Process for removing metals, sulfur and other impurities in crude oil

Abstract

A process for removing metals and sulfur (S)-containing compounds in a crude oil material. The process comprises causing the crude oil material to react with a removing agent which comprises a phosphoric acid ester.

1 . (canceled) 
     
     
         2 . A process for removing metals and sulfur (S)-containing compounds in a crude oil material, comprising the steps of:
 (a) mixing the crude oil material with a removing agent which comprises a phosphoric acid ester, and subjecting the reaction mixture to stirring for a first period of time, at a temperature which is lower than the boiling point of the removing agent;   (b) adding a first mixture of solvents including water to the reaction mixture, and subjecting the aqueous reaction mixture to stirring for a second period of time, at a temperature which is less than about 100° C.;   (c) allowing the aqueous reaction mixture to stand for a third period of time, thereby obtaining an oil phase comprising a treated oil and one or more phases including an aqueous phase; and   (d) subjecting the aqueous reaction mixture to separation thereby yielding the treated oil.   
     
     
         3 . A process according to  claim 2 , further comprising the steps of:
 (e) washing the treated oil using a second mixture of solvents including water; and   (f) retrieving a washed treated oil,   
       optionally steps (e) and (f) is repeated one time or more; 
       optionally the treated oil is further subjected to steps (b) to (d), one time or more; 
       optionally the treated oil is further subjected to steps (a) to (d), one time or more; 
       optionally step (f) is conducted at ambient temperature; 
       a length of the first period of time at step (a) and the second period of time at step (b) is the same or is different. 
     
     
         4 .- 5 . (canceled) 
     
     
         6 . A process according to  claim 3 , wherein a composition of the first mixture of solvents at step (b) and the second mixture of solvents at step (d) is the same or is different;
 optionally the first and second mixtures of solvent each independently comprises an organic solvent;   optionally the organic solvent is an alcohol such as ethanol, or benzene, or hexane, or 4-methyl-2-pentanone.   
     
     
         7 . (canceled) 
     
     
         8 . A process according to  claim 2  or  3 , wherein steps (d) and (f) each independently comprises use of a reflux system;
 optionally steps (d) and (f) each independently comprises decantation, centrifugation, filtration or a combination thereof. 
 
     
     
         9 . (canceled) 
     
     
         10 . A process according to  claim 2 , wherein the aqueous phase obtained at step (c) comprises reacted removing agent, and wherein the reacted removing agent is further subjected to a regeneration treatment to yield the removing agent;
 optionally the regenerated removing agent is re-used at step (a);   optionally the reacted removing agent comprises metal salts of the removing reacted agent.   
     
     
         11 . A process according to  claim 10 , wherein the regeneration treatment of the reacted removing agent comprises causing the treated reacted removing agent to react with an acid;
 optionally the acid is HCl.   
     
     
         12 . A process according to  claim 2 , wherein the one or more phases obtained at step (c) comprise at least one phase comprising unreacted removing agent in an organic solvent, and wherein the unreacted removing agent is re-used at step (a). 
     
     
         13 . A process according to  claim 2 , wherein the aqueous phase obtained at any of the steps is re-used in the process. 
     
     
         14 . A process according to  claim 2 , wherein an amount of the removing agent is: between about 1 vol. % to about 5 vol. % an amount of the crude oil, or between about 1 vol. % to about 4 vol. % an amount of the crude oil, or between about 1 vol. % to about 3 vol. % an amount of the crude oil, or between about 1 vol. % to about 2 vol. % an amount of the crude oil, or about 2 vol. % an amount of the crude oil; or about 1 vol. % an amount of the crude oil. 
     
     
         15 . (canceled) 
     
     
         16 . A process according to  claim 2 , wherein other impurities in the crude oil are also removed;
 optionally the metals and other impurities, as measured by Neuron Activation Analysis, comprise at least one of: Cd, U, Ca, V, Ti, Sn, Sr, Ag, Mn, Si, Al, Mg, Na, Fe, K, Zn, Cr, Cl, V, Co, Ni, Cu, As, Se, Br, Rb, Zr, Mo, In, Sn, Sb, I, Cs, Ba, La, Hf, W, Hg, Th, Sc and S;   optionally sulfur in the crude oil is in a form selected from the group consisting of: thiol, sulfide, disulfide, thiolanes, thiophene, benzothiophene, dibenzothiophene and benzonaphtothiophene.   
     
     
         17 .- 20 . (canceled) 
     
     
         21 . A process according to  claim 2 , wherein the removing agent is a phosphoric acid ester of general formula I below 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are each independently C 1  to C 20  a linear or branched, cyclic or non-cyclic, saturated or unsaturated alkyl group, optionally comprising a heteroatom which is O, S or N. 
       
     
     
         22 . A process according to  claim 21 , wherein R 1  and R 2  are each independently a C 8  to C 20  or a C 8  to C 16  or a C 16  a linear or branched, cyclic or non-cyclic, saturated or unsaturated alkyl group, optionally comprising a heteroatom which is O, S or N. 
     
     
         23 . A process according to  claim 2 , wherein the metal removing agent comprises di-(2-ethylhexyl)phosphoric acid (DEHPA or HDEHP) outlined below 
       
         
           
           
               
               
           
         
       
     
     
         24 . A process according to  claim 23 , wherein the temperature at step (a) is up to about 250° C. 
     
     
         25 . A process according to  claim 2 , wherein the metal removing agent is selected from the group consisting of: di-(2-ethylhexyl) phosphoric acid, bis(2-ethylhexyl) hydrophosphoric acid, di-(2-ethylhexyl) orthophosphoric acid, O,O-bis(2-ethylhexyl)phosphoric acid, orthophosphoric acid 2-ethylhexyl alcohol, phosphoric acid di(2-ethylhexyl) ester and Hostarex PA 216™. 
     
     
         26 . (canceled) 
     
     
         27 . A treated oil obtained by the process as defined in  claim 2 . 
     
     
         28 . A treated oil obtained by the process as defined in  claim 2 , wherein a content of the metals in the treated oil is about 75 to 90% or 80 to 90% lower than in the crude oil, and/or a content of S and S-containing compounds in the treated oil is about 50 to 55% or about 53% lower than in the crude oil. 
     
     
         29 .- 33 . (canceled) 
     
     
         34 . A treated oil obtained by the process as defined in  claim 2 , wherein: a content of V in the treated oil is about 90% lower than in the crude oil; and/or a content of Ni in the treated oil is about 79% lower than in the crude oil; and/or a content of S and S-containing compounds in the treated oil is about 53% lower than in the crude oil. 
     
     
         35 . A system for treating crude oil, which is adapted for conducting the process as defined in  claim 2 . 
     
     
         36 . An oil treatment facility, comprising the system as defined in  claim 35 ; optionally the facility is an industrial facility.