Method and compositions for inhibition of naphthenic acid induced corrosion

Abstract

Corrosion induced by the presence of naphthenic acids in hydrocarbon fluids, particularly where such fluids are at elevated temperatures, may be inhibited or controlled through use of corrosion inhibiting compositions comprising a combination of a minor portion of a phosphorus-based constituent and a major portion of a sulfur-based constituent, nitrogen-based constituent, or combination thereof. In another embodiment the sulfur-based constituent and/or nitrogen-based constituent may be used without any phosphorus-based constituent. Where the compounds are appropriately selected, the compositions may inhibit corrosion to a degree comparable or nearly comparable to the inhibition provided by an equal amount of some conventional phosphorus-based compounds alone, but are significantly less likely to impair catalyst activity in downstream cracking and refinery operations.

1 . A method for inhibiting naphthenic acid corrosion of metals in hydrocarbon fluids has been found, comprising adding to a hydrocarbon fluid, in an amount sufficient to inhibit corrosion therein, a corrosion inhibitor composition comprising
 a phosphorus-based constituent comprising at least one compound selected from the group consisting of:   a. thiophosphorus compounds of the formula   
       
         
           
           
               
               
           
         
         wherein R 1  is R 3 (OCH 2 CH 2 ) n  or R 3 (OCH 2 CH 2 ) n O; R 2  is the same as R 1  or XH, each X being independently sulfur or oxygen; provided however that at least one X is sulfur; R 3  is an alkyl group of from about 6 to about 18 carbon atoms; and n is an integer of from about 0 to about 12; 
         b. salts of the thiophosphorus compounds; 
         c. alkyl and aryl esters of the thiophosphorus compounds; and 
         d. isomers of the thiophosphorus compounds; and 
         e. phosphate ester compounds; 
       
       and a second constituent selected from
 a sulfur-based constituent comprising at least one compound conforming to one of the following formulas: 
 
       
         
           
           
               
               
           
         
       
       wherein R is —H, —SH, —SR, —SSR, or C1-12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 a nitrogen-based constituent comprising at least one compound conforming to one of the following formulas: 
 
       
         
           
           
               
               
           
         
       
       wherein R is —H, —SH, —SR, —SSR, or C1-C12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 and combinations thereof; 
 
       provided that the phosphorus-based constituent is present in minor portion. 
     
     
         2 . The method of  claim 1  wherein the sulfur-based constituent is selected from the group consisting of tropylene, 1,2,4-dithiazole-3-thione, and combinations thereof. 
     
     
         3 . The method of  claim 1  wherein the nitrogen-based compound is selected from the group consisting of acridine, phenanthridine, octahydroacridine, octahydrophenanthridine, 1,3-thiazole, and combinations thereof. 
     
     
         4 . The method of  claim 1  wherein the temperature of the hydrocarbon fluid is from about 175° C. (−347° F.) to 400° C. (−752° F.). 
     
     
         5 . The method of  claim 1  wherein the amount of the inhibitor composition is from about 10 ppm to about 5,000 ppm. 
     
     
         6 . A composition for inhibiting or controlling naphthenic acid induced corrosion in a hydrocarbon fluid comprising
 a phosphorus-based constituent comprising at least one compound selected from the group consisting of: a. thiophosphorus compounds of the formula   
       
         
           
           
               
               
           
         
         wherein R 1  is R 3 (OCH 2 CH 2 ) n  or R 3 (OCH 2 CH 2 ) n O; R 2  is the same as R 1  or XH, each X being independently sulfur or oxygen; provided however that at least one X is sulfur; R 3  is an alkyl group of from about 6 to about 18 carbon atoms; and n is an integer of from about 0 to about 12; 
         b. salts of the thiophosphorus compounds; 
         c. alkyl and aryl esters of the thiophosphorus compounds; and 
         d. isomers of the thiophosphorus compounds; and 
         e. phosphate ester compounds; 
       
       and a second constituent selected from
 a sulfur-based constituent comprising at least one compound conforming to one of the following formulas: 
 
       
         
           
           
               
               
           
         
       
       wherein R is —SH, —SR, —SSR, or C1-C12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 a nitrogen-based constituent comprising at least one compound conforming to one of the following formulas: 
 
       
         
           
           
               
               
           
         
       
       wherein R is independently —H, —SH, —SR, —SSR, or C1-C12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 and combinations thereof; 
 
       provided that the phosphorus-based constituent is present in minor portion. 
     
     
         7 . The composition of  claim 6  wherein the minor portion is no more than about 40 percent by weight of the composition. 
     
     
         8 . The composition of  claim 7  wherein the minor portion is no more than about 30 percent by weight of the composition. 
     
     
         9 . A composition for inhibiting or controlling naphthenic acid induced corrosion in a hydrocarbon fluid comprising
 a sulfur-based constituent comprising at least one compound conforming to one of the following formulas:   
       
         
           
           
               
               
           
         
       
       wherein R is —SH, —SR, —SSR, or C1-C12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 a nitrogen-based constituent comprising at least one compound conforming to one of the following formulas: 
 
       
         
           
           
               
               
           
         
       
       wherein R is independently —H, —SH, —SR, —SSR, or C1-C12 normal or partially or fully branched alkyl that is saturated or unsaturated;
 and combinations thereof; wherein the sulfur-based constituent, the nitrogen-based constituent, or combination thereof is present in major portion. 
 
     
     
         10 . The composition of  claim 9  wherein the sulfur-based constituent is selected from the group consisting of tropylene, 1,2,4-dithiazole-3-thione, and combinations thereof. 
     
     
         11 . The composition of  claim 9  wherein the nitrogen-based constituent is selected from the group consisting of acridine, phenanthridine, octahydroacridine, octahydrophenanthridine, 1,3-thiazole, and combinations thereof. 
     
     
         12 . The composition of  claim 9  comprising substantially no phosphorus-containing compound.