Method for converting a hydrocarbonaceous material to a fluid hydrocarbon product comprising p-xylene

Abstract

The invention relates to a method for producing a fluid hydrocarbon product, and more specifically, to a method for producing a fluid hydrocarbon product via catalytic pyrolysis. The reactants comprise hydrocarbonaceous materials (e.g., biomass). The catalyst comprises a zeolite catalyst treated with a silicone compound. The product comprises p-xylene.

1 . A method for producing a fluid hydrocarbon product comprising p-xylene from a hydrocarbonaceous material, comprising:
 feeding the hydrocarbonaceous material to a reactor;   pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce a pyrolysis product; and   catalytically reacting at least a portion of the pyrolysis product under reaction conditions in the presence of a zeolite catalyst to produce the fluid hydrocarbon product;   the zeolite catalyst comprising pores with pore mouth openings and catalytic sites on the external surface of the catalyst, and an effective amount of a treatment layer derived from a silicone compound to reduce the size of the pore mouth openings and to render at least some of the catalytic sites on the external surface of the catalyst inaccessible to the pyrolysis product.   
     
     
         2 . The method of  claim 1  wherein catalytic sites are positioned in the pores near the pore mouth openings, and the treatment layer renders at least some of the catalytic sites in the pores near the pore mouth openings inaccessible to the pyrolysis product. 
     
     
         3 . The method of  claim 1  or  claim 2  wherein the fluid hydrocarbon product comprises xylenes with a p-xylene selectivity in the xylenes of at least about 40%, or at least about 45%, or at least about 50%, or at least about 55%, or at least about 60%, or at least about 65%, or at least about 70%, or at least about 75%, or at least about 80%, or at least about 85%, or at least about 90%. 
     
     
         4 . The method of any of the preceding claims wherein at least about 15%, or at least about 25%, or at least about 35%, or at least about 45%, or at least about 55%, or at least about 65%, or at least about 75%, or at least about 85%, or at least about 90%, or at least about 95%, or at least about 98%, or at least about 99%, of the catalytic sites on the external surface of the catalyst are inaccessible to the pyrolysis product. 
     
     
         5 . The method of  claim 2  wherein at least about 20%, or at least about 25%, or at least about 30%, or at least about 33%, or at least about 35%, or at least about 40%, or at least about 45%, or at least about 49%, or at least about 50%, or at least about 55%, or at least about 60%, or at least about 65%, or at least about 70%, or at least about 75%, or at least about 80%, or at least about 85%, or at least about 90%, or at least about 95%, or at least about 99% of the catalytic sites in the pores near the pore mouth openings are inaccessible to the pyrolysis product. 
     
     
         6 . The method of any of the preceding claims, wherein the zeolite catalyst comprises silica and alumina, the silica to alumina molar ratio being in the range from about 10:1 to about 50:1, or in the range from about 10:1 to about 40:1, or in the range from about 10:1 to about 20:1, or about 15:1. 
     
     
         7 . The method of  claim 6 , wherein the zeolite catalyst further comprises nickel, platinum, vanadium, palladium, manganese, cobalt, zinc, copper, chromium, gallium, an oxide of one or more thereof, or a mixture of two or more thereof. 
     
     
         8 . The method of any of the preceding claims wherein the silicone compound comprises at least one group represented by the formula 
       
         
           
           
               
               
           
         
       
     
     
         9 . The method of any of the preceding claims wherein the silicone compound is represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  independently comprise hydrogen, halogen, hydroxyl, alkyl, alkoxyl, halogenated alkyl, aryl, halogenated aryl, aralkyl, halogenated aralkyl, alkaryl or halogenated alkaryl; and n is a number that is at least 2. 
     
     
         10 . The method of  claim 9  wherein R 1  and/or R 2  comprise methyl, ethyl, or phenyl. 
     
     
         11 . The method of  claim 9  or  claim 10  wherein n is a number in the range from about 3 to about 1000. 
     
     
         12 . The method of any of the preceding claims wherein the silicone compound has a number average molecular weight in the range from about 80 to about 20,000, or from about 150 to 10,000. 
     
     
         13 . The method of any of the preceding claims wherein the silicone compound comprises dimethylsilicone, diethylsilicone, phenylmethylsilicone, methylhydrogensilicone, ethylhydrogen silicone, phenylhydrogen silicone, methylethyl silicone, phenylethyl silicone, diphenyl silicone, methyltrifluoropropyl silicone, ethyltrifluoropropyl silicone, polydimethyl silicone, tetrachloro-phenylmethyl silicone, tetrachlorophenylethyl silicone, tetrachlorophenylhydrogen silicone, tetrachlorophenylphenyl silicone, methylvinyl silicone, hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaphenyl cyclotetrasiloxane, or a mixture of two or more thereof. 
     
     
         14 . The method of any of  claims 1  to  8  wherein the silicone compound comprises a tetraorthosilicate. 
     
     
         15 . The method of  claim 14  wherein the silicone compound comprises tetramethyl-orthosilicate, tetraethylorthosilicate, or a mixture thereof. 
     
     
         16 . The method of any of the preceding claims wherein the reactor comprises a continuously stirred tank reactor, a batch reactor, a semi-batch reactor, a fixed bed reactor or a fluidized bed reactor. 
     
     
         17 . The method of any of  claims 1  to  15  wherein the reactor comprises a fluidized bed reactor. 
     
     
         18 . The method of any of the preceding claims wherein the hydrocarbonaceous material comprises a solid hydrocarbonaceous material, a semi-solid hydrocarbonaceous material, a liquid hydrocarbonaceous material, or a mixture of two or more thereof. 
     
     
         19 . The method of any of the preceding claims, wherein the hydrocarbonaceous material comprises biomass. 
     
     
         20 . The method of any of the preceding claims, wherein the hydrocarbonaceous material comprises plastic waste, recycled plastics, agricultural solid waste, municipal solid waste, food waste, animal waste, carbohydrates, lignocellulosic materials, xylitol, glucose, cellobiose, hemi-cellulose, lignin, sugar cane bagasse, glucose, wood, corn stover, or a mixture of two or more thereof. 
     
     
         21 . The method of any of the preceding claims wherein the hydrocarbonaceous material comprises pyrolysis oil derived from biomass, a carbohydrate derived from biomass, an alcohol derived from biomass, a biomass extract, a pretreated biomass, a digested biomass product, or a mixture of two or more thereof. 
     
     
         22 . The method of any of  claims 1  to  18  wherein the hydrocarbonaceous material comprises furan and/or 2-methylfuran. 
     
     
         23 . The method of any of  claims 1  to  18  wherein the hydrocarbonaceous material comprises pinewood. 
     
     
         24 . The method of any of the preceding claims, wherein the reactor is at a temperature in the range from about 400° C. to about 600° C., or from about 425° C. to about 500° C., or from about 440° C. to about 460° C. 
     
     
         25 . The method of any of the preceding claims, wherein the hydrocarbonaceous material is fed to the reactor at a mass normalized space velocity of up to about 3 hour −1 , or up to about 2 hour −1 , or up to about 1.5 hour −1 , or up to about 0.9 hour −1 , or in the range from about 0.01 hour −1  to about 3 hour −1 , or in the range from about 0.01 to about 2 hour −1 , or in the range from about 0.01 to about 1.5 hour −1 , or in the range from about 0.01 to about 0.9 hour −1 , or in the range from about 0.01 hour −1  to about 0.5 hour −1 , or in the range from about 0.1 hour −1  to about 0.9 hour −1 , or in the range from about 0.1 hour −1  to about 0.5 hour −1 . 
     
     
         26 . The method of any of the preceding claims wherein the fluid hydrocarbon product comprises an aromatic compound, the aromatic carbon molar yield at least about 22%. 
     
     
         27 . The method of any of  claims 1  to  26  wherein the fluid hydrocarbon product comprises an olefinic compound, the olefin carbon molar yield being at least about 3%, or at least about 6%, or at least about 9%, or at least about 12%. 
     
     
         28 . The method of any of the preceding claims, further comprising the step of recovering the fluid hydrocarbon product. 
     
     
         29 . The method of any of the preceding claims, wherein the fluid hydrocarbon product further comprises aromatic compounds and/or olefin compounds. 
     
     
         30 . The method of any of the preceding claims, wherein the fluid hydrocarbon product further comprises benzene, toluene, ethylbenzene, methylethylbenzene, trimethylbenzene, o-xylene, m-xylene, indanes naphthalene, methylnaphthelene, dimethylnaphthalene, ethylnaphthalene, hydrindene, methylhydrindene, dimethylhydrindene, or a mixture of two or more thereof. 
     
     
         31 . The method of any of the preceding claims wherein the mass yield of p-xylene in the fluid hydrocarbon product is at least about 1.5 wt %, or at least about 2 wt %, or at least about 2.5 wt %, or at least about 3 wt %. 
     
     
         32 . The method of any of the preceding claims wherein the reactor is operated at a pressure of at least about 100 kPa, or at least about 200 kPa, or at least about 300 kPa, or at least about 400 kPa. 
     
     
         33 . The method of any of  claims 1  to  31  wherein the reactor is operated at a pressure below about 600 kPa, or below about 400 kPa, or below about 200 kPa. 
     
     
         34 . The method of any of  claims 1  to  31  wherein the reactor is operated at a pressure in the range from about 100 to about 600 kPa, or in the range from about 100 to about 400 kPa, or in the range from about 100 to about 200 kPa. 
     
     
         35 . The method of any of the preceding claims, wherein during the catalytically reacting step a dehydration, decarbonylation, decarboxylation, isomerization, oligomerization and/or dehydrogenation reaction is conducted. 
     
     
         36 . The method of any of the preceding claims wherein the pyrolysis product is formed with less than about 30 wt %, or less than about 25 wt %, or less than about 20 wt %, or less than about 15 wt %, or less than about 10% of the pyrolysis product being coke. 
     
     
         37 . The method of any of the preceding claims, wherein the pyrolyzing step and the catalytically reacting steps are carried out in a single vessel. 
     
     
         38 . The method of any of  claims 1  to  36 , wherein the pyrolyzing step and the catalytically reacting steps are carried out in separate vessels. 
     
     
         39 . The method of any of the preceding claims wherein the residence time for the hydrocarbonaceous material in the reactor is at least about 1 second, at least about 2 seconds, at least about 5 seconds, at least about 7 seconds, at least about 10 seconds, at least about 15 seconds, at least about 20 seconds, at least about 25 seconds, at least about 30 seconds, at least about 60 seconds, at least about 120 seconds, at least about 240 seconds, or at least about 480 seconds. 
     
     
         40 . The method of any of the preceding claims wherein the contact time of the pyrolysis product with the catalyst is at least about 1 second, at least about 2 seconds, at least about 5 seconds, at least about 7 seconds, at least about 10 seconds, at least about 15 seconds, at least about 20 seconds, at least about 25 seconds, at least about 30 seconds, at least about 60 seconds, at least about 120 seconds, at least about 240 seconds, or at least about 480 seconds.