Abstract:
The present invention provides an effective method of inhibiting corrosion on metallic surfaces in contact with a fluid contained in a closed loop industrial fluid system, which comprises adding to such fluid an effective corrosion controlling amount of a combination of an organic diacid, a triamine and a phosphonate compound.

Description:
FIELD OF THE INVENTION 
     The present invention relates generally to a corrosion inhibitor treatment for closed loop systems. More specifically, the present invention relates to an environmentally friendly, non-molybdenum, and non-nitrite corrosion inhibitor treatment for closed loop systems. 
     BACKGROUND OF THE INVENTION 
     Corrosion of metallic components in industrial plants may cause system failures and sometimes plant shutdowns. In addition, corrosion products accumulated on the metal surface will decrease the rate of heat transfer between the metal surface and the water or other fluid media, and therefore corrosion will reduce the efficiency of the system operation. Thus, corrosion can increase maintenance and production costs and decrease the life expectancy of the metallic components. 
     The most common way to combat corrosion is to add corrosion inhibiting additives to the fluid of such systems. However, currently available corrosion inhibiting additives are either non-biodegradable, toxic, or both, which limits the applicability of such additives. 
     Regulatory pressures have been steadily increasing to eliminate discharge of molybdate and/or nitrite to the environment. Furthermore, nitrite treatments can develop serious microbiological growth in the closed loop. In actuality, the most reliable treatments to eliminate corrosion in closed loop systems are based on molybdate, nitrite or a combination of the two. Existing all-organic treatments do not perform well in systems where corrosion has occurred, and iron and/or iron oxide levels are high, or the water in the closed system has aggressive ions. The water composition as found in closed loops can vary significantly. 
     Thus, environmental concerns are driving the use of corrosion inhibitors away from heavy metals, molybdenum and nitrite. Existing purely organic treatments, although desirable, are not reliable when applied in iron or iron oxide laden systems or aggressive waters. By their nature, closed loops are prone to have high iron. 
     Therefore, there is a strong need for an environmentally friendly, non-molybdenum, non-nitrite corrosion inhibitor treatment for closed loop systems. In the present invention, a combination of an organic acid, a triamine and a phosphonate compound surprisingly provides enhanced protection of metallic surfaces from corrosion in closed loop systems. The organic treatments of the present invention can provide good corrosion protection in aggressive water either with or without hardness, and even in corroded systems. 
     SUMMARY OF THE INVENTION 
     The present invention provides an effective method of inhibiting corrosion on metallic surfaces in contact with a fluid contained in a closed loop industrial fluid system, which comprises adding to such fluid an effective corrosion controlling amount of a combination of an organic diacid, a triamine and a phosphonate compound. The diacid may be, e.g., sebacic acid. The triamine may be, e.g., triethanolamine, while the phosphonate may be, e.g., a polyisopropenyl phosphonic material of different molecular weights, or e.g., 1,6-hexamethylenediamine-N,N,N′,N′-tetra(methylene phosphonic acid), or e.g., N,N,-dihydroxyethyl N′,N′,-diphosphonomethyl 1,3-propanediamine, N-oxide. 
     The compositions of the present invention should be added to the fluid system for which corrosion inhibition activity of the metal parts in contact with the fluid system is desired, in an amount effective for the purpose. This amount will vary depending upon the particular system for which treatment is desired and will be influenced by factors such as the area subject to corrosion, pH, temperature, water quantity and respective concentrations in the water of corrosive species. For the most part, the present invention will be effective when used at levels up to about 10,000 parts per million (ppm) of fluid, and preferably from about 2,000-10,000 ppm of the formulation in the fluid contained in the system to be treated. The present invention may be added directly to the desired fluid system in a fixed quantity and in a state of an aqueous solution, continuously or intermittently. The fluid system may be, e.g., a cooling water or boiler water system. Other examples of fluid systems which may benefit from the treatment of the present invention include aqueous heat exchanger, gas scrubber, air washer, air conditioning and refrigeration systems, as well as employed in e.g., building fire protection and water heaters. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The invention will now be further described with reference to a number of specific examples which are to be regarded solely as illustrative and not as restricting the scope of the present invention. 
     Local tap water was used for testing, with 60 ppm of Ca (as CaCO 3 ), 20 ppm Mg (as CaCO 3 ), 4 ppm SiO 2 , and 35 ppm of M-Alk (as CaCO 3 ): This water is identified as TRV. An aggressive water was tested, with 60 ppm of Ca (as CaCO 3 ), 20 ppm of Mg (as CaCO 3 ), 200 ppm of SO 4 , 4 ppm of SiO 2 , and 35 M-Alk ppm (as CaCO 3 ): This water is identified as AGG. An aggressive water, but without calcium was also tested (similar to the AGG in composition but without calcium), containing 20 ppm Mg (as CaCO 3 ), 200 ppm SO 4 , 51 ppm chloride as Cl − , 4 ppm SiO 2 , and 35 M-Alk ppm as CaCO 3 : This water is identified as AGG*. 
     In order to simulate the presence of corrosion products, 3 ppm of initially soluble Fe +2  was added to a sample of the aggressive water, AGG: This water is identified as A/Fe. Because a closed system is made of iron pipes, and there is no constant elimination of the naturally occurring iron oxides that are present, a fifth water that could represent those characteristics was also designed. The stress of a highly corroded system was simulated by adding to the local tap water (TRV) a corroded pipe section, an iron oxide in a piece (3 g), 1050 ppm of ground oxide and 4 ppm of initially soluble Fe +2 : This water is identified as CR or “iron crash test.” The iron oxides were taken from actual corroded pipes in the field. 
     In order to test corrosion, the Corrosion Beaker Test Apparatus (BCTA) was used. The tests were run generally for 18 hours, at 120° F.; beakers were stirred at 400 rpm and open to air. The metallurgy was low carbon steel coupons and probes. The test was based on measuring corrosion through the established electrochemistry technique of linear polarization. The BCTA performed consecutive measurements by automatically multiplexing 12 beakers. 
     The benchmark product was a molybdate, nitrite combination. In the set of synthetic waters, the corrosion inhibitor was challenged in different ways as the water composition changed, in order to stop corrosion. Note that a good corrosion inhibitor should be able to stop corrosion in all the waters. As shown in Table I below, such is the case for the benchmark molybdate/nitrite combination. The conventional all organic treatment is ineffective in the CR water and in AGG*, aggressive water with no calcium. It is also a weak inhibitor in A/Fe water, or water with dissolved iron. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE I 
               
             
             
               
                   
               
               
                 Corrosion rates measured in different waters, units of mils per year (mpy), 
               
               
                 for low carbon steel metallurgy with no treatment and with 
               
               
                 conventional treatments. 
               
             
          
           
               
                 Product or Chemical 
                 ppm 
                 TRV 
                 AGG 
                 AGG* 
                 A/Fe 
                 CR 
               
               
                   
               
             
          
           
               
                 Control 
                 0 
                 64; 75 
                 120; 125; 
                 94; 94; 
                 83; 99; 
                 57; 40; 47; 
               
               
                   
                   
                   
                 167 
                 85 
                 111; 78 
                 71 
               
               
                 Conventional Molybdate 
                 3000 
                 &lt;0.05; 
                 0.1; 0.3 
                 &lt;0.05; 
                 0.2; 
                 0.1; &lt;0.05; 
               
               
                 with nitrite 
                   
                 &lt;0.05 
                   
                 &lt;0.05 
                 &lt;0.05 
                 &lt;0.05 
               
               
                 Conventional all organic 
                 2000 
                 0.1; 
                 0.2; 0.5 
                 11; 10 
                 2.9; 2.6 
                 37 
               
               
                   
                   
                 &lt;0.05 
               
               
                   
               
             
          
         
       
     
     Four phosphonates were test ed. Two were experimental phosphonates (A=(N,N-dihydroxyethyl N′,N′,-diphosphonomethyl 1,3-propanediamine, N-oxide and B=1,6-hexamethylenediamine-N,N,N′,N′-tetra(methylene phosphonic acid)); the other two were poly (isopropenyl phosphonic) acid polymers (C is higher molecular weight and made in organic solution, whereas D is made in aqueous media and has smaller molecular weight). Polymers C and D were made as described in U.S. Pat. Nos. 4,446,046 and 5,519,102. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE II 
               
             
             
               
                   
               
               
                 Corrosion rates measured in waters as defined in text, units of mils 
               
               
                 per year (mpy) for low carbon steel metallurgy for phosphonates 
               
               
                 and the mixture of diacid amine. 
               
             
          
           
               
                 Chemical 
                   
                 TRV 
                 AGG 
                 AGG* 
                 A/Fe 
                 CR 
               
               
                   
               
             
          
           
               
                   
                 ppm 
                   
                   
                   
                   
                   
               
               
                 Phosphonate A 
                 10 
                 56 
               
               
                 Phosphonate A 
                 50 
                 0.4; 0.9 
                 9.2 
                 80 
                 54 
                 54 
               
               
                 Phosphonate A 
                 100 
                 &lt;0.05 
                 4.5 
                 17; 34 
                 13 
               
               
                 Phosphonate A 
                 200 
                   
                   
                 1.1 
               
               
                 Phosphonate A 
                 250 
                 0.1; 
                 1.5 
                   
                 1.8; 1.8 
                 20 
               
               
                   
                   
                 &lt;0.05 
               
               
                 Phosphonate A 
                 300 
                   
                   
                   
                 1.1 
               
               
                 Phosphonate A 
                 500 
                 0.1 
                   
                   
                 0.3 
                 10 
               
               
                 Phosphonate B 
                 50 
                 0.6; 0.7 
                 6 
                 5.2 
                 9.4 
               
               
                 Phosphonate B 
                 100 
                 0.6 
                 1.6 
                 1.6; 1.3 
                 1.3 
                 18 
               
               
                 Phosphonate B 
                 200 
                   
                   
                   
                   
                 16; 12 
               
               
                 Phosphonate B 
                 250 
                 0.5 
               
               
                 Phosphonate B 
                 500 
                 0.5 
               
               
                 Phosphonate B 
                 550 
                   
                   
                   
                   
                 12 
               
               
                 Phosphonate C 
                 25 
                 0.6 
                 60 
                 103 
                 58 
               
               
                 Phosphonate C 
                 50 
                 0.2 
                 4.6 
                 10 
                 20 
                 33 
               
               
                 Phosphonate D 
                 25 
                 1.8; 1.9 
                 65 
                 91 
               
               
                 Phosphonate D 
                 50 
                 0.1; 0.3 
                 5.2 
                 6.1 
                 9.4 
                 38 
               
               
                 Phosphonate D 
                 75 
                   
                 2.7 
                 5.2 
                 4.3 
                 34 
               
               
                 Phosphonate D 
                 100 
                   
                   
                   
                 2.4 
               
               
                   
                 ppm/ 
               
               
                   
                 ppm 
               
               
                 Sebacic 
                 50/50 
                 6.6 
               
               
                 acid/TEA 
               
               
                 Sebacic 
                 100/100 
                 1.4 
               
               
                 acid/TEA 
               
               
                 Sebacic 
                 250/250 
                 &lt;0.05 
                 30; 31 
                 32 
                 26 
                 62; 60 
               
               
                 acid/TEA 
               
               
                 Sebacic 
                 500/500 
                 &lt;0.05; 
                 47 
                 46 
                 38 
                 &lt;0.05; 
               
               
                 acid/TEA 
                   
                 &lt;0.05 
                   
                   
                   
                 &lt;0.05 
               
               
                   
               
             
          
         
       
     
     As shown in Table II, in order to obtain corrosion inhibition in the CR water, the preferred diacid is sebacic acid, at a concentration of at least 500 ppm. The preferred amine is triethanol amine (TEA). The preferred mass ratio of diacid (e.g., sebacic) to amine is at least 1:1. An increase of the concentrations of sebacic acid/TEA does not provide corrosion inhibition in all the synthetic waters. The worst protection is in the AGG, AGG* and A/Fe synthetic waters. As shown in Table II, in TRV and CR waters, sebacic acid/TEA at 500 ppm/500 ppm provides good corrosion protection, i.e., less than 0.05 mpy, in such waters. This is in contrast to its performance in AGG, AGG* and A/Fe waters; in those waters, corrosion protection is on the order of greater than 38 mpy. 
     Phosphonates are known to be useful corrosion inhibitors. However, as shown in Table II, none of the phosphonates tested offered effective corrosion protection for the CR water. The performance in the other synthetic waters was less effective than the benchmark; increasing their concentration did not radically change performance, especially in the CR water. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE III 
               
             
             
               
                   
               
               
                 Corrosion rates measured in waters as defined in text, units of mils per year 
               
               
                 (mpy) for low carbon steel metallurgy for the synergetic mixtures 
               
               
                 of phosphonates and diacids/amine. 
               
             
          
           
               
                   
                   
                 Diacid/ 
                   
                   
                   
                   
                   
                   
               
               
                 Phosphonate 
                 ppm 
                 amine 
                 ppm/ppm 
                 TRV 
                 AGG 
                 AGG* 
                 A/Fe 
                 CR 
               
               
                   
               
               
                 A 
                 75 
                 Sebacic/ 
                 500/ 
                 &lt;0.05 
                 0.1 
                 0.1 
                 0.9 
                 &lt;0.05 
               
               
                   
                   
                 TEA 
                 500 
               
               
                 A 
                 50 
                 Sebacic/ 
                 500/ 
                   
                 &lt;0.05 
                  0.05 
                  0.05 
                 0.1 
               
               
                   
                   
                 TEA 
                 500 
               
               
                 B 
                 30 
                 Sebacic/ 
                 500/ 
                 &lt;0.05; 
                 &lt;0.05; 
               
               
                   
                   
                 TEA 
                 500 
                 &lt;0.05 
                 1.5 
               
               
                 B 
                 50 
                 Sebacic/ 
                 500/ 
                 &lt;0.05 
                  0.05 
                 &lt;0.05 
                 0.1 
                 &lt;0.05 
               
               
                   
                   
                 TEA 
                 500 
               
               
                 C 
                 50 
                 Sebacic/ 
                 500/ 
                 &lt;0.05 
                 &lt;0.05; 
                 &lt;0.05; 
                 &lt;0.05; 
                 0.05; 
               
               
                   
                   
                 TEA 
                 500 
                   
                 &lt;0.05 
                 &lt;0.05; 
                 &lt;0.05 
                 0.1 
               
               
                   
                   
                   
                   
                   
                   
                 0.1 
               
               
                 D 
                 50 
                 Sebacic/ 
                 500/ 
                 &lt;0.05 
                 0.05; 
                 0.1 
                   
                 &lt;0.05 
               
               
                   
                   
                 TEA 
                 500 
                   
                 &lt;0.05 
               
               
                   
               
             
          
         
       
     
     As shown in Table III, it was found that the combination of organic diacid/triamine with any of the four phosphonates tested provided excellent corrosion protection in all the synthetic waters, when sebacic acid/triethanol amine are at least at 500 ppm of each and the phosphonates are at least 50 ppm as actives. The performance achieved at the above mentioned concentrations in the AGG, AGG* and A/Fe synthetic waters is unexpected and can be explained by a synergistic effect of the mixtures. Please note that none of the individual components can give protection of greater than 90% in that set of waters, and the combination provides protection of equal or greater than 99.9%. Table IV further demonstrates the unexpected results of the combination of diacid/amine/phosphonate, wherein a comparison of the corrosion rates in mpy as measured and as predicted is presented. The predicted corrosion rate is: a) calculated averaging the corrosion rates of the individual inhibitors phosphonate and diacid/amine, b) the corrosion rate as obtained with the best performer of the two, and c) calculated assuming a decrease in the corrosion rate of the best performer as the reduction on the rate of corrosion between the control water and the same water treated by the other inhibitor. 
     
       
         
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE IV 
               
               
                   
               
               
                 mpy as 
                 TRV 
                 AGG 
                 AAG* 
                 A/Fe 
                 CR 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Phosphonate A 50 ppm, sebacic acid 500 ppm, triethanol 
               
               
                 amine 500 ppm. 
               
             
          
           
               
                 Measured 
                   
                 &lt;0.05 
                 0.05 
                 0.05 
                 0.1 
               
               
                 Predicted by a) 
                 0.35 
                 28.1 
                 63 
                 46 
                 27 
               
               
                 Predicted by b) 
                 &lt;0.05 
                 9.2 
                 46 
                 9.4 
                 &lt;0.05 
               
               
                 Predicted by c) 
                 &lt;0.05 
                 3.1 
                 40.4 
                 22.1 
                 &lt;0.05 
               
             
          
           
               
                 Phosphonate B 50 ppm, sebacic acid 500 ppm, triethanol 
               
               
                 amine 500 ppm. 
               
             
          
           
               
                 Measured 
                 &lt;0.05 
                 0.05 
                 &lt;0.05 
                 0.1 
                 &lt;0.05 
               
               
                 Predicted by a) 
                 0.35 
                 26.5 
                 25.5 
                 23.7 
                 15 
               
               
                 Predicted by b) 
                 &lt;0.05 
                 6 
                 5.2 
                 9.4 
                 &lt;0.05 
               
               
                 Predicted by c) 
                 &lt;0.05 
                 2.1 
                 2.6 
                 3.9 
                 &lt;0.05 
               
             
          
           
               
                 Phosphonate C 50 ppm, sebacic acid 500 ppm, triethanol 
               
               
                 amine 500 ppm. 
               
             
          
           
               
                 Measured 
                   
                 &lt;0.05; 
                 &lt;0.05; 
                 &lt;0.05; 
                 &lt;0.05; 0.1 
               
               
                   
                   
                 &lt;0.05 
                 &lt;0.05; 
                 &lt;0.05 
               
               
                   
                   
                   
                 0.1 
               
               
                 Predicted by a) 
                 0.1 
                 25.8 
                 28 
                 29 
                 16.5 
               
               
                 Predicted by b) 
                 &lt;0.05 
                 9.2 
                 46 
                 9.4 
                 &lt;0.05 
               
               
                 Predicted by c) 
                 &lt;0.05 
                 1.6 
                 5.1 
                 8.2 
                 &lt;0.05 
               
             
          
           
               
                 Phosphonate D 50 ppm, sebacic acid 500 ppm, triethanol 
               
               
                 amine 500 ppm. 
               
             
          
           
               
                 Measured 
                 &lt;0.05 
                 &lt;0.05; 
                 &lt;0.05; 
                 0.1 
                 &lt;0.05 
               
               
                   
                   
                 &lt;0.05 
                 &lt;0.05 
               
               
                 Predicted by a) 
                 0.1 
                 26.1 
                 26.1 
                 23.7 
                 19 
               
               
                 Predicted by b) 
                 &lt;0.05 
                 5.2 
                 6.1 
                 9.4 
                 &lt;0.05 
               
               
                 Predicted by c) 
                 &lt;0.05 
                 1.8 
                 3.1 
                 3.9 
                 &lt;0.05 
               
               
                   
               
             
          
         
       
     
     As shown in Table IV, none of the predictions can account for the measured results. The nearest is the prediction by method c), but even by this prediction, the corrosion rate is still at least 30 times larger than any of the measured ones. 
     In a preferred embodiment, from about 200-1,000 ppm of sebacic acid, about 200-1,000 ppm of triethanolamine and about 25-100 ppm of polyisopropenyl phosphonic material may be added to the system in need of treatment. The polyisopropenyl phosphonic material may be made in organic solution or aqueous media. 
     While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims in this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.