Methods and compositions for removing sulfur from liquid hydrocarbons using ammonium adducts

Abstract

Improved desulfurization compositions are provided for removing substantial fractions of sulfur, sulfur complexes, and sulfur compounds from liquid hydrocarbons such as crude oil and fuels. The preferred compositions comprise amine adducts, such as the adduct formed by reacting benzoic acid and a fatty acid amine. The compositions may be contacted with liquid hydrocarbons in the presence of water to achieve high levels of desulfurization. Preferably, the compositions are added substantially continuously to a flowing stream of liquid hydrocarbon and water, e.g., to the output from a producing oil well or in pipeline transmission and/or refinery equipment.

1 . A method of reducing the content of sulfur and/or sulfur-bearing compounds in liquid hydrocarbon during pipeline transport and/or refining thereof, said method comprising the step of contacting the hydrocarbon with an effective amount of a desulfurization composition and in the presence of water during said pipeline transfer and/or said refining, said composition comprising the adduct reaction product of an amine and an acid, and separating some of the sulfur or sulfur-bearing compounds from said liquid hydrocarbon.  
   
   
       2 . The method of  claim 1 , said amine adduct selected from adducts of amines of the formula  
       R—(NR 1 —(CH 2 ) n —NHR 2 ) x    
     where R is selected from the group consisting of aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl, hydroxyalkyl, and alkoxyhydroxy groups and wherein the alkyl groups or moieties are selected from the C2-C24 alkyls, R 1  and R 2  are individually selected from the group consisting of H and C1-C4 alkyls, n is from about 2-12, and x is from about 1-8  
   
   
       3 . The method of  claim 2 , said adduct comprising the reaction product of a fatty acid amine and an acid.  
   
   
       4 . The method of  claim 3 , said fatty acid amine being a C8-C24 fatty acid amine.  
   
   
       5 . The method of  claim 4 , said fatty acid amine being coco-1,3-diaminopropane.  
   
   
       6 . The method of  claim 3 , said acid comprising benzoic acid.  
   
   
       7 . The method of  claim 1 , said composition being in the form of an aqueous dispersion.  
   
   
       8 . The method of  claim 7 , said aqueous dispersion comprising of from about 1-1.5 lbs. of said composition per gallon of aqueous liquid.  
   
   
       9 . The method of  claim 1 , said composition being contacted with said liquid hydrocarbon at a level of from about 100-50,000 ppm of the adduct per ppm of total sulfur in the liquid hydrocarbon.  
   
   
       10 . The method of  claim 9 , said level being from about 250-10,000 ppm.  
   
   
       11 . The method of  claim 10 , said level being from about 300-2,000 ppm.  
   
   
       12 . The method of  claim 1 , said composition consisting essentially of said adduct.  
   
   
       13 . The method of  claim 1 , said hydrocarbon being in a flowing stream with water, said method including the step of substantially continuously metering amounts of said composition into said flowing stream.  
   
   
       14 . The method of  claim 1 , said liquid hydrocarbon and water forming an oil-water emulsion, said composition being added to said emulsion.  
   
   
       15 . The method of  claim 1 , said hydrocarbon being mixed with water to form a mixture, said mixture comprising at least about 50% by weight liquid hydrocarbon.  
   
   
       16 . The method of  claim 15 , said mixture comprising at least about 80% by weight liquid hydrocarbon.  
   
   
       17 . A method of reducing the content of sulfur and/or sulfur bearing compounds in crude oil during operation of a crude oil well yielding a mixture including crude oil and water, comprising the steps of substantially continuously adding a desulfurization composition into the well during said operation thereof, said composition comprising an adduct derived from the reaction between an amine and an acid, and separating at least a portion of said water from said liquid hydrocarbon after said addition step.  
   
   
       18 . The method of  claim 17 , said composition being added by substantially continuously metering the composition into the well.  
   
   
       19 . The method of  claim 17 , said composition being added intermittently to the well, with a frequency of at least twice per day.  
   
   
       20 . The method of  claim 17 , said adduct selected from adducts of amines of the formula  
       R—(NR 1 —(CH 2 ) n —NHR 2 ) x    
     where R is selected from the group consisting of aryl, alkyl, cycloalkyl, arylalkyl, alkoxyalkyl, hydroxyalkyl, and alkoxyhydroxy groups and wherein the alkyl groups or moieties are selected from the C2-C24 alkyls, R 1  and R 2  are individually selected from the group consisting of H and C1-C4 alkyls, n is from about 2-12, and x is from about 1-8  
   
   
       21 . The method of  claim 17 , said adduct being an adduct of a fatty acid amine and an acid.  
   
   
       22 . The method of  claim 21 , said fatty acid amine being a C8-C24 fatty acid amine.  
   
   
       23 . The method of  claim 22 , said fatty acid amine being coco-1,3-diaminopropane.  
   
   
       24 . The method of  claim 21 , said acid comprising benzoic acid.  
   
   
       25 . The method of  claim 17 , said composition being in the form of an aqueous dispersion.  
   
   
       26 . The method of  claim 25 , said aqueous dispersion comprising from about 1-1.5 lbs. of said composition per gallon of aqueous liquid.  
   
   
       27 . The method of  claim 17 , said composition being contacted with said liquid hydrocarbon at a level of from about 100-50,000 ppm of the adduct per ppm of total sulfur in the liquid hydrocarbon.  
   
   
       28 . The method of  claim 27 , said level being from about 250-10,000 ppm.  
   
   
       29 . The method of  claim 28 , said level being from about 300-2,000 ppm.