EP1148155B1 - 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
EP1148155B1
EP1148155B1 EP01109242A EP01109242A EP1148155B1 EP 1148155 B1 EP1148155 B1 EP 1148155B1 EP 01109242 A EP01109242 A EP 01109242A EP 01109242 A EP01109242 A EP 01109242A EP 1148155 B1 EP1148155 B1 EP 1148155B1
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EP
European Patent Office
Prior art keywords
anolyte
ammonium
peroxodisulfate
anode
sodium
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
EP1148155B2 (fr
EP1148155A2 (fr
Inventor
Thomas Dr. Lehmann
Patrick Stenner
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Evonik Operations GmbH
Original Assignee
Degussa GmbH
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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 Alkali metal, in particular sodium and potassium and of Ammonium peroxodisulfate by anodic oxidation of a Alkali metal or ammonium sulfate or hydrogen sulfate containing aqueous solution.
  • alkali metal and ammonium peroxodisulfate by anodic oxidation of a corresponding sulfate or hydrogen sulfate-containing aqueous solution to produce and salt by crystallization from the To gain anolyte.
  • sodium peroxodisulfate is produced with a current efficiency of 70 to 80% in an electrolytic cell with a diaphragm-protected cathode and a platinum anode by a neutral aqueous anolyte solution with an initial content of 5 to 9 wt .-% sodium ions, 12 to 30% by weight of sulfate ions, 1 to 4% by weight of ammonium ions, 6 to 30% by weight of peroxodisulfate ions and a potential-increasing agent, a so-called promoter, in particular thiocyanate, using a sulfuric acid solution as the catholyte at a current density of at least 0.5 to 2 A / cm 2 is electrolyzed.
  • the mother liquor is mixed with the cathode product, neutralized and fed back to the anode.
  • Disadvantages of this process are 1. the requirement of using a promoter to reduce the evolution of oxygen, 2. the requirement of a high current density and thus a high anode potential in order to obtain an economically acceptable current efficiency, and 3. the problems associated with the production of the platinum anode with a view to obtaining a technically acceptable current efficiency and anode life.
  • EP-B 0 428 171 is an electrolysis cell from Filter press type for the production of peroxo compounds, including ammonium peroxodisulfate, sodium peroxodisulfate and Potassium peroxodisulfate known.
  • peroxo compounds including ammonium peroxodisulfate, sodium peroxodisulfate and Potassium peroxodisulfate known.
  • anodes will be here Hot isostatically applied to a valve metal Used platinum foils.
  • Anolyt becomes a promoter and sulfuric acid-containing solution of the corresponding Sulfate used. Also this method has the previously mentioned problems.
  • Peroxodisulfate by anodic oxidation of a neutral ammonium sulfate containing aqueous solution prepared is the from the anodic oxidation solution, which Contains ammonium peroxodisulfate, with sodium hydroxide or Reacted potassium hydroxide; after crystallization and Separation of the corresponding alkali metal peroxodisulfate the mother liquor is mixed with that in the electrolysis produced catolyte recycled. Also in this case takes place the electrolysis in the presence of a promoter on a Platinum electrode as anode.
  • Object of the present invention is a technical Process for the preparation of ammonium and Alkali metal peroxodisulfates show that the disadvantages the known method, at least to a lesser extent having. Surprisingly, it was found that the Preparation of ammonium and alkali metal peroxodisulfates with high current efficiency is possible by using an anode diamond thin-film electrode doped with a trivalent or pentavalent element is used. Surprisingly can completely dispense with the use of a promoter and the electrolysis at low current density be carried out, resulting in further benefits.
  • the subject of the present invention is accordingly a Process for the preparation of a peroxodisulfate from the Series of ammonium, sodium and potassium peroxodisulfate, by the anodic oxidation of a salt from the series Ammonium, sodium and potassium sulfate and / or des corresponding hydrosulfate-containing aqueous Electrolyte in an electrolytic cell comprising at least an anode, a cathode and anolyte compartment, this one separated by a separator from a Katholytraum or adjacent to a gas diffusion cathode, thereby is characterized in that one as an anode on a arranged conductive carrier and by doping with made conductive to a trivalent or pentavalent element Diamond layer used and the anolyte no promoter added.
  • the subclaims are directed to preferred Embodiments of this method.
  • the effective as an anode conductive diamond layer is at their preparation by doping with one or more trivalent or pentavalent elements with such an amount doped that sufficient conductivity results.
  • the doped diamond layer is thus an n-type conductor or a p-conductors.
  • the conductive is Diamond layer on a conductive substrate, wherein this can be selected from the series silicon, Germanium, titanium, zirconium, niobium, tantalum, molybdenum and Tungsten and carbides of said elements.
  • a conductive diamond layer can also be applied to aluminum be applied.
  • Particularly preferred carrier 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 manufacture of diamond electrodes can be done in two special CVD process (chemical vapor deposition technic). It is the microwave plasma CVD and the hot wire CVD method. In both Cases, the gas phase is created by Microwave irradiation or thermally by hot wires to the plasma is activated, from methane, hydrogen and if necessary other additives, in particular a gaseous Compound of the dopant.
  • a Boron compound such as trimethylboron
  • a gaseous phosphorus compound as Dopant will receive an n-type semiconductor.
  • Deposition of the doped diamond layer on crystalline Silicon becomes a particularly dense and non-porous layer obtained - a film thickness of 1 micron is common sufficient.
  • the deposition can also on a self-passivating metal, like titanium, tantalum, Tungsten or niobium.
  • a self-passivating metal like titanium, tantalum, Tungsten or niobium.
  • Anode space and cathode space are here by separated a separator.
  • the separator may be for example, a conventional porous material from a oxidic material, but one is preferred Ion exchange membrane.
  • Suitable cathodes are those Materials as already known in the art are, such as lead, carbon, tin, zirconium, platinum, nickel and their alloys, with lead being preferred.
  • the Electrolysis cell is the cathode in the form of a Gas diffusion electrode formed, and the cathode is supplied with an oxygen-containing gas.
  • This can be the Electrolysis at much lower cell voltages be operated, which makes a significant contribution to Energy saving means.
  • the Electrolysis can on one separate anolyte circuit as well as on a microporous or to dispense with an ion-exchanging separator, which the overall procedure considerably simplified and one significant technical improvement over all so far represents known method.
  • the Electrolysis cell a circuit for the liquid anolyte and another circuit for a liquid Catholyte.
  • the anolyte can be sulfuric or neutral and contains ammonium and / or Alkali metal cations, sulphate and / or Hydrogen sulphate anions, preferably also Peroxodisulfate anions, but no polarizer.
  • the anolyte composition may correspond to as described in the documents cited at the beginning of the Technique are mentioned, however, with the difference that no Promoter is added or otherwise present.
  • the starting anolyte preferably contains from 300 to 500 g of ammonium sulfate per liter and from 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 anodization is conveniently 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 may be recovered either directly by anodic oxidation of an anolyte containing sodium bisulfate, with the anolyte preferably containing 500 to 600 g of NaHSO 4 per liter.
  • an aqueous solution containing 300 to 400 g of H 2 SO 4 per liter and 300 to 500 g of Na 2 SO 4 per liter.
  • sodium peroxodisulfate can also be obtained in a manner known per se by reacting an anolyte containing ammonium peroxodisulfate with sodium hydroxide solution from anodic oxidation of ammonium sulfate or ammonium hydrogen sulfate, in order subsequently to crystallize out sodium peroxodisulfate and separate it off from the mother liquor - by way of example the relevant embodiments DE-OS 199 13 820 and DE-PS 27 57 861 referenced.
  • sodium peroxodisulfate can also Potassium peroxodisulfate using a potassium sulfate and ammonium sulfate or a potassium hydrogen sulfate containing solution can be prepared.
  • the example of sodium peroxodisulfate shows at medium Current density the dependence of the current yield on the Concentration of sodium peroxodisulfate with a diamond or platinum electrode and that the current efficiency at a to be used according to the invention diamond electrode 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 or above 75% anolyte solutions with a sodium peroxodisulfate content of about 400 g / l.
  • Using a conventional platinum anode and concomitant use of a promoter in the anolyte can be contrast only Peroxodisulfate concentrations of about 300 g / l, and indeed obtained at a current efficiency of about 25%.
  • 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 to take 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 in Dependence on the obtained sodium peroxodisulfate (NaPS) concentration 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 de production d'un peroxobisulfate de la série constituée par le peroxobisulfate d'ammonium, de sodium et de potassium, qui comprend l'oxydation anodique d'un électrolyte aqueux, contenant un sel de la série constituée par le sulfate d'ammonium, de sodium et de potassium et/ou l'hydrogénosulfate correspondant, dans une cellule électrolytique comprenant au moins une anode, une cathode et une chambre anolytique, celle-ci étant séparée d'une chambre catholytique par un séparateur ou adjacente à une cathode de diffusion gazeuse,
    caractérisé en ce que
    comme anode on utilise une couche de diamant disposée sur un support conducteur et rendue conductrice par dopage avec un élément trivalent ou pentavalent, et aucun promoteur n'est ajouté à l'anolyte.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    comme anode on utilise une couche de diamant dopé au bore placée sur un support fait d'un matériau de la série constituée par les éléments suivants : silicium, germanium, titane, zirconium, niobium, tantale, molybdène et tungstène, ainsi que par les carbures de ces éléments.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce que
    dans une cellule électrolytique, contenant une chambre anolytique et une chambre catholytique, ainsi qu'un séparateur (en particulier une membrane échangeuse d'ions), on produit du peroxobisulfate d'ammonium en utilisant comme anolyte une solution aqueuse comportant de 300 à 500 g de sulfate d'ammonium et de 0 à 0,2 moles d'acide sulfurique par mole de sulfate d'ammonium, et notamment un anolyte neutre, et comme catholyte une solution sulfurique de sulfate d'ammonium, en effectuant l'oxydation anodique pour une densité de courant comprise entre 50 et 1000 mA/cm2, en particulier entre 400 et 900 mA/cm2,et en cristallisant et séparant ensuite le peroxobisulfate d'ammonium, d'une manière connue, à partir de l'anolyte.
  4. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'
    on produit du peroxobisulfate de sodium en soumettant à une oxydation anodique, dans une cellule électrolytique, à l'aide d'un cycle d'anolyte et d'un cycle de catholyte séparés entre eux au moyen d'un séparateur, en particulier d'une membrane échangeuse d'ions, une solution d'anolyte contenant de l'hydrogénosulfate de sodium en quantité de 300 à 700 g/litre de NaHSO4 en présence d'une densité de courant comprise entre 50 et 1000 mA/cm2, en particulier entre 400 et 900 mA/cm2), et en utilisant comme catholyte une solution, contenant de l'acide sulfurique, d'hydrogénosulfate de sodium.
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
DE10019683 2000-04-20
DE10019683A DE10019683A1 (de) 2000-04-20 2000-04-20 Verfahren zur Herstellung von Alkalimetall- und Ammoniumperoxodisulfat

Publications (4)

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

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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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2014009536A1 (fr) 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Cellule électrolytique dépourvue de séparateur et son utilisation

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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
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
PL2872673T3 (pl) 2012-07-13 2020-12-28 United Initiators Gmbh Niepodzielone ogniwo elektrolityczne i jego zastosowanie
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
EP3932862A1 (fr) 2020-07-01 2022-01-05 Evonik Operations GmbH Graphène fonctionnalisé, procédé de fabrication d'un graphène fonctionnalisé et son utilisation
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
JP2023176312A (ja) * 2022-05-31 2023-12-13 東レ株式会社 過硫酸アンモニウムの製造方法
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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CA1090286A (fr) 1976-12-23 1980-11-25 Kenneth J. Radimer Fabrication electrolytique du persulfate de sodium
US4144144A (en) 1976-12-23 1979-03-13 Fmc Corporation Electrolytic production of sodium persulfate
DD129219A1 (de) † 1977-01-05 1978-01-04 Wolfgang Thiele Verfahren zur elektrochemischen herstellung von peroxod
FR2434872A1 (fr) * 1978-08-30 1980-03-28 Air Liquide Procede de preparation de peroxydisulfate de metaux alcalins et d'ammonium
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
TW416997B (en) 1998-03-30 2001-01-01 Mitsubishi Gas Chemical Co Process for producing persulfate
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
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
JP2001192874A (ja) * 1999-12-28 2001-07-17 Permelec Electrode Ltd 過硫酸溶解水の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2013007816A2 (fr) 2011-07-14 2013-01-17 United Initiators Gmbh & Co. Kg Cellule électrolytique non divisée et son utilisation
WO2014009536A1 (fr) 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Cellule électrolytique dépourvue de séparateur et son utilisation

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US6503386B2 (en) 2003-01-07
EP1148155A3 (fr) 2001-11-21
MXPA01003938A (es) 2003-08-20
CA2344499C (fr) 2010-08-03
ES2240269T3 (es) 2005-10-16
SK5202001A3 (en) 2002-01-07
DE50106427D1 (de) 2005-07-14
ZA200103205B (en) 2001-10-23
ES2240269T5 (es) 2012-02-03
PL347119A1 (en) 2001-10-22
EP1148155B2 (fr) 2011-09-14
IL142638A0 (en) 2002-03-10
AR027804A1 (es) 2003-04-09
ATE297477T1 (de) 2005-06-15
KR20010098758A (ko) 2001-11-08
BR0101530A (pt) 2001-12-04
CA2344499A1 (fr) 2001-10-20
JP2002004073A (ja) 2002-01-09
DE10019683A1 (de) 2001-10-25
JP5570627B2 (ja) 2014-08-13
AU3710001A (en) 2001-10-25
US20020014418A1 (en) 2002-02-07
JP5259899B2 (ja) 2013-08-07
EP1148155A2 (fr) 2001-10-24
TW524893B (en) 2003-03-21
JP2013136842A (ja) 2013-07-11
CZ20011317A3 (cs) 2002-02-13

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