Electrohydrodimerization of aliphatic olefins with electrochemical potential pulses

Patent metadata

Field	Value
Publication number	US-11313045-B2
Application number	US-202016834897-A
Country	US
Kind code	B2
Filing date	Mar 30, 2020
Priority date	Mar 30, 2019
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

Methods of making aliphatic compounds having two or more electron withdrawing groups and compositions comprising aliphatic organic compounds having one or more electron withdrawing groups. The methods are based on electrohydrodimerization of aliphatic olefinic compounds having one or more electron withdrawing groups using pulsed potential waveforms. A method may produce adiponitrile by electrolysis of acrylonitrile using pulsed waveforms. A composition may be an electrochemically produced organic phase composition. A composition may comprise one or more undesirable products, such as, for example, propionitrile, AN-derived oligomers, and the like. A composition may not have been subjected to any purification and/or separation after electrochemical production of one or more aliphatic compounds comprising two or more electron withdrawing groups.

First claim

The invention claimed is:

1. An electrohydrodimerization method for making one or more aliphatic compound comprising two or more electron withdrawing groups comprising:
electrolyzing a reaction mixture comprising:
one or more aliphatic olefinic compound comprising one or more electron withdrawing group;
one or more salts; and
water;

wherein the reaction mixture has at least an initial pH of 7 to 13,

wherein the reaction mixture is in contact with a cathode having for a selected duration at least one cathode potential sufficient to hydrodimerize the one or more aliphatic olefinic compound comprising one or more electron withdrawing group and for at least one other selected duration a higher cathode potential at which the hydrodimerization of the one or more aliphatic olefinic compound comprising one or more electron withdrawing group occurs at a slower rate or is completely suppressed, and the electrolysis is carried out using a pulsed potential waveform applied to the cathode, and
wherein the one or more aliphatic compound comprising two or more electron withdrawing groups is formed.

2. The method of claim 1 , wherein the pulsed potential waveform has a base (resting) potential selected within a range where no faradaic reaction occurs or occurs at a lower rate than during the cathodic potential and at least one cathodic (pulse) potential.

3. The method of claim 2 , wherein the base potential is applied for a resting duration of less than 50 ms and the cathodic potential is applied for a cathodic duration of from 5 ms to 2000 ms.

4. The method of claim 3 , wherein each resting duration is the same as each other resting duration and/or each cathodic duration is the same as each other cathodic duration.

5. The method of claim 2 , wherein the pulsed potential waveform alternates between the base potential and the cathodic potential.

6. The method of claim 2 , wherein each instance of base potential has a same potential value as each other instance of the base potential and/or each instance of the cathodic potential has a same potential value as each other instance of the cathodic potential.

7. The method of claim 2 , wherein each base potential is the same or varies in the range of 0 V to −4 V measured against a Ag/AgCl reference electrode and/or the cathodic potential is equal to or lower than −2 V.

8. The method of claim 2 , wherein the base potential of a pulse is constant throughout the resting duration and/or the cathodic potential of a pulse is constant throughout the cathodic duration.

9. The method of claim 2 , wherein the base potential of a pulse varies during the resting duration and/or the cathodic potential of a pulse varies during the cathodic duration.

10. The method of claim 9 , wherein the base potential of a pulse varies during the resting duration and the cathodic potential of a pulse varies during the cathodic duration.

11. The method of claim 1 , wherein the one or more aliphatic olefinic compound is at least initially present in the reaction at a concentration of 3 to 30 wt % (based on the total weight of the reaction mixture).

12. The method of claim 1 , wherein the one or more salts are chosen from buffer salts, EDTA, chelating agents, ion-orienting quaternary ammonium salts, and combinations thereof.

13. The method of claim 1 , wherein the one or more salts are at least initially present in the reaction at a concentration of 0.1 to 15 wt % (based on the total weight of the reaction mixture).

14. The method of claim 1 , wherein the one or more aliphatic olefinic compound concentration and/or salt concentration and/or pH is constant or changes as a function of time.

15. The method of claim 1 , wherein the electrolysis is carried out in an electrochemical cell comprising a cathode.

16. The method of claim 15 , wherein the electrochemical cell further comprises a metal anode and, optionally, a reference electrode.

17. The method of claim 15 , wherein the electrochemical cell further comprises a separator.

18. The method of claim 15 , wherein the cathode has an electrochemically available surface comprising a metal, a carbon, or a combination thereof.

19. The method of claim 1 , further comprising separation at least a portion of, substantially all, or all of the one or more aliphatic compound comprising two or more electron withdrawing groups from the reaction mixture.

Assignees

• Univ New York

Inventors

• Modestino Miguel A
• Blanco Jimenez Daniela Eugenia

Classifications

• C07C253/30 Primary

  by reactions not involving the formation of cyano groups · CPC title

• C25B15/02

  Process control or regulation · CPC title

• C07C255/05

  containing at least three cyano groups bound to the carbon skeleton · CPC title

• C25B3/295 Primary

  hydrodimerisation · CPC title

• C25B9/19

  with diaphragms · CPC title