Method for Removing Chlorine from High Chlorine Content Waste Oil Using Solid Acid Substances

Abstract

The present embodiment pertains to a technique for removing at least 90% of the chlorine in high Cl content oil by performing a high-temperature treatment using solid acid substances. The oil removed Cl from a waste oil can be incorporated in a refinery process and thereby converted into fuel or a chemical product. Chlorine can be removed through a high-temperature heat treatment after mixing high Cl content oil with a solid acid material. In the process of removing Cl, major impurities, such as S, N, and O, as well as Na, Ca, and Fe, which can act as catalyst poisons in the catalytic reactions of a refinery process, are also removed at the same time.

1 . A method for removing chlorine from a waste oil, the method comprising the steps of:
 a) preparing a mixture of a chlorine-containing waste oil and a solid acid material;   b) reacting the mixture to remove chlorine; and   c) separating a dechlorinated oil fraction and the solid acid material from the mixture to recover the dechlorinated oil fraction,   wherein the following Relation 1 is satisfied:
   1≤ B/A≤ 3  [Relation 1]
 
   wherein A is a wt % of components having a boiling point (bp) of 150° C. or higher with respect to a total weight of the waste oil, and B is a wt % of components having bp of 150° C. or higher with respect to a total weight of the dechlorinated oil fraction.   
     
     
         2 . The method for removing chlorine from a waste oil of  claim 1 , wherein the waste oil includes a waste plastic pyrolysis oil, a biomass pyrolysis oil, a regenerated lubricant, a crude oil having a high chlorine content, or a mixture thereof. 
     
     
         3 . The method for removing chlorine from a waste oil of  claim 1 , wherein the waste oil has a ratio (A 2 /A 1 ) of 1 to 19, the ratio being a weight (A 2 ) of components having bp of 150° C. or higher to a weight (A 1 ) of components having bp of lower than 150° C. 
     
     
         4 . The method for removing chlorine from a waste oil of  claim 1 , wherein the waste oil has a chlorine content of 10 ppm or more 
     
     
         5 . The method for removing chlorine from a waste oil of  claim 1 , wherein the solid acid material is zeolite, clay, silica-alumina-phosphate (SAPO), aluminum phosphate (ALPO), metal organic framework (MOF), silica alumina, or a mixture thereof. 
     
     
         6 . The method for removing chlorine from a waste oil of  claim 1 , wherein the solid acid material in step a) is included at 5 to 10 wt % with respect to a total weight of the mixture. 
     
     
         7 . The method for removing chlorine from a waste oil of  claim 1 , wherein the reaction in step b) is the catalytic conversion reactions that the chlorine contained in the waste oil is removed by a reaction of a direct bond to an active site of the solid acid material and/or is converted into a hydrochloric acid (HCl) at the active site of the solid acid material. 
     
     
         8 . The method for removing chlorine from a waste oil of  claim 1 , wherein the reaction of step b) is performed at a pressure of 1 bar or more and 100 bar or less under an inert gas atmosphere and at a temperature of 200° C. or higher and lower than 300° C. 
     
     
         9 . The method for removing chlorine from a waste oil of  claim 1 , wherein the reaction of step b) is performed for 0.1 to 48 hours. 
     
     
         10 . The method for removing chlorine from a waste oil of  claim 1 , wherein the reaction of step b) is performed at a stirring speed of 30 to 2000 rpm. 
     
     
         11 . The method for removing chlorine from a waste oil of  claim 1 , further comprising: step d) repeating steps a), b), and c) once or more. 
     
     
         12 . The method for removing chlorine from a waste oil of  claim 1 , wherein the dechlorinated oil fraction has a ratio (B 2 /B 1 ) of 1 to 20, the ratio being a weight (B 2 ) of components having bp of 150° C. or higher to a weight (B 1 ) of components having bp of lower than 150° C. 
     
     
         13 . The method for removing chlorine from a waste oil of  claim 1 , wherein the dechlorinated oil fraction has a chlorine content of less than 10 ppm. 
     
     
         14 . The method for removing chlorine from a waste oil of  claim 1 , wherein a weight ratio of chlorine in the dechlorinated oil fraction to chlorine in the waste oil is 0.01 to 0.25. 
     
     
         15 . The method for removing chlorine from a waste oil of  claim 1 , wherein Fe, Na, Ca, and Al contained in the waste oil are further removed. 
     
     
         16 . The method for removing chlorine from a waste oil of  claim 1 , wherein N, S, and O contained in the waste oil are further removed.