Refining method of waste plastic pyrolysis oil using sulfur source and molybdenum-based hydrogenation catalyst, and continuous operation method thereof

Abstract

Provided is a refining method of a waste plastic pyrolysis oil including: (S1) mixing a waste plastic pyrolysis oil and a sulfur source to prepare a mixed oil fraction; (S2) hydrotreating the mixed oil fraction with a reaction gas including a hydrogen gas (H 2 ) in the presence of a molybdenum-based hydrogenation catalyst; and (S3) removing by-products of the hydrotreating from the product of (S2) to obtain a refined oil.

1 . A refining method of a waste plastic pyrolysis oil, the method comprising:
 (S1) mixing a waste plastic pyrolysis oil and a sulfur source to prepare a mixed oil fraction;   (S2) hydrotreating the mixed oil fraction with a reaction gas including a hydrogen gas (H 2 ) in the presence of a molybdenum-based hydrogenation catalyst; and   (S3) removing by-products of the hydrotreating from a product of (S2) to obtain a refined oil.   
     
     
         2 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the sulfur source includes a sulfur-containing oil fraction. 
     
     
         3 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the mixed oil fraction includes 100 ppm or more of sulfur. 
     
     
         4 . The refining method of a waste plastic pyrolysis oil of  claim 2 , wherein the sulfur-containing oil fraction is included at less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. 
     
     
         5 . The refining method of a waste plastic pyrolysis oil of  claim 2 , wherein the sulfur-containing oil fraction is included at less than 50 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. 
     
     
         6 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the sulfur source includes one or two or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds. 
     
     
         7 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the reaction gas of (S2) includes a hydrogen sulfide gas (H 2 S). 
     
     
         8 . The refining method of a waste plastic pyrolysis oil of  claim 7 , wherein the hydrogen sulfide gas (H 2 S) is separated from the by-products of the hydrotreating which has been removed in (S3) and then supplied again. 
     
     
         9 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the molybdenum-based hydrogenation catalyst is a catalyst in which a molybdenum-based metal, or a metal including any one or two or more selected from nickel, cobalt, and tungsten and a molybdenum-based metal are supported on a support. 
     
     
         10 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein the molybdenum-based hydrogenation catalyst includes a molybdenum-based sulfide hydrogenation catalyst. 
     
     
         11 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein (S2) is performed at a pressure of 200 bar or less. 
     
     
         12 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein (S2) is performed at a temperature of 300° C. or higher and lower than 450° C. 
     
     
         13 . The refining method of a waste plastic pyrolysis oil of  claim 1 , wherein (S2) is performed at a liquid hourly space velocity (LHSV) of 0.1 to 5 h −1 . 
     
     
         14 . A continuous operation method of waste plastic pyrolysis oil refining equipment, the method comprising:
 (S1) mixing a waste plastic pyrolysis oil and a sulfur source to prepare a mixed oil fraction;   (S2) hydrotreating the mixed oil fraction with a reaction gas including a hydrogen gas (H 2 ) and a hydrogen sulfide gas (H 2 S) at a pressure of 200 bar or less in the presence of a molybdenum-based sulfide hydrogenation catalyst; and   (S3) removing by-products of the hydrotreating from a product of (S2) to obtain a refined oil,   wherein the hydrogen sulfide gas (H 2 S) of (S2) is separated from the by-products of the hydrotreating of (S3) and supplied again.   
     
     
         15 . The continuous operation method of waste plastic pyrolysis oil refining equipment of  claim 14 , wherein sulfur is continuously supplied from the sulfur source to maintain an activity of the molybdenum-based sulfide hydrogenation catalyst. 
     
     
         16 . The continuous operation method of waste plastic pyrolysis oil refining equipment of  claim 14 , wherein the mixed oil fraction includes 100 ppm or more of sulfur. 
     
     
         17 . The continuous operation method of waste plastic pyrolysis oil refining equipment of  claim 14 , wherein the sulfur source includes a sulfur-containing oil fraction. 
     
     
         18 . The continuous operation method of waste plastic pyrolysis oil refining equipment of  claim 17 , wherein the sulfur-containing oil fraction is included at less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. 
     
     
         19 . The continuous operation method of waste plastic pyrolysis oil refining equipment of  claim 14 , wherein the sulfur source includes one or two or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds.