Process for the production of furfural

Abstract

Furfural is produced by contacting a feedstock solution containing C 5 sugar and/or C 6 sugar with a solid acid catalyst using reactive distillation. Both high yield and high conversion are obtained, without production of insoluble char in the reaction vessel. Degradation of furfural is minimized by its low residence time in contact with the solid acid catalyst. Higher catalyst lifetime can be achieved because the catalyst is continually washed with the refluxing aqueous solution and not sitting in high-boiling byproducts like humins, which are known to be deleterious to catalyst lifetime.

1 . A process comprising:
 (a) providing a reactive distillation column comprising a top, a bottom, a reaction zone in between the top and the bottom, and a solid acid catalyst disposed in the reaction zone;   (b) bringing a feedstock solution into contact with the solid acid catalyst in the presence of a water-miscible organic solvent for a residence time sufficient to produce a mixture of water and furfural, wherein the feedstock solution comprises C 5  sugar, C 6  sugar or a mixture thereof, and the reaction zone is at a temperature in the range of 90-250° C. and a pressure in the range of 0.1-3.87 MPa;   (c) removing the mixture of water and furfural from the top of the reactive distillation column; and   (d) collecting water, unreacted sugars and nonvolatile byproducts from the bottom of the reactive distillation column in a reboiler,   wherein the water-miscible organic solvent is polyethylene glycol, isosorbide dimethyl ether, isosorbide, propylene carbonate, polyethylene glycol dimethyl ether, adipic acid, diethylene glycol, 1,3-propane diol, glycerol, gamma-butyrolactone or gamma-valerolactone.   
     
     
         2 . The process according to  claim 1 , wherein the acid catalyst comprises a heterogeneous heteropolyacid, a salt of a heterogeneous heteropolyacid, a natural or synthetic clay mineral, a cation exchange resin, a metal oxide, a mixed metal oxide, a metal sulfide, a metal sulfate, a metal sulfonate, sulfated titania, sulfated zirconia, a metal nitrate, a metal phosphate, a metal phosphonate, a metal molybdate, a metal tungstate, a metal borate, or a combination of any of these. 
     
     
         3 . The process according to  claim 2 , wherein the acid catalyst comprises a cation exchange resin that is a sulfonic-acid-functionalized polymer. 
     
     
         4 . The process according to  claim 2 , wherein the acid catalyst comprises a clay mineral that is a zeolite. 
     
     
         5 . The process according to  claim 4 , wherein the acid catalyst is a medium or large pore, acidic, hydrophobic zeolite. 
     
     
         6 . The process according to  claim 5 , wherein the zeolite comprises ZSM-5, faujasite, beta zeolite, Y zeolite, mordenite, or a combination of any of these. 
     
     
         7 . The process according to  claim 1  further comprising:
 e. removing water and unreacted sugars from the water, unreacted sugars and nonvolatile byproducts of step (d); and 
 f. concentrating by evaporation at least a portion of the water and unreacted sugars and using it as feedstock solution in step (b). 
 
     
     
         8 . The process according to  claim 1  further comprising separating the furfural from the removed water and furfural of step (c). 
     
     
         9 . The process according to  claim 1  wherein the combined concentration of C 5  sugar and/or C 6  sugar in the feedstock solution is in the range of 1-99 weight percent based on the total weight of the feedstock solution. 
     
     
         10 . The process according to  claim 9  wherein the combined concentration of C 5  sugar and/or C 6  sugar in the feedstock solution is in the range of 5-35 weight percent based on the total weight of the feedstock solution. 
     
     
         11 . The process according to  claim 1  wherein the feedstock solution comprises xylose, glucose, or a mixture thereof. 
     
     
         12 . (canceled) 
     
     
         13 . The process according to  claim 1 , further comprising a steam-stripping step, comprising feeding water or steam to the reaction zone from the bottom of the reactive distillation column. 
     
     
         14 . The process of  claim 1  further comprising the steps of:
 h) diluting at least a portion of the contents of the reboiler with water or with the feedstock solution, thereby precipitating water-insoluble byproducts; 
 i) removing the byproducts precipitated in step h); and 
 j) feeding the precipitate-free solution remaining after step i) back to the reaction zone. 
 
     
     
         15 . A process comprising the steps of:
 (a) providing a reactor comprising a reactive distillation column comprising an upper, rectifying section; a lower, stripping section; and a reboiler, wherein the stripping section or the reboiler is a reaction zone containing a solid acid catalyst,   (b) continuously feeding a feedstock solution comprising C 5  sugar, C 6  sugar or a mixture thereof to the column at a location between the rectifying section and the stripping section, allowing the solution to flow into the reaction zone into contact with the solid acid catalyst in the presence of a water-miscible organic solvent, thereby forming a reaction mixture, wherein   (i) the water-miscible organic solvent forms a monophasic solution with the water in the reaction zone and the temperature of the reaction mixture is between about 90° C. and about 250° C.   (ii) the reaction mixture is held at a pressure between atmospheric pressure and 3.87 MPa, and   (iii) the sugar solution and catalyst are in contact for a time sufficient to produce water and furfural   (c) drawing off a mixture of furfural and water at the top of the column   (d) collecting water, unreacted sugars, and nonvolatile byproducts dissolved in the water-miscible organic solvent in the reboiler;   (e) removing nonvolatile byproducts from the reboiler; and   (f) removing the water and unreacted sugars from the reboiler for further use or disposal,   wherein the water-miscible organic solvent is polyethylene glycol, isosorbide dimethyl ether, isosorbide, propylene carbonate, polyethylene glycol dimethyl ether, adipic acid, diethylene glycol, 1,3-propane diol, glycerol, gamma-butyrolactone or gamma-valerolactone.