Upgrading of petroleum resid, bitumen, shale oil, and other heavy oils by the separation of asphaltenes and/or resins therefrom by electrophilic aromatic substitution

Abstract

Heavy, high molecular weight multi ring aromatics present in petroleum resid, bitumen and heavy oils in the form of asphaltenes, heavy resids and polycyclic hetero (N) aromatic molecules are separated from the petroleum resid, bitumen and/or heavy oils, by the process comprising electrophilic aromatic substitution of polar groups onto the heavy high molecular weight multi-ring aromatics thereby rendering them insoluble in and facilitating their separation and recovery from the petroleum resid, bitumen and/or heavy oil.

1 . A method for upgrading heavy hydrocarbon feed streams by the removal therefrom of asphaltenes by functionalizing the asphaltene by selectively substituting polar substituents onto the aromatic rings of the asphaltenes present in the heavy hydrocarbon feed stream by electrophilic aromatic substitution, using an electrophilic aromatic substitution reagent the selective substitution rendering the thus substituted asphaltenes, less soluble in the heavy hydrocarbon feed stream resulting in their precipitation and separating the precipitate from the heavy hydrocarbon feed stream. 
     
     
         2 . The method of  claim 1  wherein the electrophilic aromatic substitution process is conducted on a heavy hydrocarbon feed stream heated to a temperature of between about 50 to 200° C. 
     
     
         3 . The method of  claim 1  wherein the electrophilic aromatic substitution process is conducted on a heavy hydrocarbon feed stream diluted with a light aromatic diluent. 
     
     
         4 . The method of  claim 1 ,  2  or  3  wherein the electrophilic aromatic substitution reaction is halogenation, nitration, sulfonation, Friedel-Crafts acylation or hydroxyl alkylation. 
     
     
         5 . The method of  claim 1 ,  2  or  3  wherein sufficient electrophilic aromatic substitution reagent is added to the heavy hydrocarbon feed stream in an amount sufficient to add from about 1 to 8 polar groups per asphaltene molecule. 
     
     
         6 . The method of  claim 4  wherein the electrophilic aromatic substitution reaction is sulfonation or hydroxyl alkylation. 
     
     
         7 . The method of  claim 6  wherein the sulfonation or hydroxyl-alkylated asphaltenene is further heated to dimerized/oligomerize the functionalized asphaltene. 
     
     
         8 . A method for selectively removing pyrrolic-N-containing nitrogen heterocyclic and polycyclic aromatic analogues thereof which contain at least one unsubstituted available aromatic carbon from oil feed stream by functionalizing said pyrrolic-N-containing heterocyclic and polycyclic aromatic analogue thereof with polar substituents by electrophilic aromatic substitution resulting in their precipitation and separating the precipitate from the oil feed stream. 
     
     
         9 . The method of  claim 8  wherein the oil feed stream comprises VGO. 
     
     
         10 . The method of  claim 8  wherein the oil feed stream comprises shale oil.