Process for Making Isooctenes from Aqueous Isobutanol

Abstract

The present invention relates to a catalytic process for making isooctenes using a reactant comprising isobutanol and water. The isooctenes so produced are useful for the production of fuel additives.

1 . A process for making at least one isooctene comprising contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a reaction product comprising said at least one isooctene, and recovering said at least one isooctene from said reaction product to obtain at least one recovered isooctene. 
     
     
         2 . The process of  claim 1 , wherein the reactant is obtained from a fermentation broth. 
     
     
         3 . The process of  claim 2 , wherein the reactant is obtained by subjecting the fermentation broth to a refining process that comprises at least one step selected from the group consisting of pervaporation, gas-stripping, adsorption, liquid-liquid extraction, and distillation. 
     
     
         4 . The process of  claim 3 , wherein said distillation produces a vapor phase having a water concentration of at least about 33% (by weight relative to the weight of water plus isobutanol), and wherein the vapor phase is used as the reactant. 
     
     
         5 . The process of  claim 1  or  claim 4 , wherein the at least one acid catalyst is a heterogeneous catalyst, and the temperature and the pressure are chosen so as to maintain the reactant and the reaction product in the vapor phase. 
     
     
         6 . The process of  claim 3 , wherein said distillation produces a vapor phase, wherein the vapor phase is condensed to produce an isobutanol-rich liquid phase having a water concentration of at least about 16% (by weight relative to the weight of the water plus isobutanol) and a water-rich liquid phase, wherein the isobutanol-rich liquid phase is separated from the water-rich phase, and wherein the isobutanol-rich liquid phase is used as the reactant. 
     
     
         7 . A process for making a reaction product comprising at least one isooctane, contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising at least one isooctene, recovering said at least one isooctene from said first reaction product to obtain at least one recovered isooctene, and
 (a) contacting the at least one recovered isooctene with hydrogen in the presence of at least one hydrogenation catalyst to produce said reaction product comprising at least one isooctane; and   (b) optionally recovering at least one isooctane from the reaction product to obtain at least one recovered isooctane.   
     
     
         8 . The process of  claim 7 , wherein the reactant is obtained from a fermentation broth. 
     
     
         9 . A process for making a reaction product comprising at least one isooctanol, comprising contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising at least one isooctene, recovering said at least one isooctene from said first reaction product to obtain at least one recovered isooctene, and
 (a) contacting the at least one recovered isooctene with water and at least one acid catalyst to produce said reaction product comprising at least one isooctanol; and   (b) optionally recovering at least one isooctanol from the reaction product to obtain at least one recovered isooctanol.   
     
     
         10 . The process of  claim 9 , wherein the reactant is obtained from a fermentation broth. 
     
     
         11 . A process for making a reaction product comprising at least one isooctyl alkyl ether, comprising contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising at least one isooctene, recovering said at least one isooctene from said first reaction product to obtain at least one recovered isooctene, and
 (a) contacting the at least one recovered isooctene with at least one straight-chain or branched C 1  to C 5  alcohol and at least one acid catalyst to produce said reaction product comprising at least one isooctyl alkyl ether; and   (b) optionally recovering at least one isooctyl alkyl ether from the reaction product to obtain at least one recovered isooctyl alkyl ether.   
     
     
         12 . The process of  claim 11 , wherein the reactant is obtained from a fermentation broth. 
     
     
         13 . A process for making at least one isooctane comprising:
 (a) contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising at least one isooctene;   (b) contacting said first reaction product with hydrogen in the presence of at least one hydrogenation catalyst to produce a second reaction product comprising at least one isooctane; and   (c) recovering the at least one isooctane from the second reaction product to produce a recovered isooctane.   
     
     
         14 . The process of  claim 13 , wherein the reactant is obtained from a fermentation broth. 
     
     
         15 . A process for making at least one isooctanol comprising:
 (a) contacting a reactant comprising isobutanol and at least about 5% water (by weight relative to the weight of the water plus isobutanol) with at least one acid catalyst at a temperature of about 50 degrees C. to about 450 degrees C. and a pressure from about 0.1 MPa to about 20.7 MPa to produce a first reaction product comprising at least one isooctene;   (c) contacting said first reaction product with water and at least one acid catalyst to produce a second reaction product comprising at least one isooctanol; and   (d) optionally recovering the at least one isooctanol from the second reaction product to obtain at least one recovered isooctanol.   
     
     
         16 . The process of  claim 15 , wherein the reactant is obtained from a fermentation broth.