EP1148155B2 - Procédé de production de bisulfate peroxyde de métal alcalin et d'ammonium - Google Patents

Procédé de production de bisulfate peroxyde de métal alcalin et d'ammonium Download PDF

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Publication number
EP1148155B2
EP1148155B2 EP01109242A EP01109242A EP1148155B2 EP 1148155 B2 EP1148155 B2 EP 1148155B2 EP 01109242 A EP01109242 A EP 01109242A EP 01109242 A EP01109242 A EP 01109242A EP 1148155 B2 EP1148155 B2 EP 1148155B2
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EP
European Patent Office
Prior art keywords
anolyte
anode
catholyte
ammonium
peroxodisulfate
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
Application number
EP01109242A
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German (de)
English (en)
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EP1148155A3 (fr
EP1148155B1 (fr
EP1148155A2 (fr
Inventor
Thomas Dr. Lehmann
Patrick Stenner
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Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
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Publication of EP1148155A3 publication Critical patent/EP1148155A3/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
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis

Definitions

  • the invention relates to a process for the preparation of sodium and ammonium peroxodisulfate by anodic oxidation of a sodium or ammonium sulfate or hydrogen sulfate containing aqueous solution.
  • Sodium peroxodisulfate is produced at a current efficiency of 70-80% in an electrolytic cell having a diaphragm protected cathode and a platinum anode, by adding a neutral aqueous anolyte solution having an initial content of 5 to 9% by weight of sodium ions, 12 to 30% by weight.
  • a filter press-type electrolytic cell for producing peroxo compounds, including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • peroxo compounds including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • anodes here hot isostatically applied to a valve metal platinum foils are used.
  • the anolyte used is a solution of the corresponding sulfate containing a promoter and sulfuric acid. This method also has the aforementioned problems.
  • peroxodisulfates are prepared by anodic oxidation of an aqueous solution containing neutral ammonium sulfate.
  • the solution obtained from the anodic oxidation which contains ammonium peroxodisulfate, is reacted with caustic soda or potassium hydroxide; after crystallization and separation of the corresponding alkali metal peroxodisulfate, the mother liquor is recycled in admixture with the catholyte produced during electrolysis.
  • the electrolysis takes place in the presence of a promoter on a platinum electrode as the anode.
  • PA Michaud et. al. teach in Electro Chemical and Solid State letters, 3 (2) 77-79 (2000) the production of peroxodisulfuric acid by anodic oxidation of sulfuric acid using a boron doped diamond thin film electrode.
  • This document teaches that such electrodes have a higher overvoltage for oxygen than platinum electrodes, but it can not be deduced from this document whether boron-doped diamond thin-film electrodes can also be used for the industrial production of ammonium and alkali metal peroxodisulfates.
  • sulfuric acid on the one hand and hydrogen sulphates, in particular neutral sulphates on the other hand behave very differently in anodic oxidation.
  • the major side reaction besides the anodic oxidation of sulfuric acid is the evolution of oxygen and, in addition, ozone.
  • the object of the present invention is to demonstrate a technical process for the preparation of ammonium and sodium peroxodisulfates, which has the disadvantages of the known processes, at least to a lesser extent.
  • the use of a promoter can be dispensed with completely and the electrolysis can be carried out at low current density, resulting in further advantages.
  • the present invention accordingly provides a process for the preparation of a peroxodisulfate from the series of ammonium and sodium peroxodisulfate, by the anodic oxidation of an ammonium sulfate or sodium hydrogen sulfate containing aqueous electrolyte in an electrolytic cell, comprising at least one anode, a cathode and anolyte space, this by a separator separated from a Katholytraum is characterized in that one uses as an anode disposed on a conductive support and made conductive by doping with a trivalent or pentavalent element diamond layer and added to the anolyte no promoter.
  • the subclaims are directed to preferred embodiments of this method.
  • the effective as an anode conductive diamond layer is doped in their preparation by doping with one or more tri- or pentavalent elements with such an amount that sufficient conductivity results.
  • the doped diamond layer is thus an n-conductor or a p-type conductor.
  • the conductive diamond layer is on a conductive support material, which may be selected from the series silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum and tungsten and carbides of said elements.
  • a conductive diamond layer may also be applied to aluminum.
  • Particularly preferred support materials for the diamond layer are silicon, titanium, niobium, tantalum and tungsten and carbides of these elements.
  • a particularly suitable electrode material for the anode is a boron-doped diamond thin film on silicon.
  • the preparation of the diamond electrodes can be carried out in two special CVD (chemical vapor deposition technique). These are the microwave plasma CVD and the hot wire CVD process.
  • the gas phase which is activated by microwave irradiation or thermally activated by hot wires to the plasma, from methane, hydrogen and optionally further additives, in particular a gaseous compound of the dopant.
  • a gaseous compound of the dopant By using a boron compound such as trimethylboron, a p-type semiconductor is formed.
  • a gaseous phosphorus compound as a dopant, an n-type semiconductor is obtained.
  • deposition of the doped diamond layer on crystalline silicon a particularly dense and non-porous layer is obtained - a film thickness of 1 ⁇ m is usually sufficient.
  • the deposition can also take place on a self-passivating metal, such as titanium, tantalum, tungsten or niobium.
  • a self-passivating metal such as titanium, tantalum, tungsten or niobium.
  • ammonium and sodium peroxodisulfate can be carried out in customary electrolysis cells, which may also be combined in the form of a filter pack.
  • Anode space and cathode space are separated by a separator.
  • the separator may, for example, be a conventional porous material made of an oxidic material, but an ion exchange membrane is preferred.
  • Suitable cathodes are those materials which are already known in the art, such as lead, carbon, tin, zirconium, platinum, nickel and their alloys, with lead being preferred.
  • the electrolysis cell comprises a circuit for the liquid anolyte and a further circuit for a liquid catholyte. According to the invention, no promoter is added to the anolyte.
  • the starting anolyte contains per liter 300 to 500 g of ammonium sulfate and 0 to 0.2 mol of sulfuric acid per mole of ammonium sulfate.
  • a substantially neutral starting anolyte is preferred.
  • catholyte is a sulfuric acid ammonium sulfate solution.
  • the anodic oxidation is carried out at an anodic current density in the range of 50 to 1000 mA / cm 2 , preferably 400 to 900 mA / cm 2 .
  • ammonium peroxodisulfate is obtained in a manner known per se, the work-up preferably comprising a vacuum crystallization and separation of the crystals from the mother liquor.
  • the anolyte mother liquor is recirculated into the electrolysis after increasing the content of ammonium sulfate or hydrogen sulfate - this can be done by mixing with the catholyte produced and, if necessary, adding a base.
  • Sodium peroxodisulfate is prepared by adding an anolyte solution containing sodium hydrogen sulfate in an amount of 300 to 700 g / l NaHSO 4 at a current density in the range from 50 to 1000 mA in an electrolysis cell with an anolyte and catholyte circuit separated by a separator, in particular an ion exchange membrane / cm 2 , in particular 400 to 900 mA / cm 2 , oxidized anodically, wherein the catholyte used is a sulfuric acid sodium hydrogen sulfate solution.
  • the example of sodium peroxodisulfate shows at medium current density the dependence of the current efficiency on the concentration of sodium peroxodisulfate with a diamond or platinum electrode and that the current efficiency in a diamond electrode according to the invention to be used with increasing content of sodium peroxodisulfate in the anolyte only slowly decreases - under the experimental conditions can be For example, at a current efficiency of equal to or greater than 75% anolyte solutions with a Natriumperoxodisulfatgehalt of about 400 g / l win.
  • the working current density can be significantly reduced compared to platinum anodes, whereby fewer ohmic losses occur in the system and thus the cooling effort is reduced and the degree of freedom in the design of the electrolysis cells and the cathodes is increased.
  • a further advantage is that the conductive diamond anodes to be used according to the invention can be produced in any desired form and corrosion-prone connection points, such as weld seams and the like, are not present. As a result, a longer electrode life is achieved.
  • the electrolytic cell includes a lead cathode and a boron-doped diamond anode on a Si wafer.
  • the diamond anode was connected to a metal plate (power distributor).
  • the diamond anode was replaced by a mirror-finished platinum sheet ground with diamond powder.
  • the electrolyte chambers were separated by an ion exchange membrane (DuPont, Nafion 430) in the anode compartment and cathode compartment. The distance between the electrodes was 2.2 cm.
  • the round electrode area was 38.48 cm 2 .
  • the following table shows the operating parameters and the specific energy consumption.
  • the table shows the comparison of the electrolysis results with Pt and a diamond anode.
  • NaHSO 4 was oxidized anodically in the cell described above (B1 / VB1).
  • the anolyte consisted of a NaHSO 4 solution containing 610 g NaHSO 4 / l. After setting the current density samples were taken and analyzed after a predetermined time. In calculating the current efficiency, a linear volume decrease was assumed.
  • the curves showed the current efficiency as a function of the sodium peroxodisulfate (NaPS) concentration achieved in the anolyte using a diamond electrode (B2) or a Pt anode (VB2).
  • NaPS sodium peroxodisulfate
  • the anolyte contained no promoter. Only when using an anolyte with a prohibitively high promoter concentration - 0.6 g NH 4 SCN / l - was it possible to achieve current efficiencies close to those of Example B 2.

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

Claims (4)

  1. Procédé d'obtention de peroxodisulfate d'ammonium comprenant l'oxydation anodique d'un électrolyte aqueux renfermant du sulfate d'ammonium dans une cellule électrolytique comprenant au moins une anode, une cathode et une chambre anolytique, cette chambre étant séparée d'une chambre catholytique par un séparateur,
    caractérisé en ce qu'
    en tant qu'anode, on utilise une couche de diamant disposée sur un support conducteur et rendue conductrice par dopage avec un élément trivalent ou pentavalent, aucun promoteur n'étant ajouté à l'anolyte, en tant qu'anolyte, on utilise une solution aqueuse renfermant de 300 à 500 g/l de sulfate d'ammonium et de 0 à 0,2 mol d'acide sulfurique par mole de sulfate d'ammonium, et notamment un anolyte neutre, en tant que catholyte, on utilise une solution sulfurique de sulfate d'ammonium, on effectue l'oxydation anodique avec une densité de courant dans la plage de 50 à 1000 mA/cm2, en particulier de 400 à 900 mA/cm2, puis, on cristallise le peroxodisulfate d'ammonium de façon connue en elle-même à partir de l'anolyte.
  2. Procédé d'obtention de peroxodisulfate de sodium comprenant l'oxydation anodique d'un électrolyte aqueux renfermant de l'hydrogénosulfate de sodium dans une cellule électrolytique comprenant au moins une anode, une cathode et une chambre anolytique, cette chambre étant séparée d'une chambre catholytique par un séparateur,
    caractérisé en ce qu'
    en tant qu'anode, on utilise une couche de diamant disposée sur un support conducteur et rendue conductrice par dopage avec un élément trivalent ou pentavalent, aucun promoteur n'étant ajouté à l'anolyte, la cellule électrolytique renferme un circuit d'anolyte et un circuit de catholyte séparés entre eux au moyen d'un séparateur, on effectue l'oxydation anodique d'une solution d'anolyte renfermant de l'hydrogénosulfate de sodium en quantité de 300 à 700 g/l de NaHSO4, avec une densité de courant située dans la plage de 50 à 1000 mA/cm2, en particulier de 400 à 900 mA/cm2, et en tant que catholyte, on utilise une solution sulfurique d'hydrogénosulfate de sodium.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'
    en tant qu'anode, on utilise une couche de diamant dopée au bore placée sur un support en un matériau choisi parmi les éléments suivants : silicium, germanium, titane, zirconium, niobium, tantale, molybdène et tungstène ainsi que les carbures de ces éléments.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce qu'
    en tant que séparateur, on utilise une membrane échangeuse d'ions.
EP01109242A 2000-04-20 2001-04-14 Procédé de production de bisulfate peroxyde de métal alcalin et d'ammonium Expired - Lifetime EP1148155B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10019683A DE10019683A1 (de) 2000-04-20 2000-04-20 Verfahren zur Herstellung von Alkalimetall- und Ammoniumperoxodisulfat
DE10019683 2000-04-20

Publications (4)

Publication Number Publication Date
EP1148155A2 EP1148155A2 (fr) 2001-10-24
EP1148155A3 EP1148155A3 (fr) 2001-11-21
EP1148155B1 EP1148155B1 (fr) 2005-06-08
EP1148155B2 true EP1148155B2 (fr) 2011-09-14

Family

ID=7639513

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Application Number Title Priority Date Filing Date
EP01109242A Expired - Lifetime EP1148155B2 (fr) 2000-04-20 2001-04-14 Procédé de production de bisulfate peroxyde de métal alcalin et d'ammonium

Country Status (18)

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US (1) US6503386B2 (fr)
EP (1) EP1148155B2 (fr)
JP (2) JP5259899B2 (fr)
KR (1) KR20010098758A (fr)
AR (1) AR027804A1 (fr)
AT (1) ATE297477T1 (fr)
AU (1) AU3710001A (fr)
BR (1) BR0101530A (fr)
CA (1) CA2344499C (fr)
CZ (1) CZ20011317A3 (fr)
DE (2) DE10019683A1 (fr)
ES (1) ES2240269T5 (fr)
IL (1) IL142638A0 (fr)
MX (1) MXPA01003938A (fr)
PL (1) PL347119A1 (fr)
SK (1) SK5202001A3 (fr)
TW (1) TW524893B (fr)
ZA (1) ZA200103205B (fr)

Families Citing this family (15)

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DE19948184C2 (de) * 1999-10-06 2001-08-09 Fraunhofer Ges Forschung Elektrochemische Herstellung von Peroxo-dischwefelsäure unter Einsatz von diamantbeschichteten Elektroden
DE102004026447B4 (de) * 2004-05-29 2009-09-10 Verein für Kernverfahrenstechnik und Analytik Rossendorf e.V. Verfahren und Vorrichtung zur Abtrennung von Sulfationen aus Wässern und zur Einbringung von Pufferkapazität in Wässer
DE102004027623A1 (de) * 2004-06-05 2005-12-22 Degussa Initiators Gmbh & Co. Kg Verfahren zur Herstellung von Peroxodisulfaten in wässriger Lösung
JP5207529B2 (ja) * 2008-06-30 2013-06-12 クロリンエンジニアズ株式会社 硫酸電解槽及び硫酸電解槽を用いた硫酸リサイクル型洗浄システム
DE102009004155A1 (de) 2009-01-09 2010-07-15 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Verfahren und Vorrichtung zum Regenerieren von Peroxodisulfat-Beizlösungen
JP5271345B2 (ja) * 2010-12-21 2013-08-21 クロリンエンジニアズ株式会社 導電性ダイヤモンド電極、これを用いた、硫酸電解方法及び硫酸電解装置
EP2546389A1 (fr) * 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Procédé de fabrication de peroxodisulfate alcalin ou d'ammonium dans une pièce d'électrolyse non divisée
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
TW201406998A (zh) 2012-07-13 2014-02-16 United Initiators Gmbh & Co Kg 無分隔電解槽及其用途
DE102016113727A1 (de) * 2016-07-26 2018-02-01 Condias Gmbh Verfahren zur elektrochemischen Herstellung von Peroxodicarbonat und elektrochemische Zelle zur Durchführung des Verfahrens
GB201819928D0 (en) * 2018-12-06 2019-01-23 Univ Court Univ Of Glasgow Method for generating persulfate
JP7163841B2 (ja) * 2019-03-28 2022-11-01 東レ株式会社 過硫酸アンモニウムの製造方法
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
CN116789236B (zh) * 2023-07-19 2024-06-18 北京大学 一种硫酸钠型高盐废水电解资源化利用方法

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DD129219A1 (de) † 1977-01-05 1978-01-04 Wolfgang Thiele Verfahren zur elektrochemischen herstellung von peroxod

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US4144144A (en) 1976-12-23 1979-03-13 Fmc Corporation Electrolytic production of sodium persulfate
CA1090286A (fr) 1976-12-23 1980-11-25 Kenneth J. Radimer Fabrication electrolytique du persulfate de sodium
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US4802959A (en) * 1987-06-16 1989-02-07 Tenneco Canada Inc. Electrosynthesis of persulfate
DE3938160A1 (de) 1989-11-16 1991-05-23 Peroxid Chemie Gmbh Elektrolysezelle zur herstellung von peroxo- und perhalogenatverbindungen
JP4157615B2 (ja) * 1998-03-18 2008-10-01 ペルメレック電極株式会社 不溶性金属電極の製造方法及び該電極を使用する電解槽
JP4182302B2 (ja) * 1998-03-30 2008-11-19 三菱瓦斯化学株式会社 過硫酸カリウムの製造方法
TW416997B (en) 1998-03-30 2001-01-01 Mitsubishi Gas Chemical Co Process for producing persulfate
DE19948184C2 (de) 1999-10-06 2001-08-09 Fraunhofer Ges Forschung Elektrochemische Herstellung von Peroxo-dischwefelsäure unter Einsatz von diamantbeschichteten Elektroden
DE19962672A1 (de) 1999-12-23 2001-06-28 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren und Vorrichtung zur Herstellung oder Regenerierung von Peroxodisulfaten
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Publication number Publication date
JP5259899B2 (ja) 2013-08-07
CA2344499A1 (fr) 2001-10-20
JP2002004073A (ja) 2002-01-09
JP2013136842A (ja) 2013-07-11
IL142638A0 (en) 2002-03-10
US6503386B2 (en) 2003-01-07
JP5570627B2 (ja) 2014-08-13
AR027804A1 (es) 2003-04-09
CA2344499C (fr) 2010-08-03
TW524893B (en) 2003-03-21
AU3710001A (en) 2001-10-25
EP1148155A3 (fr) 2001-11-21
BR0101530A (pt) 2001-12-04
DE10019683A1 (de) 2001-10-25
SK5202001A3 (en) 2002-01-07
US20020014418A1 (en) 2002-02-07
ES2240269T5 (es) 2012-02-03
ZA200103205B (en) 2001-10-23
PL347119A1 (en) 2001-10-22
DE50106427D1 (de) 2005-07-14
ATE297477T1 (de) 2005-06-15
EP1148155B1 (fr) 2005-06-08
CZ20011317A3 (cs) 2002-02-13
MXPA01003938A (es) 2003-08-20
ES2240269T3 (es) 2005-10-16
KR20010098758A (ko) 2001-11-08
EP1148155A2 (fr) 2001-10-24

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