Increased liquid sensitivity during Fischer-Tropsch synthesis by olefin incorporation

Abstract

An integrated process for producing liquid fuels from syngas via a two-stage Fischer-Tropsch reaction is disclosed. The first stage of the Fischer-Tropsch chemistry is performed using conditions in which chain growth probabilities are relatively low to moderate, and the product of the reaction includes a relatively high proportion of low molecular (C 2-8 ) weight olefins and a relatively low proportion of high molecular weight (C 30 +) waxes. The product from the first stage is fed into the second stage where the chain growth probabilities are relatively high. The wax and other paraffins produced in the first reaction are largely inert under these conditions. The light olefins compete with heavier olefins for chain initiation, and fewer chains will be initiated at C 20 +. With most chains initiated at C 2-8 , moderate chain growth probability will produce a relatively larger fraction in the C 5-12 range. In this manner, wax yield is minimized.

What is claimed is:  
     
         1 . An integrated process for preparing liquid fuels, the process comprising: 
 (a) subjecting syngas with a hydrogen/carbon monoxide ratio of between about 0.5 and 1.0 to Fischer-Tropsch reaction conditions where the catalyst used for the Fischer-Tropsch reaction is one which provides low to moderate chain growth probabilities;    (b) optionally removing water and/or C 5 + hydrocarbons from the product stream;    (c) subjecting the product from step (a) or (b) to Fischer-Tropsch reaction conditions where the catalyst used for the Fischer-Tropsch reaction is one which provides high chain growth probabilities, where the hydrogen/carbon monoxide ratio is between about 1.0 and 2.0; and    (d) isolating the product of the reaction.    
     
     
         2 . The process of  claim 1 , wherein the catalyst with low to moderate chain growth probabilities is an iron-containing catalyst.  
     
     
         3 . The process of  claim 1 , wherein the catalyst with high chain growth probabilities is a cobalt-containing catalyst.  
     
     
         4 . The process of  claim 1 , wherein step a) is conducted at a temperature between about 270° C. and 280° C. and at a pressure of between about 1 and 20 ATM.  
     
     
         5 . The process of  claim 1 , wherein step (a) is conducted in a slurry reactor or a fluidized bed reactor.  
     
     
         6 . The process of  claim 1 , wherein the product stream is cooled to less than 100° C. and at least a portion of the water produced during the reaction is removed.  
     
     
         7 . The process of  claim 1 , wherein a C5+ fraction is isolated after step (a) and before step (c).  
     
     
         8 . The process of  claim 1 , wherein at least a portion of the olefins prepared in step (a) are isomerized before being subjected to the Fischer-Tropsch reaction conditions in step (c).  
     
     
         9 . The process of  claim 1 , wherein step (c) is conducted at a temperature between about 200° C. and 250° C. and at a pressure between about 1 and 30 ATM.  
     
     
         10 . The process of  claim 1 , wherein the product of step (a) in the C 2-4  range includes about 75% olefins by weight.  
     
     
         11 . The process of  claim 1 , wherein the Fischer-Tropsch reactions in steps (a) and/or (c) are run in a slurry reactor.  
     
     
         12 . The process of  claim 1 , wherein olefin hydrogenation in steps (a) and/or (c) is minimized by adding a manganese-containing compound to the reaction.  
     
     
         13 . The process of  claim 1 , wherein the hydrogen/carbon monoxide ratio in step (c) is between about 1.0 and 1.5.  
     
     
         14 . The process of  claim 1 , wherein unreacted syngas is recycled.  
     
     
         15 . The process of  claim 14 , wherein a at least a portion of the carbon dioxide is removed from the syngas before it is recycled.  
     
     
         16 . A hydrocarbon product obtained by the steps of: 
 (a) subjecting syngas with a hydrogen/carbon monoxide ratio of between about 0.5 and 1.0 to Fischer-Tropsch reaction conditions where the catalyst used for the Fischer-Tropsch reaction is one which provides low to moderate chain growth probabilities;    (b) optionally removing water and/or C 5 + products from the product stream;    (c) subjecting the product from step (a) or (b) to Fischer-Tropsch reaction conditions where the catalyst used for the Fischer-Tropsch reaction is one which provides high chain growth probabilities, where the hydrogen/carbon monoxide ratio is between about 1.0 and 2.0; and    (d) isolating the product of the reaction.