EP1753894B1 - Verfahren zur herstellung von peroxodisulfaten in wässriger lösung - Google Patents

Verfahren zur herstellung von peroxodisulfaten in wässriger lösung Download PDF

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Publication number
EP1753894B1
EP1753894B1 EP05756088A EP05756088A EP1753894B1 EP 1753894 B1 EP1753894 B1 EP 1753894B1 EP 05756088 A EP05756088 A EP 05756088A EP 05756088 A EP05756088 A EP 05756088A EP 1753894 B1 EP1753894 B1 EP 1753894B1
Authority
EP
European Patent Office
Prior art keywords
electrodes
diamond
bipolar
coated
electrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP05756088A
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German (de)
English (en)
French (fr)
Other versions
EP1753894A2 (de
Inventor
Wolfgang Thiele
Hans-Jürgen KRAMER
Hans-Jürgen FÖRSTER
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United Initiators GmbH and Co KG
United Initiators Inc
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United Initiators GmbH and Co KG
United Initiators Inc
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Publication of EP1753894A2 publication Critical patent/EP1753894A2/de
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Publication of EP1753894B1 publication Critical patent/EP1753894B1/de
Anticipated expiration legal-status Critical
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/29—Persulfates
    • 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
    • C25B11/036—Bipolar electrodes
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/059—Silicon
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes

Definitions

  • the invention relates to a process for the preparation or regeneration of peroxydisulphuric acid and its salts by electrolysis of an aqueous solution containing sulfuric acid and / or metal sulphates.
  • metal sulfates includes sulfates of metals such as zinc, nickel or iron, as well as sulfates of alkali metals, alkaline earth metals or ammonium sulfate.
  • alkali metal sulfates or alkaline earth sulfates can be used as the metal sulfates, alkali metal sulfates or ammonium sulfate are preferably used.
  • diamond-coated electrodes can be used made of valve metals, preferably of niobium, or of ceramic materials, preferably of silicon [ DE 199 48 184.9 . DE 100 19 683 ].
  • the diamond layer is rendered conductive by doping with a trivalent or pentavalent element, preferably with boron.
  • platinum anodes used in the production of peroxodisulfate
  • thiocyanates as polarizers but it comes to cyanide-loaded anode gases, which require complex gas purification measures required.
  • diamond-coated anodes can be dispensed with.
  • Another advantage of the diamond-coated anodes in peroxodisulfate production is that even with lower sulfate content in the anolyte even significantly higher current yields can be achieved than when using platinum anodes.
  • FR 2790268 B1 is proposed such a bipolar electrolysis cell, wherein the bipolar electrodes consist of a ceramic substrate which is completely covered with a diamond film.
  • this cell is not specifically proposed for the production of peroxodisulfates, but for applications for pollutant degradation or for water disinfection.
  • DE 200 05 681 describes the use of double-sided diamond-coated bipolar electrodes.
  • an electrolysis cell construction suitable for different applications is proposed, which can be monopolar or bipolar, as undivided or split cell.
  • bipolar design diamond-coated silicon wafer electrodes are again used exclusively on both sides.
  • peroxodisulfates these cells can be used effectively with diamond electrodes coated on both sides and the relatively complex cell construction only for small persulfate throughputs. If you want to increase the throughput to technically relevant areas by a larger number of bipolar single cells, it comes in this construction to yield reductions by the strongly with the total voltage leakage currents in the supply and discharge lines.
  • the object underlying the present invention was therefore to provide a process for the preparation or regeneration of peroxodisulfuric acid and / or their salts, wherein the disadvantages of the previous methods and electrolysis cells shown at least partially be avoided. It has been found that peroxodisulfates can advantageously be produced in undivided or divided electrolysis cells in a simple manner using bipolar, unilaterally doped diamond-coated silicon electrodes, the uncoated silicon backs acting directly as cathodes.
  • the coating of the silicon electrode has a thickness of about 1 to about 20 ⁇ m, preferably about 5 ⁇ m.
  • the method of the invention advantageously enables the production of peroxodisulfuric acid and / or its salts on a true bipolar electrode with high current efficiency and low electrical energy consumption, although only the low-conductivity silicon is used as the cathode. In addition, there are no costs for a cathode coating.
  • bipolar, single-sided diamond coated silicon electrodes of the present invention is the lower catalytic activity of the silicon back surface as compared to a metallized back electrode, e.g. made of platinum or stainless steel. It has been found that this results in lower reduction losses of peroxodisulfate when electrolyzed in an undivided electrolysis cell. This results in undivided cells that the increase in the peroxodisulfate concentration with the electrolysis time is somewhat steeper and the achievable final concentration is higher than when using a metallized cathode under otherwise identical electrolysis conditions.
  • the process according to the invention for the preparation of peroxodisulfuric acid and / or its salts can be carried out both in undivided electrolysis cells and in electrolysis cells which are divided, for example by ion exchange membranes or porous diaphragms.
  • the bipolar, one-sided diamond-coated silicon electrodes according to the invention are particularly suitable for relatively simple constructed undivided electrolysis cells, as they are eg in DE G 200 05 681.6 for the disinfection of waters. It is advantageous for the current input when the monopolar edge anodes from a consist of diamond-coated valve metal.
  • valve metal refers to a metal that coats with anodic poling with an oxide layer that does not become conductive even at high voltages. When connected as an anode, the metal blocks. Connected as a cathode, the oxide layer dissolves and current flows reasonably uninhibited. Valve metals behave like a rectifier with different polarity. Examples of suitable valve metals are, for example, tantalum, titanium, niobium and zirconium. In the context of the present invention, preference is given to using niobium.
  • the monopolar edge cathodes are preferably made of a suitable, highly conductive material, such as e.g. Stainless steel, hastelloy, platinum and impregnated graphite. Highly alloyed stainless steels or Hastelloy are preferably used in the context of the present invention. Also, a metallized backside silicon peripheral cathode contacted with a power supply plate made of a highly conductive material, e.g. Copper, because of the good durability in undivided cells can be used. In particular, when using edge electrodes made of metallic materials, the current input due to the good conductivity in a simple manner and without major voltage drops can be optimally realized.
  • a suitable, highly conductive material such as e.g. Stainless steel, hastelloy, platinum and impregnated graphite. Highly alloyed stainless steels or Hastelloy are preferably used in the context of the present invention.
  • Electrodes stacks consisting of bipolar electrodes and edge electrodes with a current supply can also be electrically connected in parallel. If necessary, the distance of the bipolar electrodes can be adjusted or fixed by spacers. By means of such electrode stacks connected in parallel, it is possible to accommodate larger current capacities in an electrolytic cell without requiring an unacceptably high total voltage. Thus, the voltage can also be optimally adapted to the available rectifier voltage. In addition, by the short-circuit currents in the common supply and discharge lines for the electrolyte solutions can be further minimized, which also in a known manner by the arrangement can be supported by additional resistance paths in these lines.
  • Undivided bipolar cells constructed according to the invention can be used particularly advantageously if the peroxodisulfate concentration does not have to be too high for the particular application in question, such as e.g. for oxidative pollutant degradation in process solutions and wastewater.
  • the peroxodisulfate concentration does not have to be too high for the particular application in question, such as e.g. for oxidative pollutant degradation in process solutions and wastewater.
  • sodium peroxodisulfate reaction solutions containing 50 to 100 g / l still with current efficiencies between 75 and 50% and specific electrical energy consumption between 1.3 and 1.9 kWh / kg are produced very effectively.
  • An analog DE G 200 05 681.6 constructed undivided bipolar electrolysis cell contained 9 bipolar silicon electrodes, coated on one side with about 3 microns boron-doped diamond (average about 3,000 ppm boron).
  • the edge anode used was a power supply-equipped, one-sided diamond-coated niobium electrode.
  • the peripheral cathode with power supply was Hastelloy.
  • the bipolar electrodes had a dimension of 100 x 33 mm (33 cm 2 ).
  • the average distance of the approximately 1 mm thick bipolar electrodes was set by spacers to about 2 mm.
  • the electrolysis current was adjusted to 16.5 A constant, corresponding to an anodic and cathodic current density of 0.5 A / cm 2 .
  • the electrolyte used was 2 l of a 300 g / l sodium sulfate and 200 g / l sulfuric acid-containing aqueous solution. It was circulated from a recycle vessel at a rate of about 600 l / h via a heat exchanger and through the cell (batch mode). The electrolysis operation was maintained over 5000 h, with only the evaporated or decomposed water was added. In steady state, a concentration between 170 and 190 g / l sodium peroxodisulfate at a steady state temperature of about 35 ° C was. The total voltage at start-up was 50 V.
  • the mean cell voltage developed in the course of continuous operation as follows: Operating time of 5 h 50 h 500 h 5000 h Mean cell voltage 4.95 V 4,60 V 4.35 V 4.18 v
  • the electrodes were removed and weight loss determined. From this, the average decrease of the silicon electrode thickness to an average of 3 ⁇ m was calculated. The thickness of the silicon cathode thus only decreases by about 10 ⁇ m per year.
  • the nine bipolar electrodes and the two monopolar edge electrodes of the undivided electrolysis cell used in Examples 1 to 3 were used in a bipolar split cell.
  • For the separation of anolyte and catholyte cation exchange membranes were used, fixed on both sides by anode and cathode spacers made of plastic. The limited by sealing frame anodes and cathode compartments had a thickness of 2 - 3 mm.
  • Anolyte and catholyte were circulated in separate circuits with the interposition of a heat exchanger.
  • the catholyte used was a 500 g / l sulfuric acid.
  • the anolyte again consisted of a 200 g / l sulfuric acid and 300 g / l of sodium sulfate-containing aqueous solution.
  • 100 g / l were in the anolyte during the electrolysis Dissolved sodium sulfate (in total so 400 g / l sodium sulfate).
  • the anodic and cathodic current density was set to 0.5 A / cm 2, respectively.
  • the mean cell voltages were in the range of 5.5 and 6 V.
  • a still very low specific electric energy consumption of about 1.8 kWh / kg could be achieved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP05756088A 2004-06-05 2005-06-03 Verfahren zur herstellung von peroxodisulfaten in wässriger lösung Expired - Lifetime EP1753894B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004027623A DE102004027623A1 (de) 2004-06-05 2004-06-05 Verfahren zur Herstellung von Peroxodisulfaten in wässriger Lösung
PCT/EP2005/006008 WO2005121408A2 (de) 2004-06-05 2005-06-03 Verfahren zur herstellung von peroxodisulfaten in wässriger lösung

Publications (2)

Publication Number Publication Date
EP1753894A2 EP1753894A2 (de) 2007-02-21
EP1753894B1 true EP1753894B1 (de) 2007-09-12

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EP05756088A Expired - Lifetime EP1753894B1 (de) 2004-06-05 2005-06-03 Verfahren zur herstellung von peroxodisulfaten in wässriger lösung

Country Status (10)

Country Link
US (3) US20070187254A1 (https=)
EP (1) EP1753894B1 (https=)
JP (1) JP4852037B2 (https=)
KR (1) KR20070042141A (https=)
CN (1) CN100591805C (https=)
AT (1) ATE373118T1 (https=)
BR (1) BRPI0511816B1 (https=)
DE (2) DE102004027623A1 (https=)
ES (1) ES2290917T3 (https=)
WO (1) WO2005121408A2 (https=)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009004155A1 (de) * 2009-01-09 2010-07-15 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Verfahren und Vorrichtung zum Regenerieren von Peroxodisulfat-Beizlösungen
JP5106523B2 (ja) 2009-12-16 2012-12-26 株式会社東芝 エッチング処理方法、微細構造体の製造方法、およびエッチング処理装置
JP5751884B2 (ja) * 2011-03-29 2015-07-22 森永乳業株式会社 複極式電解槽
EP2697730A4 (en) * 2011-04-15 2015-04-15 Advanced Diamond Technologies Inc ELECTROCHEMICAL SYSTEM AND METHOD FOR PROPORTION OF OXIDIZERS AT HIGH CURRENT DENSITY
EP2546389A1 (de) * 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Verfahren zur Herstellung eines Ammonium- oder Akalimetallperosodisulfats im ungeteilten Elektrolyseraum
TW201406998A (zh) * 2012-07-13 2014-02-16 United Initiators Gmbh & Co Kg 無分隔電解槽及其用途
PL2872673T3 (pl) 2012-07-13 2020-12-28 United Initiators Gmbh Niepodzielone ogniwo elektrolityczne i jego zastosowanie
CN104487615B (zh) * 2012-07-13 2017-08-25 联合引发剂有限责任两合公司 不分离的电解槽及其应用
DE102021115850B4 (de) 2021-06-18 2022-12-29 Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts Verfahren zur Laugung metallhaltiger Erze mittels elektrochemisch hergestellter Laugungslösung
KR20250116685A (ko) * 2022-11-29 2025-08-01 에콕스 글로벌 피티이 엘티디 전기화학적 산화 방법 및 공정

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US3926770A (en) * 1972-06-08 1975-12-16 Ppg Industries Inc Electrolytic cell having silicon bipolar electrodes
TW364024B (en) * 1995-08-17 1999-07-11 Eilenburger Elektrolyse & Umwelttechnik Gmbh Process for the combined electrochemical preparation of sodium peroxodisulfate and sodium hydroxide solution
US5681445A (en) * 1995-12-21 1997-10-28 Hydro-Quebec Modified surface bipolar electrode
JP3554630B2 (ja) * 1996-04-11 2004-08-18 ペルメレック電極株式会社 耐久性を有する電解用電極
JPH1161472A (ja) * 1997-08-08 1999-03-05 Shinko Pantec Co Ltd 水素酸素発生装置の電解セルおよびその電極板
FR2790268B1 (fr) * 1999-02-25 2001-05-11 Suisse Electronique Microtech Cellule d'electrolyse a electrode bipolaire comportant du diamant
DE19911746A1 (de) * 1999-03-16 2000-09-21 Basf Ag Diamantelektroden
DE19948184C2 (de) * 1999-10-06 2001-08-09 Fraunhofer Ges Forschung Elektrochemische Herstellung von Peroxo-dischwefelsäure unter Einsatz von diamantbeschichteten Elektroden
DE10015209A1 (de) * 2000-03-27 2001-10-11 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren und Vorrichtung zur elektrochemischen Desinfektion von Wässern
DE20005681U1 (de) * 2000-03-27 2000-06-21 Eilenburger Elektrolyse- und Umwelttechnik GmbH, 04838 Eilenburg Elektrolysezelle zur Desinfektion von Wässern
DE10019683A1 (de) * 2000-04-20 2001-10-25 Degussa Verfahren zur Herstellung von Alkalimetall- und Ammoniumperoxodisulfat
EP1229149A1 (fr) * 2001-01-31 2002-08-07 CSEM Centre Suisse d'Electronique et de Microtechnique SA Electrode de grandes dimensions
EP1254972A1 (fr) * 2001-05-01 2002-11-06 CSEM Centre Suisse d'Electronique et de Microtechnique SA Cellule electrochimique modulaire
JP2004099914A (ja) * 2002-09-04 2004-04-02 Permelec Electrode Ltd ペルオキソ二硫酸塩の製造方法

Also Published As

Publication number Publication date
ES2290917T3 (es) 2008-02-16
EP1753894A2 (de) 2007-02-21
US9840783B2 (en) 2017-12-12
BRPI0511816B1 (pt) 2015-07-28
US20160186338A1 (en) 2016-06-30
WO2005121408A2 (de) 2005-12-22
KR20070042141A (ko) 2007-04-20
DE102004027623A1 (de) 2005-12-22
WO2005121408A3 (de) 2006-06-08
CN1965107A (zh) 2007-05-16
JP2008501856A (ja) 2008-01-24
BRPI0511816A (pt) 2007-12-26
ATE373118T1 (de) 2007-09-15
CN100591805C (zh) 2010-02-24
US20110132771A1 (en) 2011-06-09
DE502005001500D1 (de) 2007-10-25
US20070187254A1 (en) 2007-08-16
JP4852037B2 (ja) 2012-01-11

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