Method for Removing Chlorine from Waste Oil Fractions Containing High Content of Chlorine Using Solid Acid Material

Abstract

Provided is a technology of removing 90% or more chlorine by treating an oil fraction having a high Cl content at a high temperature using a solid acid catalyst. The dechlorinated oil fraction may be introduced to a refinery process and converted into a fuel or a chemical product. The solid acid catalyst and the oil fraction having a high Cl content are mixed and then chlorine is removed by a heat treatment at a high temperature. Main impurities such as S, N, and O and Na, Ca, Fe, and the like which may act as a catalyst poison in the catalyst reactions of a refinery process are removed simultaneously with the process of removing Cl.

1 . A method for removing chlorine from a waste oil fraction, the method comprising the steps of:
 a) preparing a mixture of a chlorine-containing waste oil fraction and a solid acid material;   b) reacting the mixture at a pressure of 1 bar or more and 100 bar or less under an inert gas atmosphere to remove chlorine; and   c) separating a dechlorinated oil fraction and the solid acid material from the mixture and recovering the dechlorinated oil fraction,   wherein the waste oil fraction includes 5 to 50 wt % of components having a boil fractioning point (bp) of lower than 150° C. with respect to a total weight of the waste oil fraction and   satisfies the following Relation 1:
   0.85< B/A< 1.15  [Relation 1]
 
   wherein A is a wt % of components having bp of 150° C. or higher with respect to the total weight of the waste oil fraction, 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 fraction of  claim 1 , wherein the waste oil fraction includes a waste plastic pyrolysis oil, a biomass pyrolysis oil, a regenerated lubricant, a crude oil fraction having a high chlorine content, or a mixture thereof. 
     
     
         3 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein the waste oil fraction has a chlorine content of 10 ppm or more. 
     
     
         4 . The method for removing chlorine from a waste oil fraction 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. 
     
     
         5 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein the solid acid material in a) is included at 5 to 10 wt % with respect to a total weight of the mixture. 
     
     
         6 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein the reaction in step b) is the catalytic conversion reactions that chlorine contained in the waste oil fraction 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. 
     
     
         7 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein the reaction in step b) is performed at a temperature of higher than 280° C. and lower than 380° C. 
     
     
         8 . The method for removing chlorine from a waste oil fraction of  claim 1 , further comprising: step d) repeating steps a), b), and c) once or more. 
     
     
         9 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein the dechlorinated oil fraction has a chlorine content of less than 10 ppm. 
     
     
         10 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein a weight ratio of chlorine in the dechlorinated oil fraction to chlorine in the waste oil fraction is 0.01 to 0.1. 
     
     
         11 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein Fe, Na, Ca, and Al contained in the waste oil fraction are further removed. 
     
     
         12 . The method for removing chlorine from a waste oil fraction of  claim 1 , wherein N, S, and O contained in the waste oil fraction are further removed.