EP3481973A1 - Hydrogénation électrochimique sélective d'alkynes en alcènes - Google Patents

Hydrogénation électrochimique sélective d'alkynes en alcènes

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Publication number
EP3481973A1
EP3481973A1 EP17758461.2A EP17758461A EP3481973A1 EP 3481973 A1 EP3481973 A1 EP 3481973A1 EP 17758461 A EP17758461 A EP 17758461A EP 3481973 A1 EP3481973 A1 EP 3481973A1
Authority
EP
European Patent Office
Prior art keywords
copper
chemical formula
alkyne
layer
electrode
Prior art date
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Granted
Application number
EP17758461.2A
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German (de)
English (en)
Other versions
EP3481973B1 (fr
Inventor
Bernhard Schmid
Günter Schmid
Christian Reller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
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Siemens AG
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Publication of EP3481973A1 publication Critical patent/EP3481973A1/fr
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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes

Definitions

  • the present invention relates to a process for alignl ⁇ len electrochemical hydrogenation of alkynes by the chemical formula (I) to alkenes,
  • R and R A are selected from inorganic and / or organic radicals
  • alkenes such as ethene or propene currently takes place mainly through the catalytic cleavage of
  • Crude oil (Naphta).
  • alkynes eg ethyne
  • These can also be represented for example from coal or carbides and are therefore not dependent on crude oil.
  • selectivity problems occur.
  • ⁇ fig over-reduction to the alkane take place.
  • the necessary for the hydrogenation, hydrogen is also currently derived from coal gasification or steam reforming ⁇ and is therefore also associated with oil production.
  • the catalytic hydrogenation of alkynes has been achieved by special poisoned noble metal catalysts.
  • An example of this is the Lindlar catalyst, which is a palladium catalyst poisoned with lead and quinoline.
  • Another possibility is the "Birch analogue"
  • the latter process is very expensive, but selective for E-alkenes, and new approaches to the production of hydrocarbons from, for example, carbon dioxide or carbon monoxide are emerging as part of the electrification of the chemical industry.
  • electrochemical hydrogenation of ethyne to ethene is known from X. Song, H. Du, Z. Liang, Z. Zhu, D. Duan, S. Liu, Int. J. Electrochem. Sei., 2013, 8,
  • the present invention relates to a process for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes,
  • R and R A are selected from inorganic and / or organic radicals, wherein the compound of the chemical formula (I) is hydrogenated on a copper-containing electrode.
  • R and R A are selected from inorganic and / or organic radicals.
  • R and R x are selected from inorganic and / or organic radicals, comprising:
  • An electrolysis cell (1) comprising a copper-containing Elect ⁇ rode, which is adapted to the alkyne to reduce the chemical ⁇ For mel (I) to alkene;
  • Figure 1 shows a schematic representation of the erfindungsge ⁇ MAESSEN device.
  • R and R A are selected from inorganic and / or organic radicals
  • Alkynes are all chemical compounds which have a triple bond between 2 carbon atoms. The method is therefore not limited to ethyne but can be applied to other alkynes.
  • the good selectivity comes from the low
  • the copper-containing electrode is not particularly limited and may include copper in addition to other components such as other metals and / or ceramics as a substrate, but may also be made of copper. It may also be chemically treated, for example for oxide formation. Likewise, it may be formed as a solid electrode or as a gas diffusion electrode.
  • the better substrate availability for alkynes means that Tere, so the gas diffusion electrode particularly suitable, in particular for gaseous alkynes such as ethyne, propyne, 1-butyne or 2-butyne.
  • gaseous alkynes such as ethyne, propyne, 1-butyne or 2-butyne.
  • the present copper-containing electrodes are much less expensive.
  • Electrode can be obtained by a layer comprising a Cu + / Cu-containing catalyst is deposited on a non-copper substrate, as described in DE 10 2015 203 245, or else by the layer on a copper substrate from ⁇ divorced.
  • the Cu + / Cu-containing catalyst is also referred to below as a copper / copper ion catalyst, copper catalyst or the like or simply as a catalyst, if not otherwise stated in the text, so these Be ⁇ handles in the context of to understand the present invention synonymous.
  • the non-copper substrate is also referred to simply as Sub ⁇ strat, so does not result from the text otherwise.
  • the non-copper substrate contains copper, as long as it does not consist essentially of copper.
  • the substrate can also be made of brass or brass.
  • the non-copper substrate comprises less than 60% by weight of copper, based on the total weight of the substrate, preferably less than 50% by weight, more preferably less than 40% by weight and particularly preferably less than 20% by weight of copper , example ⁇ as no copper.
  • the substrate comprises at least one metal such as silver, gold, platinum, nickel, lead, titanium, nickel, iron, manganese, or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon, Si, boron nitride (BN), boron-doped diamond, etc., and / or at least one conductive oxide such as indium tin oxide (ITO), aluminum zinc oxide (AZO), or fluorinated tin oxide (FTO), for example for manufacturing of photoelectrodes, and / or at least one polymer based on polyacetylene, polyethoxythiophene, polyaniline or polypyrrole for the preparation of polymer-based electrodes.
  • the preparation of the CuVCu-containing catalyst can be carried out in various manners and is not particularly limited, and the various preparation processes of the CuVCu-containing catalyst can also be carried out on copper substrates.
  • electro-reduction catalysts can be obtained when the catalyst is deposited in-situ on the electrode substrate.
  • ex-situ deposition is not excluded according to the invention.
  • the substrate here does not necessarily have to comprise copper or be copper, but may contain any conductive material, in particular also conductive oxides.
  • the porous Substituted ⁇ staltungen of such an electrode in order to obtain gas diffusion electric ⁇ are.
  • Charge compensation in the Cu + / Cu-containing catalyst can take place by incorporation of anions in solution during production, for example hydroxide ions (OH - ), O 2 - , halide ions (halogen), for example fluoride, chloride, bromide, iodide, Sulfate, bicarbonate, carbonate or phosphates etc.
  • anions in solution during production for example hydroxide ions (OH - ), O 2 - , halide ions (halogen), for example fluoride, chloride, bromide, iodide, Sulfate, bicarbonate, carbonate or phosphates etc.
  • the copper-comprising layer can also be deposited from a solution comprising copper ions on the surface of the electrode.
  • dendritic structures can be applied from solution in the coating, in which case no complete coating of the substrate has to be achieved, that is to say parts of the substrate are also removed. Strats can be visible.
  • the coating of the substrate, as well as the structures of the catalyst may in this case at ⁇ play, by means of scanning electron microscopy (SEM) or transmission electron microscopy (TEM) to be analyzed.
  • the substrate is not necessarily completeness, ⁇ dig covered by the coating.
  • the Bede ⁇ ckung the coating as a surface for example, be 10 to 99, 9%, relative to the surface of the substrate, preferably 50 to 95%, more preferably 70 to 90%.
  • the substrate is only covered in such a way that the growth of the Katalysa ⁇ tors carried dendritic.
  • the CuVCu-containing catalyst in this case may have pores in a size of 10 nm to 100 ym, preferably from 50 nm to 50 ym, more preferably from 100 nm to 10 ym.
  • the Cu catalyst Cu-containing + / can dendritic struc ⁇ ren with fine structure, for example the distance between two dendrites which have a size of 1 to 100 nm preferably from 2 to 20 nm, more preferably 3 to 10 nm.
  • the Be ⁇ For example, layering is porous.
  • the Cu + / Cu-containing catalyst may be at least 40 wt.% Crystalline, based on the catalyst, more preferably at least 70 wt.%, Particularly preferably at least 80 wt.%, Where the Cu + / Cu containing catalyst and / or the coating may be crystalline.
  • the substrate can be porous, for example in order to be able to produce gas diffusion electrodes.
  • the substrate may have pores in a size of 10 nm to 100 ym, preferably from 50 nm to 50 ym, more preferably from 100 nm to 10 ym. Due to the porous design of the non-copper substrate, or Also, a copper substrate, such as a Gasdif ⁇ fusion electrode, a good transport of a gaseous alkyne for Cu + / Cu-containing catalyst can be ensured and the efficiency of the electrolysis can be further improved. In particular, it can be ensured by a suitable pore size ei ⁇ ne targeted guidance to certain sections of the catalyst.
  • the concentration of Cu + in the porous copper catalyst layer / the coating comprising the catalyst Cu + / Cu-containing for example, greater than 1 mol%, preferably greater than 5 mole%, more preferably more than 10 mol%, particular ⁇ DERS preferably greater than 20 mole%, and for example up to 99.9 mole%, based on the coating.
  • the substrate may be porous.
  • the substrate may in this case have pores in a size of 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m. This is for example the case for preferred embodiments in which the electrode is a gas diffusion electrode.
  • the substrate comprises playing at least one metal such as silver, platinum, nickel, lead, titanium, nickel, iron, manganese or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon, Si, boron nitride (BN), boron-doped Di ⁇ amant, etc., and / or at least one conductive oxide, such as indium tin oxide (ITO), aluminum zinc oxide (AZO), or fluorinated tin oxide (FTO) - for example for the production of photo ⁇ electrode, and / or at least one polymer based on polyacetylene, polyethoxythiophene, polyaniline or polypyrrole, such as in polymer-based electrodes.
  • a metal such as silver, platinum, nickel, lead, titanium, nickel, iron, manganese or chromium or their alloys such as stainless steels
  • non-metal such as carbon, Si, boron nitride (BN), boron-d
  • the coating is at least partially crystalline.
  • execution ⁇ catalyst Cu + / Cu-containing by weight is at least 40.% Crystalline, based on the catalyst, more preferably at least 70 wt.%, Particularly preferably at least 80 min ⁇ wt.%.
  • the Cu + / Cu-containing catalyst and / or the coating is crystalline.
  • the coating of the copper-containing electrode is microporous to nanoporous and / or has a particularly high surface area of, for example, more than 500 m 2 / g, preferably equal to or greater than 800 m 2 / g, more preferably equal to or greater than 1000 m 2 / g. According to certain embodiments, the coating is therefore porous.
  • the Cu + / Cu-containing catalyst may have pores in a size of 10 nm to 100 ⁇ m, preferably from 50 nm to 50 ⁇ m, more preferably from 100 nm to 10 ⁇ m.
  • the catalyst Cu + / Cu-containing can dendritic structures with a fine structure, for example the distance between two Dend ⁇ rites, having a size of 1 to 100 nm, preferably 2 to 20 nm, more preferably 3 to 10 nm.
  • the concentration of Cu + layer in the porous copper catalyst is, for example, greater than 1 mol%, preferably RESIZE ⁇ SSER than 5 mol%, more preferably more than 10 mol%, particularly preferably greater than 20 mole%, and up to 99, 9 Mol%, based on the coating.
  • the coverage of the coating as a surface in the kupferhalti- gen electrode may, for example, 10 to 99, amounted to 9%, ⁇ be attracted to the surface of the substrate, preferably 50 to 95%, more preferably 70 to 90%.
  • the substrate is covered such that the growth of the catalyst is dendritic.
  • the copper-containing electrode is formed as the gas diffusion electrode (GDE)
  • GDE gas diffusion electrode
  • a gas diffusion electrode as a copper-containing electrode comprises, for example, a preferably copper-containing carrier, preferably in the form of a sheet, and a first
  • the (first) layer hydrophilic and hydrophobic Po ⁇ ren and / or channels comprises, further comprising a second layer comprising copper and at least one binder, wherein the second layer is on the support and the first layer on the second layer, wherein the content of binder in the first layer is smaller than in the second layer.
  • hydrophobic water repellent is understood here. Hydro ⁇ phobic pores and / or channels are thus those which reject water.
  • hydrophobic properties are associated with substances or molecules with nonpolar groups. In contrast, the ability to
  • the second layer may comprise hydrophilic and / or hydrophobic pores and / or channels.
  • gas diffusion electrode comprising a, preferably copper-containing, carrier, preferably in the form of a sheet, and
  • a first layer comprising at least copper and at least one binder, the layer comprising hydrophilic and hydrophobic polymers and / or channels.
  • the hydrophilic and hydrophobic regions of the GDE can achieve a good three-phase relationship liquid, solid, gaseous. It can be found for example in the electrode to electric ⁇ lytseite hydrophobic channels or areas and hydrophilic Kanae ⁇ le or areas, wherein in the hydrophilic regions Ka low activity catalysts. Furthermore, inactive catalyst sites are located on the gas side. Particularly active centers are in Dreipha ⁇ sen capable liquid, solid, gaseous.
  • An ideal GDE has so-on with a maximum penetration of the bulk material with hydro ⁇ hydrophilic and hydrophobic channels to get as many three-phase ⁇ areas for active centers. In this respect, it is preferable to ensure that the first layer comprises hydrophilic and hydrophobic pores and / or channels.
  • the carrier is not particularly limited as above, insofar as it is suitable for a gas diffusion electrode and is preferably copper-containing.
  • parallel wires can form a carrier in extreme cases.
  • the carrier is a sheet, more preferably a mesh, most preferably a copper mesh.
  • the carrier consists of copper.
  • a preferred copper-containing carrier is, according to certain embodiments, a copper mesh with a mesh width w of 0.3 mm ⁇ w ⁇ 2.0 mm, preferably 0.5 mm ⁇ w ⁇ 1.4 mm and a wire diameter x of 0.05 mm ⁇ x ⁇ 0.5 mm, Favor 0.1 mm ⁇ x ⁇ 0.25 mm.
  • the binder comprises a polymer, for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • a suitable adjustment of the hydrophobic pores or channels can be achieved.
  • Suitable PTFE powders include, for example, Dyneon® TF 9205 and Dyneon TF 1750.
  • Suitable binder particles for example, PTFE particles may at ⁇ play, be approximately spherical, for example sphe ⁇ driven, and can be prepared for example by Emulsionspolymerisati ⁇ on. In certain embodiments, the binder particles are free of surfactants.
  • the particle size can be determined, for example, according to ISO 13321 or D4894-98a and can correspond, for example, to the manufacturer's instructions (eg TF 9205: medium
  • the first layer comprises at least copper, which may be present for example in the form of metallic copper and / or copper oxide and which acts as a catalyst center.
  • the first layer preferably contains metal ⁇ metallic copper in the oxidation state 0th
  • the first layer may, for example, copper oxide contained ⁇ th, in particular CU 2 O.
  • the oxide can in this case contribute to stabilize the oxidation states of +1 of the copper and thus to obtain the selectivity for ethylene long-term stability. Under electrolysis conditions, it can be reduced to copper.
  • the first layer comprises at least 40 at. %
  • the first layer may also hold other promoters ent ⁇ which improve in cooperation with the copper, the specific catalytic activity of the GDE.
  • the first layer contains at least one metal oxide, preferably ZrÜ 2 , Al 2 O 3 , CeÜ 2 , Ce 2 ⁇ 03, ZnÜ 2 , MgO; and / or at least one copper ⁇ rich intermetallic phase, preferably at least a Cu-rich phase, which is selected from the group of binary systems Cu-Al, Cu-Zr, Cu-Y, Cu-Hf, Cucé, Cu-Mg and the ternary systems Cu-Y-Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce with Cu contents> 60 at .-%; and / or copper-containing at least one metal oxide, preferably ZrÜ 2 , Al 2 O 3 , CeÜ 2 , Ce 2 ⁇ 03, ZnÜ 2 , MgO; and / or at least one copper ⁇ rich intermetallic phase, preferably at least a Cu-rich phase, which is selected from the group of binary systems Cu-Al, Cu-
  • Perovskites and / or defect perovskite and / or perovskite related compounds preferably YBa 2 Cu307-s, wherein ⁇ ⁇ ⁇ ⁇ ⁇ (corresponding YBa2Cu307- 6 X a), CaCu3 i 4 0I2,
  • Preferred promoters here are the metal oxides.
  • the metal oxide used is preferably water-insoluble, since ⁇ can be used with aqueous electrolytes in an electrolysis using Verwen ⁇ tion of the gas diffusion electrode according to the invention.
  • the metal oxides are not inert, but are intended to represent hydrophilic reaction centers that can serve for the provision of protons.
  • the promoters in particular the metal oxide, can in this case promote the function and production of long-term stable electrocatalysts by stabilizing catalytically active Cu nanostructures.
  • the structural promoters can reduce the high surface mobilities of the Cu nanostructures and thus their sintering tendency.
  • the concept comes from the heterogeneous catalysis and is recognized ⁇ rich used within high temperature processes.
  • the oxides mentioned are not added as additives, but part of the Catalyst itself are.
  • the oxide met in addition to his radio ⁇ tion as a promoter also the feature copper in the oxidation state I to stabilize. Particularly preferred are for such gas diffusion electric ⁇ the metal oxide-copper catalyst structures which are produced as follows.
  • CU6AI 2 CO3 (OH) 1 6 .4 (H 2 O) which can be obtained in greater yield.
  • the entspre ⁇ sponding precursors may be prepared by co-dosage of a metal salt solution and a basic carbonate pH are precipitated controlled. A special feature of these materials is the presence of ultra-fine copper crystallites with egg ner size of 4-10 nm, which are stabilized struc ⁇ rell through the existing oxide.
  • drying can be carried out with subsequent calcination in the 0 2 / Ar gas stream.
  • Oxid precursors can also be connected directly in one
  • H2 / Ar gas flow can be reduced, whereby only the CU 2 O or CuO is reduced to Cu and the oxide promoter is maintained.
  • the activation step can also be done afterwards electrochemical ⁇ mixed.
  • Copper powder in similar particle size can be added to increase speed.
  • Another possibility of producing suitable electrocatalysts is based on the approach of producing copper-rich intermetallic phases such as, for example, CusZr, CuioZr 7 ,
  • Cu5iZri 4 which can be produced from the melt. Suitable ingots can subsequently be ground and completely or partially calcined in the O 2 / argon gas stream and converted into the oxide form.
  • Copper-rich phases are, for example, E. Kneller, Y. Khan, U. Gorres, The Alloy System Copper zirconium, Part I. Phase Diagram and structural relations, Journal of Me ⁇ tallischen 77 (1), pp 43-48, 1986 for Cu-Zr phases, from
  • the content of copper is preferably greater than 40 at.%, Further be ⁇ vorzugt greater than 50 at.%, Particularly preferably greater than 60 At. %.
  • intermetallic ⁇ phases also contains non-metal elements such as oxygen, nitrogen, sulfur, selenium and / or phosphorus, so for example, oxides, sulfides, selenides, nirides and / or
  • Phosphides are included.
  • the intermetallic ⁇ intermetallic phases are partially oxidized.
  • copper-containing perovskite structures and / or defect perovskites and / or perovskite-related compounds can be used for electrocatalysts: YBa 2 Cu 3 O 7 - 6 , where ⁇ ⁇ ⁇ , CaCu 3 Ti 4 O 2,
  • the catalyst particles comprising or consisting of copper for example, copper particles used to prepare the GDE, have a uniformity
  • the Catalyst particles preferably have a high purity without foreign ⁇ metal traces.
  • the promoters for example the metal oxides, may have an appropriate particle size in the production.
  • Cu powder aggregates having a particle diameter of 50 to
  • the particle diameter of these additives is for example 1 / 3-1 / 10 of the total layer thickness of the layer.
  • the addition may also be an inert material such as a metal oxide. As a result, an improved formation of pores or channels can be achieved.
  • the first layer comprises less than 5 wt.%, More preferably less than 1 wt.%, And even more preferably no carbon- and / or carbon black-based, for example, conductive, filler with respect to the layer.
  • the first layer does not contain any surface-active substances.
  • the first and / or second layer do not contain a sacrificial material, eg a sacrificial material with a release temperature of approximately below 275 ° C, eg below 300 ° C or below 350 ° C, in particular no pore former, which or more commonly wise in the production of electrodes using such a material at least partially in the electrode to ⁇ backward can.
  • the content and proportion of binder such as PTFE, may wt at ⁇ play 3-30.%, Preferably 3-20 wt.%, More before Trains t ⁇ 3-10 % By weight, even more preferably 3-7% by weight, based on the one (first) layer.
  • the GDE described above further comprising a second layer of copper and at least one binder, wherein the two ⁇ th layer is located on the support and the first layer on the second layer, wherein the content of the binder in the first layer is smaller than in the second layer. Dane ⁇ Ben, the second layer coarser Cu or
  • Particle diameters of 50 to 700 ym, preferably 100-450 ym include, in order to provide a suitable channel or pore structure ready ⁇ .
  • the second layer here comprises 3 to 30% by weight of binder, preferably 10 to 30% by weight of binder, more preferably 10 to 20% by weight of binder, preferably 10% by weight of binder, more preferably more than 10% by weight. and up to 20% by weight of binder, based on the second layer, and the first layer of 0-10% by weight of binder, eg 0.1 to 10% by weight of binder, preferably 1 to 10% by weight of binder, more preferably 1 to 7% by weight, even more preferably 3 to 7% by weight of binder, based on the first layer.
  • the binder can be the same as in the first one
  • the Parti ⁇ kel for the preparation of the second layer in accordance with certain embodiments of the first corresponding to those however also be different from this.
  • the second layer is in this case a metal particle layer (metal particle layer, MPL), which un ⁇ terrenz the catalyst layer is (CL).
  • MPL metal particle layer
  • CL catalyst layer
  • MPL metal particle layer
  • the second layer partially penetrates the first layer. This allows a good transition between the layers in terms of diffusion.
  • the GDE according to the invention may also have further layers, for example on the first layer and / or on the other side of the support.
  • a mixture for an MPL based on a highly conductive Cu mixture of dendritic Cu having particle sizes between 5-100 ⁇ m, preferably less than 50 ⁇ m and coarser Cu or inert material particles can be used
  • MPL better mechanical stability, ei ⁇ ne further reduction of the penetration of electrolyte and better conductivity, especially when using networks as carriers, can be achieved.
  • a stepwise production of the GDE by each sieving and rolling of each individual layer can lead to a lower adhesion between the layers and is therefore less preferred.
  • the degree of fibrillation of the binder for example PTFE, (structural parameter ⁇ ) correlates directly with the applied shear rate, since the binder, for example a polymer, behaves as a shear-thinning (pseudoplastic) fluid upon swelling. After extrusion, the resulting layer has an elastic character due to the fibrillation. This structural change is irreversible, so that this effect can no longer be subsequently enhanced by further rolling, but the layer is damaged by the elastic behavior upon further action of shear forces.
  • a particularly strong fibrillation can disadvantageously lead to a layer-side coiling of the electrode, so that too high contents of binder should be avoided.
  • the base layer can be characterized by a very high conductivity, for example 7 mOhm / cm or more, and preferably has a high porosity, for example of 50-70%, and a hydrophobic character.
  • the binder content, for example PTFE can be selected, for example, between 3-30% by weight, for example 10-30% by weight.
  • the intermediate copper layer as the second layer can be catalytically active in the region of the overlap zone to the catalyst layer as the first layer itself, and serves in particular for better planar electrical connection of the electrocatalyst. Using this method, the required amount of catalyst can be reduced by a factor of 20-30.
  • the method of the two-layer structure offers the possibility of dispensing with binder materials as the first layer within the catalyst layer, as a result of which better electrical conductivity can be achieved. It can also handle very ductile or brittle powder Parti ⁇ kel.
  • a subsequent activation of the electrochemical receive ⁇ NEN electrode may optionally be carried out, for example by chemical or electrochemical activation, and is not particularly limited.
  • An electrochemical Aktvie ⁇ approximately procedure may lead to the conducting salt of the electrolyte cations (eg, KHC0 3, K 2 S0 4 NaHC0 3, KBr, NaBr) to penetrate into the hydrophobic channels GDE and characterized hydrophilic regions are created.
  • the process according to the invention is suitable for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes,
  • R and R A are selected from inorganic and / or organic radicals.
  • the inorganic and / or organic radicals are not particularly limited, and the inorganic radicals may also comprise organic substructures, for example in adducts or complexes.
  • Organic radicals according to certain embodiments comprise 1 to 100 C atoms, for example 1 to 40 C atoms, preferably 1 to 20 C atoms, for example 1 to 10, 1 to 6, 1 to 4, 1 to 2 C atoms or else also only 1 C atom.
  • Suitable inorganic radicals are all inorganic radicals. Derivatives of inorganic radicals and / or substituted organic radicals are also suitable.
  • ⁇ organic and / or organic radicals are, for example, -H, -D, -OH, -OR *, -SH, -SR *, -NH 2, -NR * R *, -COOH, -COOR *, -CHO , - COR *, -PH 2, -PR * R *, -F, -Cl, -Br, -I, -NO, -N0 2, and substi ⁇ -substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl groups conceivable, wherein R * and R * likewise be ⁇ undesirables organic, for example having 1 to 100 carbon atoms, for example 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, for example 1 - 10, 1 to 6, 1 to 4, 1 to 2 carbon atoms or but also only 1 C atom, or inorganic side chains, such as - H, -D, -OH, -SH,
  • Electrochemical finds the reaction THROUGH USE of electricity, for example, in an electrolysis cell ⁇ instead.
  • the inorganic and / or organic radicals R and R x are selected from substituted or unsubstituted alkyl, alkenyl, alkynyl and / or aryl radicals, preferably alkyl and / or aryl radicals, preferably from 1 to 40 carbon atoms.
  • Atoms preferably 1 to 20 C atoms, eg 1 to 10, 1 to 6, 1 to 4, 1 to 2 C atoms or even only 1 C atom, -H, -D, -OH, -OR * , -SH, -SR *, -NH 2 , _NR * R *, -COOH, -COOR *, -CHO, -COR *, -PH 2 , -PR * R *, -F, -Cl, -Br, -I, - NO, and -NO 2 , where R * and R * represent organic and / or inorganic radicals, which are preferably selected from -H, - D, -OH, -SH, -NH 2 , -COOH, - CHO, -PH 2 , -F, -Cl, -Br, -I, -NO, - NO 2 , as well as substituted or unsubstituted alkyl, alkenyl, al
  • Suitable substituents for the substituted or unsubstituted alkyl, alkenyl, alkynyl and aryl groups or radicals are, for example, -D, -OH, -SH, -NH 2 , -COOH, -CHO, -PH 2 , - F, - Cl, -Br, -I, -NO, -NO 2 in question. So it can be func- side-chains such as -CH 2 -OH or fluorinated alkyl and / or aryl radicals such as -CF 3 .
  • R and R x are each -H or -D, then the compound of the chemical formula (I) is the special case of ethyne. If either R or R is not both, -H or -D, the alkyne is called a terminal alkyne. For internal alkynes, neither R nor R x is -H or -D. In the case of terminal alkenes, the amount of charge used is preferably precisely controlled, since overhydration, albeit with poor efficiency, is possible. According to certain embodiments, due to this necessary control, neither R nor R x is -H or -D, so internal alkynes are hydrogenated.
  • alkyne of the chemical formula (I) has no electron withdrawing groups.
  • the elec- Ronen-withdrawing groups are selected from -COOH, -COOR *, and fluo ⁇ tured alkyl and / or aryl groups, preferably perfluorinated alkyl and / or aryl radicals as -CF. 3
  • alkynes which do not carry any functional groups which, in turn, can be converted by electroreduction preference is likewise given to alkynes which do not carry any functional groups which, in turn, can be converted by electroreduction.
  • a simultaneous electro-reduction of a reducible side chain or a reducible radical is possible.
  • chain alkynes with a reducible side or a reducible rest are alkynes which func tional ⁇ groups such as -CHO, -COR *, -NO, or -NO 2 or their carry side chains containing these residues.
  • aldehydes (-CHO), ketones (-COR *) and nitro compounds (- NO 2 ) could be confirmed experimentally.
  • the alkyne of the chemical formula (I) has no further reducible functional groups other than the triple bond.
  • Particular preference is in the novel process gas ⁇ shaped or water-soluble / water-miscible alkynes, wherein ⁇ play, gaseous alkynes, alkyne of the chemical ⁇ For mel (I). Examples of such suitable compounds are ethyne,
  • the copper-containing electrode is formed as a gas diffusion electrode, wherein the alkyne of the chemical formula ⁇ (I) is present in gaseous form.
  • the hydrogenation is carried out with a proton donor selected from water and alcohols having 1 to 20 C atoms, preferably water and alcohols having 1 to 12, eg 1 to 6 or 1 to 4 C atoms, more preferably Water.
  • the water may in this case also be partially or completely deuterated, ie include as HDO or D 2 O, or else tritium, for example in the production of radioactive markers.
  • an electrolyte which can be used in the method of the present invention is not particularly limited, an aqueous electrolyte is thus advantageously used.
  • any conductive salts and / or ionic liquid be used.
  • mixtures of water with inert organic solvents such as 1,4-dioxane can be used to improve substrate solubility.
  • the present invention relates to the use of a copper-containing electrode for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes,
  • R and R A are selected from inorganic and / or organic radicals.
  • the copper-containing electrode in this case corresponds to that which has been described in connection with the method according to the invention.
  • the present invention relates to a device for the partial electrochemical hydrogenation of alkynes of the chemical formula (I) to alkenes,
  • R and R A are selected from inorganic and / or organic radicals, comprising an electrolytic cell (1) comprising a copper-containing Elekt ⁇ rode, which is adapted to reduce the alkyne of the chemical For ⁇ mel (I) to alkene;
  • a source of the alkyne of the chemical formula (I) (3) which is designed to provide the alkyne of the chemical formula (I) be ⁇ ; and a first feed means (2) for the alkyne of the chemical formula (I), which is adapted to supply the alkyne of chemi ⁇ 's formula (I) from the source of the alkyne of chemical formula (I) of the electrolytic cell.
  • the electrolytic cell is not particularly limited insofar as it has the copper-containing electrode which may correspond to that in the method according to the invention.
  • the inventive method can be carried out with the device according to the invention.
  • the copper-containing electrode can act as a cathode.
  • the further Be ⁇ constituents of the electrolytic cell as the anode, possibly the membrane, power source, etc. are not particularly limited, such as not their arrangement.
  • Examples of a possible cell arrangement are as follows.
  • a cathode compartment II can be designed such that a
  • Catholyte is supplied from below and then leaves the Ka ⁇ method space II upwards.
  • the catholyte may be supplied from above but, as for example in case ⁇ film-electrodes.
  • the oxidation of a substance takes place in an anode space I, which is supplied from below, for example with an anolyte the anolyte leaves with the product of the oxidation then the anode compartment.
  • Anode space and cathode space can be separated by a membrane M.
  • a reaction gas such as an alkyne of the chemical formula (I) may be replaced by a
  • Gas diffusion electrode can be promoted as a cathode in the cathode compartment II for reduction.
  • Embodiments with a porous anode are also conceivable. Rooms I and II can be separated by a membrane M as described.
  • a cathode K for example a gas diffuser
  • sion electrode and an anode A directly to the membrane M, where ⁇ is separated by the anode compartment I from the cathode compartment II.
  • a structure may be provided with a Gasdif ⁇ fusion electrode provided for example catholyte which is not connected to the membrane, whereas the anode may be due to the membrane on anolyte.
  • a Gasdif ⁇ fusion electrode provided for example catholyte which is not connected to the membrane, whereas the anode may be due to the membrane on anolyte.
  • other hybrid forms or other embodiments of the exemplified electrode spaces are conceivable.
  • Electrolyte and the anode-side electrolyte thus be identical, and the electrolysis cell / electrolysis unit can do without membrane. However, it is not excluded that the electrolysis cell in such embodiments has a membrane ⁇ ran, but this is ver ⁇ connected with additional effort in terms of the membrane as well as the applied voltage. Catholyte and anolyte can be mixed again optional and outside the electric ⁇ lysezelle.
  • the membrane can also be multi-layered, so that separate feeds of anolyte or catholyte are made possible. Separation effects in aqueous electric ⁇ LYTEN achieved for example by the hydrophobicity of intermediate layers ⁇ . Nevertheless, conductivity can be ensured if conductive groups are integrated in such separation layers.
  • the membrane may be an ion-conducting membrane, or a separator, which causes only a mechanical separation and is permeable to cations and anions.
  • a gas diffusion electrode By using a gas diffusion electrode, it is mög ⁇ Lich to establish a three-phase electrode.
  • a gas can be guided from behind to the front side of the electrically active electrode to carry out an electrically ⁇ chemical reaction there.
  • the gas diffusion electrode may also only to be traversed, ie a gas such as the alkyne of the chemical formula (I) is passed past the rear side of the gas diffusion electrode in relation to the electrolyte, wherein the gas can then penetrate through the pores of the gas diffusion electrode and the product can be discharged behind.
  • the gas flow during the backflow is reversed to the flow of
  • Electrolytes so that any squeezed liquid can be transported from ⁇ .
  • a cell variant made ⁇ light direct active flow through the GDE with a gas.
  • the resulting products are made by the
  • the second cell variant describes a mode of operation in which the gas flows in the rear region of the GDE through an adapted gas pressure.
  • the gas pressure should be chosen so that it is equal to the hydrostatic pressure of the electrolyte in the cell, so that no electrolyte is pushed through.
  • a film can be deposited on the side remote from the electrolyte side of the gas diffusion electrode to prevent the electrolyte on conversion to gas.
  • the film may in this case be suitably provided and is, for example, hydrophobic.
  • the electrolytic cell on a diaphragm which separates the cathode chamber and the anode chamber of the electrolytic cell to prevent a mixing of the electric ⁇ LYTEN.
  • the membrane is not particularly limited here, as long as it separates the cathode space and the anode space. In particular, it essentially prevents one
  • a preferred membrane is an ion exchange membrane, for example polymer based. Next Polymer membranes can also be used ceramic membranes.
  • the material of the anode is not particularly limited and depends primarily on the desired reaction.
  • exemplary anode materials include platinum or platinum alloys, palladium or palladium alloys, and glassy carbon.
  • Other anode materials are also conductive Oxi ⁇ de such as doped or undoped Ti0 2, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), iridium oxide, etc. If necessary, these catalytic acti ⁇ ven compounds may be deposited on the surface even in thin-film technology, for example on a titanium carrier.
  • the source of the alkyne of the chemical formula (I) and a first feeding means (2) of the alkyne of the chemical formula (I) are not particularly limited.
  • the alkyne of the chemical formula (I) may be derived for example from a pre ⁇ storage container or other container as well as of a sepa- rate reactor, etc. as a source.
  • a first feeder for example, pipes, hoses, etc. are used.
  • the source of the alkyne of the chemical formula (I) and the first feed means (2) of the alkyne of the chemical formula (I) are adapted to the particular alkyne with respect to the materials used so that they are not affected by the alkyne of the chemical formula ( I) are attacked.
  • feeding devices e.g. be provided for electrolyte, discharge devices, pumps, heating and / or cooling devices, etc.
  • the copper-containing electrode is designed as a gas diffusion electrode, wherein the first feed device (2) for the alkyne of the chemical formula (I) feeds the alkyne of the chemical formula (I) of the Gasdiffusi ⁇ onselektrode.
  • the four following embodiments were performed in an H cell.
  • a 2 cm 2 solid Cu electrode was used, which was coated with high purity Cu from a CuSC ⁇ solution.
  • a constant current of 30 mA was applied.
  • KBr was USAGE ⁇ det 0.
  • IM aqueous As the electrolyte, KBr was USAGE ⁇ det 0. IM aqueous.
  • the ano ⁇ denraum was separated by a Nafion N 117 membrane.
  • Example 3 Reduction of 1-butyn-1-ol: The cell was purged with argon throughout the experiment. After a 10 minute run-in phase, butyn-1-ol (32 ⁇ , 0.43 mmol) was added to the electrolyte. The imple ⁇ Zung Butin-l-ol to crotyl alcohol was complete. The initial current efficiency is over 90%. Despite a used equivalent charge of 4.8 F / mol (2 F / mol required), no overreduction to n-butanol was observed.
  • the cell was purged with argon throughout the experiment. After a 10 minute break-in period were
  • Fumaric acid (58.7 mg, 0.51 mmol) and KOH (200 ⁇ M 5M, lmmol) were added.
  • Acetylene, propargyl alcohol and 2-butyne-l-ol were evaluated as Substra ⁇ te. None of the 3 substrates is considered to be activated, which underlines the high activity of the catalytic process. Propargyl alcohol and 2-butyn-1-ol are known as to consider difficult substrates, since both carry electron-donating ⁇ substituents. In addition, 2-butyn-1-ol is an internal alkyne that is also sterically hindered. The alkyne hydrogenation described here can be used in addition to
  • high-volume compounds are also used for the electro-organic synthesis of specialty chemicals such as drugs or feed additives.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé d'hydrogénation électrochimique partielle d'alkynes de formule chimique (I) en alcènes, (I) R et R' étant sélectionnés parmi des groupes inorganiques et/ou organiques, le composé de formule chimique (I) étant hydrogéné sur une électrode cuivreuse, l'utilisation d'une électrode cuivreuse pour une telle hydrogénation électrochimique partielle, ainsi qu'un dispositif de mise en oeuvre du procédé.
EP17758461.2A 2016-09-22 2017-08-16 Hydrogénation électrochimique sélective d'alkynes en alcènes Active EP3481973B1 (fr)

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DE102016218230.7A DE102016218230A1 (de) 2016-09-22 2016-09-22 Selektive elektrochemische Hydrierung von Alkinen zu Alkenen
PCT/EP2017/070699 WO2018054612A1 (fr) 2016-09-22 2017-08-16 Hydrogénation électrochimique sélective d'alkynes en alcènes

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EP3571331B1 (fr) 2018-03-26 2021-01-13 Total Se Électrocatalyseurs multicouches composites destinés à la réduction de co2 et procédés associés
WO2021007508A1 (fr) 2019-07-10 2021-01-14 California Institute Of Technology La stabilisation d'un intermédiaire à liaison covalente par accord moléculaire favorise la conversion du co2 en éthylène
CN110438523B (zh) * 2019-09-05 2021-12-03 南京大学 一种以重水为氘源的无催化剂电化学氘代方法
CN112301369A (zh) * 2020-10-24 2021-02-02 西北工业大学 一种电催化半氢化气相炔烃合成烯烃的方法
CN112342562B (zh) * 2020-10-24 2023-03-07 西北工业大学 一种电催化乙炔偶联制1,3－丁二烯的方法
CN112301373A (zh) * 2020-10-24 2021-02-02 西北工业大学 一种电催化选择性还原烯烃中炔烃杂质的方法
CN113388853B (zh) * 2021-05-27 2022-05-17 杭州师范大学 一种对碳碳叁键高选择性加氢的电化学催化方法
DE102021119761A1 (de) 2021-07-29 2023-02-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verfahren zur selektiven katalytischen Hydrierung organischer Verbindungen sowie Elektrode und elektrochemische Zelle für dieses Verfahren
CN114411177A (zh) * 2021-12-31 2022-04-29 西北工业大学 一种用于合成氘代烯烃的电催化方法
CN114411179B (zh) * 2021-12-31 2024-09-06 西北工业大学 一种电催化1，4-丁炔二醇加氢制备1，4-丁二醇的方法
CN114196984B (zh) * 2022-01-20 2023-12-08 辽宁大学 一种碳纸上恒电流电沉积铜基催化剂及其制备方法和在电催化4-乙炔基苯胺中的应用
CN114606518B (zh) * 2022-03-11 2023-09-22 湖南大学 一种电化学乙炔选择性加氢生成乙烯的方法
DE102022133773A1 (de) 2022-12-16 2024-06-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verfahren zur elektrokatalytischen Hydrierung von Alkinen und elektrochemische Zelle für dieses Verfahren

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US20190276941A1 (en) 2019-09-12
WO2018054612A1 (fr) 2018-03-29
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AU2017329370B2 (en) 2019-10-31
DE102016218230A1 (de) 2018-03-22
EP3481973B1 (fr) 2020-10-14

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