Synthetic diesel fuel compositions, and systems and methods of making the same

Abstract

Diesel fuel compositions, include both fully formulated fuel compositions and paraffinic compositions, are disclosed made from a carbon source gas, such as carbon dioxide, and a reduction gas, such as hydrogen gas. Also disclosed are methods and systems of making diesel fuel compositions from carbon dioxide.

1 . A CO 2 -derived, synthetic diesel fuel composition comprising:
 0% to about 30 wt % monocyclic aromatics;   0% to about 1 wt % polycyclic aromatics;   greater than 0% to about 35 wt % cyclo-paraffins;   about 5 wt % to about 40 wt % n-paraffins;   about 15 wt % to about 80 wt % iso-paraffins; and   0 wt % to about 15 wt % oxygenates; and   wherein the composition comprises over about 80 wt % C 9 -C 20  hydrocarbons; and   wherein the composition comprises less than about 5 ppm total sulfur.   
     
     
         2 .- 8 . (canceled) 
     
     
         9 . A CO 2 -derived, synthetic paraffinic diesel fuel composition comprising:
 0% to about 5 wt % monocyclic aromatics;   0% to about 1 wt % polycyclic aromatics   0% to about 5 wt % cyclo-paraffins;   greater than about 95 wt % of n-paraffins and iso-paraffins; and   0 wt % to about 15 wt % oxygenates; and   wherein the composition comprises over about 80 wt % C 9 -C 20  hydrocarbons; and   wherein the composition comprises less than about 5 ppm total sulfur.   
     
     
         10 .- 39 . (canceled) 
     
     
         40 . A method of making a diesel fuel composition comprising:
 i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford: a light hydrocarbon product mixture comprising one or more C 2-4  paraffins and/or olefins; a medium hydrocarbon product mixture comprising one or more C 5-8  paraffins and/or olefins; and a target hydrocarbon product mixture comprising one or more C 9-20  paraffins and/or olefins;   ii) contacting a first portion of the light hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas, with an aromatic catalyst to afford a light aromatic product mixture comprising one or more C 6-8  aromatics;   iii) contacting a second portion of the light hydrocarbon product mixture and the light aromatic product mixture with an alkylation catalyst to afford a target alkyl arene product mixture comprising one or more C 9+  aromatics;   iv) contacting the medium hydrocarbon product mixture with an oligomerization catalyst to afford a target oligomerized product mixture comprising one or more C 9+  olefins and/or paraffins;   v) hydrogenating the target hydrocarbon product mixture, the target alkyl arene product mixture, and the target oligomerized product mixture to yield a target paraffin product mixture, a target cycloparaffin product mixture, and a target aromatic product mixture; and   vi) blending the target paraffin product mixture, the target cycloparaffin product mixture, and the target aromatic product mixture to afford the diesel fuel.   
     
     
         41 . The method of  claim 40 , further comprising removing oxygenates from the second portion of the light hydrocarbon product mixture before step iii. 
     
     
         42 . The method of  claim 40 , further comprising removing oxygenates from the medium hydrocarbon product mixture before step iv. 
     
     
         43 . The method of  claim 40 , wherein the step of hydrogenating comprises:
 a) selectively hydrogenating a first portion of the target alkyl arene product mixture to afford the target aromatic product mixture; and   b) fully hydrogenating the target hydrocarbon product mixture, a second portion of the target alkyl arene product mixture, and the target oligomerized product mixture to afford the target paraffin product mixture, and the target cycloparaffin product mixture.   
     
     
         44 . The method of  claim 42 , further comprising combining a third portion of the light hydrocarbon product mixture with the medium hydrocarbon product mixture before the step of contacting with the oligomerization catalyst. 
     
     
         45 . The method of  claim 42 , further comprising: removing oxygenates from the light hydrocarbon product mixture and the medium hydrocarbon product mixture. 
     
     
         46 . The method of  claim 40 , further comprising distilling the target paraffin product mixture, the target cycloparaffin product mixture, and/or the target aromatic product mixture before blending. 
     
     
         47 . The method of  claim 40 , further comprises separating the light hydrocarbon product mixture into a first portion of the light hydrocarbon product and a second portion of the light hydrocarbon product. 
     
     
         48 . The method of  claim 40 , wherein contacting the first portion of the light hydrocarbon product mixture, with the aromatic catalyst affords the light aromatic product mixture comprising one or more C 6-8  aromatics, and another target aromatic product mixture comprising one or more C 9-14  aromatics. 
     
     
         49 . A method of making a diesel fuel composition comprising:
 (i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford a hydrocarbon product mixture comprising olefins and paraffins;   (ii) hydrogenating the hydrocarbon product mixture to yield a target paraffin product mixture;   (iii) contacting a second reduction gas and a second carbon source gas with an aromatic catalyst to afford an aromatic product mixture comprising one or more aromatics and/or cyclic paraffins;   (iv) hydrogenating a first portion of the aromatic product mixture to yield a target cycloparaffin product mixture;   (v) hydrogenating a second portion of the aromatic product mixture to yield a target aromatic product mixture; and   (vi) blending the target paraffin product mixture, the target cycloparaffin product mixture and the target aromatic product mixture to afford diesel fuel.   
     
     
         50 . The method of  claim 49 , further comprising contacting the target paraffin product mixture with an isomerization catalyst before blending. 
     
     
         51 . The method of  claim 49 , wherein the step of hydrogenating the second portion of the aromatic product mixture to yield the target aromatic product mixture occurs at a lower temperature than the steps of hydrogenating the first portion of the aromatic product mixture and hydrogenating the hydrocarbon product mixture. 
     
     
         52 . The method of  claim 49 , wherein:
 a. the step of hydrogenating the second portion of the aromatic product mixture to yield the target aromatic product mixture occurs at a first hydrogenation temperature between about 80° C. and about 150° C. and a first hydrogenation pressure of about 100 to about 400 psig; and   b. the step of hydrogenating the first portion of the aromatic product mixture to yield the target cycloparaffin product mixture occurs at a second hydrogenation temperature between about 180° C. and about 250° C. and a second hydrogenation pressure of about 200 to about 800 psig.   
     
     
         53 . The method of  claim 51 , wherein the step of hydrogenating the hydrocarbon product mixture occurs at a third hydrogenation temperature between about 180° C. and about 250° C. and a third hydrogenation pressure of about 300 to about 800 psig. 
     
     
         54 . The method of  claim 49 , further comprising distilling one or more of the target paraffin product mixture, the target cycloparaffin product mixture and the target aromatic product mixture before blending. 
     
     
         55 . A method of making synthetic paraffinic diesel fuel comprising:
 (i) contacting a first reduction gas and a first carbon source gas with a reduction catalyst to afford a light hydrocarbon product mixture comprising one or more C 2-4  paraffins and/or olefins; a medium hydrocarbon product mixture comprising one or more C 5-8  paraffins and/or olefins, and a target hydrocarbon product mixture comprising one or more C 9+  paraffins and/or olefins;   (ii) removing oxygenates from the light hydrocarbon product mixture and the medium hydrocarbon product mixture to afford a converted light hydrocarbon product mixture and a converted medium hydrocarbon product mixture;   (iii) contacting the converted light hydrocarbon product mixture and the converted medium hydrocarbon product mixture, optionally a second reduction gas, and optionally a second carbon source gas, with an oligomerization catalyst to afford a target oligomerization product mixture;   (iv) hydrogenating the target oligomerization product mixture and the target hydrocarbon product mixture to yield a target paraffin product mixture and a target cycloparaffin product mixture; and   (v) blending the target paraffin product mixture and the target cycloparaffin product mixture to make paraffinic diesel fuel.   
     
     
         56 . The method of  claim 40 , wherein the first reduction gas, the second reduction gas, when present, and the third reduction gas, when present, are independently selected from H 2 , a hydrocarbon, synthesis gas (CO/H 2 ), or from a gas that is, or is derived from, flare gas, waste gas, or natural gas. 
     
     
         57 . The method of  claim 40 , where the first reduction gas, the second reduction gas, when present, and the third reduction gas, when present, comprise H 2 . 
     
     
         58 . The method of  claim 40 , wherein the first carbon source gas and/or the second carbon source gas comprise CO 2 . 
     
     
         59 . The method of  claim 40 , wherein the first carbon source gas and/or the second carbon source gas comprise CO. 
     
     
         60 . (canceled) 
     
     
         61 . (canceled) 
     
     
         62 . The method of  claim 40 , wherein the reduction catalyst comprises:
 iron;   a first element selected from copper, zinc, cobalt, or a combination thereof; and   optionally one or more second elements selected from Group IA and IIA metals.   
     
     
         63 . The method of  claim 62 , wherein the first element is copper, zinc, or a combination thereof. 
     
     
         64 . The method of  claim 62 , wherein the first element is zinc; and wherein the catalyst does not contain copper or cobalt. 
     
     
         65 .- 72 . (canceled) 
     
     
         73 . The method of  claim 40 , wherein the aromatic catalyst comprises a zeolite. 
     
     
         74 .- 83 . (canceled) 
     
     
         84 . The method of  claim 40 , wherein the oligomerization catalyst is a zeolite or molecular sieve. 
     
     
         85 . (canceled) 
     
     
         86 . (canceled) 
     
     
         87 . (canceled) 
     
     
         88 . The method of  claim 40 , wherein the alkylation catalyst is an acid, such as HF, SPA (solid phosphoric acid), a Friedel-Crafts alkylation catalyst (e.g., HF/AlCl 3 ), tungsten, platinum, or a zeolite. 
     
     
         89 . (canceled) 
     
     
         90 . (canceled) 
     
     
         91 . A system for the production of diesel fuel comprising:
 a first reduction gas feed;   a first carbon source gas feed;   a reduction reactor comprising a reduction catalyst, said reduction reactor having a first reduction gas feed inlet, a first carbon source feed inlet, and a mixed hydrocarbon outlet; wherein the first reduction gas feed inlet is coupled to the first reduction gas feed, and the first carbon source gas feed inlet is coupled to the first carbon source gas feed;   a first separator having a mixed hydrocarbon inlet, a light hydrocarbon outlet, a medium hydrocarbon outlet, and a target hydrocarbon outlet; and   an oligomerization reactor comprising an oligomerization catalyst, said oligomerization reactor having a medium hydrocarbon inlet and a target oligomerization product outlet, wherein the medium hydrocarbon inlet is coupled to the medium hydrocarbon outlet on the first separator;   a first hydrogenator having a target oligomerization product inlet and a target paraffin product outlet, wherein the target oligomerization product inlet is coupled to the target oligomerization product outlet; and   a blender.   
     
     
         92 .- 102 . (canceled)