Electrolysis cell for hydrogen chloride electrolysis
View Patent ↗Apparatus for hydrogen chloride electrolysis, comprising a cathode that has a layer of nitrogen-doped carbon nanotubes having functional groups containing nitrogen.
1. Apparatus for the electrolysis of hydrochloric acid having an HCl concentration in the range from 10 to 25% by weight, having an electrode chamber (A) having a cathode ( 1 ) and a further electrode chamber (B) having an anode ( 2 ), with electrode chamber (A) and electrode chamber (B) being separated by an ion-conducting membrane (M) and the cathode and anode ( 1 and 2 ) being electrically conductively connected to a power supply (S), wherein the cathode ( 1 ) has an electrically conductive core ( 1 a ) on which a layer ( 1 b ), having a thickness of 30 μm to 1 mm comprising a polytetrafluoroethylene (PTFE) binder and nitrogen-doped carbon nanotubes and, optionally, a further layer ( 1 c ) between core ( 1 a ) and layer ( 1 b ), with the nitrogen-doped carbon nanotubes having functional groups containing nitrogen.
2. Apparatus according to claim 1 , wherein electrode chamber (A) is provided with a feed line ( 3 ) for an aqueous electrolyte solution containing oxygen gas or for air or oxygen-containing gases.
3. Apparatus according to claim 1 , wherein the electrode chamber (B) is provided with a feed line ( 4 ) for hydrochloric acid or a gas containing hydrogen chloride.
4. Apparatus according to claim 1 , wherein the carbon nanotubes doped with nitrogen-containing groups are produced by the following process:
a. precipitation of at least one metal (M) from a solution of a metal salt (MS) of the at least one metal (M) in a solvent (L) to give a solids suspension (S) containing metals (M),
b. separation of the solid (F) from the suspension (S) and if appropriate after-treatment of the solid (F) to give a metal catalyst (K),
c. introduction of the metal catalyst (K) into a fluidized bed,
d. reaction of at least one nitrogen-containing carbon compound as starting material (E1), or of at least two starting materials (E2, E2′), where at least one starting material comprises a carbon compound and at least one starting material comprises a nitrogen compound, in the fluidized bed over the metal catalyst (K) at a temperature of at least 300° C., in the presence of hydrogen gas or hydrogen-containing compounds to form nitrogen-doped carbon nanotubes (NCNTs),
e. discharge of the nitrogen-doped carbon nanotubes (NCNTs) from the fluidized bed.
5. Apparatus according to claim 4 , wherein the catalyst is based on manganese, cobalt, Al 2 O 3 and MgO, where Mn is present in a proportion by mass of from 2 to 65% and Co is present in a proportion by mass of from 2 to 80%, Al 2 O 3 is present in a proportion by mass of from 5 to 75% and MgO is present in a proportion by mass of from 5 to 70%.
6. Apparatus according to claim 1 , wherein the core ( 1 a ) of the cathode ( 1 ) is present in the form of an electrically conductive gauze, mesh, nonwoven fabric or woven fabric.
7. Apparatus according to claim 1 , wherein the cathode ( 1 ) is electrically connected to a current distributor made up of one or more materials selected from the group consisting of copper, graphite, titanium, titanium alloy containing noble metal, in particular TiPd, and the Ni alloys Hastelloy® and Incolloy®.
8. Apparatus according to claim 1 , wherein the layer ( 1 b ) comprises a proportion of at least 10% by weight of nitrogen-doped carbon nanotubes.
9. Apparatus according to claim 1 , wherein the nitrogen-doped carbon nanotubes have a proportion of nitrogen of at least 1% by weight.
10. Apparatus according to claim 1 , wherein the thickness of the layer ( 1 b ) is not more than 200 μm.
11. Apparatus according to claim 1 , wherein the ion-conducting membrane (M) is a polymer membrane.
12. Apparatus according to claim 11 , wherein the polymer membrane is based on polymeric perfluorosulfonic acids.
13. Apparatus according to claim 1 , wherein the ion-conducting membrane (M) and the layer ( 1 b ) of the electrode ( 1 ) are in direct contact.
14. Apparatus according to claim 1 , wherein a further layer ( 1 c ) is present between the core ( 1 a ) and the layer ( 1 b ).
15. Apparatus according to claim 14 , wherein the further layer ( 1 c ) comprises at least one electrically conductive material and a hydrophobic material.
16. A method for the electrolysis of hydrogen chloride which comprises carrying out said electrolysis in the apparatus of claim 1 .
17. Apparatus of claim 15 , wherein said electrically conductive material is graphite and said hydrophobic material is PTFE.