Process to upgrade oil using metal oxides

Abstract

Described herein are compositions and methods for using metal oxides to upgrade oil. Metal oxides may be used as catalysts to reduce the TAN of the oil by converting carboxylic acids such as naphthenic acids into non-corrosive products. In some cases, the conversion occurs by a decarboxylation of the carboxylic acid to produce CO 2 . A second process promoted by metal oxides is hydrocarbon cracking. Cracking decreases the viscosity and increases the API, and produces lower molecular-weight hydrocarbons that are useful for many fuels and lubricants. Reductions in TAN and the increases in API improve the quality of increase the value of oil.

1 . A method for upgrading oil, comprising contacting a quantity of an oil with an amount of a metal oxide agent sufficient to upgrade the quantity of oil.  
   
   
       2 . The method of  claim 1 , wherein the metal oxide agent is selected from the group consisting of alkaline earth metal oxides, oxidative transition metal oxides, rare earth metal oxides, and combinations thereof.  
   
   
       3 . The method of  claim 2 , wherein the alkaline earth metal oxide is selected from the group consisting of oxides of beryllium (Be), oxides of magnesium (Mg), oxides of calcium (Ca), oxides of strontium (Sr), oxides of barium (Ba), and combinations thereof.  
   
   
       4 . The method of  claim 3 , wherein the alkaline earth metal oxide is selected from the group consisting of calcium oxide (CaO), magnesium oxide (MgO), and combinations thereof.  
   
   
       5 . The method of  claim 2 , wherein the oxidative transition metal oxide is selected from the group consisting of oxides of silver (Ag), oxides of copper (Cu), oxides of manganese (Mn), oxides of lead (Pb), oxides of nickel (Ni), and combinations thereof.  
   
   
       6 . The method of  claim 5 , wherein the oxidative transition metal oxide is selected from the group consisting of AgO, Ag 2 O, and combinations thereof.  
   
   
       7 . The method of  claim 2 , wherein the rare earth metal oxide is selected from the group consisting of oxides of cerium (Ce), oxides of lanthanum (La), oxides of yttrium (Y), oxides of zirconium (Zr), and combinations thereof.  
   
   
       8 . The method of  claim 1 , wherein contacting is performed within a temperature range selected from the group consisting of from about 200° C. to about 450° C., from about 250° C. to about 450° C., from about 300° C. to about 450° C., from about 350° C. to about 450° C., and from about 400° C. to about 450° C.  
   
   
       9 . The method of  claim 1 , wherein contacting is performed within a temperature range of from about 300° C. to about 370° C.  
   
   
       10 . The method of  claim 1 , wherein contacting is carried out in a reaction system selected from the group consisting of a sealed glass tube, an autoclave, a flow reactor, a batch reactor, a slurry reactor, and combinations thereof.  
   
   
       11 . The method of  claim 1 , wherein the quantity of oil is located in a subsurface reservoir.  
   
   
       12 . The method of  claim 1 , wherein the oil is a fat-based oil.  
   
   
       13 . The method of  claim 1 , further comprising adding a quantity of water to dissolve water-soluble impurities.  
   
   
       14 . The method of  claim 1 , further comprising adding a quantity of pyridine to promote acid conversion.  
   
   
       15 . The method of  claim 1 , further comprising adding a quantity of nickel (Ni) to promote acid conversion.  
   
   
       16 . The method of  claim 1 , further comprising adding a quantity of copper (Cu) to promote acid conversion.  
   
   
       17 . The method of  claim 1 , further comprising adding a quantity of Al 2 O 3  to promote acid conversion.  
   
   
       18 . The method of  claim 1 , further comprising contacting the quantity of oil with an amount of an adsorbent material sufficient to reduce the total acidity of the quantity of oil.  
   
   
       19 . The method of  claim 18 , wherein the adsorbent material is a clay mineral or a mixture of clay minerals.  
   
   
       20 . The method of  claim 18 , wherein the clay mineral is selected from the group consisting of kaolinite, illite, illite-smectite, palygorskite, montmorillonite, Ca-montmorillonite, sepiolite, hectorite, Na-montmorillonite, and combinations thereof.  
   
   
       21 . The method of  claim 18 , wherein contacting the quantity of oil with the amount of the metal oxide agent and contacting the quantity of oil with the adsorbent material occur in parallel, in series, or simultaneously.  
   
   
       22 . The method of  claim 18 , wherein the adsorbent material catalyzes acid conversion.  
   
   
       23 . A method for reducing the total acidity of a quantity of oil, comprising contacting the quantity of oil with an amount of a metal oxide agent sufficient to reduce the total acidity of the quantity of oil.  
   
   
       24 . The method of  claim 23 , further comprising reducing the total acid number of the oil.  
   
   
       25 . The method of  claim 23 , further comprising reducing a quantity of naphthenic acids in said quantity of oil.  
   
   
       26 . A method of reducing the viscosity of a quantity of oil, comprising contacting the quantity of oil with an amount of a metal oxide agent sufficient to reduce the viscosity of the quantity of oil.  
   
   
       27 . The method of  claim 26 , further comprising increasing the API gravity of the quantity of oil.  
   
   
       28 . A composition comprising a quantity of an upgraded oil, produced by a process, comprising: 
 providing a quantity of an oil; and    contacting the quantity of oil with an amount of a metal oxide agent sufficient to upgrade the quantity of oil,    whereby the quantity of upgraded oil is produced.    
   
   
       29 . The composition of  claim 28 , wherein the metal oxide agent is selected from the group consisting of alkaline earth metal oxides, oxidative transition metal oxides, rare earth metal oxides, and combinations thereof.  
   
   
       30 . The composition of  claim 28 , wherein the process further comprises contacting the quantity of oil or the quantity of upgraded oil with an amount of an adsorbent material sufficient to reduce the total acidity of the quantity of oil or the quantity of upgraded oil.