# US 10,119,196 B2 · Electrochemical production of synthesis gas from carbon dioxide

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- Number: US 10,119,196 B2
- Document ID: US10119196B2
- Status: Granted
- Kind: B2
- Application number: 14/253,964
- Filed: 2014-04-16
- Published: 2014-08-28
- Granted: 2018-11-06
- Earliest claimed: 2010-03-19
- Assignees: Avantium Knowledge Centre B.V.
- Applicants: Liquid Light, Inc.
- Inventors: Narayanappa Sivasankar; Emily Barton Cole; Kyle Teamey
- Web page: https://patentgrep.com/patent/US10119196B2

## CPC

- C25B 1/02: Hydrogen or oxygen
- C25B 1/00: Electrolytic production of inorganic compounds or non-metals
- C25B 1/23: Carbon monoxide or syngas
- C25B 1/55: Photoelectrolysis
- B01D 53/326: {in electrochemical cells}
- B01D 2256/12: Oxygen
- B01D 2257/504: Carbon dioxide
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- Y02P 20/151: Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method for electrochemical production of synthesis gas from carbon dioxide is disclosed. The method generally includes steps (A) to (C). Step (A) may bubble the carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode generally reduces the carbon dioxide into a plurality of components. Step (B) may establish a molar ratio of the components in the synthesis gas by adjusting at least one of (i) a cathode material and (ii) a surface morphology of the cathode. Step (C) may separate the synthesis gas from the solution.

## Claims

### Claim 1

A method for electrochemical production of synthesis gas from water and carbon dioxide, comprising the steps of:
(A) bubbling carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell, wherein
(i) said divided electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, wherein said cathode comprises an electrode material present as particles or nanoparticles loaded onto a substrate,
where the electrode material is selected from the group consisting of Al, Au, Ag, Cd, C, Co, Cr, Cu, Cu alloys, Ga, Hg, In, Ir, Mo, Nb, Ni, Ni alloys, Ni—Fe alloys, Os, Pd, Pt, Rh, Ru, Sn, Sn alloys, Ti, V, W, Zn, stainless steel, austenitic steel, terrific steel, duplex steel, martensitic steel, Nichrome, elgiloy, degenerately doped p-Si, degenerately doped p-Si:As and degenerately doped p-Si:B, and wherein the substrate comprises graphite, carbon fiber or another conductor,
(ii) said carbon dioxide is reduced at the cathode into a plurality of components, said components comprising carbon monoxide, and the water is oxidized into protons and oxygen at the anode and said protons from the oxidized water are reduced to hydrogen gas at the cathode; and
(B) separating the synthesis gas from the solution.

### Claim 2 (depends on 1)

The method according to claim 1, wherein said cathode comprises a mix of electrode materials present as particles or nanoparticles loaded onto a substrate,
where the electrode materials are selected from the group consisting of Al, Au, Ag, Cd, C, Co, Cr, Cu, Cu alloys, Ga, Hg, In, Ir, Mo, Nb, Ni, Ni alloys, Ni—Fe alloys, Os, Pd, Pt, Rh, Ru, Sn, Sn alloys, Ti, V, W, Zn, stainless steel, austenitic steel, ferritic steel, duplex steel, martensitic steel, Nichrome, elgiloy, degenerately doped p-Si, degenerately doped p-Si:As and degenerately doped p-Si:B; and
wherein the substrate comprises graphite, carbon fiber or another conductor.

### Claim 3 (depends on 1)

The method according to claim 1, wherein said cathode comprises an alloy and/or aggregate of electrode materials, present as particles or nanoparticles loaded onto the substrate,
where the electrode materials are selected from the group consisting of Al, Au, Ag, Cd, C, Co, Cr, Cu, Cu alloys, Ga, Hg, In, Ir, Mo, Nb, Ni, Ni alloys, Ni—Fe alloys, Os, Pd, Pt, Rh, Ru, Sn, Sn alloys, Ti, V, W, Zn, stainless steel, austenitic steel, ferritic steel, duplex steel, martensitic steel, Nichrome, elgiloy, degenerately doped p-Si, degenerately doped p-Si:As and degenerately doped p-Si:B; and
wherein the substrate comprises graphite, carbon fiber or other conductor.

### Claim 4 (depends on 1)

The method according to claim 1, wherein said cathode comprises a combination of electrode materials present as particles or nanoparticles loaded onto a substrate,
wherein one electrode material is selected from the group consisting of C, Cr, Nb, Sn and stainless steel and
wherein another electrode material is selected from the group of Ni, V Ni, V, Ir, Os, Pd, Pt, Rh and Ru; and
wherein the substrate comprises graphite, carbon fiber or another conductor.

### Claim 5 (depends on 1)

The method according to claim 1, wherein hydrogen gas and carbon monoxide are produced at the cathode in a ratio of one or more moles of hydrogen gas per mole of carbon monoxide.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the catalyst is a substituted or unsubstituted aromatic heterocyclic amine.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the catalyst is selected from pyridines, imidazoles, bipyridines, thiazoles, oxazoles, quinolines, adenine, benzimidazole and 1,10-phenanthroline.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the half cell potentials at the cathode range from 0.7 volts to 1.5 volts relative to a saturated calomel electrode.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the electrolyte is at least one of Na2SO4, KCl, NaNO3, NaCl, NaF, NaClO4, KClO4, K2SiO3, CaCl2, a H cation, a Li cation, a Na cation, a K cation, a Rb cation, a Cs cation, a Ca cation, an ammonium cation, an alkylammonium cation, a F anion, a Cl anion, a Br anion, an I anion, an At anion, an alkyl amine, berates, carbonates, nitrites, nitrates, phosphates, polyphosphates, perchlorates, silicates, sulfates, and a tetraalkyl ammonium salt.