Fluidized catalytic cracking of retorted kerogen and other oils

Abstract

The disclosed technology is a fundamental improvement to existing art for producing valuable products from kerogen ore (oil shale). The disclosure teaches the techniques and benefits of integrating a pyrolysis process with a fluidized catalytic cracking (FCC) unit. Preferred embodiments are based on the use of pyrolysis products from a pyrolysis reactor as feedstock to an FCC unit; within the FCC unit a mixture of high-purity oxygen and carbon dioxide replaces air for coke combustion. To continuously regenerate the FCC catalyst, a coke-oxidation gas contains from 9 mol % to 35 mol % oxygen and from 50 mol % to 90 mol % carbon dioxide. In various embodiments, carbon dioxide is used in place of nitrogen, or used in place of steam, or both of these replacements. Several process configurations are shown, utilizing different recycle schemes and different distillation strategies, among other options. Many valuable co-products are described, including fuels and chemicals.

What is claimed is: 
     
         1 . A process of converting kerogen ore to multiple products, said process comprising:
 (a) providing a starting kerogen ore;   (b) retorting said starting kerogen ore to obtain a kerogenate and a spent ore;   (c) distilling said kerogenate in a retort main column, to generate one or more kerogenate products as well as a retort column bottoms stream;   (d) conveying said retort column bottoms stream to a vacuum column, to generate a sour gas, a light vacuum gas oil, a heavy vacuum gas oil, and a residue stream;   (e) conveying said light vacuum gas oil and said heavy vacuum gas oil to a riser reactor, wherein said riser reactor is configured to receive a catalyst to catalytically crack said light vacuum gas oil and said heavy vacuum gas oil, wherein said catalyst is fluidized by a lift gas, and wherein said catalyst becomes a coked catalyst within said riser reactor;   (f) transferring said coked catalyst to a regenerator, configured to oxidize said coked catalyst with a coke-oxidation gas, to form a regenerated catalyst, wherein said coke-oxidation gas contains from about 9 mol % to about 35 mol % oxygen and from about 50 mol % to about 90 mol % carbon dioxide;   (g) transferring said regenerated catalyst from said regenerator to said riser reactor; and   (h) fractionating reaction products obtained from said riser reactor in a FCC main column, to generate light ends, heavy cracked naphtha, light cycle oil, heavy cycle oil, and a heavies stream,   wherein at least a portion of said carbon dioxide, contained within said coke-oxidation gas, is obtained from a recycle gas, and wherein said recycle gas is derived from recovering a portion of CO 2  produced during coke oxidation in said regenerator.   
     
     
         2 . The process of  claim 1 , wherein said vacuum column utilizes a motive gas comprising steam and at least 40 mol % carbon dioxide. 
     
     
         3 . The process of  claim 1 , wherein said vacuum column utilizes a motive gas comprising at least 80 mol % carbon dioxide. 
     
     
         4 . The process of  claim 1 , wherein said lift gas contains from about 80 mol % to about 100 mol % carbon dioxide. 
     
     
         5 . The process of  claim 4 , wherein said lift gas contains from about 85 mol % to about 95 mol % carbon dioxide. 
     
     
         6 . The process of  claim 1 , wherein said coke-oxidation gas contains from about 55 mol % to about 85 mol % carbon dioxide. 
     
     
         7 . The process of  claim 6 , wherein said coke-oxidation gas contains from about 60 mol % to about 80 mol % carbon dioxide. 
     
     
         8 . The process of  claim 1 , wherein said heavy cycle oil from step (h) is recycled to said riser reactor. 
     
     
         9 . The process of  claim 1 , wherein said heavies stream from step (h) is conveyed to said vacuum column. 
     
     
         10 . The process of  claim 1 , wherein said process is continuous or semi-continuous. 
     
     
         11 . A process of converting kerogen ore to multiple products, said process comprising:
 (a) providing a starting kerogen ore;   (b) retorting said starting kerogen ore to obtain a kerogenate and a spent ore;   (c) optionally, pre-flashing said kerogenate using a pre-flash unit, to remove a light fraction;   (d) distilling said kerogenate in a main column, to generate one or more kerogenate products as well as a main column bottoms stream;   (d) conveying said main column bottoms stream to a vacuum column, to generate a sour gas, a light vacuum gas oil, a heavy vacuum gas oil, and a residue stream;   (e) conveying said light vacuum gas oil and said heavy vacuum gas oil to a riser reactor, wherein said riser reactor is configured to receive a catalyst to catalytically crack said light vacuum gas oil and said heavy vacuum gas oil, wherein said catalyst is fluidized by a lift gas, and wherein said catalyst becomes a coked catalyst within said riser reactor;   (f) transferring said coked catalyst to a regenerator, configured to oxidize said coked catalyst with a coke-oxidation gas, to form a regenerated catalyst, wherein said coke-oxidation gas contains from about 9 mol % to about 35 mol % oxygen and from about 50 mol % to about 90 mol % carbon dioxide;   (g) transferring said regenerated catalyst from said regenerator to said riser reactor; and   (h) fractionating reaction products obtained from said riser reactor in said main column, to generate said kerogenate products,   wherein at least a portion of said carbon dioxide, contained within said coke-oxidation gas, is obtained from a recycle gas, and wherein said recycle gas is derived from recovering a portion of CO 2  produced during coke oxidation in said regenerator.   
     
     
         12 . The process of  claim 11 , wherein said vacuum column utilizes a motive gas comprising steam and at least 40 mol % carbon dioxide. 
     
     
         13 . The process of  claim 11 , wherein said vacuum column utilizes a motive gas comprising at least 80 mol % carbon dioxide. 
     
     
         14 . The process of  claim 11 , wherein said lift gas contains from about 80 mol % to about 100 mol % carbon dioxide. 
     
     
         15 . The process of  claim 14 , wherein said lift gas contains from about 85 mol % to about 95 mol % carbon dioxide. 
     
     
         16 . The process of  claim 11 , wherein said coke-oxidation gas contains from about 55 mol % to about 85 mol % carbon dioxide. 
     
     
         17 . The process of  claim 16 , wherein said coke-oxidation gas contains from about 60 mol % to about 80 mol % carbon dioxide. 
     
     
         18 . The process of  claim 11 , wherein said pre-flash unit is present, and wherein step (h) includes (1) conveying said reaction products through said pre-flash unit to generate an overhead vapor and a liquid bottoms, and (2) feeding said liquid bottoms to said main column to generate said kerogenate products. 
     
     
         19 . The process of  claim 11 , wherein said kerogenate products produced in step (h) comprise light ends, heavy cracked naphtha, light cycle oil, and/or heavy cycle oil. 
     
     
         20 . The process of  claim 11 , wherein said process is continuous or semi-continuous.