Abstract:
A synergistic antimicrobial composition having two components. The first component is a hydroxymethyl-substituted phosphorus compound. The second component is cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride.

Description:
[0001]    This invention relates to combinations of biocides, the combinations having greater activity than would be observed for the individual antimicrobial compounds. 
         [0002]    Use of combinations of at least two antimicrobial compounds can broaden potential markets, reduce use concentrations and costs, and reduce waste. In some cases, commercial antimicrobial compounds cannot provide effective control of microorganisms, even at high use concentrations, due to weak activity against certain types of microorganisms, or relatively slow antimicrobial action, or instability under certain conditions such as high temperature and high pH. Combinations of different antimicrobial compounds are sometimes used to provide overall control of microorganisms or to provide the same level of microbial control at lower use rates in a particular end use environment. For example, WO 2009/015088 discloses combinations of phosphonium salts and oxazolidines, but this reference does not suggest any of the combinations claimed herein. Moreover, there is a need for additional combinations of antimicrobial compounds having enhanced activity to provide effective control of the microorganisms. The problem addressed by this invention is to provide such additional combinations of antimicrobial compounds. 
       STATEMENT OF THE INVENTION 
       [0003]    The present invention is directed to a synergistic antimicrobial composition comprising: (a) a hydroxymethyl-substituted phosphorus compound selected from the group consisting of tetrakis(hydroxymethyl)phoshponium salts and tris(hydroxymethyl)phosphine; and (b) cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride (CTAC); wherein a weight ratio of the hydroxymethyl-substituted phosphorus compound to cis- 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is from 15:1 to 1:15. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0004]    As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise. The term “antimicrobial compound” refers to a compound capable of inhibiting the growth or propagation of microorganisms, and/or killing microorganisms; antimicrobial compounds include bactericides, bacteristats, fungicides, fungistats, algaecides and algistats, depending on the dose level applied, system conditions and the level of microbial control desired. The term “microorganism” includes, for example, fungi (such as yeast and mold), bacteria and algae. The following abbreviations are used throughout the specification: ppm=parts per million by weight (weight/weight), mL=milliliter, Unless otherwise specified, temperatures are in degrees centigrade (° C.), and references to percentages are by weight (wt %). Percentages of antimicrobial compounds in the composition of this invention are based on the total weight of active ingredients in the composition, i.e., the antimicrobial compounds themselves, exclusive of any amounts of solvents, carriers, dispersants, stabilizers or other materials which may be present. The hydroxymethyl-substituted phosphorus compound is selected from the group consisting of tetrakis(hydroxymethyl)phosphonium salts (e.g., tetrakis(hydroxymethyl)phosphonium sulfate (THPS) and tetrakis(hydroxymethyl)phosphonium chloride) and tris(hydroxymethyl)phosphine. More than one hydroxymethyl-substituted phosphorus compound may be present, in which case the biocide ratio is calculated from the total content of such compounds. 
         [0005]    In some embodiments of the invention, a weight ratio of the hydroxymethyl-substituted phosphorus compound to CTAC is from 12:1 to 1:15, alternatively from 10:1 to 1:15, alternatively from 12:1 to 1:12, alternatively from 12:1 to 1:10, alternatively from 10:1 to 1:12, alternatively from 9:1 to 1:12, alternatively from 9:1 to 1:10, alternatively from 9:1 to 1:9; alternatively from 8:1 to 1:9, alternatively from 8:1 to 1:8, alternatively from 7.6:1 to 1:8. In some embodiments of the invention, the composition is used to prevent microbial growth in a medium at higher temperatures and high sulfide levels, i.e., at least 50° C. and 2 ppm sulfide, conditions which typically are present in oil and gas wells. In these embodiments, the weight ratio of the hydroxymethyl-substituted phosphorus compound to CTAC is from 5:1 to 1:15; alternatively from 5:1 to 1:12; alternatively from 5:1 to 1:10; alternatively from 5:1 to 1:9; alternatively from 3:1 to 1:12; alternatively from 3:1 to 1:10; alternatively from 3:1 to 1:9; alternatively from 3:1 to 1:8; alternatively from 2:1 to 1:10; alternatively from 2:1 to 1:9; alternatively from 2:1 to 1:8. In some embodiments of the invention, a higher temperature and high-sulfide medium is one having a temperature at least 60° C. and a sulfide level at least 4 ppm. In some embodiments, the temperature is at least 65° C.; alternatively at least 70° C.; alternatively at least 75° C.; alternatively at least 80° C. In some embodiments, the medium contains at least 5 ppm sulfide, alternatively at least 6 ppm sulfide, alternatively at least 7 ppm sulfide, alternatively at least 8 ppm sulfide, alternatively at least 9 ppm sulfide, alternatively at least 10 ppm sulfide. In some embodiments of the invention, the high-temperature and high-sulfide environment is anaerobic. In some embodiments of the invention, the medium to which the antimicrobial composition is added contains sulfate-reducing bacteria. In some embodiments of the invention, the high-temperature and high-sulfide environment contains sulfate-reducing bacteria. In some embodiments of the invention, the medium to which the antimicrobial composition is added is an aqueous medium, i.e., one comprising at least 60% water, alternatively at least 80% water. In some embodiments of the invention, the aqueous medium is a high-temperature and high-sulfide medium. 
         [0006]    In some embodiments of the invention, the antimicrobial composition is substantially free of oxazolidine compounds, i.e, it has less than 5% oxazolidine compounds relative to total biocide active ingredient content, alternatively less than 2%, alternatively less than 1%, alternatively less than 0.5%, alternatively less than 0.1%. 
         [0007]    In some embodiments of the invention, the antimicrobial combination of this invention is useful in oil and gas field injection, produced fluids, fracturing fluids and other functional fluids, oil and gas wells, oil and gas operation, separation, storage, and transportation systems, oil and gas pipelines, oil and gas vessels, and fuel. The combination is especially useful in aqueous fluids added to or produced by oil and gas well. The composition also is useful for controlling microorganisms in other industrial water and water containing/contaminated matrixes, such as cooling water, air washer, heat exchangers, boiler water, pulp and paper mill water, other industrial process water, ballast water, wastewater, metalworking fluids, latex, paint, coatings, adhesives, inks, tape joint compounds, pigment, water-based slurries, personal care and household products such as detergent, filtration systems (including reverse osmosis and ultrafiltration systems), toilet bowel, textiles, leather and leather production system, or a system used therewith. 
         [0008]    Typically, the amount of the biocide combinations of the present invention to control the growth of microorganisms is from 10 ppm to 5,000 ppm active ingredient. In some embodiments of the invention, the active ingredients of the composition are present in an amount of at least 20 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm, alternatively at least 200 ppm. In some embodiments, the active ingredients of the composition are present in an amount of no more than 2,000 ppm, alternatively no more than 1,000 ppm, alternatively no more than 500 ppm, alternatively no more than 400 ppm, alternatively no more than 300 ppm, alternatively no more than 250 ppm, alternatively no more than 200 ppm, alternatively no more than 100 ppm, alternatively no more than 50 ppm. Concentrations mentioned above are in a liquid composition containing the biocide combinations. Biocide concentrations in a high-sulfide and high-temperature environment typically will be higher than in other environments. In some embodiments of the invention, active ingredient concentrations downhole in an oil well are from 30 to 500 ppm, alternatively from 50 to 250 ppm. In some embodiments of the invention, active ingredient concentrations for top side treatment at an oil well are from 10 to 300 ppm, alternatively from 30 to 100 ppm. 
         [0009]    The present invention also encompasses a method for preventing microbial growth in the use areas described above, especially in oil or natural gas production operations, by incorporating the claimed biocide combination into the materials. 
       EXAMPLES 
     Example 1  
     Synergistic effect of THPS and CTAC against sulfate reducing bacteria (SRB) 
       [0010]    Inside an anaerobic chamber (BACTRON anaerobic chamber), a deaerated sterile salt solution (3.1183 g of NaCl, 1.3082 mg of NaHCO 3 , 47.70 mg of KCl, 72.00 mg of CaCl 2 , 54.49 mg of MgSO 4 , 172.28 mg of Na 2 SO 4 , 43.92 mg of Na 2 CO 3  in 1 L water) was contaminated with an oil field isolated anaerobic consortium, mainly SRB, at final bacterial concentrations of 10 6 to 10 7  CFU/mL. The aliquots of this contaminated water were then treated with THPS and CTAC, or the THPS/CTAC combination at different active concentration levels. After the mixtures were incubated at 40° C. for 24 hour, the biocidal efficacy was determined by minimum tested biocide concentration for complete bacteria kill in the aliquots (MBC). Table 1 summarizes the efficacy of each biocide and their blends, and the Synergy Index* of each combination. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Biocidal efficacy of THPS, CTAC, THPS/CTAC  
               
               
                 combination, and Synergy Index 
               
             
          
           
               
                   
                 Ratio of THPS to 
                 MBC (active 
                   
               
               
                   
                 CTAC (active 
                 ppm) 
                 Synergy 
               
             
          
           
               
                   
                 w/w) 
                 THPS 
                 CTAC 
                 Index* 
               
               
                   
                   
               
             
          
           
               
                   
                 1:0 
                 4.1 
                 0.0 
                   
               
               
                   
                 7.6:1   
                 &lt;2.7 
                 &lt;0.4 
                 &lt;0.68 
               
               
                   
                 3.4:1   
                 &lt;2.3 
                 &lt;0.7 
                 &lt;0.59 
               
               
                   
                 1:1 
                 &lt;1.6 
                 &lt;1.6 
                 &lt;0.43 
               
               
                   
                   1:3.4 
                 &lt;1.6 
                 &lt;5.3 
                 &lt;0.55 
               
               
                   
                   1:7.6 
                 &lt;1.0 
                 &lt;7.9 
                 &lt;0.51 
               
               
                   
                 0:1 
                 0.0 
                 31.1 
               
               
                   
                   
               
               
                   
                 *Synergy Index = Ca/CA + Cb/CB 
               
               
                   
                 Ca: Concentration of biocide A required to achieve a complete bacterial kill when used in combination with biocide B 
               
               
                   
                 CA: Concentration of biocide A required to achieve a complete bacterial kill when used alone 
               
               
                   
                 Cb: Concentration of biocide B required to achieve a complete bacterial kill when used in combination with biocide A 
               
               
                   
                 CB: Concentration of biocide B required to achieve a complete bacterial kill when used alone 
               
               
                   
                 SI values below 1 indicate synergy 
               
             
          
         
       
     
       Example 2  
     Evaluation of biocidal efficacy of THPS, CTAC, and their combination against anaerobic bacteria for a high temperature and sulfide-rich environment. 
       [0011]    Inside an anaerobic chamber (BACTRON IV), biocides solutions were challenged with 10 4  to 10 5 CFU/mL of an oilfield SRB consortium and 10 ppm sulfide ion (added in the form of sodium sulfide). The biocide solutions were then incubated at 80° C. under anaerobic condition for 7 days, with daily challenge of the SRB consortium (10 4 to 10 5 CFU/mL) and sulfide ion (10 ppm). Then the biocidal efficacy was evaluated against the field SRB consortium at 2 hours and 7 days. The biocidal efficacy was determined by the biocide dosage required for 99.999% bacterial reduction. Synergy Index was then calculated. Table 2 summarizes the efficacy of each biocide and their blends, and the Synergy Index of each combination. 
         [0000]    
       
         
               
             
               
               
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Biocidal efficacy evaluation of THPS, CTAC, and THPS/CTAC  
               
               
                 combination for a high temperature and  
               
               
                 sulfide-rich environment, and Synergy Index 
               
             
          
           
               
                   
                 Concentration (active 
                   
               
               
                   
                 ppm) required for 
                   
               
               
                   
                 99.999% bacterial 
                   
               
               
                 Ratio of THPS to 
                 reduction (active ppm) 
                 Synergy 
               
             
          
           
               
                 CTAC (active w/w) 
                 THPS 
                 CTAC 
                 Index 
               
               
                   
               
             
          
           
               
                 1:0 
                 45.0 
                 0.0 
                   
               
               
                 2:1 
                 22.5 
                 11.3 
                 0.56 
               
               
                 1:1 
                 22.5 
                 22.5 
                 0.63 
               
               
                 1:2 
                 11.3 
                 22.5 
                 0.38 
               
               
                 1:4 
                 5.6 
                 22.5 
                 0.25 
               
               
                 1:8 
                 2.8 
                 22.5 
                 0.19 
               
               
                 0:1 
                 0 
                 180 
               
               
                   
               
             
          
         
       
     
         [0012]    Table 2 shows that the THPS and CTAC combination was synergistic for a high temperature and sulfide-rich environment.