Intensified reactor and process heat integration for conversion of alcohol to fuels

Abstract

A method including: introducing a feed comprising an alcohol and an activator into a reactor comprising a solid acid catalyst; contacting the alcohol and the activator in the presence of the solid acid catalyst under conditions effective to convert at least a portion of the alcohol and the activator to produce a product stream comprising C8-C16 olefins and water; thermally contacting at least a portion of the C8-C16 olefins and/or water with a working fluid to heat the working fluid to form a heated working fluid; and introducing at least a portion of the C8-C16 olefins and water from the product stream into a distillation column and forming a bottoms stream comprising a majority of the C8-C16 olefins from the product stream, wherein a reboiler thermally coupled to the distillation column is at least partially heated by the heated working fluid.

1 . A method comprising:
 introducing a feed comprising an alcohol and an activator into a reactor comprising a solid acid catalyst;   contacting the alcohol and the activator in the presence of the solid acid catalyst under conditions effective to convert at least a portion of the alcohol and the activator to produce a product stream comprising C 8 -C 16  olefins and water;   thermally contacting at least a portion of the C 8 -C 16  olefins and/or water with a working fluid to heat the working fluid to form a heated working fluid; and   introducing at least a portion of the C 8 -C 16  olefins and water from the product stream into a distillation column and forming a bottoms stream comprising a majority of the C 8 -C 16  olefins from the product stream, wherein a reboiler thermally coupled to the distillation column is at least partially heated by the heated working fluid.   
     
     
         2 . The method of  claim 1  wherein the alcohol comprises an alcohol with a carbon number in a range from C 1  to C 7 . 
     
     
         3 . The method of  claim 1  wherein the alcohol comprises ethanol. 
     
     
         4 . The method of  claim 1  where in the activator comprises a C 3 -C 16  alcohol and/or C 3 -C 16  olefin. 
     
     
         5 . The method of  claim 1  wherein the activator comprises at least one activator selected from the group consisting of propylene, isopropyl alcohol, 1-propanol, n-butene, 2-butene, 1-butanol, 2-butanol, tert-butyl alcohol, iso-butyl alcohol, isobutylene, 4-methyl-1-pentene, 2,4,4, trimethyl-1-pentene, and combinations thereof. 
     
     
         6 . The method of  claim 1  wherein the alcohol and/or activator contain at least 50 wt. % biogenic carbon as measured by ASTM D6866. 
     
     
         7 . The method of  claim 1  wherein the solid acid catalyst comprises silica-alumina materials with 8, 10, 11, 12 and/or 14 membered rings. 
     
     
         8 . The method of  claim 1  wherein the solid acid catalyst comprises a framework selected from the group consisting of MWW, MFI, MRE*, MTW, DON, FAU, -ITN*, -EWT, BEA, MOR, DDR, FER, SZR, EUO, MTT, TON, MEL, MFS, IMF, MSE, MEI, IWV, EMT, MAZ, LTL, and combinations thereof. 
     
     
         9 . The method of  claim 1  wherein the solid acid catalyst comprise a zeolite selected form the group consisting of EMC-2, EMM-10, EMM-12, EMM-13, EMM-20, EMM-23, EMM-34, EMM-57, EMM-72, ERB-1, ITQ-1, ITQ-2, ITQ-27, ITQ-39, MCM-22, MCM-36, MCM-49, MCM-56, MCM-68, MIT-1, PSH-3, SUZ-4, SSZ-25, USY, H-form USY, NH4-USY, USC-Beta, UZM-8, UZM-8HS, UZM-37, ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-58, ZSM-50, ZSM-57, COK-5, Mazzite, Linde Type L, and combinations thereof. 
     
     
         10 . The method of  claim 1  wherein the solid acid catalyst comprises at least one solid acid catalyst selected from the group consisting of Cs 2.5 PW 12 O 40 , H 3 PW 12 O 40 , H 3 PMo 12 O 40 , H 3 PMo 6 V 6 O 40 , H 5 PMo 10 V 2 O 40 , mixed metal oxides, including but not limited to mixed metal oxide that is at least partially crystalline and comprises tungsten, zirconium, and a variable oxidation state metal selected from the group consisting of Fe, Mn, Co, Cu, Ce, Ni and any combination thereof, and silica-alumina hydrates containing BrØnsted-acidic sites, and combinations thereof. 
     
     
         11 . The method of  claim 1  wherein thermally contacting the portion of the C 8 -C 16  olefins and/or water with the working fluid comprises thermally contacting utilizing a heat exchanger disposed within the reactor. 
     
     
         12 . The method of  claim 1  wherein thermally contacting the portion of the C 8 -C 16  olefins and/or water with the working fluid comprises thermally contacting utilizing a heat exchanger disposed outside of the reactor. 
     
     
         13 . A method comprising:
 introducing a feed comprising an alcohol and an activator into a tubular reactor, the tubular reactor comprising a shell and a plurality of tubes disposed within the shell, wherein the plurality of tubes comprise a solid acid catalyst disposed within the plurality of tubes; and   contacting the alcohol and the activator in the presence of the solid acid catalyst under conditions effective to convert at least a portion of the alcohol and the activator to produce a product stream comprising C 8 -C 16  olefins and water.   
     
     
         14 . The method of  claim 13  further comprising introducing a working fluid into the shell and thermally contacting the working fluid with the plurality of tubes to produce a heated working fluid. 
     
     
         15 . The method of  claim 14  further comprising introducing at least a portion of the C 8 -C 16  olefins and water from the product stream into a distillation column and forming a bottoms stream comprising a majority of the C 8 -C 16  olefins from the product stream, wherein a reboiler thermally coupled to the distillation column is at least partially heated by the heated working fluid. 
     
     
         16 . The method of  claim 13  wherein the alcohol comprises an alcohol with a carbon number in a range from C 1  to C 7 . 
     
     
         17 . The method of  claim 13  where in the activator comprises a C 3 -C 16  alcohol and/or C 3 -C 16  olefin. 
     
     
         18 . The method of  claim 13  wherein the solid acid catalyst comprises silica-alumina materials with 8, 10, 11, and/or 12 membered rings. 
     
     
         19 . The method of  claim 13  wherein the solid acid catalyst comprises a framework selected from the group consisting of MWW, MFI, MRE*, MTW, DON, FAU, -ITN*, -EWT, BEA, MOR, DDR, FER, SZR, EUO, MTT, TON, MEL, MFS, IMF, MSE, MEI, IWV, EMT, MAZ, LTL, and combinations thereof. 
     
     
         20 . The method of  claim 13  wherein the solid acid catalyst comprise a zeolite selected form the group consisting of EMC-2, EMM-10, EMM-12, EMM-13, EMM-20, EMM-23, EMM-34, EMM-57, EMM-72, ERB-1, ITQ-1, ITQ-2, ITQ-27, ITQ-39, MCM-22, MCM-36, MCM-49, MCM-56, MCM-68, MIT-1, PSH-3, SUZ-4, SSZ-25, USY, H-form USY, NH4-USY, USC-Beta, UZM-8, UZM-8HS, UZM-37, ZSM-5, ZSM-11, ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-58, ZSM-50, ZSM-57, COK-5, Mazzite, Linde Type L, and combinations thereof. 
     
     
         21 . The method of  claim 13  wherein the solid acid catalyst comprises at least one solid acid catalyst selected from the group consisting of Cs 2.5 PW 12 O 40 , H 3 PW 12 O 40 , H 3 PMo 12 O 40 , H 3 PMo 6 V 6 O 40 , H 5 PMo 10 V 2 O 40 , mixed metal oxides, including but not limited to mixed metal oxide that is at least partially crystalline and comprises tungsten, zirconium, and a variable oxidation state metal selected from the group consisting of Fe, Mn, Co, Cu, Ce, Ni and any combination thereof, and silica-alumina hydrates containing BrØnsted-acidic sites, and combinations thereof. 
     
     
         22 . A method comprising:
 introducing a feed comprising an alcohol and an activator into a first reactor comprising a solid acid catalyst;   contacting the alcohol and the activator in the first reactor the presence of the solid acid catalyst under conditions effective to convert at least a portion of the alcohol and the activator to produce a first product stream comprising C 8 -C 16  olefins, water, and unreacted alcohol;   introducing at least a portion of the first product stream into an inter-stage heat exchanger and thermally contacting at least the portion of the first product stream with a working fluid to produce a heated working fluid;   introducing at least the portion of the first product stream into a second reactor comprising the solid acid catalyst; and   contacting the unreacted alcohol and the activator in the second reactor the presence of the solid acid catalyst under conditions effective to convert at least a portion of the unreacted alcohol and the activator to produce a second product stream comprising C 8 -C 16  olefins and water.   
     
     
         23 . The method of  claim 20  further comprising introducing at least a portion of the second product stream into a distillation column and forming a bottoms stream comprising a majority of the C 8 -C 16  olefins from the second product stream, wherein a reboiler thermally coupled to the distillation column is at least partially heated by the heated working fluid. 
     
     
         24 . The method of  claim 22  wherein the alcohol comprises an alcohol with a carbon number in a range from C 1  to C 7 . 
     
     
         25 . The method of  claim 22  where in the activator comprises a C 3 -C 16  alcohol and/or C 3 -C 16  olefin.