches to reducing the level of sulfides in industrial fluids. One approach included the removal of sulfides from liquids after their formation. However, this approach of removing after education was often uneconomical or impractical, especially when working in the oil fields. Another approach was the treatment of liquids containing SRB, biocides or metabolic inhibitors for the destruction or inhibition by the growth of SRB before substantial formation of biogenic sulfide. However, in many cases it requires high concentrations of biocides or metabolic inhibitors to effective inhibition of the production of sulfides SRB. Costs associated with the use of biocides or metabolic inhibitors in such high concentration is, can hinder him.

It is therefore desirable to develop a method and composition for more effective and efficient inhibition of the production of biogenic sulfide.

In addition, it is desirable to provide a composition, which is effective for inhibiting the production of sulfide SRB in relatively low concentrations, the composition of the invention.

It should be understood that the above requirements are only illustrative. Other objectives and advantages of the present invention will become apparent from the detailed description of the preferred option implementation, claims and drawings.

Accordingly, one aspect of the present invention relates to a method of inhibiting the production of sulfide SRB. The method comprises the stage of: (a) contact the SRB with the first concentration of the biocidal component, where the first concentration is less than about 90% minimum inhibitory concentration (MIC) biocidal component; and (b) contact the SRB from the second concentration of the component of the metabolic inhibitor, where the second concentration is less than about 90% MIC component of the metabolic inhibitor.

Another aspect of the present invention relates to a method that includes contact with SRB processed by the environment, including aldehyde and a metabolic inhibitor. Metabolic inhibitor selected from the group consisting of the C nitrite, of molybdate, and combinations thereof. The aldehyde and the metabolic inhibitor are present in the treated medium at a molar ratio of aldehyde to a metabolic inhibitor in the range of from about 50:1 to about 1:50.

Another aspect of the present invention relates to compositions for the effective inhibition of the production of sulfide SRB. The composition includes: (a) component of the biocide, can directly destroy the first portion of the SRB; and (b) component of the metabolic inhibitor, can inhibit regenerating sulfate growth of the second portion of the SRB without direct destruction of the second part of the SRB. Component of the biocide is present in the composition in a first concentration that is less than about 90% MIC component of the biocide. Component of the metabolic inhibitor is present in the composition in the first concentration that is less than about 90% MIC component of the biocide.

Another aspect of the present invention relates to compositions comprising an aldehyde and a metabolic inhibitor selected from the group consisting of nitrite, molybdate, and combinations thereof. The aldehyde and the metabolic inhibitor present in the composition at a molar ratio of aldehyde to a metabolic inhibitor in the range of from about 50:1 to about 1:50.

The applicant has found that the production of sulfide, sulfate reducing bacteria (SRB) over e is effective and economical to inhibit the processing of SRB certain synergistic combinations of nutrient inhibitors sulphides (BSI). Used herein, the term "sulfate reducing bacteria" or "SRB" shall mean one or more type of bacteria that can contribute to the restoration of sulfates to sulfides. Used herein, the terms "nutrient inhibitor sulphides" or "BSI" is used as a generic term to refer to any compound that inhibits the production of sulfide of at least one type of healing sulfate bacteria. BSI particular importance in the present invention include biocides and metabolic inhibitors. Used herein, the term "biocide" is to indicate a compound that directly destroys at least one type of healing sulfate bacteria through contact with it. Used herein, the term "metabolic inhibitor" shall mean a compound that inhibits regenerative sulfate activity of at least one type of healing sulfate bacteria without direct destruction inhibited healing sulfate bacteria after contact with it. Metabolic inhibitors deprive SRB ability to produce ATP and, as a result, cells are unable to grow and/or share. This inability to grow or share may eventually cause death of some of the SRB; however, the death of cells is not a direct financial p is tatom contact with metabolic inhibitors, as it would be for biocides.

In accordance with one embodiment of the present invention SRB in contact with the processed environment that includes more than one BSI, for synergistic inhibition by this biogenic production of sulfide. Preferably, the treated environment includes at least one biocide and at least one metabolic inhibitor. Biocides suitable for use in the present invention include both oxidizing and non-oxidizing biocides. Preferably, use non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (such as formaldehyde, glutaraldehyde and acrolein), connection type amine (for example, the compounds of the Quaternary amine and cacodemon), halogenated compounds (e.g., bronopol and 2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g., isothiazole, carbamates and metronidazole) and salts of Quaternary phosphonium (e.g., sulfate, tetrakis(hydroxymethyl)phosphonium (THPS)). Metabolic inhibitors suitable for use in the present invention include, for example, nitrite, molybdate, tungstate, selenate and anthraquinone. There may be other equivalent metabolic inhibitors for the SRB, but they are not known or anticipated at the time of filing the present patent application.

Synergistic inhibin is in store effect resulting from the combined use of more than one BSI (e.g., biocide and metabolic inhibitor), can be demonstrated by a comparison of the inhibitory effect of combined BSI with the inhibiting effect of each individual BSI in a stand-alone application. This synergistic inhibitory effect can be quantitatively assessed by comparing the concentrations of the combined BSI required for effective inhibition of biogenic sulfide concentrations of each individual BSI required for effective inhibition of sulfide, when each individual BSI is used individually.

Concentrations of individual BSI necessary for effective inhibition of sulfide production SRB, can be expressed as the minimum inhibitory concentration (MIC). Used herein, the terms "minimum inhibitory concentration" or "MIC" shall mean the minimum concentrations of individual BSI necessary to prevent the production of sulfide SRB, within 30 days after the start of contact with the SRB. Each BSI has a unique MIC. For example, applicants have found that in certain test conditions, the concentration of glutaraldehyde (biocide) 5 mm (millimolar) in a treated environment represents the minimum concentration of glutaraldehyde, the mu is necessary to prevent the production of sulfide defined SRB, within 30 days after the first contact of the treated environment with SRB. Thus, in the conditions of this test MIC glutaraldehyde is 5 mm.

In this patent MIC various BSI is used as a benchmark to demonstrate that it is possible to achieve a synergistic inhibition of biogenic sulfide, when certain combinations of BSI are used in concentrations which are significantly less than the MIC of each individual BSI. Thus, the amount or concentration of a particular BSI used for processing the SRB can be expressed as a percentage MIC this particular BSI. However, it should be noted that specific MIC BSI can vary, depending on numerous factors, such as, for example, the type of SRB, the processed media composition and temperature, which are the SRB and the processing environment. Thus, when SRB are processed by a certain number of BSI, which is expressed as a percentage MIC for this BSI, it is assumed that the MIC for this BSI was defined in the same terms in which SRB currently being processed. For example, if a particular processed environment, including glutaric aldehyde and nitrite, used for processing a particular SRB in certain conditions and certain environment contains glutaric aldehyde at 50% (in moles) MIC glutaric is legido, the concentration of glutaraldehyde in the treated environment is half the concentration of one of glutaraldehyde (i.e. without nitrite) in the treated environment, which would prevent the production of sulfide SRB within 30 days under the same conditions.

One variant of implementation of the present invention can be in contact SRB at least one biocide and at least one metabolic inhibitor, or simultaneous, or sequential form. Preferably, the components of the biocide and the metabolic inhibitor introduced simultaneously into contact with the SRB, first combining the biocide or the biocide precursor) and a metabolic inhibitor (and/or predecessor metabolic inhibitor) in the treated environment, and then enter into contact with SRB processed by the environment. Nitrate is one example of a precursor of nitrite. A certain composition of the treated environment may significantly vary depending on the particular application for which it was intended inhibition of biogenic sulfide. Thus, the treated medium may be any medium suitable for inclusion component of the biocide and the metabolic inhibitor. Preferably, the treated medium is water-based, preferably, the treated environment including the AET at least about 2% of the mass. water, more preferably at least about 50 wt%. water, and most preferably at least 90% of the mass. water. SRB, which contacts the treated medium may be in the treated environment or on the surface (for example, on the surface of a subterranean formation or on the inner surface of the pipe or vessel), which comes into contact with the treated environment. In one application, the processed medium is a saline solution (for example, a salt solution of the oil), which contains sulfate, SRB, biocide and a metabolic inhibitor. In certain cases, the biocide may be present as part of normal chemical compounds used in the oil industry, such as corrosion inhibitors. Thus, it may be preferable to use biocides that show other preferred properties, such as inhibition of corrosion. For example, the Quaternary amines are good biocides and corrosion inhibitors.

Synergistic inhibition provided by the combined components of the biocide and the metabolic inhibitor treated environment, provide for effective inhibition of biogenic sulfide in concentrations substantially smaller than the minimum inhibiting concentration (MIC) of the individual components. Thus, suppose the equipment, to component concentration of biocide and metabolic inhibitors were less than the MIC of the individual components of the biocide and the metabolic inhibitor. Preferably, the concentration of biocide, and the metabolic inhibitor is less than about 90% of their respective MIC. More preferably, the concentration of one of the biocide and the metabolic inhibitor, or both less than approximately 75% of their respective MIC. More preferably, the concentration of one of the biocide and the metabolic inhibitor, or both less than about 50% of their respective MIC. More preferably, the concentration of one of the biocide and the metabolic inhibitor, or both less than about 35% of their respective MIC. Most preferably, the concentration of one of the biocide and the metabolic inhibitor, or both less than about 25% of their respective MIC.

In a preferred embodiment of the present invention, the biocide is an aldehyde, and the metabolic inhibitor is a nitrite and/or molybdate. When the biocide is an aldehyde, and the metabolic inhibitor is a nitrite and/or molybdate, it is preferable that the processed environment had biocide to a metabolic inhibitor in the range of from about 50:1 to about 1:50, preferably from about 20:1 to the ome 1:20, more preferably, from about 10:1 to about 1:10, and most preferably, from about 5:1 to about 1:5. In addition, when the biocide is an aldehyde, preferably, the concentration of biocide in the treated medium was in the range of from about 0.1 to about 5 mm (millimoles), preferably, from about 0.1 to about 3 mm, and most preferably, from 0.1 to 2 mm. When the metabolic inhibitor is a nitrite and/or molybdate, it is preferable that the concentration of the metabolic inhibitor in the treated medium was in the range of from about 0.1 to about 5 mm, preferably, from about 0.1 to about 3 mm, and most preferably, from 0.1 to 2 mm. In a particularly preferred embodiment of the present invention, the component of the biocide in contact with SRB, essentially consists of glutaraldehyde, and the component of the metabolic inhibitor in contact with SRB, essentially consists of nitrite.

Processed environment and SRB can contact or intermittent (i.e. parties), or in a continuous manner. Preferably, the present invention is carried out essentially in a continuous manner. In any case, the component concentration of the biocide and the metabolic inhibitor, described above, are expressed in the form of time-averaged concentrations. For example, if the SRB contact is together with the processed medium in the form of parties, with a frequency of 1 times/24 hours (1440 minutes), the duration of 14.4 min and the concentration in the batch of 100 mm, the average concentration should be 1 mm (i.e. 100 mm × 14,4 min/1440 min). The following example is intended to illustrate the present invention and instructing the average person skilled in the art to obtain and use the invention. This example is in no way intended to limit the invention.

EXAMPLE

In this example, the effect of different combinations and concentrations of biocide and metabolic inhibitor investigated to determine their combined effect on the production of sulfide SRB.

Consortium sulfate reducing bacteria (SRB)used in this study was enriched from the process water obtained from a field near Coleville Kindersely, Sadkatchewan, Canada. Serial enrichment of salt Postgate medium C ("sPGC") led to stable consortiums SRB, which was maintained for a period of more than one year before the beginning of the experiments of contact with the biocide and the metabolic inhibitor described above. The SRB consortia supported by weekly transfer in the environment " sPGC " and incubation at 30°C. Salt Postgate medium C ("sPGC") is a modification of the environment described in the publication Postgate, J.R. The Sulfate-Reducing Bacteria. Cambridge: Cambridge Unversity Press, pp. 30-34 (1984). "sPGC " contained the following components per 1 liter of distillirovannoi: 7 g NaCl; 1.2 g MgCl26H2O; 0.5 g KH2PO4; 1 g NH4Cl; 4.5 g Na2SO4; 0,042 g CaCl22H2O; 0.03 g MgSO47H2O; 0.004 g FeSO47H2O; 0.28 g of sodium citrate; 10 g of 60% sodium lactate; 1 g yeast extract and microcaecilia of resazurin.

Culture used in this study were grown in 100 ml of modified synthetic saline environment Coleville (mCSB) in 160-ml serum bottles with a free space above the product from 5% N2, 10% CO2and the rest of the N2. mCSB described in the publication (Nematy M., G.E. Jenneman, G. VoordouwA mechanistic study on microbial control of souring in oil reservoirs. Biotechnol. Bioeng. 74: 424-434 (2001). mCSB contained the following components in 950 ml of distilled water: 7 g NaCl; 0,027 g KH2PO4; 0.02 g NH4Cl; 0,024 g CaCl22H2O; 0,68 g MgSO47H2O; 1 g (NH4)2SO4; of 0.68 g of sodium acetate; 5.6 g of syrup of sodium lactate (60% vol./vol.); 1,9 g NaHCO3; and 50 ml of specific micronutrients. The solution of specific micronutrients contained the following components in 900 ml of distilled water: 2 g nitryltriacetic acid; 0,006 grams FeCl3; 1.2 g CaSO42H2O; 2 g MgSO47H2O; 0.16 g NaCl; 1.4 g Na2HPO4; 0,72 g KH2PO4and 10 ml of trace element solution. 10 ml of trace element solution contained the following components: 0.5 ml of H2SO4; 2.28 g MnSO4 2O; 0.5 g ZnSO47H2O; 0.5 g of H3BO3; 0.025 g CuSO45H2O; 0.025 g NaMoO42H2O and 0,045 g CoCl26H2O.

In all cases used 2% inoculum grown fresh enriched Coleville SRB. After inoculation of the culture incubated overnight at 30°C until until the produced sulfide in the cultures was approximately 5 mmol (mm) (maximum concentration of the produced sulfide in these cultures is approximately 12 mm). At this time, the added combination of biocide/metabolic inhibitor. Cultures were incubated for 1 month after addition of biocide and metabolic inhibitor. If the recovery of sulfate and sulfide production was resumed for 1-month incubation period, the inhibition was considered unsuccessful.

The sulfate content was measured using the turbidimetric method described in American Public Health Association,Standard Methods for the Examination of Water and Wastewater. Washington, DC: American Water Works Association and Water Pollution Control Federation, pp. 439-440 (1992) modification of the method described in the publication Nemati M., G.E. Jenneman, VoordouwG., A mechanistic study on microbial control of souring in oil reservoirs,Biotechnol Bioeng. 74:424-434 (2001). Sulfide was analyzed by the colorimetric method described in the publication Cord-Ruwisch, R.,A quick method for determination of dissolved and precipitated sulfides in cultures of sulfate-reducing bacteria,J. Environ. Meth. 4:33-36 (1985). The content of nitrite assess the Ali colorimetric method, described in the publication Nemati M., G.E. Jenneman, G. Voordouw,A mechanistic study on microbial control of souring in oil reservoirs,Biotechnol. Bioeng. 74:424-434 (2001). Monitoring cell growth did not; the optical density and color of different cultures was significantly changed after the addition of some biocides or inhibitors, which interfere with obtaining readings of optical density.

Tried different combinations of biocides and metabolic inhibitors. For this example, biocides are defined as agents which directly kill the microorganisms. Two of the tested metabolic inhibitor and specific for SRB, and is known to inhibit various stages of recovery of sulfate to sulfide. Inhibition of recovery of sulfate deprives SRB ability to produce ATP (material handling cellular energy), therefore, the cells are unable to grow or to share and may eventually die, but the death of cells does not necessarily occur as a result of contact with these compounds, in particular, at low concentrations, where the production of energy can be reduced, but not completely ingibirovany.

For each of the tested biocide and metabolic inhibitor was determined by minimum inhibitory concentration (MIC, minimum amount of biocide required for inhibition of the recovery of sulfate and sulfide production in the culture of SRB is for 1 month). Combinations of pairs of biocides were tested at various concentrations to determine the MIC of several concentrations of each in the mix. Evaluate the effectiveness of various combinations of biocides. The effects of combinations of biocides were divided into 5 categories: antagonistic (one biocide had a negative effect on the other, so that the inhibition was required more than one MIC to one biocide separately plus the second biocide in any quantity), additive (e.g., inhibition requires 25% MIC one biocide and 75% of the other, or Vice versa); indifferent, less than additive (for inhibition requires more than an additive amount of the pair of biocides, but less than the MIC of each) or synergistic (for inhibition requires less than additive, the number of pairs of biocides).

The last assessment of metabolic inhibitors represented molybdate and nitrite. Six non-oxidizing biocides were evaluated separately and in combination with nitrite or molybdate (oxidizing biocides were not considered in this study). And glutaric aldehyde and formaldehyde are biocides type of aldehyde. Benzylaniline is representative of the Quaternary amino group of biocides. Combinations of biocides in the form of compounds, Quaternary amines and glutaraldehyde are commercially available for use in the oil fields and in the other situation is Yah. Cocodamine consist of amine and Daminova groups of biocide. Academicaly biocide used in this study consisted of a T-397, provided Brenntag Canada. Bronopol (2-bromo-2-nitropropane-1,3-diol) is halogenosilanes biocide. Sulfate, tetrakis(hydroxymethyl)phosphonium (THPS) is a salt of Quaternary phosphonium. The biocides of several groups, typically used in field situations were deliberately selected to allow a General assessment of the performance of each group in combination with certain metabolic inhibitors.

The test results for various combinations of biocides with metabolic inhibitors (nitrite or molybdate) is shown in figure 1-10. Figure 1-10 where there's no shading triangles (δ) represent concentrations that are not successfully inhibited the production of sulfide over a full month, while the shaded diamonds (♦) represent concentrations that are successfully inhibited the production of sulfide over a full month. The diagonal line on each graph represents what would have been inhibitory concentration, if the biocide and the metabolic inhibitor had a purely additive effect. Thus, the data points for successful inhibition (i.e. the shaded diamonds) lower left of the diagonal line is led to a synergistic effect of biocide/metabolic inhibitor. A combination of several biocides with nitrite or molybdate resulted in synergistic inhibitory effects. In particular, nitrite plus glutaric aldehyde (figure 1) or benzylaniline (figure 2) and molybdate plus glutaric aldehyde (6) showed a strong synergistic effect. Nitrite plus bronopol (figure 3) gave less synergistic effect. Nitrite plus cacodemon (figure 4) and molybdate plus benzylaniline (Fig.7), cacodemon (Fig.9) or bronopol (Fig) gave the lowest synergistic effect. Nitrite plus THPS (figure 5) and molybdate plus THPS (figure 10) showed the effect less than additive. This effect less than additive when using THPS could represent an isolated phenomenon for a particular SRB and conditions used in this study. None of the tested combinations did not give vague or antagonistic effects. Thus, all combinations other than the combination with THPS, has resulted in a more than additive inhibitory effects.

Preferred forms of the invention described above should be used only as an illustration and should not be used in a limiting sense to interpret the scope of the present invention. Specialists in this field can easily make obvious modifications in the illustrative embodiments of the above, without departing from the essence of the tee of the present invention.

The present applicants indicate their intention to rely on the Doctrine of equivalents to determine and assess appropriate resulting volume of the present invention, as it pertains to any apparatus not materially departing from the scope of the invention set forth in the following claims, but beyond its literal scope.

1. A method of inhibiting the production of sulfide, sulfatoxymelatonin bacteria (SRB), and this method involves the following stages:
(a) contact the SRB with biocidal component in the first concentration, the first concentration is less than about 90% minimum inhibitory concentration (MIC) biocidal component; and
(b) contact with SRB metabolic inhibitor second concentration where the specified second concentration is less than about 90% MIC component of the metabolic inhibitor, thereby producing a synergistic effect on the inhibition of sulfide production, sulfatoxymelatonin bacteria.

2. The method according to claim 1, where at least one of these first and second concentration is less than about 50% of the MIC.

3. The method according to claim 1, where these first and second concentration less than about 75% of their respective MIC.

4. The method according to claim 1, where at least one of the specified first and second concentrations extending t is less than approximately 25% of the MIC.

5. The method according to claim 4, where these first and second concentration less than about 50% of their respective MIC.

6. The method according to claim 1, where at least one of the specified first and the second concentration is less than about 20% - in MIC.

7. The method according to claim 6, where these first and second concentration less than about 35% of their respective MIC.

8. The method according to claim 1, where the specified second concentration is in the range from about 0.1 mm to about 5 mm.

9. The method of claim 8, where the specified first concentration of less than about 50% MIC biocidal component.

10. The method according to claim 1, where the specified component of the biocide is a combination of more than one individual biocide and/or a specified component of the metabolic inhibitor is a combination of more than one separate metabolic inhibitor.

11. The method according to claim 1, where the specified component biocide, essentially, does not include sulfate, tetrakis(hydroxymethyl)phosphonium (THPS).

12. The method according to claim 1, where the specified component biocide selected from the group consisting of aldehydes, compounds of the type amine, halogenated compounds, sulfur compounds, salts of Quaternary phosphonium, and combinations of one or more of these compounds.

13. The method according to claim 1, where the specified component of the metabolic inhibitor selected from the group consisting of nitrite, molybdate, wolf is Amata, of selenate, anthraquinone and combinations of one or more of these compounds.

14. The method according to claim 1, where the specified component biocide selected from the group consisting of formaldehyde, glutaraldehyde, acrolein, compounds, Quaternary amine, cocodimama, bronopol, 2-dibrom-3-nitrilopropionamide (DBNPA), isothiazolone, carbamates, metronidazole and combinations of one or more of them.

15. The method according to claim 1, where the specified component of the biocide comprises glutaric aldehyde, and the specified component of the metabolic inhibitor includes nitrite.

16. The method according to claim 1, where the specified component biocide consisting essentially of glutaraldehyde, and the specified component of the metabolic inhibitor consists essentially of a nitrite.

17. The method according to claim 1, where the phase (a) includes direct destruction of the first portion of the SRB, and stage (b) includes the inhibition of sulfate reducing the growth of the second portion of the SRB without direct destruction of the second portion of the SRB.

18. The method according to claim 1, where steps (a) and (b) are performed essentially continuously, and these first and second concentrations represent the average concentration over time.

19. The method according to claim 1, where steps (a) and (b) are discontinuous, and these first and second concentrations represent the average concentration over time.

20. The method according to claim 1, where steps (a) and (b) are the simultaneity is temporal.

21. The method according to claim 1, further comprising a stage (C) combining the component biocide and a component of the metabolic inhibitor in the treated environment before stages a) and (b).

22. The method according to item 21, where stage (a) and (b) include the provision of contact SRB treated with the environment.

23. The method according to item 21, where the specified processed medium is water-based.

24. The method according to item 21, where the specified processed environment includes at least primarr 50 wt.% water.

25. The method according to item 21, where the specified processed environment includes nitrite in the range from about 0.1 mm to about 5 mm.



 

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4 tbl, 5 ex

FIELD: medicine.

SUBSTANCE: according to the invention, versions of an immunobiological antiallergic agent contain Lactobacillus acidophilus 100 "аш" PA strain, collection No. 207, is stored in the State collection of microorganisms of normal microflora Federal State Research Institution Gabrichevskiy Moscow Research Institution of Epidemiology and Microbiology of Federal Service for Supervision of Consumer Rights and Human Welfare in a culture medium in amount 106-1010 CFU/ml. The immunobiological antiallergic agent additionally contains species-specific virulent bacteriophages and bacteriophages with induced virulence, a biomass of Lactobacillus acidophilus "КзШз4" strain in a culture medium in amount 106-1010 CFU/ml, a biomass of Lactobacillus acidophilus NKi strain in the culture medium in amount 106-1010 CFU/ml and a biomass of Bifidobacterium bacteria in the culture medium in amount 106-1010 CFU/ml. The immunobiological antiallergic agent additionally contains target additives in amount 0.01-95.0 wt % from mass of the agent. The additives are selected from a number of: glycine, cysteine, copper sulphate, copper gluconate, quinosol, chitosan, licorice root extract, hips extract, origanum extract, cranberry extract and a flavouring agent. The immunobiological antiallergic agent is presented in the form of a suspension. The Lactobacillus acidophilus 100 "аш" PA strain is produced by means of a sequence of multiple passages through a nutrient medium MPC with added sources of histamine, Cu1+, Cu2+, Co2+, Ni2+ ions and at culture pH 6.2-7.4. The agent is used for prevention and treatment of allergic or pseudo-allergic disease without an accompanying pathology or in a combination with an infectious disease, intestinal dysbacteriosis and psychological adaptation disorders.

EFFECT: more efficient antiallergic action of the immunobiological agent on the basis of lactobacilli.

10 cl, 3 tbl

FIELD: medicine.

SUBSTANCE: invention refers to a mutant bacterium producing higher levels of intracellular and/or extracellular folate as compared with a wild type which is sensitive to methotrexate, and has growth rate at least 0,1 µ/hour when grown on a medium which contains methotrexate 1.25 mg/l and no folate-dependent metabolites. Also, the invention refers to a composition for foodstuff or food additive enrichment containing said bacterium, and to a method of sampling said bacteria.

EFFECT: invention allows producing high-folate bacteria.

13 cl, 3 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to biotechnology. The biological preparation is obtained by mixing culture liquid of Brevibacillus laterosporus VKPM B-10531 bacteria with granules of expanded perlite sand in ratio between 4:1 and 3:2, followed by drying. The destruction of plankton and biofilm forms of microalgae results in change of their colour and further decolouration.

EFFECT: invention increases efficiency of microalgae control in a water environment.

2 tbl, 7 ex

FIELD: food industry.

SUBSTANCE: growth stimulant for lactic-acid bacteria in milk contains MnSO4, FeSO4, KJ, ZnSO4 and CuSO4 at preset components ratios.

EFFECT: invention allows to decrease the quantity of introduced starter microorganisms and reduce the period of clot formation.

2 tbl, 2 ex

FIELD: medicine.

SUBSTANCE: digestive agent represents a complex enzyme preparation containing protease produced by Bacillus licheniformis bacteria, alpha amylase produced by Bacillus amyloliquefaciens bacteria and lipase produced by Yarrowia lipolytica yeast. The ration (activity unit) is specified to be equal to 0.055:0.85:1 respectively.

EFFECT: extended range of digestive agents of high pharmacological activity of microbial enzymes.

6 tbl, 8 ex

FIELD: food industry.

SUBSTANCE: fermented food product based on linseed is produced by defatting linseed, its crushing and milling, blending crushed and milled linseed with water, probably with addition of other cereals or plant seeds or linseed fraction at a concentration of nearly 3 - nearly 8 wt % to produce a suspension. The suspension is fermented with a starter, i.e. Bifidobacterium lactis Bb12 strain, enriched and stabilised to produce a viscous or fermented drinkable snack product.

EFFECT: invention allows to produce a product enriched with probiotic bacteria and having low fat content.

15 cl, 15 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to 2-(carboxy-n-alkyl)ethyltriphenyl phosphonium bromides of general formula I, having bactericidal and fungicidal activity, heat resistance and surfactant resistance, which can be used in veterinary, medicine and agriculture , where R = n-C10H21 n-C12H25, n-C14H29, n-C16H33, n-C18H37.

EFFECT: obtaining novel biologically active compounds.

1 cl, 6 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a new improved method of producing onium tetrafluoroborates through reaction of an onium halide with trialkyloxonium tetrafluoroborate, trialkylsulphonium tetrafluoroborate or triphenylcarbonium tetrafluoroborate, characterised by that the halide has formula (1) [XR4]+ Hal-, where X denotes N, P, Hal denotes Cl, Br or I and R in each case independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (2) [(R1R2N)-C(=SR7)(NR3R4)]+ Hal- (2), where Hal denotes Br or I R1-R7 each independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (3) [C(NR1R2)(NR3R4)(NR5R6)]+ Hal- (3), where Hal denotes CI, Br or I and R1-R6 each independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (4) [HetN]+ Hal- , where Hal denotes CI, Br or I and HetN+ denotes a heterocyclic cation selected from a group comprising imidazolium pyrrolidinium pyridinium where each of substitutes R1' - R4' independently denotes hydrogen, CN, linear or branched alkyl having 1-8 C atoms, dialkylamine containing alkyl groups having 1-4 C atoms but which is not attached to he heteroatom of the heterocyclic ring.

EFFECT: method enables to obtain products with low content of halides with high purity and high output.

5 cl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to ionic liquid used in electrical energy accumulation devices and as a solvent which contains a cation of general formula where X1, X2 and X3 denote N, O, S or C; R1-R11, X1, R1, R2 and R3, X2, R6, R7 and R8, X3, R9, R10 and R11 can form ring structures; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, PF6-, [RfPF5]-, BF4-, [RfBF3]-, SO42-, HSO4-, NO3- I-, bis(oxalate)borate; R, R1-R11 are selected from hydrogehn, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl, halogen, CN- or NO2-; the carbon in R and R1-R11 can be substituted with O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N= -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R4 -P(O)R'-O-, -O-P(O)R'-O- and -P(R')2=N-; where R' denotes alkyl, fluoroalkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl; Rf denotes a fluorine-containing substitute.

EFFECT: obtaining novel ionic liquids which are stable in liquid state in a wide temperature range.

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to ionic liquid used in electrical energy accumulation devices and as a solvent which contains a cation of general formula where X1, X2 and X3 denote N, O, S or C; R1-R11, X1, R1, R2 and R3, X2, R6, R7 and R8, X3, R9, R10 and R11 can form ring structures; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, PF6-, [RfPF5]-, BF4-, [RfBF3]-, SO42-, HSO4-, NO3- I-, bis(oxalate)borate; R, R1-R11 are selected from hydrogehn, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl, halogen, CN- or NO2-; the carbon in R and R1-R11 can be substituted with O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N= -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R4 -P(O)R'-O-, -O-P(O)R'-O- and -P(R')2=N-; where R' denotes alkyl, fluoroalkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl; Rf denotes a fluorine-containing substitute.

EFFECT: obtaining novel ionic liquids which are stable in liquid state in a wide temperature range.

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to ionic liquids based on a cation of formula (1): where substituting groups R1-R9 are selected from hydrogen, alkyl; any carbon atom in R1-R9 can be substituted with a -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2- or -SO3- group; X is S, O or C; R8 and R9 exist only when X is carbon; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(FSO2)3C]-, [RCH2OSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [B(OR)4]-, [N(CF3)2]-, [N(CN)2]-, [AlCl4]-, PF6-, BF4-, SO42-, HSO4-, NO3-; where R is hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, Rf is a fluorine-containing substituting group.

EFFECT: obtaining new ionic liquids with improved electrochemical properties.

15 cl, 18 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to copolymers of diallylaminophosphonium salts with sulphur dioxide demonstrating antimicrobial activity with respect to a number of bacteria, as well as to yeast-like fungi and spores, and can be applied as antiseptic and disinfecting means. Claimed copolymers of diallylaminophosphonium salts with sulphur dioxide aree characterised by general formula where A=Cl- or BF4-. They are soluble in methanol, DMSO, DMFA or if A=Cl- are soluble in water. They are obtained by copolymerisation of equimolar amounts of sulphur dioxide and diallylaminophosphonium salt, selected from tris(diethylamino)diallylaminophosphonium chloride or tris(diethylamino)diallylaminophosphonium tetrafluoroborate.

EFFECT: obtaining novel efficient and low-toxic compounds which do not cause corrosion of processed metals.

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention concerns the salts containing bis(trifluoromethyl)imide anions and saturated, partially or completely unsaturated heterocyclic cations, method of production and application thereof as ionic liquids.

EFFECT: production of new salts to be used as ionic liquids.

19 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to organic chemistry, namely, to method of production of functionally substituted fullerenes to be applied as complexing agents, sorbents, biologically active compounds, as well as for production of new materials with specified electronic, magnetic and optical properties. Substance of the method consists in production of 2,3-fullero[60]-7-phenyl-7-phosphabicycklo[2.2.1]heptanes of formula (I) as resulted from reaction of fullerene C60 and phenylphospholane with catalyst Cp2TiCl2 added in toluol medium at temperature 140-160°C within 4-8 hours.

EFFECT: new method of selective production of functionally substituted fullerenes with end product yield 46-68%.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: in phosphazene, applied on carrier, catalyst for cyclic monomer polymerisation or for substituent substitution in compound or for carrying out reaction with formation of carbon-carbon bond, carrier is insoluble in used solvent and has group, which is able to form bond with group described with general formula (1) where n is integer in interval from 1 to 8 and represents number of phosphazene cations, Zn- is anion of compound, containing atoms of active hydrogen in form obtained as result of release of n protons from compound, which contains atoms of active hydrogen, in which there are , at most, 8 atoms of active hydrogen; each of a, b, c and d represents positive integer equal 3 or less; R represents similar or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R, located on each common nitrogen atom, can be bound with each other with formation of ring structure; R1 represents hydrogen atom or hydrocarbon group, containing from 1 to 10 carbon atoms; D represents direct bond or divalent group able to bind N with carrier. Described are phosphazene compound and phosphazene salts and methods of cyclic monomer polymerisation, substitution of substituent in compound and carrying out of reaction with formation of carbon-carbon bond using applied on carrier catalyst. According to invention method polymerisation of cyclic monomers, substitution of substituents, reactions with formation of carbon-carbon bond, etc. can be carried out with extremely high efficiency.

EFFECT: increase of efficiency of carrying out different organic reactions and absence of activity decrease even after removal and re-use of catalyst, economic benefit.

10 cl

FIELD: biology, medicine, organic chemistry.

SUBSTANCE: invention proposes compound of the general formula (I): wherein A means effector group; L means a linker link; B represents Skulachev-ion Sk or charged hydrophobic peptide. Compound can be used in preparing a pharmaceutical composition for target (directed) delivery of active substances in mitochondria carried out by electrochemical potential of hydrogen ions into mitochondria. Also, invention can be useful in treatment of diseases and states associated with disturbance of normal function of mitochondria, in particular, diseases associated with increased formation of free radicals and active forms of oxygen. The claimed invention owing to directed accumulation of biologically active substance in mitochondria provides enhancing the effectiveness of substance, to decrease total dose, probability and strength of adverse effects.

EFFECT: improved and valuable properties of method and pharmaceutical composition.

26 cl, 14 dwg, 16 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to new compounds of the general formula: {[R1]yKt}+-N(CF3)2 (I) representing stable salts used as precursors of organic compounds. In the formula (I) Kt means nitrogen atom (N), phosphorus atom (P); R1 means similar or different values and each means unsubstituted or substituted with phenyl (CnH2n+1)-alkyl, unsubstituted phenyl; groups bound with Kt can be similar or different and wherein n = 1-18; y = 4 with exception for (C2H5)4N+ -N(CF3)2. Also, invention relates to a method for preparing these compounds wherein compound of the formula: D+-N(CF3)2 (II) wherein D is taken among group including alkaline metals, or compound of the formula: GN(CF3)2 (IV) wherein G represents fluorinated sulfonamides are subjected for interaction with salt of the general formula: {[R1]yKt}+-E (III) in polar organic solvent and wherein -E means F-, Cl-, Br-, J-, BF-4, ClO-4, AsF-6, SbF-6 or PF-6.

EFFECT: improved method for preparing.

6 cl, 6 ex

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