Hydrocarbon upgrading process with recycle

Abstract

A process for upgrading a bio-oil stream is disclosed. The process comprises reacting a bio-oil stream with hydrogen in the presence of a catalyst and a stable oil in a reactor to produce an upgraded bio-oil stream. A recycle oil stream is taken from the upgraded bio-oil stream. The recycle oil stream is recycled to the reactor to provide the stable oil. The content of the reactor can be measured using various techniques and characterized based on the concentration of one or more functional groups for example oxygenates. Further, a fuel oil stream can be taken from the upgraded bio-oil stream.

1 . A process for upgrading a bio-oil stream, comprising:
 reacting a bio-oil stream with hydrogen in the presence of a catalyst and a stable oil in a reactor to produce an upgraded bio-oil stream;   taking a recycle oil stream from said upgraded bio-oil stream; and   recycling said recycle oil stream to the reactor to provide the stable oil.   
     
     
         2 . The process of  claim 1  further comprising taking a fuel oil from said upgraded bio-oil stream. 
     
     
         3 . The process of  claim 1  further comprising:
 passing said recycle oil stream to the reactor to provide a mixture comprising said recycle oil stream and said bio-oil stream in the reactor, wherein a ratio of said mixture to a partially upgraded bio-oil stream inside the reactor is about 0:100 to about 85:15 by mass. 
 
     
     
         4 . The process of  claim 1 , wherein a content of the reactor comprises at least one or more of an aldehyde at a concentration of about 0 mol % H to about 3 mol % H, at least one of the group ketones and aldehydes at a concentration of about 0 mol % C to about 6 mol % C, at least one of the group carboxylic acids and esters at a concentration of about 0 mol % C to about 6 mol % C, at least one of the group ethers, alcohols, phenyl methoxy groups, and carbohydrates at a concentration of about 0 mol % C to about 6 mol % C. 
     
     
         5 . The process of  claim 1 , wherein a content of the reactor comprises a ratio of oxygenates of one or more of a (C—O)/C ratio from about 0 to about 0.7, a (C═O)/C ratio from about 0 to about 0.5, an OH/C ratio from about 0 to 2.5, and an O/C ratio from about 0 to 1.7. 
     
     
         6 . The process of  claim 1 , wherein a content of the reactor is characterized by an acid number of no more than 60 mg KOH/g. 
     
     
         7 . The process of  claim 1 , wherein the reactor is operated at a temperature of about 300° C. to about 500° C., and a pressure of about 6.8 MPa to about 13.8 MPa. 
     
     
         8 . The process of  claim 1  further comprising:
 passing said upgraded bio-oil stream to a hot separator; and 
 separating said upgraded bio-oil stream in the hot separator to provide a hot overhead stream and a hot bottoms stream comprising at least a portion of the stable oil. 
 
     
     
         9 . The process of  claim 8  further comprising:
 passing said hot overhead stream to a cold separator to separate gaseous components and provide a bottoms light oil stream; and 
 separating water from said bottoms light oil stream to produce a light upgraded bio-oil stream. 
 
     
     
         10 . The process of  claim 8  further comprising:
 separating a stream containing catalyst from said hot bottoms stream to provide a heavy oil stream and said recycle oil stream comprising the catalyst. 
 
     
     
         11 . The process of  claim 10  further comprising:
 separating a stream containing catalyst from said heavy oil stream to provide a heavy oil product stream and a concentrated catalyst stream; 
 combining said concentrated catalyst stream with said recycle oil stream to provide a combined recycle oil stream; and 
 recycling said combined recycle oil stream to the reactor to provide the stable oil. 
 
     
     
         12 . The process of  claim 11 , wherein said heavy oil stream is passed to a filtration vessel, a vacuum distillation column, a wiped film evaporator, a centrifuge, or a combination thereof for separating the catalyst. 
     
     
         13 . The process of  claim 9  further comprising charging said light oil stream to an FCC unit, a hydroprocessing unit, or a reforming unit. 
     
     
         14 . A process for upgrading a bio-oil stream, comprising:
 reacting a bio-oil stream with hydrogen in the presence of a catalyst and a stable oil in a reactor to produce an upgraded bio-oil stream;   separating the catalyst from said upgraded bio-oil stream to provide a recycle oil stream comprising the catalyst and a heavy upgraded bio-oil stream; and   recycling the recycle oil stream to the reactor to provide the stable oil.   
     
     
         15 . The process of  claim 14  wherein at least 50 wt % of the feed to the reactor is bio-derived. 
     
     
         16 . The process of  claim 15 , wherein a content of the reactor comprises at least one or more of an aldehyde at a concentration of about 0 mol % H to about 3 mol % H, at least one of the group ketones and aldehydes at a concentration of about 0 mol % C to about 6 mol % C, at least one of the group carboxylic acids and esters at a concentration of about 0 mol % C to about 6 mol % C, at least one of the group ethers, alcohols, phenyl methoxy groups, and carbohydrates at a concentration of about 0 mol % C to about 6 mol % C. 
     
     
         17 . The process of  claim 15 , wherein a content of the reactor comprises a ratio of oxygenates of one or more of a (C—O)/C ratio from about 0 to about 0.7, a (C═O)/C ratio from about 0 to about 0.5, an OH/C ratio from about 0 to 2.5, and an O/C ratio from about 0 to 1.7. 
     
     
         18 . The process of  claim 15  further comprising:
 passing said upgraded bio-oil stream to a hot separator; and 
 separating said upgraded bio-oil stream in the hot separator to provide a hot overhead stream and a hot bottoms stream comprising the stable oil. 
 
     
     
         19 . The process of  claim 18  further comprising separating catalyst from said hot bottoms stream to provide a heavy oil stream and said recycle oil stream comprising the catalyst. 
     
     
         20 . A process for upgrading a bio-oil stream, comprising:
 reacting a bio-oil stream with hydrogen in the presence of a catalyst and a stable oil in a reactor to produce an upgraded bio-oil stream;   separating said upgraded bio-oil stream in a separator to provide a light upgraded bio-oil stream and a bottoms stream;   separating catalyst from said bottoms stream to provide a heavy oil stream and a recycle oil stream comprising the catalyst; and   recycling said recycle oil stream to the reactor to provide the stable oil.