Carbon dioxide hydrogenation systems

Abstract

A method of carbon dioxide hydrogenation comprises introducing gaseous water to a positive electrode of an electrolysis cell comprising the positive electrode, a negative electrode, and a proton-conducting membrane between the positive electrode and the negative electrode. The proton-conducting membrane comprises an electrolyte material having an ionic conductivity greater than or equal to about 10−2 S/cm at one or more temperatures within a range of from about 150° C. to about 650° C. Carbon dioxide is introduced to the negative electrode of the electrolysis cell. A potential difference is applied between the positive electrode and the negative electrode of the electrolysis cell to generate hydrogen ions from the gaseous water that diffuses through the proton-conducting membrane and hydrogenates the carbon dioxide at the negative electrode. A carbon dioxide hydrogenation system is also described.

1 . A carbon dioxide hydrogenation system, comprising:
 a source of liquid water;   a source of carbon dioxide;   a steam generator configured and positioned to receive a liquid water stream from the source of liquid water and to generate a gaseous water stream therefrom; and   an electrochemical apparatus in fluid communication with the steam generator and the source of carbon dioxide, and comprising:
 a housing structure configured and positioned to receive the gaseous water stream from the steam generator into a first region of an internal chamber thereof and to receive a carbon dioxide stream from the source of carbon dioxide into a second region of the internal chamber thereof; and 
 an electrolysis cell within the internal chamber of the housing structure, and comprising:
 a positive electrode adjacent the first region of the internal chamber and comprising one or more of MBa 1-x Sr x Co 2-y Fe y O 5+δ  and A 2 NiO 4−δ , where:
 M is Pr, Nd, or Sm, 
 A is La, Pr, Gd, or Sm, 
 x and y are dopant levels, and 
 δ is oxygen deficit; 
 
 a negative electrode adjacent the second region of the internal chamber; and 
 a proton-conducting membrane between the positive electrode and the negative electrode and comprising at least one perovskite material having an ionic conductivity greater than or equal to about 10′ S/cm at one or more temperatures within a range of from about 150° C. to about 650° C. 
 
   
     
     
         2 . The carbon dioxide hydrogenation system of  claim 1 , wherein the housing structure and the electrolysis cell are configured and positioned to expose the positive electrode of the electrolysis cell to the gaseous water stream without exposing the negative electrode to the gaseous water stream. 
     
     
         3 . The carbon dioxide hydrogenation system of  claim 1 , further comprising at least one heating apparatus operatively associated with the electrochemical apparatus and configured to heat the gaseous water stream to a temperature within the range of from about 150° C. to about 650° C. 
     
     
         4 . The carbon dioxide hydrogenation system of  claim 1 , wherein the at least one perovskite material of the proton-conducting membrane has a H +  conductivity greater than about 10 −2  S/cm at one or more temperatures within a range of from about 350° C. to about 650° C. 
     
     
         5 . (canceled) 
     
     
         6 . (canceled) 
     
     
         7 . The carbon dioxide hydrogenation system of  claim 1 , wherein the positive electrode and the negative electrode are formulated to remain substantially adhered to the proton-conducting membrane at current densities greater than or equal to about 0.1 A/cm 2 . 
     
     
         8 . The carbon dioxide hydrogenation system of  claim 1 , wherein the at least one perovskite material comprises one or more of yttrium- and ytterbium-doped barium-zirconate-cerate (BZCYYb), yttrium- and ytterbium-doped barium-strontium-niobate (BSNYYb), and Ba 2 (YSn)O 5.5 . 
     
     
         9 . The carbon dioxide hydrogenation system of  claim 1 , wherein the at least one perovskite material comprises yttrium- and ytterbium-doped barium-zirconate-cerate (BZCYYb). 
     
     
         10 . The carbon dioxide hydrogenation system of  claim 1 , wherein the at least one perovskite material comprises Ba 2 (YSn)O 5.5 . 
     
     
         11 . The carbon dioxide hydrogenation system of  claim 1 , wherein the at least one perovskite material comprises a stack of at least two different perovskite materials each having the ionic conductivity greater than or equal to about 10 −2  S/cm at the one or more temperatures within the range of from about 150° C. to about 650° C., at least one of the at least two different perovskite materials comprising one or more of yttrium- and ytterbium-doped barium-zirconate-cerate (BZCYYb), yttrium- and ytterbium-doped barium-strontium-niobate (BSNYYb), and Ba 2 (YSn)O 5.5 . 
     
     
         12 . The carbon dioxide hydrogenation system of  claim 1 , wherein the positive electrode comprises the MBa 1-x Sr x Co 2-y Fe y O 5+δ . 
     
     
         13 . The carbon dioxide hydrogenation system of  claim 12 , wherein the MBa 1-x Sr x Co 2-y Fe y O 5+δ  comprises one of PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ , NdBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ , and SmBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ.    
     
     
         14 . The carbon dioxide hydrogenation system of  claim 1 , wherein the negative electrode comprises a cermet material comprising at least one metal and at least one perovskite. 
     
     
         15 . The carbon dioxide hydrogenation system of  claim 1 , wherein the negative electrode comprises nickel and one of yttrium- and ytterbium-doped barium-zirconate-cerate (BZCYYb), yttrium- and ytterbium-doped barium-strontium-niobate (BSNYYb), and Ba 2 (YSn)O 5.5 . 
     
     
         16 . A carbon dioxide hydrogenation system, comprising:
 a liquid water source;   a carbon dioxide source;   a steam generator downstream of the liquid water source and configured to generate gaseous water from liquid water received from the liquid water source; and   an electrochemical apparatus downstream of each of the steam generator and the carbon dioxide source, the electrochemical apparatus comprising:
 a housing structure defining an internal chamber comprising:
 a first region configured and positioned to receive the gaseous water from the steam generator; and 
 second region configured and positioned to receive carbon dioxide from the carbon dioxide source; and 
 
 electrolysis cells within the internal chamber of the housing structure and interposed between the first region and the second region, the electrolysis cells individually comprising:
 a first electrode exposed to the first region of the internal chamber and comprising one or more of MBa 1-x Sr x Co 2-y Fe y O 5+δ  and A 2 NiO 4−δ , where:
 M is Pr, Nd, or Sm, 
 A is La, Pr, Gd, or Sm, 
 x and y are dopant levels, and 
 δ is oxygen deficit; 
 
 a second electrode exposed to the second region of the internal chamber comprising a metal and a perovskite; and 
 a membrane between the first electrode and the second electrode and comprising one or more of yttrium- and ytterbium-doped barium-zirconate-cerate (BZCYYb), yttrium- and ytterbium-doped barium-strontium-niobate (BSNYYb), and Ba 2 (YSn)O 5.5 . 
 
   
     
     
         17 . The carbon dioxide hydrogenation system of  claim 16 , wherein the membrane comprises two or more of the BZCYYb, the BSNYYb, and the Ba 2 (YSn)O 5.5 . 
     
     
         18 . The carbon dioxide hydrogenation system of  claim 16 , wherein the membrane has a thickness within a range of from about 5 micrometers to about 1000 micrometers. 
     
     
         19 . The carbon dioxide hydrogenation system of  claim 16 , further comprising a Pr—Ni—Fe oxide in physical contact with the first electrode. 
     
     
         20 . The carbon dioxide hydrogenation system of  claim 16 , further comprising one or more of Cu, Fe, Ni, Co, Pt, Pd, Rh, and oxides thereof in physical contact with the second electrode. 
     
     
         21 . The carbon dioxide hydrogenation system of  claim 16 , further comprising a heating apparatus at least partially surrounding the housing structure of the electrochemical apparatus, the heating apparatus comprising one or more of a combustion heater, an electrical resistance heater, an inductive heater, and an electromagnetic heater. 
     
     
         22 . A carbon dioxide hydrogenation system including an electrochemical apparatus comprising:
 a housing structure defining an internal chamber comprising:
 a region in fluid communication with a steam generator; and 
 an additional region in fluid communication with a source of carbon dioxide; and 
   one or more electrolysis cells within the internal chamber defined by the housing structure, and individually comprising:
 a membrane comprising perovskite material having H +  conductivity greater than or equal to about 10 −2  S/cm at one or more temperatures within a range of from about 350° C. to about 650° C.; 
 a positive electrode interposed between the membrane and the region of the internal chamber and comprising one or more of PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ , NdBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ , and SmBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ ; and 
 a negative electrode interposed between the membrane and the additional region of the internal chamber.