Upgrading of hdo heavy products

Abstract

The present disclosure provides a method for producing an oxygenated hydrocarbons from an aqueous feed stream, which involves hydrodeoxygenation (HDO) and catalytically upgrading the heavy components of the HDO products. The oxygenate streams from the HDO products and the upgraded heavy components can be combined to form an upgraded oxygenate stream, which can then be converted to useful compounds by acid condensation (AC). Advantageously, the present method can reduce coking on the AC catalysts while maintaining high overall yield of useful compounds.

1 . A method for producing an oxygenate product, the method comprising:
 (i) reacting an aqueous feed stream comprising an oxygenated hydrocarbon with hydrogen in the presence of a hydrodeoxygenation catalyst to produce an intermediate stream;   (ii) fractionating the intermediate stream into a first oxygenate stream comprising a first pool of C 1+ O 1-3  hydrocarbons and a heavy residual stream;   (iii) reacting the heavy residual stream with hydrogen in the presence of an upgrading catalyst to produce a second oxygenate stream comprising a second pool of C 1+ O 1-3  hydrocarbons, wherein the upgrading catalyst catalyzes hydrodeoxygenation, hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream; and   (iv) combining at least a portion of the first oxygenate stream and at least a portion of the second oxygenate stream to form an upgraded oxygenate stream.   
     
     
         2 . The method of  claim 1 , wherein the intermediate stream has a H/C eff  of 1.6 or less. 
     
     
         3 . The method of  claim 1 , wherein the heavy residual stream has a water content of less than 25% by weight. 
     
     
         4 . The method of  claim 1 , wherein the heavy residual stream has a boiling point that is higher than a boiling point of the first oxygenate stream. 
     
     
         5 . The method of  claim 1 , wherein the heavy residual stream has a H/C eff  of 1.3 or less. 
     
     
         6 . The method of  claim 1 , wherein step (i) is carried out in a first reactor and step (iii) is carried out in a second reactor, and wherein the first and second reactors are different. 
     
     
         7 . The method of  claim 1 , wherein step (i) and step (iii) are carried out in a single reactor. 
     
     
         8 . The method of  claim 1 , wherein the hydrodeoxygenation catalyst is a first hydrodeoxygenation catalyst and the upgrading catalyst is a second hydrodeoxygenation catalyst. 
     
     
         9 . The method of  claim 8 , wherein the first hydrodeoxygenation catalyst and the second hydrodeoxygenation catalyst are identical. 
     
     
         10 . The method of  claim 1 , wherein the upgrading catalyst catalyzes hydrogenation, hydrocracking, or a combination thereof, of the heavy residual stream. 
     
     
         11 . The method of  claim 1 , wherein the upgrading catalyst comprises a heterogeneous catalyst comprising palladium, molybdenum, and tin. 
     
     
         12 . The method of  claim 11 , wherein the upgrading catalyst further comprises tungsten. 
     
     
         13 . The method of  claim 11 , wherein the upgrading catalyst comprises a support. 
     
     
         14 . The method of  claim 13 , wherein the support is selected from the group consisting of nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, zeolites, tungstated zirconia, titania zirconia, sulfated zirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina, iron aluminate, phosphated alumina, theta alumina, niobia, niobia phosphate, oxides of the foregoing, and mixtures thereof. 
     
     
         15 . The method of  claim 13 , wherein the support further comprises a modifier selected from the group consist of tungsten, titania, sulfate, phosphate, or silica. 
     
     
         16 . The method of  claim 6 , wherein the second reactor has a reaction pressure from 70 psig to 2000 psig. 
     
     
         17 . The method of  claim 6 , wherein the second reactor has a reaction temperature from 100° C. to 300° C. 
     
     
         18 . The method of  claim 1 , wherein the heavy residual stream is contacted with the upgrading catalyst at a weight hour space velocity of at least 0.01 grams of the oxygenated hydrocarbon per gram of upgrading catalyst per hour. 
     
     
         19 . The method of  claim 1 , wherein the upgrading catalyst is in operation for at least 20 days without a regeneration of the catalyst. 
     
     
         20 . A method for producing a C 4+  compound, the method comprising:
 producing the upgraded oxygenate stream according to the method of  claim 1 ; and 
 reacting the upgraded oxygenate stream in the presence of a condensation catalyst to produce the C 4+  compound.