Upgrading of Bio-Oil by Reaction with Olefins in the Presence of a Catalyst

Abstract

Systems, methods, and apparatuses are provided for upgrading a bio-oil by reaction with an olefin in the presence of a catalyst. For example, upgraded bio-oil may have improved miscibility with hydrophobic fuels.

1 . A method for upgrading a bio-oil, the method comprising contacting the bio-oil with an olefin in the presence of a catalyst to form an upgraded bio-oil, the upgraded bio-oil comprising, compared to the bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight. 
     
     
         2 . The method of  claim 1 , further comprising pyrolyzing a biomass to form the bio-oil prior to contacting the bio-oil with the olefin in the presence of the catalyst. 
     
     
         3 . The method of  claim 1 , the olefin comprising a C 3 -C 5  alkene. 
     
     
         4 . The method of  claim 1 , the olefin comprising one or more of: propylene, isobutylene, or isoprene. 
     
     
         5 . The method of  claim 1 , further comprising contacting the bio-oil with a hydrogen donor. 
     
     
         6 . The method of  claim 5 , the hydrogen donor comprising a C 1 -C 10  aliphatic compound that comprises at least one hydroxyl group bonded to an alkyl carbon. 
     
     
         7 . The method of  claim 1 , further comprising contacting the bio-oil with at least one of: a C 3 -C 5  alcohol, a C 3 -C 5  diol, or a C 3 -C 5  triol. 
     
     
         8 . The method of  claim 1 , the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst. 
     
     
         9 . The method of  claim 1 , the catalyst comprising a supported propylsulfonic acid. 
     
     
         10 . The method of  claim 1 , the bio-oil being at least partially in a vapor phase. 
     
     
         11 . A method for upgrading bio-oil in a vapor phase, the method comprising:
 providing a vapor phase bio-oil; and   contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide an upgraded bio-oil.   
     
     
         12 . The method of  claim 11 , the upgraded bio-oil comprising, compared to the bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight. 
     
     
         13 . The method of  claim 11 , further comprising:
 mixing the vapor phase bio-oil with the olefin in gas or vapor form to provide a vapor phase mixture of bio-oil and olefin; and   contacting the vapor phase mixture of bio-oil and olefin to the catalyst to provide the upgraded bio-oil.   
     
     
         14 . The method of  claim 11 , conducted as a continuous process. 
     
     
         15 . The method of  claim 11 , the providing the vapor phase bio-oil comprising pyrolyzing a biomass to form the vapor phase bio-oil. 
     
     
         16 . The method of  claim 11 , the olefin comprising a C 3 -C 5  alkene. 
     
     
         17 . The method of  claim 11 , the olefin comprising one or more of propylene, isobutylene, or isoprene. 
     
     
         18 . The method of  claim 11 , the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst. 
     
     
         19 . The method of  claim 11 , the catalyst comprising a supported propylsulfonic acid. 
     
     
         20 . The method of  claim 11 , the vapor phase bio-oil comprising water, further comprising separating an alcohol from the upgraded bio-oil, the alcohol produced by contacting the vapor phase bio-oil comprising water with the olefin in the presence of the catalyst. 
     
     
         21 . A process for converting a pyrolysis oil to one or more hydrocarbon fuel range products, the process comprising:
 (a) reacting a pyrolysis oil with a feed comprising an olefin in the presence of a catalyst to form a product mixture comprising at least one of an esterification product and an etherification product; and   (b) contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into one or more fuel range hydrocarbon products.   
     
     
         22 . The process of  claim 21 , further comprising pyrolyzing a biomass to form the pyrolysis oil prior to reacting the pyrolysis oil with the feed comprising the olefin in the presence of the catalyst. 
     
     
         23 . The process of  claim 21 , wherein the olefin comprises a C 3 -C 5  alkene. 
     
     
         24 . The process of  claim 21 , the olefin comprising one or more of propylene, isobutylene, or isoprene. 
     
     
         25 . The process of  claim 21 , further comprising contacting the pyrolysis oil with a hydrogen donor. 
     
     
         26 . The process of  claim 25 , the hydrogen donor comprising one or more of: a C 1 -C 10  aliphatic compound that comprises at least one hydroxyl group bonded to an alkyl carbon. 
     
     
         27 . The process of  claim 21 , further comprising contacting the pyrolysis oil with at least one of: a C 3 -C 5  alcohol, a C 3 -C 5  diol, or a C 3 -C 5  triol. 
     
     
         28 . The process of  claim 21 , the catalyst comprising one or more of: a solid acid catalyst, a transition metal catalyst, a liquid phase acid catalyst, or a vapor phase acid catalyst. 
     
     
         29 . The process of  claim 21 , wherein the catalyst comprises a supported propylsulfonic acid. 
     
     
         30 . The process of  claim 21 , wherein the pyrolysis oil is at least partially in a vapor phase. 
     
     
         31 . The process of  claim 21 , wherein the hydrotreating catalyst comprises one or more catalysts selected from the group consisting of: cobalt (Co), molybdenum (Mo), nickel (Ni), titanium (Ti), tungsten (W), zinc (Zn), antimony (Sb), bismuth (Bi), cerium (Ce), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), manganese (Mn), rhenium (Re), iron (Fe), platinum (Pt), iridium (Ir), palladium (Pd), osmium (Os), rhodium (Rh), ruthenium (Ru), nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated chromium oxide (Cu/Cr), nickel aluminum oxide (Ni/Al 2 O 3 ), palladium aluminum oxide (PdAl 2 O 3 ), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), nickel molybdenum tungsten (NiMoW), sulfided cobalt molybdenum (CoMo), sulfided nickel molybdenum (NiMo), and a metal carbide;
 or a composite or combination thereof.   
     
     
         32 . The process of  claim 21 , wherein the hydrotreating catalyst comprises:
 a) a metal oxide support selected from the group consisting of a titanium oxide (TiO 2 ) support, a silicon oxide support, a zirconia oxide (ZrO 2 ) support, a niobium oxide (Nb 2 O 5 ) support, and a support comprising one or more mixtures of non-alumina metal oxides; and   b) a noble metal composition on the metal oxide support, the noble metal composition comprising one or more noble metals selected from the group consisting of: rhodium (Rh), palladium (Pd), gold (Au), and ruthenium (Ru).   
     
     
         33 . An upgraded bio-oil, the upgraded bio-oil produced by a process comprising contacting a crude bio-oil with an olefin in the presence of a catalyst to form the upgraded bio-oil, the upgraded bio-oil comprising, compared to the crude bio-oil, one or more of: a reduced hydroxyl value; a reduced acid value; a reduced polarity; a reduced miscibility in a polar solvent; a reduced oxygen concentration, a reduced water concentration; or an increased average molecular weight. 
     
     
         34 . An upgraded bio-oil, the upgraded bio-oil produced by a process comprising:
 providing a vapor phase bio-oil; and   contacting the vapor phase bio-oil with an olefin in the presence of a catalyst to provide the upgraded bio-oil.   
     
     
         35 . A composition comprising one or more hydrocarbon fuel range products, the mixture of one or more hydrocarbon fuel range products produced from a pyrolysis oil by a process comprising:
 (a) reacting the pyrolysis oil with a feed comprising an olefin in the presence of a catalyst to form a product mixture comprising at least one of an esterification product and an etherification product; and   (b) contacting the at least one of the esterification product and the etherification product in a reaction zone with a hydrotreating catalyst in the presence of hydrogen under reaction conditions sufficient to convert at least a portion of the at least one of the esterification product and the etherification product into the mixture of the one or more fuel range hydrocarbon products.   
     
     
         36 . A method  800  of improving miscibility of a bio-oil in a hydrophobic fuel, comprising:
   802  providing a miscible bio-oil, the miscible bio-oil being upgraded, catalytic, or upgraded and catalytic compared to a starting material bio-oil; and 
   804  contacting the miscible bio-oil to a hydrophobic fuel to form a miscible mixture, 
 the miscible bio-oil being characterized by greater miscibility in the hydrophobic fuel compared to the bio-oil starting material. 
 
     
     
         37 . The method of  claim 36 , further comprising contacting an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture. 
     
     
         38 . The method of  claim 37 , the alcohol including a C 3 -C 5  alcohol. 
     
     
         39 . The method of  claim 37 , the alcohol including one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol. 
     
     
         40 . The method of  claim 36 , further comprising contacting a surfactant to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture. 
     
     
         41 . The method of  claim 40 , the surfactant including one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant. 
     
     
         42 . The method of  claim 36 , further comprising contacting a surfactant and an alcohol to the miscible bio-oil and the hydrophobic fuel to form the miscible mixture. 
     
     
         43 . The method of  claim 36 , including upgrading the bio-oil starting material to provide the miscible bio-oil by one or more of:
 contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil; or   contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil,   the miscible bio-oil being reduced in one or more of a hydroxyl value, an acid value, or a water concentration compared to the bio-oil starting material.   
     
     
         44 . The method of  claim 36 , the hydrophobic fuel including one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha. 
     
     
         45 . The method of  claim 36 , the bio-oil starting material including one or more of: water, organic acids, aldehydes, alkyl hydroxyls, phenols, or sugars. 
     
     
         46 . A bio-oil composition, comprising a miscible ternary mixture according to each triplet of miscible or partly miscible ranges in any one of  FIG. 7A, 7B, 7C , or  7 D, or a combination thereof, including:
 a bio-oil, an upgraded bio-oil, a catalytic bio-oil, or an upgraded catalytic bio-oil in a percentage according to each corresponding range;   an alcohol in a percentage according to each corresponding range of 1-butanol; and   a hydrophobic fuel in a percentage according to each corresponding range of diesel.   
     
     
         47 . The bio-oil composition of  claim 46 , the miscible ternary mixture being according to each triplet of miscible or partly miscible ranges in any one of  FIG. 7B, 7C , or  7 D, or a combination thereof. 
     
     
         48 . The bio-oil composition of  claim 46 , at least one said percentage being within the corresponding miscible percentage range. 
     
     
         49 . The bio-oil composition of  claim 46 , each said corresponding percentage range being within each corresponding miscible percentage range. 
     
     
         50 . The bio-oil composition of  claim 46 , consisting substantially of the miscible ternary mixture. 
     
     
         51 . The bio-oil composition of  claim 46 , consisting essentially of the miscible ternary mixture. 
     
     
         52 . The bio-oil composition of  claim 46 , the alcohol including a C 3 -C 5  alcohol. 
     
     
         53 . The bio-oil composition of  claim 46 , the alcohol including one or more of n-butanol, sec-butanol, iso-butanol, tert-butanol, n-propanol, or 2-propanol. 
     
     
         54 . The bio-oil composition of  claim 46 , the hydrophobic fuel including one or more of: diesel, fuel oil, heating oil, bunker fuel, gasoline, jet fuel, kerosene, white gas, liquefied coal fuel, or naphtha. 
     
     
         55 . The bio-oil composition of  claim 46 , further comprising a surfactant. 
     
     
         56 . The bio-oil composition of  claim 46 , further comprising one or more of an anionic surfactant, a cationic surfactant, an amphiphilic surfactant, or a nonionic surfactant. 
     
     
         57 . The bio-oil composition of  claim 46 , the miscible bio-oil being prepared from a bio-oil starting material in a process including one or more of:
 contacting the bio-oil starting material with an olefin in the presence of a solid acid catalyst to provide the miscible bio-oil; or   contacting the bio-oil starting material with the olefin in a vapor phase in the presence of a catalyst to provide the miscible bio-oil,   the miscible bio-oil being reduced in one or more of a hydroxyl value, an acid value, and a water concentration compared to the bio-oil starting material.