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( 12 ) United States Patent US010344650B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 , 344, 650 B2 Skulason ( 45 ) Date of Patent : Jul. 9 , 2019 ( 54 ) ELECTROLYTIC PRODUCTION OF (56 ) References Cited AMMONIA U . S . PATENT DOCUMENTS (71 ) Applicant: HÁSKÓLI ÍSLANDS , Reykjavik ( IS ) 3 ,416 , 891 A 12 / 1968 Roubin et al . (72 ) Inventor: Egill Skulason , Reykjavik ( IS ) 6 , 881, 308 B2 4 /2005 Denvir et al . ( 73 ) Assignee: HASKOLI ISLANDS , Reykjavik ( IS ) (Continued ) FOREIGN PATENT DOCUMENTS ( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 CH 395036 A 7 / 1965 U . S . C . 154 (b ) by 201 days . DE 1948183 Al 4 / 1971 ( 21 ) Appl. No .: 15 /318 ,525 ( Continued ) ( 22 ) PCT Filed : Jun . 12 , 2015 OTHER PUBLICATIONS Abghoui et al. , “ Enabling Electrochemical Reduction of Nitrogen to ( 86 ) PCT No .: PCT/ IS2015 /050012 Ammonia at Ambient Conditions Through Rational Catalyst Design ” , $ 371 ( c ) ( 1 ) , Physical Chemistry Chemical Physics , vol . 17 , 2015, pp . 4909 ( 2 ) Date : Dec . 13 , 2016 4918 . ( 87) PCT Pub. No. : W02015 / 189865 ( Continued ) PCT Pub. Date : Dec . 17 , 2015 Primary Examiner — Arun S Phasge (65 ) Prior Publication Data ( 74 ) Attorney , Agent, or Firm — Workman Nydegger US 2017 /0122173 A1 May 4 , 2017 ( 30 ) Foreign Application Priority Data ( 57 ) ABSTRACT Jun. 13 , 2014 (IS ) .. .. .. 050086 A process and system for electrolytic production ammonia . The process comprises feeding gaseous nitrogen to an (51 ) Int . CI. electrolytic cell , where it comes in contact with a cathode C25B 1 /00 ( 2006 .01 ) electrode surface , wherein said surface has a catalyst surface FOIN 3 / 20 ( 2006 .01 ) comprising a nitride catalyst, said electrolytic cell compris (Continued ) ing a proton donor , and running a current through said ( 52 ) U . S . CI. electrolytic cell , whereby nitrogen reacts with protons to CPC .. .. .. FOIN 3 /2073 (2013 . 01 ) ; BOID 53 /50 form ammonia . The process and system of the invention (2013 . 01 ) ; B01D 53 / 56 ( 2013 .01 ) ; B01D uses an electrochemical cell with a cathode surface having 53 / 92 ( 2013 .01 ) ; a catalytic surface which is preferably charged with one or (Continued ) more of Vanadium nitride , Chromium nitride , Zirconium (58 ) Field of Classification Search nitride , Niobium nitride , Iron nitride or Osmium nitride. CPC . .. FOIN 3 /2073 ; FO1N 2610 /02 ; B01D 53 /56 ; B01D 53/ 92; B01D 53 / 50 ; C01C 1 / 0494 ; (Continued ) 19 Claims, 13 Drawing Sheets Heaction Cwrdinate US 10 ,344 ,650 B2 Page 2 (51 ) Int. CI. Howalt et al . , “ DFT Based Study of Transition Metal Nano - Clusters C25B 11 / 00 ( 2006 . 01) for Electrochemical NH3 Production ” , Physical Chemistry Chemi C25B 11 / 04 cal Physics , 2013 , 11 Pages . ( 2006 . 01 ) Howalt et al. , “ Electrochemical Ammonia Production on Molybde B01D 53 /50 ( 2006 .01 ) num Nitride Nanoclusters” , Physical Chemistry Chemical Physics , BOID 53 / 56 ( 2006 . 01 ) Oct . 2 , 2013 , 26 Pages. B01D 53 /92 ( 2006 .01 ) Howalt et al. , “ The Role of Oxygen and Water on Molybdenum C01C 1 /04 ( 2006 . 01) Nanoclusters for Electro Catalytic Ammonia Production " , Down (52 ) U . S . CI. loaded on Jul. 26 , 2017 . CPC .. .. .. .. .. C01C 1 /0494 ( 2013 .01 ) ; C25B 1 / 00 International Search Report from PCT Application No. PCT /IS2015 / ( 2013 . 01 ) ; C25B 11/ 00 ( 2013 .01 ) ; C25B 11 / 04 050012 , dated Sep . 4 , 2015 . ( 2013 .01 ) ; C25B 11 /0447 ( 2013 .01 ) ; FOIN Danish Search Report from Application No . 050086 /SE201401411 , dated Jan . 2013 . 2610 /02 (2013 .01 ) Kordali et al ., “ Electrochemical Synthesis of Ammonia at Atmo ( 58 ) Field of Classification Search spheric Pressure and Low Temperature in a Solid Polymer Electro CPC . .. .. C25B 11 / 04 ; C25B 11 /00 ; C25B 11/ 0447 ; lyte Cell ” , Chem . Commun . , 2000 , pp . 1673 - 1674 . C25B 1 / 00 ; YO2A 50 /2344 Marnellos et al . , “ Ammonia Synthesis at Atmospheric Pressure” , See application file for complete search history . Science, vol. 282 , Oct . 2 , 1998 , pp . 98 - 99 . Marnellos et al ., " Synthesis of Ammonia at Atmospheric Pressure (56 ) References Cited with the Use of Solid State Proton Conductors ” , Journal of Cataly sis , vol . 193 , 2000 , pp . 80 - 87 . U . S . PATENT DOCUMENTS Murakami et al. , “ Electrolytic Synthesis of Ammonia in Molten Salts Under Atmospheric Pressure ” , American Chemical Society , 2011 /0243823 A1 * 10 / 2011 Botte .. C25B 1 / 00 vol. 125 , 2003 , pp . 334 - 335 . 423 / 235 Ouzounidou et al. , “ Catalytic and Electrocatalytic Synthesis of NH3 2013/ 0281285 Al 10 / 2013 Kotaro et al. in a H + Conducting Cell by Using an Industrial Fe Catalyst ” Solid State Ionics, vol. 178 , 2007 , pp . 153 - 159 . FOREIGN PATENT DOCUMENTS Pappenfus et al. , “ Wind to Ammonia : Electrochemical Processes in Room Temperature Ionic Liquids” , ECS Transactions , vol. 16 , No . 1191846 A 5 / 1970 49 , 2009 , pp . 89 -93 . 2001096163 A 4 / 2001 Pickett et al. , “ Electrosynthesis of Ammonia ” , Nature vol . 317 , Oct . 2001239163 A 9 / 2001 17 , 1985 , pp . 652 -653 . Gees 2005272856 A 10 / 2005 Rod et al. , “ Ammonia Synthesis at Low Temperatures ” , Journal of 2008013435 A 1 / 2008 Chemical Physics, vol. 112 , No . 12 . Mar. 22 , 2000 , pp . 5343 -5347 . Skulason et al. , “ A Theoretical Evaluation of Possible Transition OTHER PUBLICATIONS Metal Electro -Catalysts for N2 Reduction ” , Phys . Chem . Chem . Phys ., vol. 14 , 2012 , pp . 1235 - 1245 . Amar et al . , “ Electrochemical Synthesis of Ammonia Based on a Song et al . , “ Structure and Reactivity of Ru Nanoparticles Sup Carbonate - Oxide Composite Electrolyte ” , Solid State Ionics , vol. ported on Modified Graphite Surfaces : A Study of the Model 182 , 2011 , pp . 133 - 138 . Catalysts for Ammonia Synthesis ” , JACS Articles . Baker et al. , “ Ancient Boomerangs Discovered in South Australia " , Nature , vol. 253 , Jan . 3 , 1975 , 2 Pages . * cited by examiner U. S . Patenatent Jul. 9 , 2019 Sheet 1 of 13 US 10 ,344 ,650 B2 * . -* Figurela Figure1b U . S . Patent Jul. 9 , 2019 Sheet 2 of 13 US 10 , 344 ,650 B2 YN SCN CUN wow-. *TINZIN RUN Figure2 HEN CrN CON N?N haveone AEya/eV ww. AgN NA *ONMANFEN #PAN #RhN#RhN NON NOW RS(100)*ZB(110) me .www . www wer. www eV / vac, Ea U. S . Patentatent JulJul9. .9 ,2019 2019 SheetSheet 3 3 01of 13 US 10 , 344 ,650 B2 Figure3 XXXXX KU coronaatent Jul. 9 , 2019 Sheet 4 of 13 .US. 10 ,. 344 ,650. .B2 WWWWWWWWWWWWWWWWWWWWW RS(100)ZB(110) OSN FeN RUN VN Figure4 CON NON ZIN eVAGI - atent Jul. 9 , 2019 Sheet 5 of 13 US 10 , 344 ,650 B2 OSN REN FEN VN Figure5 CIN NON ZIN eV / x -AGN atent Jul. 9 , 2019 Sheet 6 of 13 US 10 , 344 ,650 B2 NH310) JRS(100) ZB(110) ANH3ig AN3g BNH weswew-swewenuvannavawenenwen ANH, ANH, VNCINMnNYNZINNONHENTANMONOSNRUN ?????? Figure6 BNH2 wewnWuaWANAWA ANH319) BNH? BNHANH8 LILL.ANH3(g) ANH ANH"NH, ANHBÊNH, -AwesenwewemHvannwesweswawNanna SCNTIN 21 eV / AGRDS U .S . Patentatent Jul. 9 , 2019 Sheet 7 of 13 US 10 ,344 ,650 B2 wwwwwwwwwwww WHENN*' NH 2014 Sony WWWWHEN IN,NHNH1Z1 NHN? ZHÁNH SHNqHIZCHN+ Zy **DA * NO, ,HN + HN H4Z ReactionCoordinate HSO,HSOOSE ReactionCoordinate H+ZXHN HZ HNHO 6.85 * essssssssssssssss * * wwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwwww WWWWWWWWWWWW eV / energy Free Figure7a Figure7b atent Jul. 9 , 2019 Sheet 8 of 13 US 10 ,344 ,650 B2 RS(100)ZB(110) BNH3CO) ca 19 RUN ANH OsN ADOSH- DNH2AFNHERMAN ANH )e+ * H (12 ttetett ADMOH- MON e A,BNHNHDNH2 )e * * H (9 MnQ Figure8 ANH )"e * * H ( 6 VN ANH“NH CN ABNDHANH N?N ZN * eV / AGROS U . S . Patent Jul. 9 , 2019 Sheet 9 of 13 US 10 ,344 , 650 B2 (0)'N Awwahvv XXX w ReactionCoordinate Figure9 ANN 22 mm * g 10.54ev * aRS(100) b-RS(111) CZB(110) dZB(100) eV / energy Free U . S . Patent Jul. 9 , 2019 Sheet 10 of 13 US 10 , 344 ,650 B2 AVAer*STAS 22< 1911 se) .O . ReactosCoordinata hoactionCoordinate . M89833 . * (a) BissellineVK )b( wz14:18 decades excixŠYXOXwas 10000 w A ) Ajoua da 10 Absaus 2015 10BFigure Figure10D y v i anani zlasesses lasten)(b ReactionCoordinata ReactionCoordinace tas 0788V HANAYGP3858 WZ(0038 -Dissociativeways A220RSEAS NA0915 sod 3. mui lov shergy Free ADX AB . 35 23 Figure10A Figure10C U. S . Patentatent Jul. 9 , 2019 SheetShe 1111 of 13 13 US 10 ,344 ,650 B2 sv-VNVN-SV VN-dv NON-S VN-dv sv.ZINZrN-SV CrN-dvCrN-dv 3 AE/eV CrN-dv Figure11 NON-dy NBN-dv ZrN-dy 4 ZrN-dv 5 tutututututut #RS(100) *RS(111) YZB(100) )110(ZB* VN-dv. ww w 6 54.1 1.04 0.5 0.07 eV Eal U . S . Patent Jul. 9 , 2019 Sheet 12 of 13 US 10 , 344 ,650 B2 A,BNH2 CNH B-DNH,PNH) 8888 ) + H( 12 B-DNHANH,ANH ANH3 AMVK )® * * 1214 SESSO VN AMVK WOO ( 0 + H ) 6 BNHANH D.MVK 10 + xH )91 ACTH ANH ACrh*br ) e + * H( 12 A-DNH2 )e * * 121 ?mmensenCrNewman C,DNH BNH2 RS(100)RS(111) ZB(100) ZB(110) DeteDMVK )* * * H ( 8 ne Figure12 BNH. DMVK )( e + 34* H)( 6 T ANbHANH2 BNH )e + * 1414 A-MVK )' e +* H( 8 B-DNHANH2 BNH2 A,BNbH ANH D-MVK (. ? + H )81 A-DZRH *T2 B-DNH ANH2 OK 195 ) sHNa' ZHNG ANH? AMYK le + H )01 . -ZINZ AZTH ANH ) e + * H( 8 T 2.07 eV / AGpps U . S . Patent Jul. 9 , 2019 Sheet 13 of 13 US 10 ,344 ,650 B2 2 ICONCIN •VNVN ZZIN crnaCONA ZIN ZIN VN AEvac/eV Figure13 WVN NON CrN VN NON www NON RS(100) R$(111) ZB(100) ZB(110) we eV/ vac, Ea US 10 ,344 ,650 B2 ELECTROLYTIC PRODUCTION OF processes for producing ammonia . This has lead to the AMMONIA present invention , that makes possible ammonia production at ambient room temperature and atmospheric pressure . FIELD In a first aspect , the invention sets forth a process for 5 producing ammonia , the process comprising feeding gas The invention is within the field of process chemistry , and eous nitrogen to an electrolytic cell , where it comes in specifically relating to production of ammonia with electro contact with a cathode electrode surface , wherein said lytic methods, and new catalysts therefor .
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