Methods for removing metallic and non-metallic impurities from hydrocarbon oils

Abstract

An embodiment of the invention is directed to a treatment method for reducing the level of metallic and nonmetallic impurities in an oil. The method includes the step of contacting the oil with a porous silica adsorbent material. The adsorbent material is characterized by a Brunauer-Emmett-Teller (BET) surface area value (total) of at least about 15 m 2 /g; and a Barrett-Joyner-Halenda (BJH) pore volume (total) of at least about 0.5 cc/g.

1 . A treatment method for reducing the level of metallic and nonmetallic impurities in an oil, comprising the step of contacting the oil with a porous silica adsorbent material, wherein the adsorbent material is characterized by a Brunauer-Emmett-Teller (BET) surface area value (total) of at least about 15 m 2 /g; and a Barrett-Joyner-Halenda (BJH) pore volume (total) of at least about 0.5 cc/g. 
   
   
       2 . The method of  claim 1 , wherein the silica adsorbent material has a cumulative pore volume distribution of at least about 20% of particles having a pore diameter in the range of about 3 nm and about 20 nm. 
   
   
       3 . The method of  claim 1 , wherein the porous silica adsorbent material comprises a hydrogel or a xerogel. 
   
   
       4 . The method of  claim 1 , wherein the silica adsorbent material comprises a combination of a silica gel material and a magnesium silicate material. 
   
   
       5 . The method of  claim 1 , carried out as a batch process, a semi-batch process, or a continuous process. 
   
   
       6 . The method of  claim 1 , wherein the oil is substantially deasphalted, prior to contact with the porous silica adsorbent material. 
   
   
       7 . The method of  claim 1 , wherein contact between the oil and the porous silica material is carried out in the presence of at least one organic solvent which is substantially compatible with the oil. 
   
   
       8 . The method of  claim 7 , wherein the organic solvent comprises a non-polar, branched or linear alkane containing at least about 3 carbon atoms. 
   
   
       9 . The method of  claim 7 , wherein the organic solvent is selected from the group consisting of benzene, naphthalene, alkyl oxalate, decaline, tetraline, xylene, decane triethylene glycol dimethyl ether, tetraethylene glycol dialkyl ether, anisol, dimethoxy benzene, dimethoxy toluene, propane, butane, pentane, petroleum ether; and combinations of any of the foregoing. 
   
   
       10 . The method of  claim 1 , wherein contact between the oil and the porous silica material is carried out in at least one stirred or agitated mixing vessel which also contains at least one organic solvent. 
   
   
       11 . The method of  claim 10 , wherein contact between the oil and the porous silica material is carried out at a temperature in the range of about 0° C. to about 60° C. 
   
   
       12 . The method of  claim 10 , wherein contact in the mixing vessel results in a mixture which comprises organic solvent; treated oil; and silica particles which contain impurities from the oil, said impurities being adsorbed on the surface of the silica particles; within the pores of the silica particles, or within the pores and on the surface of the silica particles. 
   
   
       13 . The method of  claim 12 , wherein the mixture is subjected to a separation step, so as to separate the treated oil from the remainder of the mixture. 
   
   
       14 . The method of  claim 13 , wherein the separation step comprises at least one technique selected from the group consisting of settling, centrifugation, filtering, hydrocycloning, and decantation. 
   
   
       15 . The method of  claim 1 , wherein contact between the oil and the porous silica material is carried out by passing the oil through at least one bed packed with the porous silica material. 
   
   
       16 . The method of  claim 1 , wherein the metallic impurity comprises at least one metal selected from the group consisting of nickel and vanadium. 
   
   
       17 . The method of  claim 16 , wherein substantially all of the metallic impurity is bound within at least one organometallic compound. 
   
   
       18 . The method of  claim 17 , wherein the metal is vanadium, and the organometallic compound is a porphyrin compound. 
   
   
       19 . The method of  claim 16 , wherein the level of vanadium in the oil after treatment is less than about 0.2 ppm. 
   
   
       20 . The method of  claim 1 , wherein the non-metallic impurity comprises at least one sulfur compound or an asphaltene material, or both a sulfur compound and an asphaltene material. 
   
   
       21 . The method of  claim 20 , wherein the sulfur compound is an organic compound selected from the group consisting of thiophenes, benzothiophenes, dibenzothiophenes, mercaptans, sulfides, disulfides, and combinations thereof. 
   
   
       22 . The method of  claim 1 , wherein the oil is selected from the group consisting of coker oils, coker gas oils, atmospheric residual oil, vacuum residual oil, fluid catalytic cracker feeds; deasphalted oils, deasphalted resins, processed residual oil, heavy oils, light crude oil, kerosene, diesel fuel, lubricating oils, wax, tar, and combinations thereof. 
   
   
       23 . The method of  claim 1 , wherein the oil is a fuel for a gas turbine engine. 
   
   
       24 . A method for treating crude oil to reduce the level of at least one impurity selected from the group consisting of vanadium compounds, nickel compounds, sulfur compounds, and asphaltene materials, comprising the step of contacting the crude oil with a porous silica adsorbent material in an organic solvent, wherein the adsorbent material is characterized by a Brunauer-Emmett-Teller (BET) surface area value (total) of at least about 15 m 2 /g; and a Barrett-Joyner-Halenda (BJH) pore volume (total) of at least about 0.5 cc/g; so that the impurities are adsorbed on the surface of the silica particles; within the pores of the silica particles, or within the pores and on the surface of the silica particles; and then separating the treated oil from the organic solvent and the impurity-containing adsorbent.