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    • 专利摘要:
    Process for the electrochemical conversion of organic compounds contained in residues or obtained as residues, the residues being or being dissolved, suspended or emulsified in an electrolyte solution and the electrolyte solution being alkaline or being alkalized, the electrolyte solution being in at least one single-chamber flow cell (2 ) designed electrolysis cell, which has an electrode package (6) from at least two to a voltage source (9) connected to the contact electrodes (6a) is continuously fed and discharged, wherein it flows through the electrode stack (6), and wherein in the electrolysis cell by adjusting Process parameters from at least one of the organic compounds, a gaseous fuel is formed, which is discharged from the electrolytic cell and dissipated.
    公开号:AT518544A4
    申请号:T50387/2016
    申请日:2016-04-29
    公开日:2017-11-15
    发明作者:
    申请人:Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg；
    IPC主号:
    专利说明:

    per aqua diamond electrodes production GmbH & Co KG PA 8589 AT
    description
    Process for the electrochemical conversion of organic compounds contained in residues or obtained as residues and use of a single-cell flow cell designed as an electrolytic cell for the electrochemical conversion of organic compounds contained in residues or as residues in a gaseous fuel
    The invention relates to a process for the electrochemical conversion of residual compounds or residual organic compounds.
    The invention further relates to the use of a single-cell flow cell designed as an electrolytic cell for the electrochemical conversion of residual substances contained in or as residual organic compounds in a gaseous fuel.
    It is common in industrial processes accumulating residues, such as those incurred in the production of cellulose by-product lignin-containing black liquor to burn. Black liquor combustion covers a significant part of the energy needed for cellulose production. Furthermore, it is known to produce biogas from black liquors in biogas plants, whose main components are methane and carbon dioxide.
    From EP 2 276 877 Bl a process for the electrochemical cleavage of lignin is known in which an aqueous solution or a suspension of lignin is electrolyzed in an electrolysis cell. The electrolytic cell has, for example, a diamond electrode as anode, as cathode material, for example platinum, nickel or molybdenum can be used. The aqueous solution or suspension has a pH of at most 11, the process preferably being carried out in an acidic solution having a pH of <3. In the electrochemical cleavage of lignin liquid hydroxybenzaldehyde derivatives and / or phenol derivatives are formed, which can be removed from the reaction product via distillation or extraction. The derivatives formed by the electrochemical cleavage include, in particular, guaiacol, vanillin and acetovanillon.
    A recovery or a specific workup of contained in residues or accumulating as such organic compounds is not provided by the known methods. i
    The invention is therefore based on the object contained in industrial production or recycling processes contained in residues or accumulating as residual organic compounds to environmentally friendly way of alternative utilization with high efficiency and high yield.
    The stated object is achieved by a
    Process for the electrochemical conversion of organic compounds contained in residues or as residues, the residues being dissolved, suspended or emulsified in an electrolyte solution and the electrolyte solution being alkaline or being alkalized, the electrolyte solution being designed as a flow cell in at least one single-chamber An electrolytic cell, which has an electrode stack comprising at least two contact electrodes connected to a voltage source, is continuously conducted in and out, wherein it flows through the electrode packet, and wherein in the electrolysis cell by adjusting one or more process parameters of at least one of the organic compounds gaseous fuel is formed, which is discharged from the electrolysis cell and discharged.
    The stated object is further achieved by the use of a single-cell electrolysis cell designed as a flow cell, which has an electrode stack comprising at least two contact electrodes connected to a voltage source, for the electrochemical conversion of residual organic compounds into a gaseous fuel, wherein the Residues are dissolved, suspended or emulsified in an alkaline electrolyte solution, wherein the electrolytic solution flows through the electrolysis cell and thus the electrode packet continuously, and wherein in the electrolytic cell of at least one of the organic compounds, a gaseous fuel is formed, which is discharged and discharged from the electrolytic cell ,
    Preferably, one or more of the group consisting of hydrogen and gaseous hydrocarbons, in particular ethane, propane, butane, ethene, propene and butene, is or are formed as combustible main component or as combustible main constituents of the gaseous fuel. Likewise, the use of the electrolytic cell to form such a gaseous fuel is preferred.
    With the method according to the invention or the use according to the invention, it is possible to convert organic compounds obtained as residues or contained in residues electrochemically into a gaseous fuel. i
    The hydroxide ions of the alkaline electrolyte solutions polarize functional groups of the organic compounds contained therein, which, for example, form carboxylic anions from carboxylic acids. Both the polarized compounds and the possibly formed strongly polar anions can advantageously be converted particularly easily electrochemically. Ideally, the hydroxide ions also react with insoluble organic compounds to form soluble organic compounds. For example, water-insoluble fats contained in residues or accumulating as residues are cleaved by the reaction with hydroxide ions into water-soluble salts of the fatty acids and water-soluble alcohols (saponification). The organic compounds thus dissolved in the electrolytic solution can also be electrochemically converted into a gaseous fuel.
    The gaseous fuel formed can advantageously be used as a secondary raw material; in particular, the gaseous fuel or main constituents of the fuel can be converted by steam reforming into a synthesis gas, which is ideally suited for the production of further industrially usable organic compounds. For example, synthesis gas can be used for the production of methanol or for Fischer-Tropsch syntheses. Furthermore, electrical energy and heat can be obtained from the gaseous fuel formed in a combined heat and power plant. In addition, from the electrolyzed alkaline solution from which the fuel was recovered, chemicals i can be recovered.
    In a preferred embodiment of the invention, the electrolytic solution in an electrolytic cell, the electrode packet between the contact electrodes has at least one further, in particular a bipolar electrode, continuously on and out of this. By providing additional electrodes, the fuel yield is increased.
    It is particularly preferred if the electrolysis cell has at least one diamond electrode, in particular a diamond particle electrode, between the contact electrodes. Diamond electrodes, in particular diamond particle electrodes, are distinguished by their chemical stability and by their high oxygen overvoltage, by means of which the oxygen formation, which competes with the electrochemical oxidation of organic compounds, can be minimized, so that the fuel yield is further increased.
    According to the invention, the electrolytic cell can contain as contact electrodes and as any further electrode (s) directly contacted diamond electrodes, in particular diamond particle electrodes, platinum-coated titanium electrodes, mixed oxide electrodes, in particular Ir / Ru-coated titanium electrodes, or electrodes of glassy carbon, graphite or carbon. i
    The process parameter (s) that is / are set in the method according to the invention is or are at least one of the following parameters: the
    Residence time of the electrolyte solution in the electrolytic cell, the temperature of the electrolyte solution, the pH of the electrolyte solution, the ion concentration of the electrolyte solution, the current intensity and / or the voltage of the voltage source. In particular, by adjusting the current intensity and the voltage of the voltage source, an electrochemical conversion of the organic compounds into a gaseous fuel can be brought about particularly comfortably, wherein particularly fine fuel yields can be achieved by fine-tuning these parameters.
    The alkaline electrolyte solution supplied to the electrolysis cell or used in the electrolysis cell for electrolysis preferably has an ion concentration of at least 0.1 mol / l. Such electrolyte solutions are particularly well accessible to electrolysis. The maximum ion concentration of the electrolyte solution for the respective ions is determined by the saturation concentration of the ions.
    In one possible variant of the invention, at least one compound for forming alkali metal ions, preferably potassium ions and / or sodium ions, is added to the electrolyte solution prior to introduction into the electrolysis cell until the ion concentration is at least 0.1 mol / l. The electrolytic cell is therefore used for the electrolysis of an alkaline electrolyte solution containing alkali metal ions, preferably potassium ions and / or sodium ions. These ions are particularly suitable because of their high water solubility and are advantageously not involved in the electrochemical conversion, since their standard electrode potential is lower than that of hydrogen. Furthermore, potassium and sodium ions form water-soluble organic salts with the organic compounds and thus electrochemically convertible compounds. Potassium ions are furthermore particularly suitable because the hydrate shell forming around them in aqueous solution is particularly small. Therefore, potassium ions have a particularly low hydrodynamic resistance and are accordingly particularly well mobile in aqueous solutions, so that the electrical conductivity of an electrolyte solution containing potassium ions is also particularly high.
    In a preferred variant of the invention, the alkaline electrolyte solution has a pH of at least 8, in particular of at least 10, or is adjusted to such a pH. The present at this pH concentration of hydroxide ions contributes to a rapid and effective polarization of organic compounds contained in the residues, such as carboxylic acids, which, as described above, favors the electrochemical conversion of these compounds into a gaseous fuel. Further, the hydroxide ions in the electrolytic solution convert water-insoluble organic compounds into water-soluble organic compounds, for example, in soaps. These can also be converted electrochemically into a gaseous fuel as already explained.
    The electrolyte solution is preferably an aqueous or an organic, in particular alcoholic or phenolic, electrolyte solution.
    Preference is given to a use of the electrolysis cell for forming a gaseous fuel from a lignin-containing black liquor obtained in the sulfate process of the pulp industry. Therefore, such a black liquor is preferably also treated electrolytically in the process according to the invention as residue for forming a gaseous fuel. i
    Also preferred is a use of the electrolytic cell to form a gaseous fuel from spent liquors resulting from the alkaline hydrolysis of animal carcasses. It is therefore also preferred if in the process according to the invention such waste liquors are treated electrolytically to form a gaseous fuel.
    A further advantage is the use of the electrolysis cell to form a gaseous fuel from fats containing alkaline wastewater, which are incurred in particular in the sanitation and disinfection. In the process according to the invention, wastewaters of this type are thus treated electrolytically to form a gaseous fuel.
    According to a further preferred embodiment of the invention, the electrolytic cell is used to form a gaseous fuel from the dissolved and / or finely suspended organic substances as a result of an alkali treatment. In the process according to the invention, such solutions are treated electrolytically as residues.
    Furthermore, use of the electrolytic cell to form a gaseous fuel from solutions of sodium or potassium salts of fatty acids is also preferred. In the process according to the invention, such solutions are treated electrolytically as residues. i
    Further features, advantages and details of the invention will now be described in more detail with reference to the single figure, Fig. 1, which shows a schematic side view of an embodiment according to the invention of an apparatus for the electrochemical conversion of organic compounds.
    The terms used in the following description, such as "top", "bottom", "below" and the like, refer to the representation as shown in Fig.l. The term "liquid medium" in the context of the subject invention includes liquids, suspensions and emulsions. i
    The device for electrochemical conversion has at least one single-cell and designed as a flow cell 2 electrolytic cell. 1 shows a device with a single flow cell 2 and with a closed container 1. The example cuboid or cylindrical container 1 has a container bottom la, a preferably removable container lid lb and a container wall lc. In the area of the upper half of the container 1 opens into the container wall lc a liquid supply line 3 a, via which liquid media can be introduced into the interior of the container 1. Below the liquid feed line 3a, a liquid discharge 3b opens into the container wall 1c in the region of the lower half of the container 1. In the upper region of the container 1 opens just below the container lid lb a gas line 4 in this one. The gas line 4 may also be connected to the container lid lb.
    The flow cell 2 has a non-illustrated multi-part housing 5, in which an electrode package 6 is arranged. Between the container 1 and the flow cell 2 runs a feed line 7a and a return line 7b, wherein the feed line 7a just above the container bottom la and the return line 7b i above the supply line 7a and in the embodiment shown in the region of the upper half of the container 1 in the container wall lc opens. Compared with the flow cell 2, the feed line 7a and the return line 7b are arranged such that the medium entering the flow cell 2 flows through the electrode packet 6 and is then returned to the container 1 via the return line 7b. In the exemplary embodiment shown, a pump 8 is provided in the region of the feed line 7a, by means of which the liquid medium can be transported into the flow cell 2. Between the pump 8 and the container 1, a heat exchanger can be positioned, via which the liquid medium flowing through the feed line 7a is heated or cooled. All lines 3a, 3b, 4, 7a, 7b are liquid and gas tight connected to the container 1 and to the housing 5 of the flow cell 2 via flange connections, not shown, and the housing 5 and the container 1 itself, with the exception of the respective Connection points, liquid and gas-tight. i
    The electrode package 6 of the flow cell 2 is inserted into the housing 5 such that it is secured against displacement. In the illustrated embodiment, the electrode package 6 at the edge each have a contact electrode 6a, to each of which a not shown in Fig. 1 spacer of an electrically insulating material, preferably made of plastic, connects, which separates the respective contact electrode 6a of a bipolar diamond particle electrode 6b. Preferably, a plurality of, in the embodiment shown, four bipolar diamond particle electrodes 6b are provided which are also separated from each other by thin, electrically insulating spacers. In the simplest embodiment of the electrode package 6, a single bipolar diamond particle electrode 6b, two spacers and the two contact electrodes 6a are provided. In further embodiments, a larger number of bipolar diamond particle electrodes may be provided between the two contact electrodes 6a and also further contact electrodes may be present, the diamond particle electrodes 6b being separated from each other and from the contact electrodes by a separate spacer. All electrodes and spacers are preferably made substantially rectangular. The electrode package 6 is held together, for example, by retaining clips (not shown) from the outside.
    In the simplest, not shown embodiment, the electrolysis cell has only two contact electrodes. In a further embodiment, at least one further, either contacted and supplied with voltage further electrode between the mentioned contact electrodes is provided or a bipolar electrode.
    As contact electrodes 6a or as further electrodes, for example directly contactable diamond electrodes, in particular diamond particle electrodes, also platinum coated titanium electrodes, mixed oxide electrodes, such as Ir / Ru coated titanium electrodes, as well as electrodes made of glassy carbon, graphite or carbon can be used. The contact electrodes 6a may be plate-shaped or grid-shaped, which is coated with the electrode material. For contacting the provided contact electrodes 6a, one to three titanium rods, which are welded, for example, are provided per contact electrode 6a. i
    The diamond particle electrodes 6b are preferably constructed in accordance with WO0200 / 005585 A1 and manufactured according to the method described there. They therefore consist of doped diamond particles which are embedded in one layer and without mutual contact with one another in a plastic carrier layer. The diamond particles are in particular produced in a high-pressure / high-temperature process, preferably with boron, or with nitrogen, phosphorus, arsenic, antimony, niobium, lithium, sulfur or oxygen doped industrial diamonds (single crystals). Furthermore, the diamond particles have particle sizes of 100 pm to 2 mm, in particular from 160 pm to 350 pm. The particles within an electrode are essentially the same size or particles of a grain size range. The i carrier layer consists of one or more polymers, in particular of polytetrafluoroethylene, polyvinylidene fluoride, Perfluoralkoxylalkan, fluorinated ethylpropylene, ethylene-tetrafluoroethylene, polyether ketone, polyethylene, polypropylene,
    Polyvinyl chloride or polyphenylene sulfide. On both sides of the carrier layer, the particles are partially exposed.
    The diamond particle electrodes 6b used are distinguished by their chemical stability and by their high oxygen overvoltage, by means of which the oxygen formation which occurs competitively in the electrochemical oxidation of organic compounds can be minimized.
    By means of a voltage source 9, the electrode package 6 is supplied with electrical i DC voltage such that the current density at the surface of the electrodes 6a, 6b 10 mA / cm2 to 2000 mA / cm2, in particular 100 mA / cm2 to 800 mA / cm2.
    As will be explained in more detail below, the device is used for the electrochemical conversion of dissolved, emulsified or organic compounds dissolved in an alkaline electrolyte solution (organic electrosynthesis). An alkaline electrolyte solution is understood to be one which has a pH greater than 7. The alkaline electrolyte solution preferably has a pH of at least 8, in particular of at least 10.
    Electrochemically convertible are those organic compounds whose molecules contain at least one double or one triple bond and / or have a π-electron system and / or contain at least one heteroatom and thus at least one polar atomic bond.
    Particularly good electrochemically convertible are therefore organic compounds whose molecules have at least one double or triple bond between a carbon atom and a heteroatom. In the electrochemical conversion, the molecules are preferably cleaved at a multiple bond or a polar atomic bond.
    In the subject invention is in particular the recycling or processing of resulting in industrial processes residues, which contain at least one electrochemically convertible biogenic organic compound, preferably more of these compounds, in the foreground. The molecules of these biogenic organic compounds usually contain at least one heteroatom, in particular a nitrogen, an oxygen or a sulfur atom, and thus a polar atomic bond. Most commonly, the molecules contain at least one oxygen atom. In particular, the molecules of biogenic organic compounds further have at least one double bond between a carbon atom and a heteroatom, wherein the molecules may also have a plurality of different heteroatoms.
    Residues containing non-biogenic organic compounds, for example hydrolyzable plastics, such as polyesters, polyamides, polyurethanes or polycarbonates, can also be electrochemically converted with the device.
    In the context of the subject invention, in particular the following enumerated residues are recycled or processed: - lignin-containing black liquors accumulating in the sulfate process of the pulp industry; - waste liquors arising from the alkaline hydrolysis of animal carcasses; i - fats containing alkaline wastewater, which in particular in the sanitation and disinfection, for example, in the cleaning of slaughterhouses incurred; - dissolved or finely suspended organic substances by alkali treatment; - Solutions of sodium or potassium salts of fatty acids (soap solutions).
    The residues and thus the organic compounds may therefore already be dissolved and / or suspended and / or emulsified in an alkaline electrolyte solution, e.g. in black liquors or in soap solutions. If these electrolyte solutions have an ion concentration of at least 0.1 mol / l, they can be electrolyzed directly in the flow cell 2. If the ion concentration of the respective electrolyte solution is less than 0.1 mol / l, the electrolyte solutions are concentrated in such a way that their ion concentration increases to at least 0.1 mol / l. Alternatively or additionally, corresponding compounds, for example salts, acids or bases, can be added to the electrolyte solutions to increase their ion concentration. If the residues are not present in any electrolyte solution, they are introduced into an alkaline electrolyte solution whose ion concentration is at least 0.1 mol / l or compounds corresponding to the residues are added to form such. The electrolyte solution is preferably an aqueous or an organic, in particular alcoholic or phenolic, electrolyte solution. The maximum ion concentration for the respective ions is determined by the saturation concentrations of the ions in the electrolyte solution. i
    When the pH of the electrolytic solution is <7 (neutral or acidic electrolytic solution), bases, preferably an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution, are added to raise the pH.
    The hydroxide ions of the alkaline electrolyte solutions polarize functional groups of the organic compounds contained therein, which, for example, form carboxylic anions from carboxylic acids. Since the anions formed are highly polar, they can advantageously be converted very easily electrochemically. Furthermore, the hydroxide ions react with insoluble organic compounds to form soluble organic compounds. For example, water-insoluble fats, i. Fatty acid esters, split by the reaction with hydroxide ions in water-soluble salts of fatty acids and water-soluble alcohols (saponification). The organic salts dissolved in this way are subsequently converted electrochemically.
    The cations contained in the electrolytic solution are preferably ions of the alkali metals, in particular potassium ions and / or sodium ions. These ions are particularly suitable because of their high water solubility and are advantageously not involved in the electrochemical conversion, since their standard electrode potential is lower than that of hydrogen. Furthermore, potassium and sodium ions with the organic compounds form readily water-soluble organic salts and thus electrochemically convertible compounds. Potassium ions are also particularly suitable because the hydrate shell forming around them in aqueous solution is smaller than that which forms around sodium ions. Therefore, potassium ions have a particularly low hydrodynamic resistance and accordingly are particularly mobile in aqueous solutions, so that the electrical conductivity of an electrolyte solution containing potassium ions is also particularly high.
    I
    The electrolyte solution which is already suitable or adjusted with regard to the pH and the ion concentration is pumped via the liquid feed line 3a into the container 1 and from there by means of the pump 8 via the feed line 7a into the flow cell 2. Viscous electrolyte solutions are preferably heated before being introduced into the flow cell 2 via the already mentioned between the pump 8 and the container 1 arranged heat exchanger, in particular to a temperature of up to 60 ° C. In principle, any electrolyte solution can be heated to a temperature which is below its boiling point. Particularly preferred are temperatures in the range of 70 ° C to 90 ° C. The electrochemical conversion is carried out in particular at the present in the device or adjusting pressure ratios, but can also be carried out at a pressure relative to the ambient pressure increased, which is preferably up to 10 bar, in particular <4 bar. During operation, the supply and discharge of the electrolyte solution in and out of the container 1 is regulated such that the level of the liquid medium in the container 1 does not reach the gas line 4 and the electrode package 6 of the flow cell 2 is continuously circulated during operation ,
    The reactions taking place in the flow cell 2 are influenced by the process parameters. These process parameters include, in particular, the residence time of the electrolyte solution in the flow cell 2, the temperature and / or the pH value and / or the ion concentration of the electrolyte solution and the current intensity and the voltage of the voltage source 9. These process parameters are selected or set in advance in such a way, the organic compounds present in each case in the electrolytic solution are converted via redox reactions at the electrodes 6a, 6b of the electrode assembly 6 into a gaseous fuel. In the course of this conversion, the molecules of the organic compounds contained in the electrolyte solution are therefore fragmented and defunctionalized. In particular, by adjusting the current intensity and the voltage of the voltage source 9, an electrochemical conversion of the organic compounds into a gaseous fuel can be brought about particularly comfortably, with particularly high fuel yields being achieved by fine-tuning these parameters.
    In the context of the subject invention, gaseous fuel designates a gas mixture suitable as a fuel, whose combustible main components are hydrogen and gaseous hydrocarbons, in particular ethane, propane, butane, ethene, propene and butene. As combustible gaseous secondary constituents, for example, hydrogen sulfide or ammonia can be formed. As additional secondary constituents, gaseous organic compounds whose molecules contain heteroatoms, in particular oxygen, can be formed at the temperatures prevailing in the apparatus. These include, for example, aldehydes, alcohols, esters, ketones or carbon dioxide.
    The gaseous fuel formed is discharged via the return line 7b from the flow cell 2 and transported back into the container 1, where it leaves the electrolyte solution, collects in a gas above the level of the electrolyte solution in the container 1 gas space 10 and is transported away via the gas line 4, i sucked in particular. Any secondary constituents of the fuel condensing in the gas line 4 can be separated from the combustible main constituents in a simple manner.
    The formed gaseous fuel can be thermally utilized in a combined heat and power plant, so that electrical energy and / or heat is recovered. Alternatively, the constituents of the fuel may be isolated by means of a suitable separator. Subsequently, constituents of the fuel can be converted via a steam reforming into a synthesis gas, wherein in the context of the subject invention a synthesis gas is understood to mean a gas mixture suitable for the synthesis of further organic compounds, which consists mainly of carbon monoxide and hydrogen. From the synthesis gas formed further organic compounds can be prepared in a conventional manner. In particular, synthesis gas for
    Fischer-Tropsch synthesis can be used. Another possible use of the synthesis gas is, for example, in its conversion to methanol.
    The most frequently occurring as heteroatom in biogenic organic compounds oxygen is largely converted into carbon dioxide or other under the prevailing temperatures gaseous organic compound and transported together with the gaseous fuel via the gas line 4. Sulfur atoms are, for example, oxidized to sulfate and nitrogen atoms in particular converted to nitrites, nitrates, ammonia or nitrogen molecules. These sulfur and nitrogen compounds either remain in the electrolyzed solution or leave it together with the gaseous fuel via the gas line 4. Furthermore, the electrolyzed solution contains inorganic secondary constituents of the residues, such as calcium carbonate, silicon compounds, metal salts, metal oxides, sulfates and / or nitrates , From this remaining alkaline electrolyzed solution chemicals, especially alkalis, can be recovered.
    The following equations give the processes taking place primarily in the electrochemical reaction in general form, where A, B, C denote organic molecules: i A -> - A - + + e "Equation (1) A + e '-> A' Equation (2) B '-► B- + e Equation (3) C + + e' - »C 'Equation (4)
    In the respective primary process of the electrochemical reaction, usually only a single electron is transferred between the electrode and a molecule of the organic compound, whereby from neutral molecules radial ions (equation (1) and (2)), from anions by oxidation radicals (equation ( 3)) and from cations by reduction of i radicals (equation (4)). Accordingly, reactive intermediates are formed at the electrodes by electron absorption or electron donation, which can react further accordingly.
    Another chemical reaction taking place in the flow cell 2 can be, for example, a Kolbe electrolysis in which carboxylic acids or salts of the carboxylic acids are converted to alkanes and carbon dioxide. Furthermore, for example, an electrochemical oxidation take place, in which hydroxyl radicals are involved.
    Further processes taking place in the course of the electrochemical conversion are, for example, the hydrogenation of the molecules of the organic compounds, which is initiated by atomic hydrogen (nascent hydrogen) freshly formed at the electrodes.
    In a further embodiment variant of the invention, the gas line 4 is connected directly to the flow cell 2 or to the return line 7b. Furthermore, the electrolyte solution can also be directly into the flow cell 2 and derived from this, so that no container 1 is provided. Since the amount of inflowing electrolytic solution intended for the conversion can fluctuate, the container 1 is preferably provided, by way of which these fluctuations can be compensated, so that the flow cell 2 is particularly reliably continuously flushed around by the electrolyte solution. 5 Reference numbers 3 1 ................. Container la ............... Container bottom lb .......... ..... Tank lid lc ............... Tank wall 2 ................. Flow cell 3 3 a ..... .......... Liquid supply 3b ............... Liquid discharge 4 ................. Gas line 5 .. ............... Housing 6 ................. Electrode Package) 6a ............. .. Contact electrode 6b ............... Diamond particle electrode 7a ............... Supply pipe 7b ........... .... Return line 8 ................. Pump »9 ................. Voltage source 10 ..... .......... gas space
    权利要求:
    Claims (28)
    [1]
    claims
    A process for the electrochemical conversion of organic compounds contained in residuals or as residuals, wherein the residuals are dissolved, suspended or emulsified in an electrolytic solution and the electrolytic solution is alkaline or alkaline, the electrolytic solution being at least one single-cell flow cell (2) designed electrolysis cell, which has an electrode package (6) from at least two to a voltage source (9) connected to the contact electrodes (6a), is continuously fed and discharged, wherein it flows through the electrode stack (6), and wherein in the electrolysis cell Setting of one or more process parameters (s) from at least one of the organic compounds, a gaseous fuel is formed, which is discharged and discharged from the electrolysis cell.
    [2]
    2. The method according to claim 1, characterized in that as the combustible main component or as combustible main components of the gaseous fuel one or more from the group hydrogen and gaseous hydrocarbons, in particular ethane, propane, butane, ethene, propene and butene is formed or become.
    [3]
    3. The method according to claim 1 or 2, characterized in that the electrolyte solution in an electrolysis cell, the electrode package between the contact electrodes (6a) has at least one further, in particular a bipolar electrode, continuously on and is discharged from this.
    [4]
    4. The method according to claim 3, characterized in that the electrolyte solution in an electrolysis cell, the electrode package between the contact electrodes (6a) at least one diamond electrode, in particular a diamond particle electrode, continuously on and is discharged from this.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the electrolytic cell as contact electrodes (6a) and as any provided further electrode (s) directly contactable diamond electrodes, in particular diamond particle electrodes, platinum-coated titanium electrodes, mixed oxide electrodes, in particular Ir / Ru-coated titanium electrodes , or electrodes of glassy carbon, graphite or carbon.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the or the process parameters or which is or are set, the residence time of the electrolyte solution in the electrolytic cell, the temperature of the electrolyte solution, the pH of the electrolyte solution , the ion concentration of the electrolyte solution, the current and the voltage of the voltage source (9) is or are.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the electrolytic cell supplied alkaline electrolyte solution has an ion concentration of at least 0.1 mol / 1.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the electrolytic solution prior to introduction into the electrolysis cell at least one compound for the formation of alkali metal ions, preferably potassium ions and / or sodium ions is added until the ion concentration of at least 0.1 mol / 1 amounts to.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the alkaline electrolyte solution has a pH of at least 8, in particular of at least 10, or is adjusted to such a pH. I
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that an aqueous or an organic, in particular an alcoholic or phenolic, electrolytic solution is used as the alkaline electrolyte solution.
    [11]
    11. The method according to any one of claims 1 to 10, characterized in that a lignin-containing black liquor obtained in the sulfate process of the pulp industry is used as the residue.
    [12]
    12. The method according to any one of claims 1 to 10, characterized in that the waste liquors used in the alkaline hydrolysis of Tierkadavem be used.
    [13]
    13. The method according to any one of claims 1 to 10, characterized in that as waste material containing fats alkaline wastewater, which are incurred in particular in the sanitation and disinfection, are used.
    [14]
    14. The method according to any one of claims 1 to 10, characterized in that are used as residues in an alkali treatment dissolved and / or finely suspended organic substances.
    [15]
    15. The method according to any one of claims 1 to 10, characterized in that solutions of sodium or potassium salts of fatty acids are used as residues.
    [16]
    16. The use of a single-cell flow cell (2) designed electrolytic cell, which has an electrode package (6) of at least two connected to a voltage source (9) contact electrodes (6a), for the electrochemical conversion of residual substances contained in or as residual organic compounds in one gaseous fuel, wherein the residues are dissolved, suspended or emulsified in an alkaline electrolyte solution, wherein the electrolytic solution, the electrolysis cell and thus the electrode assembly (6) flows continuously, and wherein in the electrolytic cell of at least one of the organic compounds, a gaseous fuel is formed, which discharged from the electrolysis cell and is derived.
    [17]
    17. Use of an electrolytic cell according to claim 16 for the formation of a gaseous fuel whose combustible main component or combustible main components from the group of hydrogen and gaseous hydrocarbons, in particular ethane, propane, butane, ethene, propene and butene, is or are.
    [18]
    18. Use of an electrolytic cell according to claim 16 or 17, the electrode packet between the contact electrodes (6 a) at least one further electrode, in particular a bipolar electrode having.
    [19]
    19. Use of an electrolytic cell according to claim 18, the electrode packet between the contact electrodes (6a) has at least one diamond electrode, in particular a diamond particle electrode.
    [20]
    20. Use of an electrolytic cell according to one of claims 16 to 19, which as contact electrodes (6a) and as possibly provided further electrode (s) directly contactable diamond electrodes, in particular diamond particle electrodes, platinum-coated titanium electrodes, mixed oxide electrodes, in particular Ir / Ru-coated titanium electrodes, or electrodes of glassy carbon, graphite or carbon.
    [21]
    21. Use of an electrolytic cell according to claim 16, for the electrolysis of an alkaline electrolyte solution having an ion concentration of at least 0.1 mol / l. 22. Use of an electrolytic cell according to claim 16 or 21, for the electrolysis of an alkaline electrolyte solution containing alkali metal ions, preferably potassium ions and / or sodium ions.
    [23]
    23. Use of an electrolytic cell according to one of claims 16, 21 or 22, i for the electrolysis of an alkaline electrolyte solution which has a pH of at least 8, in particular of at least 10.
    [24]
    24. Use of an electrolytic cell according to any one of claims 16 or 21 to 23, for the electrolysis of an aqueous or an organic, especially alcoholic or phenolic, electrolyte solution.
    [25]
    25. Use of an electrolytic cell according to any one of claims 16 to 24 for the formation of a gaseous fuel from a obtained in the sulfate process of the pulp industry ligninhaltigen black liquor. i
    [26]
    26. Use of an electrolytic cell according to any one of claims 16 to 24 for the formation of a gaseous fuel from waste liquors incurred in the alkaline hydrolysis of animal carcasses.
    [27]
    27. Use of an electrolytic cell according to one of claims 16 to 24 for the formation of a gaseous fuel from fats containing alkaline wastewaters, which are incurred in particular in the sanitation and disinfection.
    [28]
    28. Use of an electrolytic cell according to any one of claims 16 to 24 for the formation of a gaseous fuel from dissolved in an alkali treatment and / or finely suspended organic substances.
    [29]
    29. Use of an electrolytic cell according to any one of claims 16 to 24 for the formation of a gaseous fuel from solutions of sodium or potassium salts of fatty acids.
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    EP3449041B1|2020-12-23|
    WO2017186682A1|2017-11-02|
    AT518544B1|2017-11-15|
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    引用文献:
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    GB1113497A|1965-07-05|1968-05-15|Universal Oil Prod Co|Process for electrolytic oxidation of anions|
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    WO2009138368A1|2008-05-14|2009-11-19|Basf Se|Method for electrochemically cleaving lignin on a diamond electrode|
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    法律状态:
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    EP17720746.1A| EP3449041B1|2016-04-29|2017-04-25|Method for the electrochemical conversion of organic compounds contained in residual materials or arising as residual materials|
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