EP3504359A1 - System and process for the production of renewable fuels and chemicals - Google Patents
System and process for the production of renewable fuels and chemicalsInfo
- Publication number
- EP3504359A1 EP3504359A1 EP17780538.9A EP17780538A EP3504359A1 EP 3504359 A1 EP3504359 A1 EP 3504359A1 EP 17780538 A EP17780538 A EP 17780538A EP 3504359 A1 EP3504359 A1 EP 3504359A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyzer
- fuel
- reactor
- membrane
- renewable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 34
- 239000000126 substance Substances 0.000 title claims description 29
- 230000008569 process Effects 0.000 title claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001868 water Inorganic materials 0.000 claims abstract description 39
- 239000012528 membrane Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- -1 cyclic amine Chemical class 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 98
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 68
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000013461 design Methods 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000003446 ligand Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000004404 heteroalkyl group Chemical group 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 241000724182 Macron Species 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WLUJHMKCLOIRSK-UHFFFAOYSA-N 1,2,4,5-tetramethylimidazole Chemical compound CC=1N=C(C)N(C)C=1C WLUJHMKCLOIRSK-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the present invention relates to a system that can easily be switched from the production of renewable fuels to the production of renewable chemicals, and that uses a CO2 electrolyzer with a special membrane that enables CO2 electrolysis to be accomplished at temperatures up to 120°C.
- the process will involve the use of carbon dioxide and water electrolyzers to produce a mixture of carbon monoxide and hydrogen that promotes the production of fuels or that promotes the production of chemicals.
- the process will then use a series of reactors to produce a desired product.
- the economics associated with the production of renewable fuel are also favorable.
- the EISA set up a trading system for Renewable Identification Number (RIN) certificates, where one RIN is awarded for each gallon of "ethanol equivalent" fuel produced. If one produces renewable gasoline, then each gallon of gasoline would be awarded 1.56 RINs. "D3" RINs currently sell for about $2.70/gallon. California has a related low carbon fuel certificate (LCFS), by which the producer is awarded one LCFS certificate for each metric ton (MT) of CO 2 that is converted into fuel. A California LCFS certificate currently sell for $70. Calculations indicate that the sales of certificates from a 150 megawatt (MW) electrolyzer-based renewable gasoline plant would generate over $42,000,000 of revenue ($1.63/gal), thereby lowering the net cost of producing gasoline using the present system.
- MW megawatt
- MW metric ton
- Missing at present is a way to take advantage of the growing market for renewable fuels to also produce renewable chemicals.
- constructing a large plant that can produce either renewable fuels or renewable chemicals In that way, the plant could serve two markets, so the cost of the plant construction could be divided over the two markets.
- Such a large-scale plant does not exist today, but if it could be built, it would serve the renewable fuel market and would also lower the cost of the renewable chemicals, to help that market develop.
- the system comprises:
- the CO2 electrolyzer comprises an anion- conducting polymeric membrane.
- the anion conducting membrane comprises a terpolymer of styrene, vinylbenzyl-Rs and vinylbenzyl-Rx, where:
- Rx is at least one constituent selected from the group
- the total weight of the vinylbenzyl-Rx groups is greater than 0.3% of the total weight of the membrane.
- the anion conducting membrane comprises a polymer blend or mixture of a copolymer consisting essentially of styrene and vinylbenzyl-Rs with at least one polymeric constituent selected from the group consisting of:
- a polymer excluding polystyrene, comprising at least one of a phenylene group and a phenyl group
- Rs is a preferably positively charged cyclic amine group, and the total weight of the at least one polymeric constituent in the membrane is less than the weight of the copolymer in the membrane.
- [0013 j Rs is preferably tetra-methyl-imidazolium.
- the fuel produced by the foregoing system can be synthetic gasoline, diesel, jet fuel and/or avgas.
- the chemicals produced by the foregoing system are preferably alcohols, olefins, or ethers, most preferably ethylene, propylene, or mixtures thereof.
- the CO 2 electrolyzer runs at temperatures above 25°C, preferably above 35°C, most preferably above 40°C.
- a suitable membrane for the CO2 electrolyzer satisfies the following test:
- a cathode is prepared as follows:
- Silver ink is made as follows. A mixture of 2 mg carbon black (for example, Vulcan XC 72RXC72, from Fuel Cell Earth), 0.2 ml of a 1% solution of the membrane polymer and 0.5 ml ethanol (SigmaAldrich, USA) is sonicated for 5 minutes. 100 mg of silver nanoparticles (for example, 20-40 nm, 45509, Alfa Aesar, Ward Hill, MA) with 1.5 ml ethanol are added and then sonicated for 5 more minutes.
- carbon black for example, Vulcan XC 72RXC72, from Fuel Cell Earth
- 0.2 ml of a 1% solution of the membrane polymer and 0.5 ml ethanol (SigmaAldrich, USA) is sonicated for 5 minutes.
- 100 mg of silver nanoparticles for example, 20-40 nm, 45509, Alfa Aesar, Ward Hill, MA
- 1.5 ml ethanol are added and then sonicated for 5 more minutes.
- the silver ink is then hand-painted onto a gas diffusion layer (for example, Sigracet 35 BC GDL, Ion Power Inc., New Castle, DE) covering an area of 5 cm x 5 cm. It is sintered at 80°C for 15 minutes, followed by 120°C for 15 minutes. It is then soaked in a 1 M KOH bath for 1 hour with the painted side face down.
- a gas diffusion layer for example, Sigracet 35 BC GDL, Ion Power Inc., New Castle, DE
- IrO 2 ink is made by mixing 100 mg of IrO 2 (Alfa Aesar) with 1 ml deionized water (18.2 Mohm Millipore), 2 ml isopropanol (3032-16, Macron) and 0.101 ml of 5% Nafion solution (1100EW, DuPont, Wilmington, DE).
- the IrO 2 ink is then hand-painted onto a 5% wet proofed carbon fiber paper (for example, TGP-H-120 5% Teflon Treated Toray Paper, from Fuel Cell Earth) covering an area of 6 cm x 6 cm. Then, the carbon paper is sintered at 80°C for 30 min.
- a 5% wet proofed carbon fiber paper for example, TGP-H-120 5% Teflon Treated Toray Paper, from Fuel Cell Earth
- a 50-300 micrometer thick membrane of a "test" material is made by conventional means such as casting or extrusion.
- the membrane is sandwiched between a 3x3 cm piece of the anode material and a 2.5x2.5 cm piece of the cathode material with the metal layers on the anode and cathode facing the membrane.
- the membrane electrode assembly is mounted in Fuel Cell Technologies (Albuquerque, NM) 5 cm 2 fuel cell hardware assembly with serpentine flow fields.
- CO 2 humidified at 65°C is fed into the cathode at a rate of 20 seem and 10 mM KHCO3 is fed into the anode flow field at a flow rate of 3 ml/min.
- the cell is heated to 50°C, and a power supply is connected.
- the cell is maintained at 3 V for 2 hours, then is switched to constant current mode at 200 mA/cm 2 .
- the cell is maintained in constant current mode for at least 100 hours.
- the series of reactors preferably includes at least 3 reactors.
- the series of reactors preferably includes a first reactor that converts the CO and H 2 to methanol, then the methanol is converted dimethyl ether in a second reactor, and the dimethyl ether is converted in a third reactor to a synthetic fuel and/or a chemical.
- the conversion of dimethyl ether to a synthetic fuel and/or a chemical preferably employs a zeolite catalyst such as ZSM-5 or SAPO-34.
- the zeolite preferably consists of material with an SiO 2 /Al 2 O 3 weight ratio of 2 to 9, a Bmnauer-Emmett-Teller (BET) surface of 250 to 500 m 2 /g, and an Na content under 200 ppm, such as the catalyst described in U.S. Patent No. 9, 174,204.
- BET Bmnauer-Emmett-Teller
- a process for the production of renewable fuel in a CO 2 collection unit for extracting CO 2 from a sustainable source :
- the fuel produced by the foregoing process can be synthetic gasoline and/or diesel, jet fuel and/or avgas (aviation gasoline).
- the sustainable source of CO 2 can be atmospheric air or CO 2 output from a fermenter, a municipal waste treatment facility, a wood processing unit, or a landfill.
- the extracted CO 2 in the foregoing process is preferably substantially pure.
- the H 2 produced in the foregoing process is also preferably substantially pure. More preferably, both the extracted CO 2 and the H 2 produced in the foregoing process are substantially pure.
- FIG. 1 is a schematic diagram of the present renewable fuel production system.
- FIG. 2 is a schematic diagram of the present renewable fuel production system configured to produce mainly gasoline.
- FIG. 3 is a schematic diagram the present renewable fuel production system configured to produce mainly olefins, preferable propylene.
- FIG. 4 is a schematic diagram of an alternate design of the present renewable fuel production system in which the system produces both gasoline and olefins.
- the present production system converts air, water, and renewable electricity into renewable fuel and/or chemicals.
- the system includes the following subsystems:
- electrochemical conversion of CO 2 refers to any electrochemical process in which carbon dioxide, carbonate, or bicarbonate is converted into another chemical substance in any step of the process.
- polymer electrolyte membrane refers to both cation exchange membranes, which generally comprise polymers having multiple covalently attached negatively charged groups, and anion exchange membranes, which generally comprise polymers having multiple covalently attached positively charged groups.
- Typical cation exchange membranes include proton conducting membranes, such as the per fluoro sulfonic acid polymer available under the trade designation NAFION from E. I. du Pont de Nemours and Company (DuPont) of Wilmington, DE.
- anion exchange membrane electrolyzer refers to an electrolyzer with an anion-conducting polymer electrolyte membrane separating the anode from the cathode.
- liquid free cathode refers to an electrolyzer where there are no bulk liquids in direct contact with the cathode during electrolysis. There can be a thin liquid film on or in the cathode, however, and occasional washes or rehydration of the cathode with liquids could occur.
- radar efficiency refers to the fraction of the electrons applied to the cell that participate in reactions producing carbon- containing products.
- ME A refers to a membrane electrode assembly
- GC gas chromatograph
- imidazolium refers to a positively charged ligand containing an imidazole group. This includes a bare imidazole or a substituted imidazole.
- Ri- R 5 are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- pyridinium refers to a positively charged ligand containing a pyridine group. This includes a bare pyridine or a
- R 6 -Rii are each independently selected from hydrogen, halides, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.
- phosphonium refers to a positively charged ligand containing phosphorous. This includes substituted phosphorous.
- positively charged cyclic amine refers to a positively charged ligand containing a cyclic amine. This specifically includes imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums,
- PSTMIM Solution refers to a solution prepared as described in Specific Example 3 herein.
- sustainable source refers to a source of CO 2 other than a CO 2 well or other natural CO2 source. Sustainable sources specifically include CO2 captured from the air, CO2 from a fermenter, CO2 from a municipal waste facility and CO2 from a landfill.
- FIG. 1 is a schematic flow diagram of the present renewable fuel production system 100.
- System 100 includes electrolyzers 111 and 112, reactors 102, 103, 104, 105 and 106, separator 107, compressor 108, valves 169, 170, 171, 172, 173, 174, 175, 176, 177, 178 and 179, controller 150, and mix point 133. As further shown in FIG.
- system 100 also includes a source of renewable CO2 131, a source of water 132, a source of bio-methanol 152, a combined CO and CO2 stream 161 exiting electrolyzer 111 and directed to mix point 133, an H2 stream 162 exiting electrolyzer 112 and directed to mix point 133, an O2 outlet stream 163 exiting electrolyzer 112, and an O2 outlet stream 164 exiting electrolyzer 111.
- a methanol stream 181 exits reactor 102 and is directed to the inlet stream of reactor 103.
- a dimethyl ether stream 182 exits reactor 103 and is directed to the inlet stream of reactor 104.
- a combined gasoline, propylene and tar stream 183 exits reactor 104 and is directed to the inlet stream of reactor 105 and/or to the inlet stream of separator 107.
- the streams exiting separator 107 include propylene exit stream 135, gasoline exit stream 136, a combined H2, CO and CO2 stream 184 and an H2O stream 185.
- a renewable energy source 161 powers electrolyzer 111.
- a renewable energy source 162 powers electrolyzer 112.
- Electrolyzer 111 converts CO 2 to CO via the reaction CO 2 -» CO + 1 ⁇ 2 O2.
- a preferred design is set forth in Example 1 of co-owned U.S. Patent No. 9,481,939.
- Electrolyzer 112 converts H 2 O to H 2 via the reaction H 2 O ⁇ H 2 + 1 ⁇ 2 O 2 .
- a preferred design is set forth in co-owned U.S. patent application Serial No. 15/406,909.
- Controller 150 adjusts the ratio of CO, H 2 , CO 2 and H 2 O.
- Mix point 133 is designed to mix the output streams from the CO 2 and water electrolyzers.
- Reactor 102 converts mixtures of CO, CO 2 and H 2 to methanol.
- Reactor 102 preferably contains a Cu/ZnO catalyst such as MK-151 FENCETM from Haldor-Topsoe (Linyi, Denmark).
- Reactor 103 converts methanol to dimethyl ether.
- Reactor 103 preferable contains a ⁇ - ⁇ 1 2 ⁇ 3 catalyst such as BASF G-250 catalyst.
- Reactor 104 converts dimethyl ether to either olefins, such as propylene, or into gasoline.
- Reactor 104 preferably contains a zeolite catalyst such as ZSM-5 or SAPO-34.
- the zeolite consists of material with an SiO 2 /Al 2 O 3 weight ratio of 2 to 9, a BET surface of 250 to 500 m 2 /g, and an Na content under 200 ppm, such as the catalyst described in U.S. Patent No. 9,174,204.
- Reactor 105 hydrogenates durene and other tar molecules.
- Reactor 105 preferably contains a nickel on alumina catalyst such as Criterion KL6515, or a cobalt molybdate on alumina catalyst, such as Alfa Aesar 45579.
- Reactor 106 converts the C 5 + molecules (molecules containing 5 or more carbons) back to CO, H 2 and light olefins via reaction with steam.
- Reactor 106 preferably contains either a ZSM-5 catalyst or a nickel on alumina catalyst.
- FIG. 2 illustrates operation of renewable fuel production system 100 to produce mainly fuels such as gasoline.
- valves 173, 174, 175, 176 and 178 are closed, as depicted by the circle-and-backlash symbol (($>) over eacn of those valves, and reactor 106 is shut down or placed into a regeneration cycle.
- the tar is hydrogenated in reactor 105 before the separation step, and olefins produced are recycled back to reactor 104 to produce more gasoline.
- FIG. 3 shows how the device will be operated to produce mainly olefins such as propylene.
- valves 169, 170, 172, 177 and 179 are closed, as depicted by the circle-and-backlash symbol ( ⁇ 5 ) over each of those valves, and reactor 105 is shut down or placed into a regeneration cycle.
- the controller 201 adjusts the CO, CO 2 to H 2 to promote gasoline production.
- the tar and gasoline is sent to reactor 106 and the gasoline, tar and other hydrocarbons are cracked to produce light olefins, CO, CO 2 and H 2 .
- renewable fuel production system and process described herein is carbon negative and provides energy-efficient generation of energy-dense liquid fuels or chemicals from renewable energy, water and air.
- FIG. 4 shows an alternate system embodiment 200 in which both propylene and gasoline are produced.
- the design is simplified to omit reactor 106 in system 100 shown in FIG. 1.
- System 200 includes electrolyzers 211 and 212, reactors 202, 203, 204 and 205, separator 207, compressor 208, controller 250, and mix point 233. As further shown in FIG.
- system 200 also includes a source of renewable CO 2 231, a source of water 232, a combined CO and CO2 stream 261 exiting electrolyzer 211 and directed to mix point 233, an H 2 stream 262 exiting electrolyzer 212 and directed to mix point 233, an H 2 stream 287 exiting electrolyzer 212 and directed to reactor 205, an O 2 outlet stream 263 exiting electrolyzer 212, and an O 2 outlet stream 264 exiting electrolyzer 211.
- a methanol stream 281 exits reactor 202 and is directed to the inlet stream of reactor 203.
- a dimethyl ether stream 282 exits reactor 203 and is directed to the inlet stream of reactor 204.
- a combined gasoline, propylene and tar stream 283 exits reactor 204 and is directed to the inlet stream of separator 207.
- the streams exiting separator 207 include propylene exit stream 235, a combined gasoline and tar exit stream 236, a combined H 2 , CO and CO 2 stream 284 and an H 2 O stream 285.
- a gasoline stream 289 exists reactor 205.
- a renewable energy source 261 powers electrolyzer 211.
- a renewable energy source 262 powers electrolyzer 212.
- Electrolyzer 211 converts CO 2 to CO via the reaction CO 2 -» CO + 1 ⁇ 2 O 2 .
- a preferred design is set forth in Example 1 of co-owned U.S. Patent No. 9,481,939.
- Electrolyzer 212 converts H 2 O to H 2 via the reaction H 2 O— » H 2 + 1 ⁇ 2 O 2 .
- a preferred design is set forth in co-owned U.S. patent application Serial No. 15/406,909.
- Controller 250 adjusts the ratio of CO, H 2 , CO 2 and H 2 O.
- Mix point 233 is designed to mix the output streams from the CO 2 and water electrolyzers.
- Reactor 202 converts mixtures of CO, CO 2 and H 2 to methanol.
- Reactor 202 preferably contains a Cu/ZnO catalyst such as MK-151 FENCETM from Haldor-Topsoe (Lyngby, Denmark).
- Reactor 203 converts methanol to dimethyl ether.
- Reactor 203 preferable contains a ⁇ - ⁇ 1 2 ⁇ 3 catalyst such as BASF G-250 catalyst.
- Reactor 204 converts dimethyl ether to either olefins, such as propylene, or into gasoline.
- Reactor 104 preferably contains a zeolite catalyst such as ZSM-5 or SAPO-34. Most preferably, the zeolite consists of material with an SiO 2 /Al 2 O 3 weight ratio of 2 to 9, a BET surface of 250 to 500 m 2 /g, and an Na content under 200 ppm, such as the catalyst described in U.S. Patent No. 9,174,204.
- Reactor 205 hydrogenates durene and other tar molecules.
- Reactor 205 preferably contains a nickel on alumina catalyst such as Criterion KL6515, or a cobalt molybdate on alumina catalyst, such as Alfa Aesar 45579.
- the objective of this example is to demonstrate that a terpolymer of styrene, vinylbenzyl-Rs and vinylbenzyl-Rx, has significant advantages as a membrane for the CO 2 electrolyzer, where
- Rx is at least one constituent selected from the group consisting of CI, OH and a reaction product between an OH or CI and a species other than a simple amine or a cyclic amine, and
- the total weight of the vinylbenzyl-Rx groups is greater than 0.3% of the total weight of the membrane.
- a terpolymer membrane is prepared as described in specific Example 17 in co-owned U.S. patent application Serial No. 15/400,775 as described below.
- Step 1 Production of PSTMIM solution,
- Inhibitor-free styrene was prepared by adding a volume V of styrene (Sigma- Aldrich, Saint Louis, MO) and a volume equal to V/4 of 4% aqueous sodium hydroxide into a separatory funnel, followed by agitating the funnel to mix the water and styrene, then decanting the styrene layer. The process was repeated five times until the water layer did not show discernible color change. The procedure was repeated using pure water instead of sodium hydroxide solution until the water layer pH was neutral.
- Washed styrene was put into a freezer overnight before weighing, to confirm that residual water was mainly in ice form and was then separated from styrene by filtration or decantation.
- 4- vinylbenzyl chloride (4-VBC) was treated in the same manner as styrene.
- the membranes were prepared by casting the polymer solutions prepared above directly onto a polyethylene terephthalate (PET) liner.
- the thickness of the solution on the liner was controlled by a film applicator (MTI Corporation, Richmond, CA) with an adjustable doctor blade.
- the membranes were then dried in a vacuum oven with temperature increased to 70°C and held for 1 hour. After one more hour in the vacuum oven with temperature slowly decreased, the membrane was taken out of the oven and put into a 1 M KOH solution overnight, during which time the membrane fell from the liner.
- the KOH solution was changed twice, each with a few hours of immersion, to make sure the membrane chloride ions were substantially completely exchanged, so that the membranes were substantially fully converted into the hydroxide form.
- a cathode material was prepared as follows. Silver ink was made as follows. A mixture of 2 mg of carbon black (Vulcan XC 72RXC72, Fuel Cell Earth), 0.2 ml of a 1% solution of the membrane polymer and 0.5 ml ethanol (SigmaAldrich, USA) was sonicated for 5 minutes. 100 mg of silver
- nanoparticles (20-40 nm, 45509, Alfa Aesar, Ward Hill, MA) with 1.5 ml ethanol were added and then sonicated for 5 more minutes.
- the silver ink was then hand-painted onto a gas diffusion layer (Sigracet 35 BC GDL, Ion Power Inc., New Castle, DE) covering an area of 5 cm x 5 cm. It was sintered at 80°C for 15 min followed by 120°C for 15 min. It was then soaked in a 1 M KOH bath for 1 hour with the painted side face down.
- An anode material was prepared as follows. IrO 2 ink was made by mixing 100 mg of IrO 2 (Alfa Aesar) with 1 ml deionized water (18.2 Mohm Millipore), 2 ml isopropanol (3032-16, Macron) and 0.101 ml of 5% NAFION solution (1100EW, DuPont, Wilmington, DE). The IrO 2 ink was then hand- painted onto a 5% wet proofed carbon fiber paper (TGP-H-120 5% Teflon Treated Toray Paper, Fuel Cell Earth) covering an area of 6 cm x 6 cm. The ink covered carbon fiber paper was then sintered at 80°C for 30 minutes.
- IrO 2 ink was made by mixing 100 mg of IrO 2 (Alfa Aesar) with 1 ml deionized water (18.2 Mohm Millipore), 2 ml isopropanol (3032-16, Cell) and 0.101 ml of 5% NAFION
- the membrane was sandwiched between the a 3x3 cm piece of the anode material and a 2.5x2.5 cm piece of the cathode material with the metal layers on the anode and cathode facing the membrane, and the entire assembly was mounted in a Fuel Cell Technologies 5 cm 2 fuel cell hardware assembly with serpentine flow fields.
- CO 2 humidified at 25 °C was fed into the cathode flow field at a rate of 20 seem, and 10 mM KHCO3 was fed into the anode flow field at a flow rate of 3 ml/min.
- the cell was connected to a power supply and the cell was run at a fixed voltage of 3 V for 2 hours, then switched to constant current mode at 200 mA/cm 2 for 250 hours. The cell was stable for 250 hours.
- the selectivity was over 90%, as shown in FIG. 5 in the '775 application.
- a second membrane was prepared as above and mounted in a cell as above.
- CO2 humidified at 65 °C was fed into the cell at a rate of 30 seem, and 10 mM KHCO3 was fed into the anode flow field at a flow rate of 3 ml/min.
- the cell was heated to 50°C, and the power supply was connected. Again, the cell was maintained at 3 V for 2 hours, and then switched to a constant current mode at 600 mA/cm 2 .
- the cell was stable for 250 hours at 600 mA/cm 2 with a CO selectivity over 97%.
- a third membrane was prepared as above and mounted in a cell as above.
- CO2 humidified at 65 °C was fed into the cell at a rate of 30 seem, and 10 mM KHCO3 was fed into the anode flow field at a flow rate of 3 ml/min.
- the cell was heated to 50°C, and the power supply was connected. Again, the cell was maintained at 3 V and the current was measured. Subsequently the temperature was raised to 60°C, 70°C, and 80°C for 2 hours each, and the current was measured. Table 1 summarizes these results. Table 1. Cell current density, measured as a function of temperature
- the objective of this example is to demonstrate that a membrane comprising a polymer blend or mixture of a copolymer consisting essentially of styrene and vinylbenzyl-R s with at least one polymeric constituent selected from the group consisting of:
- a polymer excluding polystyrene, comprising at least one of a phenylene group and a phenyl group
- R s is a positively charged cyclic amine group, and wherein the total weight of the at least one polymeric constituent in the membrane is less than the weight of the copolymer in the membrane, as described in co-owned U.S. Patent No. 9,580,824.
- Step 1 A PSTMIM solution was prepared as described in Specific Example 3.
- Step 2 The PSTMIM solution was diluted to 20% solids with ethanol.
- Step 3 A BKY (Geretsried, Germany) Automatic Film Applicator L was used to cast a thin film of the polymer solution onto a polypropylene backing sheet (Home Depot, Atlanta, GA) using a doctor blade. The solution was allowed to dry in ambient environment for 30 minutes to yield an
- Step 4 a 10 ⁇ thick porous expanded polytetrafluoroethylene (ePTFE) film (Philips Scientific Inc., Rock Hill, SC) was submerged for 30 minutes in a bath of ethanol to activate its surface for better wettability. The porous ePTFE film was then laid carefully taut over the deposited polymer film. The ePTFE film was also stretched in both x and y directions to fully open its pore structure as it was laid over the polymer film.)
- ePTFE expanded polytetrafluoroethylene
- Step 5 A 15 ⁇ layer of the PSTMIM polymer solution was deposited on top of the ePTFE. The polymer film was left to settle for 15 minutes in ambient conditions before the whole reinforced membrane was placed in an oven at 65°C for 60 minutes to improve adhesion of the polymer with the ePTFE. After the heating step, the membrane was then separated from the polypropylene backing sheet with the help of a razor blade and tweezers, and then activated in 1 M KOH, as described in Specific Example 3.
- Numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit, provided that there is a separation of at least two units between a lower value and a higher value.
- concentration of a component or value of a process variable such as, for example, size, angle, pressure, time and the like, is, for example, from 1 to 98, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like, are expressly enumerated in this specification.
- one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662380917P | 2016-08-29 | 2016-08-29 | |
US15/400,775 US9849450B2 (en) | 2010-07-04 | 2017-01-06 | Ion-conducting membranes |
PCT/US2017/048637 WO2018044720A1 (en) | 2016-08-29 | 2017-08-25 | System and process for the production of renewable fuels and chemicals |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3504359A1 true EP3504359A1 (en) | 2019-07-03 |
Family
ID=60022149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17780538.9A Withdrawn EP3504359A1 (en) | 2016-08-29 | 2017-08-25 | System and process for the production of renewable fuels and chemicals |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP3504359A1 (en) |
JP (1) | JP2020500258A (en) |
KR (1) | KR20190043156A (en) |
CN (1) | CN109642332A (en) |
WO (1) | WO2018044720A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10774431B2 (en) | 2014-10-21 | 2020-09-15 | Dioxide Materials, Inc. | Ion-conducting membranes |
JP2020506978A (en) * | 2017-01-20 | 2020-03-05 | ダイオキサイド マテリアルズ,インコーポレイティド | Method for producing anion exchange membrane |
GB201810534D0 (en) | 2018-06-27 | 2018-08-15 | Univ Oxford Innovation Ltd | Hydrogen production |
EP3722462A1 (en) * | 2019-04-08 | 2020-10-14 | Siemens Aktiengesellschaft | Installation and method for storing electrical energy |
DE102019127037A1 (en) * | 2019-10-08 | 2021-04-08 | Forschungszentrum Jülich GmbH | Production of carbon monoxide |
DE102019007672A1 (en) * | 2019-11-05 | 2021-05-06 | Linde Gmbh | Process and plant for the production of monoethylene glycol |
AU2021261991B2 (en) * | 2020-05-01 | 2023-12-07 | Ihi Corporation | Electrolysis system and electrolysis method |
US20230302403A1 (en) * | 2020-05-14 | 2023-09-28 | Nitto Denko Corporation | Carbon-dioxide capture and treatment system and carbon-dioxide negative emissions plant |
JP2022143980A (en) * | 2021-03-18 | 2022-10-03 | 株式会社東芝 | Carbon compound manufacturing system and control method for carbon compound manufacturing system |
CN113174603A (en) * | 2021-04-28 | 2021-07-27 | 河钢集团有限公司 | For capturing and electrolyzing CO2Compositions and methods of |
JP2023011306A (en) * | 2021-07-12 | 2023-01-24 | 東洋エンジニアリング株式会社 | Method for producing synthetic fuel |
JP2023011307A (en) * | 2021-07-12 | 2023-01-24 | 東洋エンジニアリング株式会社 | Method for producing synthetic fuel |
CN114307908B (en) * | 2022-01-19 | 2023-03-28 | 华中科技大学 | Method for synthesizing C8+ aviation fuel oil by catalytic hydrogenation of carbon dioxide |
WO2024035474A1 (en) * | 2022-08-12 | 2024-02-15 | Twelve Benefit Corporation | Acetic acid production |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894102A (en) * | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Conversion of synthesis gas to gasoline |
JPS63128097A (en) * | 1986-11-18 | 1988-05-31 | Res Assoc Petroleum Alternat Dev<Rapad> | Conversion of synthetic gas to aromatic hydrocarbon |
JP4371601B2 (en) * | 2001-04-11 | 2009-11-25 | 株式会社トクヤマ | Bipolar membrane |
US8075746B2 (en) * | 2005-08-25 | 2011-12-13 | Ceramatec, Inc. | Electrochemical cell for production of synthesis gas using atmospheric air and water |
US7378561B2 (en) * | 2006-08-10 | 2008-05-27 | University Of Southern California | Method for producing methanol, dimethyl ether, derived synthetic hydrocarbons and their products from carbon dioxide and water (moisture) of the air as sole source material |
KR20100036317A (en) * | 2007-07-13 | 2010-04-07 | 유니버시티 오브 써던 캘리포니아 | Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol |
DE102010005704A1 (en) | 2010-01-26 | 2011-07-28 | Süd-Chemie AG, 80333 | Improved zeolite-based catalyst for the production of olefins and oligomerization of olefins |
US9481939B2 (en) | 2010-07-04 | 2016-11-01 | Dioxide Materials, Inc. | Electrochemical device for converting carbon dioxide to a reaction product |
US20110237830A1 (en) * | 2010-03-26 | 2011-09-29 | Dioxide Materials Inc | Novel catalyst mixtures |
WO2016064440A1 (en) | 2014-10-21 | 2016-04-28 | Dioxide Materials | Electrolyzer and membranes |
US8686206B2 (en) * | 2010-11-09 | 2014-04-01 | Primus Green Energy Inc. | Single loop multistage fuel production |
FR2971789B1 (en) * | 2011-02-22 | 2013-02-22 | Areva | PROCESS FOR PRODUCING METHANOL OR HYDROCARBONS FROM CARBONACEOUS MATERIAL WITH A REFORMING STEP WHOSE CONDITIONS OF OPERATION ARE SELECTIVELY ADJUSTED |
WO2012137344A1 (en) * | 2011-04-08 | 2012-10-11 | トヨタ自動車株式会社 | Device for generating mixed gas |
US20130105304A1 (en) * | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide |
AU2013318507A1 (en) * | 2012-09-19 | 2015-03-26 | Avantium Knowledge Centre B.V. | Electrochemical reduction of CO2 with co-oxidation of an alcohol |
CN105814010B (en) * | 2013-12-20 | 2020-04-03 | 埃克森美孚研究工程公司 | Catalyst for converting oxygenates to aromatics |
US10570524B2 (en) * | 2014-09-08 | 2020-02-25 | 3M Innovative Properties Company | Ionic polymer membrane for a carbon dioxide electrolyzer |
-
2017
- 2017-08-25 CN CN201780052076.0A patent/CN109642332A/en active Pending
- 2017-08-25 JP JP2019511737A patent/JP2020500258A/en active Pending
- 2017-08-25 WO PCT/US2017/048637 patent/WO2018044720A1/en unknown
- 2017-08-25 KR KR1020197008480A patent/KR20190043156A/en unknown
- 2017-08-25 EP EP17780538.9A patent/EP3504359A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CN109642332A (en) | 2019-04-16 |
JP2020500258A (en) | 2020-01-09 |
KR20190043156A (en) | 2019-04-25 |
WO2018044720A1 (en) | 2018-03-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10280378B2 (en) | System and process for the production of renewable fuels and chemicals | |
EP3504359A1 (en) | System and process for the production of renewable fuels and chemicals | |
Ogungbemi et al. | Fuel cell membranes–Pros and cons | |
Lees et al. | Gas diffusion electrodes and membranes for CO2 reduction electrolysers | |
Merino‐Garcia et al. | Productivity and selectivity of gas‐phase CO2 electroreduction to methane at copper nanoparticle‐based electrodes | |
Park et al. | Membrane strategies for water electrolysis | |
Ma et al. | An overview of flow cell architecture design and optimization for electrochemical CO 2 reduction | |
Hong et al. | Potential ion exchange membranes and system performance in reverse electrodialysis for power generation: A review | |
Varcoe et al. | Anion-exchange membranes in electrochemical energy systems | |
Albert et al. | Radiation-grafted polymer electrolyte membranes for water electrolysis cells: evaluation of key membrane properties | |
EP3453065A1 (en) | REACTOR WITH ADVANCED ARCHITECTURE FOR THE ELECTROCHEMICAL REACTION&#xA;OF CO2, CO, AND OTHERCHEMICAL COMPOUNDS | |
JP7475072B2 (en) | Equipment for the production of hydrogen | |
US20200063273A1 (en) | System And Process For The Production Of Renewable Fuels And Chemicals | |
AU2018369463A1 (en) | Ethylene-selective electrode with a mixed valence Cu4O3 catalyst | |
Cermenek et al. | Alkaline direct ethanol fuel cell | |
Drioli et al. | Membrane materials for addressing energy and environmental challenges | |
Qiu et al. | Recent developments in ion conductive membranes for CO2 electrochemical reduction | |
Im et al. | Research and development trend of electrolyte membrane applicable to water electrolysis system | |
Zhao et al. | A focus on the electrolyte: Realizing CO2 electroreduction from aqueous solution to pure water | |
CN114481158A (en) | High-temperature alkaline water electrolysis hydrogen production system and method | |
AU2013217231B2 (en) | Method and apparatus for producing gas | |
CN114622234A (en) | Flexible gas diffusion electrode structure and application thereof in electrochemical reduction of carbon dioxide | |
Yu et al. | Preparation and research progress of anion exchange membranes | |
CN107004869A (en) | For using electrolyte membrance in an electrochemical cell | |
Gaieck et al. | Challenges and opportunities for ion-exchange membranes in solar fuels devices |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20190326 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20200127 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20200714 |