Hydrogenation and refining technology of mixed oil including waste bio-oil

Abstract

A hydrogenation treatment method of a mixed oil including a waste bio-oil and a waste plastic pyrolysis oil, and a method for producing a refined oil including the hydrogenation treatment method providing a refined oil having reduced impurities to a refined raw material level, and, in particular, significantly reduced oxygen impurities which have been contained in a large amount.

What is claimed is: 
     
         1 . A hydrogenation treatment method of a mixed oil, the method comprising:
 hydrogenating a mixed oil including a waste plastic pyrolysis oil and a waste bio-oil with a reaction gas including a hydrogen gas in the presence of a plurality of molybdenum-based hydrogenation catalysts,   wherein the plurality of molybdenum-based hydrogenation catalysts are two or more molybdenum-based hydrogenation catalysts including different metal supports from each other.   
     
     
         2 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the plurality of molybdenum-based hydrogenation catalysts includes a molybdenum-based hydrogenation catalyst including an alumina support and a molybdenum-based hydrogenation catalyst including a zirconia support. 
     
     
         3 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein hydrogenating the mixed oil includes hydrogenating the mixed oil with a multi-stage catalyst layer formed of the molybdenum-based hydrogenation catalysts including different metal supports in the catalyst layer of each stage. 
     
     
         4 . The hydrogenation treatment method of a mixed oil of  claim 3 , wherein the multi-stage catalyst layer includes a catalyst layer formed of a molybdenum-based hydrogenation catalyst including an alumina (Al 2 O 3 ) support and a molybdenum-based hydrogenation catalyst including a zirconia (ZrO 2 ) support. 
     
     
         5 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the waste bio-oil in the mixed oil is 0.01 to 90 wt % of the total mass of the mixed oil. 
     
     
         6 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the waste bio-oil includes 5 wt % or more of oxygen impurities with respect to the total mass of the waste bio-oil. 
     
     
         7 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the waste bio-oil has a boiling point of 200° C. or higher. 
     
     
         8 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein a reaction temperature of the hydrogenating process of the mixed oil is 330 to 500° C. 
     
     
         9 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the hydrogen gas s introduced to the hydrogenation treatment method of the mixed oil is 100 bar or less. 
     
     
         10 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein a volume ratio between the hydrogen gas and the mixed oil introduced to the hydrogenation treatment method of a mixed oil is 300:1 to 3000:1. 
     
     
         11 . The hydrogenation treatment method of a mixed oil of  claim 1 , wherein the hydrogenation treatment method of a mixed oil has a liquid hourly space velocity (LHSV) of 0.1 to 10 h −1 . 
     
     
         12 . A method for producing a refined oil, the method comprising:
 producing a product by the hydrogenation treatment method of a mixed oil of  claim 1 ; and   removing hydrogenated impurities included in the product.   
     
     
         13 . The method for producing a refined oil of  claim 12 , wherein the refined oil includes 5 ppm or less of chlorine, 40 ppm or less of nitrogen, 5 ppm or less of sulfur, 5 wt % or less of olefin, 1 wt % or less of conjugated diolefin, and 5 ppm or less of a metal-based compound with respect to the total mass. 
     
     
         14 . The method for producing a refined oil of  claim 12 , wherein the refined oil includes less than 5 wt % of oxygen with respect to the total mass. 
     
     
         15 . A method for producing a refined oil from a mixed oil, the method comprising:
 subjecting a mixed oil to a multi-stage hydrogenation treatment including a first stage and a second stage, each stage including a molybdenum-based hydrogenation catalyst including a different metal support.   
     
     
         16 . The method of  claim 15 , wherein the different metal supports include an alumina support and a zirconia support. 
     
     
         17 . The method of  claim 15 , wherein the mixed oil includes waste bio-oil in an amount of 0.01 to 90 wt % of the total mass of the mixed oil, wherein the waste bio-oil has a boiling point of 200° C. or higher, and at least 5 wt % oxygen. 
     
     
         18 . The method of  claim 15 , wherein a reaction temperature of the hydrogenating treatment of the mixed oil is 330 to 500° C.