# US 9,752,239 B2 · Electrochemical reduction device and method for manufacturing hydride of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,752,239 B2
- Document ID: US9752239B2
- Status: Granted
- Kind: B2
- Application number: 14/566,901
- Filed: 2014-12-11
- Published: 2015-04-02
- Granted: 2017-09-05
- Earliest claimed: 2012-06-12
- Assignees: Jx Nippon Oil & Energy Corporation
- Applicants: JX Nippon Oil & Energy Corporation
- Inventors: Yasushi Sato; Kota Miyoshi; Kojiro Nakagawa; Yoshihiro Kobori
- Web page: https://patentgrep.com/patent/US9752239B2

## CPC

- C25B 3/25: Reduction
- C25B 3/03: Acyclic or carbocyclic hydrocarbons
- C25B 3/05: Heterocyclic compounds
- C25B 3/09: Nitrogen containing compounds
- C25B 15/02: Process control or regulation
- C25B 15/023: Measuring, analysing or testing during electrolytic production
- C25B 15/033: Conductivity
- 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)

## Abstract

An electrochemical reduction device comprises an electrode unit including an electrolyte membrane, a reduction electrode, and an oxygen evolving electrode; a power control unit that applies a voltage Va between the reduction electrode and the oxygen evolving electrode; a hydrogen gas generation rate measurement unit that measures a hydrogen gas generation rate F1; and a control unit that controls the power control unit so as to gradually increase the Va within a range that satisfies a relationship of F1≦F0 and VCA>VHER−acceptable potential difference (APD), when the potential at a reversible hydrogen electrode is VHER, the potential of the reduction electrode is VCA, the acceptable upper limit of the hydrogen gas generation rate is F0, and the APD is a potential difference that defines an upper limit of a potential difference between VCA and VHER.

## Claims

### Claim 1

An electrochemical reduction device comprising:
an electrode unit including an electrolyte membrane having ionic conductivity, a reduction electrode that is provided on one side of the electrolyte membrane and that contains a reduction catalyst for hydrogenating a benzene ring of an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound, and an oxygen evolving electrode that is provided on the other side of the electrolyte membrane;
a power control unit that applies a voltage Va between the reduction electrode and the oxygen evolving electrode so that the reduction electrode has a basic potential and the oxygen evolving electrode has a noble potential;
a hydrogen gas generation rate measurement unit that measures a generation rate F1 per unit time of a hydrogen gas generated by an electrolytic reaction of water which competes with a benzene ring hydrogenation reaction of the aromatic hydrocarbon compound or the nitrogen-containing heterocyclic aromatic compound; and
a control unit that controls the power control unit so as to gradually increase the voltage Va within a range that satisfies a relationship of F1≦F0 and VCA>VHER−(acceptable potential difference), where the potential at a reversible hydrogen electrode, the potential of the reduction electrode and the acceptable upper limit of the hydrogen gas generation rate are expressed as VHER, VCA and F0, respectively, and the acceptable potential difference is defined as a potential difference that defines an upper limit of a potential difference between VCA and VHER.

### Claim 2 (depends on 1)

The electrochemical reduction device according to claim 1, wherein the acceptable potential difference is 20 mV.

### Claim 3 (depends on 1)

The electrochemical reduction device according to claim 1, further comprising:
a reference electrode that is arranged to be in contact with the electrolyte membrane and to be electrically isolated from the reduction electrode and the oxygen evolving electrode and that is held at a reference electrode potential VRef; and
a voltage detection unit that detects a potential difference ΔVCA between the reference electrode and the reduction electrode, wherein the control unit acquires the potential VCA of the reduction electrode based on the potential difference ΔVCA and the reference electrode potential VRef.

### Claim 4

An electrochemical reduction device comprising:
an electrode unit assembly in which a plurality of electrode units are electrically connected to one another in series, the electrode units each including an electrolyte membrane having ionic conductivity, a reduction electrode that is provided on one side of the electrolyte membrane and that contains a reduction catalyst for hydrogenating a benzene ring of an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound, and an oxygen generating electrode that is provided on the other side of the electrolyte membrane;
a power control unit that applies a voltage VA between a positive electrode terminal and a negative electrode terminal of the electrode unit assembly so that in each electrode unit, the reduction electrode has a basic potential and the oxygen generating electrode has a noble potential;
a hydrogen gas generation rate measurement unit that measures a generation rate F1′ per unit time of a hydrogen gas generated by an electrolytic reaction of water which competes with a benzene ring hydrogenation reaction of the aromatic hydrocarbon compound or the nitrogen-containing heterocyclic aromatic compound in the whole of the plurality of electrode units; and
a control unit that controls the power control unit so as to gradually increase the voltage VA within a range that satisfies a relationship of F1′≦N×F0 and VCA>VHER−(acceptable potential difference), where the potential at a reversible hydrogen electrode, the potential of the reduction electrode, the acceptable upper limit of the hydrogen gas generation rate per electrode unit and the number of electrode units are expressed as VHER, VCA, F0 and N, respectively, and the acceptable potential difference is defined as a potential difference that defines an upper limit of a potential difference between VCA and VHER.

### Claim 5 (depends on 4)

The electrochemical reduction device according to claim 4, wherein the acceptable potential difference is 20 mV.

### Claim 6 (depends on 4)

The electrochemical reduction device according to claim 4, further comprising:
a reference electrode that is arranged to be in contact with the electrolyte membrane of any one of the electrode units included in the electrode unit assembly and to be electrically isolated from the reduction electrode and the oxygen evolving electrode of the electrode unit; and
a voltage detection unit that detects a potential difference ΔVCA between the reference electrode and the reduction electrode of the electrode unit,
wherein the control unit acquires the potential VCA of the reduction electrode of the electrode unit based on the potential difference ΔVCA and the reference electrode potential VRef.

### Claim 7 (depends on 1)

A method for manufacturing a hydride of an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound, comprising introducing an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound to the reduction electrode side of the electrode unit, circulating water or a humidified gas to the oxygen evolving electrode side, and hydrogenating a benzene ring of the aromatic hydrocarbon compound or the nitrogen-containing heterocyclic aromatic compound introduced to the reduction electrode side, by using the electrochemical reduction device according to claim 1.

### Claim 8 (depends on 7)

The method for manufacturing a hydride of an aromatic hydrocarbon compound or a nitrogen-containing heterocyclic aromatic compound according to claim 7, wherein the aromatic hydrocarbon compound or the nitrogen-containing heterocyclic aromatic compound to be introduced to the reduction electrode side is introduced to the reduction electrode side in a liquid state at a reaction temperature.