Co-current adiabatic reaction system for conversion of triacylglycerides rich feedstocks

Abstract

A process for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels is disclosed. The process may include: reacting a triacylglycerides-containing oil-water-hydrogen mixture in a single reactor at a temperature in the range from about 250° C. to about 650° C. and a pressure greater than about 75 bar to convert at least a portion of the triacylglycerides via homogeneously catalyzed hydrothermolysis and heterogeneously catalyzed hydrotreatment.

What is claimed: 
     
         1 . A process for converting triacylglycerides-containing oils or fatty acids derived from plants, algae, organic wastes or animal sources into crude oil precursors and/or distillate hydrocarbon fuels, the process comprising:
 feeding hydrogen, water, and a triacylglyceride-containing oil into a co-current reactor having a homogeneously catalyzed hydrothermolysis reaction zone and a heterogeneously catalyzed hydrotreatment zone;   hydrothermolyzing at least a portion of the triacylglyceride-containing oil in the hydrothermolysis reaction zone to form a hydrothermolysis reaction product; and   hydrotreating the hydrothermolysis reaction product directly without any componential separations in the catalytic hydrotreatment zone; and   recovering an effluent from the catalytic hydrotreatment zone.   
     
     
         2 . The process of  claim 1 , wherein the hydrothermolysis reaction zone and the catalytic hydrotreatment zone are adiabatic reaction zones. 
     
     
         3 . The process of  claim 1 , wherein the hydrothermolysis reaction zone and the catalytic hydrotreatment zone are contained within the same reactor vessel. 
     
     
         4 . The process of  claim 3 , wherein the hydrothermolysis reaction zone contains one or more beds of inert solids to promote mixing. 
     
     
         5 . The process of  claim 3 , wherein the catalytic hydrotreatment zone comprises one or more beds containing one or more hydrotreating catalysts. 
     
     
         6 . The process of  claim 1 , further comprising feeding at least one of hydrogen and water intermediate the hydrothermolysis reaction zone and the catalytic hydrotreatment zone. 
     
     
         7 . The process of  claim 1 , further comprising indirectly heating the triacylglyceride-containing oil feed to the co-current reactor with the effluent recovered from the catalytic hydrotreatment zone. 
     
     
         8 . The process of  claim 1 , wherein the reactor is operated at a temperature in the range of 250° C. to 650° C. and a pressure of at least 75 bar. 
     
     
         9 . The process of  claim 1 , wherein the co-current reactor is a downflow reactor. 
     
     
         10 . The process of  claim 1 , wherein the hydrothermolysis reaction product is heated by direct heat exchange with a superheated hydrogen/water mixture prior to hydrotreating the hydrothermolysis reaction product. 
     
     
         11 . A reactor system for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the reactor system comprising:
 a homogeneously catalyzed hydrothermolysis reaction zone for hydrothermolyzing at least a portion of a triacylglyceride-containing oil to form a hydrothermolysis reaction product; and   a heterogeneously catalyzed hydrotreatment zone for hydrotreating the hydrothermolysis reaction product.   
     
     
         12 . The reactor system of  claim 11 , wherein the hydrothermolysis reaction zone and the catalytic hydrotreatment zone are fluidly coupled within the same reactor. 
     
     
         13 . The reactor system of  claim 11 , wherein the hydrothermolysis reaction zone is in a first reactor and the catalytic hydrotreatment zone is in a second reactor, the first and second reactor being fluidly coupled. 
     
     
         14 . The reactor system of  claim 11 , wherein the hydrothermolysis reaction zone and the catalytic hydrotreatment zone are adiabatic reaction zones. 
     
     
         15 . The reactor system of  claim 11 , wherein the hydrothermolysis reaction zone contains one or more beds of inert solids to promote mixing, and wherein the catalytic hydrotreatment zone comprises one or more beds containing one or more hydrotreating catalysts. 
     
     
         16 . The reactor system of  claim 15 , wherein the catalytic hydrotreatment comprises a first catalyst bed containing a catalyst having hydrogenation activity and a second catalyst bed containing a catalyst having hydrocracking activity. 
     
     
         17 . A process for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the process comprising:
 mixing hydrogen with water to form a superheated mixed water stream;   injecting the mixed water stream into a co-current reaction system comprising a hydrothermolysis adiabatic reaction zone and a catalytic adiabatic hydrotreatment zone;   injecting a triacylglyceride-containing oil into the co-current reaction system;   reacting the first portion of the mixed water stream and the triacylglyceride-containing oil in a first hydrothermolysis adiabatic reaction zone under reaction conditions sufficient to convert at least a portion of the triacylglycerides via hydrothermolysis to produce a hydrothermolysis reaction product comprising one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, and aromatics;   feeding hydrogen and the hydrothermolysis reaction product to a first catalytic adiabatic hydrotreatment zone to hydrotreat at least a portion of the reaction product; and   recovering a hydrotreated effluent.   
     
     
         18 . The process of  claim 17 , wherein the adiabatic hydrothermolysis reaction zone is operated at a temperature in the range from about 250° C. to about 650° C. 
     
     
         19 . The process of  claim 17 , wherein the reaction system is operated at a pressure of at least 75 bar. 
     
     
         20 . The process of  claim 17 , wherein the hydrothermolysis reaction conditions comprise a pressure and a temperature greater than the critical pressure and temperature of water. 
     
     
         21 . The process of  claim 17 , wherein the mass ratio of water to triacylglyceride-containing oil ranges from about 0.001:1 to about 1:1. 
     
     
         22 . The process of  claim 17 , wherein the mixed water feed has a hydrogen to water mass ratio in the range from about 0.005:1 to about 500:1. 
     
     
         23 . The process of  claim 17 , further comprising mixing a non-renewable hydrocarbon feedstock with the triacylglyceride-containing oil. 
     
     
         24 . The process of  claim 17 , wherein the triacylglycerides-containing oil comprises a renewable oil from at least one of camelina, carinata, cotton, jatropha, karanja, moringa, lesquerella, physaria, palm, castor, corn, linseed, peanut, soybean, sunflower, tung, babassu, or at least one triacylglycerides-containing oil from at least one of canola, shea butter, tall oil, tallow, algal oil, and pongamia, or at least one of animal-derived fats/oils from at least one of tallow, lard, chicken fats, butter fat, fish oil, or at least one of organic wastes from at least one of municipal solid wastes, sewage sludge solids, Kraft plant waste liquor, restaurant greases and used vegetable oils. 
     
     
         25 . The process of  claim 17 , further comprising fractionating the hydrotreated effluent to recover one or more hydrocarbon fractions boiling in the range of naphtha, diesel, or jet. 
     
     
         26 . The process of  claim 25 , further comprising quenching the hydrotreated effluent with a hydrogen stream prior to fractionating the hydrotreated effluent. 
     
     
         27 . The process of  claim 25 , further comprising recovering a heavy hydrocarbon fraction having a boiling point greater than end point of the diesel fraction and recycling the heavy hydrocarbon fraction to the co-current reaction system. 
     
     
         28 . A system for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the system comprising:
 a mixing device for mixing hydrogen with water to form a hydrogen-water mixture;   at least one co-current adiabatic reaction system comprising;
 at least one hydrothermolysis reaction zone for reacting the hydrogen-water mixture and triacylglycerides-containing oils at a temperature in the range of 250° C. to about 650° C. and a pressure greater than about 75 bar to produce a hydrothermolysis effluent; and 
 at least one hydrotreatment zone for hydrotreating the hydrothermolysis effluent to produce a hydrotreated effluent. 
   
     
     
         29 . The system of  claim 28 , further comprising one or more fluid conduits for recycling a compressed hydrogen stream to the mixing device for mixing hydrogen. 
     
     
         30 . The system of  claim 28 , further comprising a fractionator for fractionating hydrocarbons in the co-current adiabatic reaction system effluent to form one or more hydrocarbon fractions boiling in the naphtha, jet or diesel range. 
     
     
         31 . The system of  claim 28 , further comprising a heat exchange apparatus for exchanging heat between the co-current adiabatic reaction system effluent and the triacylglycerides-containing oils. 
     
     
         32 . The system of  claim 28 , wherein the at least one hydrotreatment zone comprises at least two catalyst beds, and wherein:
 a first catalyst bed comprising at least one catalyst bed comprising a catalyst having hydrogenation activity;   a second catalyst bed downstream the first catalyst bed, the second catalyst bed comprising at least one catalyst bed comprising a catalyst having hydrocracking activity.   
     
     
         33 . The system of  claim 32 , wherein the first catalyst bed of the hydrotreatment zone comprises a catalyst useful for at least one of:
 decarboxylation of carboxylic groups;   hydrodeoxygenation of unsaturated or saturated free fatty acids to produce C6-C24 paraffins;   saturation of mono-, di- and tri-olefins contained in the alkyl backbone of the free fatty acids;   hydrodenitrogenation of trace organic nitrogen compounds; and   catalyst tolerance for water coming in with the hydrocarbonaceous feed.   
     
     
         34 . The system of  claim 28 , further comprising one or more fluid conduits for co-processing a non-renewable hydrocarbon feedstock with the triacylglycerides-containing oils in at least one of the hydrothermolysis reaction zone and the hydrotreatment zone. 
     
     
         35 . The system of  claim 28 , wherein the at least one hydrothermolysis reaction zone comprises at least two beds comprised of one or more of aluminas, ceramics, foams, wires, meshes, microchannels, rods, and tubes having little or no chemical conversion activity for pyrolysis, thermolysis, hydrothermolysis or hydrotreatment reactions. 
     
     
         36 . The system of  claim 25 , further comprising one or more fluid conduits for feeding at least one of hydrogen and water intermediate the beds of the hydrothermolysis reaction zone. 
     
     
         37 . The system of  claim 28 , wherein a cumulative weight hourly space velocity defined as kilograms triacylglycerides-containing oils fed per hour per kilogram total active hydrotreatment catalyst inventory is at least 0.5:1. 
     
     
         38 . A process for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the process comprising:
 injecting a superheated mixed water stream comprising water and hydrogen into a co-current adiabatic reaction system;   co-currently, injecting a triacylglyceride-containing oil into the co-current adiabatic reaction system; and   reacting the mixed water stream and the triacylglyceride-containing oil in a plurality of adiabatic reaction zones under reaction conditions sufficient to convert the triacylglycerides via hydrothermolysis and hydrotreatment to produce a hydrotreated effluent comprising one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, and aromatics.   
     
     
         39 . The process of  claim 38 , wherein the plurality of adiabatic reaction zones includes a plurality of hydrothermolysis reaction zones and a plurality of hydrotreatment reaction zones. 
     
     
         40 . The process of  claim 38 , further comprising injecting at least one of hydrogen and water stream between the plurality of adiabatic reaction zones. 
     
     
         41 . The process of  claim 38 , further comprising pre-heating the triacylglyceride-containing oil via indirect heat exchange with the hydrotreated effluent. 
     
     
         42 . A process for converting triacylglycerides-containing oils into crude oil precursors and/or distillate hydrocarbon fuels, the process comprising:
 mixing hydrogen with water to form a superheated mixed water stream;   injecting a first portion of the mixed water stream into a co-current reactor system including a hydrothermolysis reaction zone, comprising at least a first hydrothermolysis reaction zone and a second hydrothermolysis reaction zone, and a hydrotreatment reaction zone, comprising at least a first hydrotreatement reaction zone and a second hydrotreatment reaction zone;   injecting a triacylglyceride-containing oil into the co-current reaction system;   reacting the first portion of the mixed water stream and the triacylglyceride-containing oil in the first hydrothermolysis reaction zone under reaction conditions sufficient to convert at least a portion of the triacylglycerides via hydrothermolysis to produce a first intermediate product comprising one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, aromatics, and unreacted triacylglyceride-containing oil;   mixing a second portion of the mixed water stream and the first intermediate product intermediate the first hydrothermolysis reaction zone and the second hydrothermolysis reaction zone;   reacting the second portion of the mixed water stream and the first intermediate product in the second hydrothermolysis reaction zone under reaction conditions sufficient to convert at least a portion of the first intermediate product via hydrothermolysis to produce a hydrothermolysis product comprising one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, and aromatics;   mixing the hydrothermolysis product from the second hydrothermolysis reaction zone, with a first portion of an unheated hydrogen stream intermediate the second hydrothermolysis reaction zone and the first hydrotreatment reaction zone;   hydrotreating a portion of the hydrothermolysis product in the first hydrotreatment reaction zone to form a partially hydrotreated product;   mixing the partially hydrotreated product with a second portion of the unheated hydrogen stream intermediate the first and second hydrotreatment reaction zones;   hydrotreating the partially hydrotreated product in the second hydrotreatment reaction zone to form a hydrotreated product;   recovering a hydrotreated effluent from the co-current reactor system.   
     
     
         43 . The system of  claim 28 , further comprising a heat exchange apparatus for exchanging heat between the hydrotreated effluent and the triacylglycerides-containing oils. 
     
     
         44 . The system of  claim 28 , further comprising a heat exchange apparatus for exchanging heat between the hydrothermolysis effluent and the hydrotreated effluent. 
     
     
         45 . The system of  claim 28 , further comprising a heat exchange apparatus for exchanging heat between the hydrothermolysis effluent and the triacylglycerides-containing oils.