US3915816A - Process for the electrolytic production of sodium peroxodisulfate - Google Patents

Process for the electrolytic production of sodium peroxodisulfate Download PDF

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Publication number
US3915816A
US3915816A US448610A US44861074A US3915816A US 3915816 A US3915816 A US 3915816A US 448610 A US448610 A US 448610A US 44861074 A US44861074 A US 44861074A US 3915816 A US3915816 A US 3915816A
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solution
sodium
cell
sulfuric acid
electrolysis
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US448610A
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Erwin Rossberger
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United Initiators GmbH and Co KG
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United Initiators GmbH and Co KG
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    • 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

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  • ABSTRACT [30] Foreign Application Priority Data Sodium peroxodisulfate is produced by direct electrol- Sept. 18, 1973 Germany 2346945 W y electrolyzing, at to amperes P Square centimeter, a solution containing sodium sulfate and [52] US. Cl. 204/82 lf ric acid in such quantity that the solubility of the [51] Int. Cl.
  • This invention relates to the production of sodium peroxodisulfate. More specifically, the invention relates to a novel process for the production of this material by direct electrolysis.
  • sodium peroxidisulfate (hereinafter referred to simply as sodium persulfate) by direct electrolysis have been described in the past. However, the processes involved have not been successfully applied in practice. In the electrolysis of sodium hydrogen sulfate solutions, for example, relatively high current yields of about 80% and more are achieved at the beginning of the electrolysis, but it is soon observed, i.e., within several hours, that the current yield rapidly diminishes, and may drop to negative values, mathmatically speaking. Various measures which have been described in the literature, such as the use of mercury as cathode, have not produced useful results. This discouraging situation has been interpreted in part as being due to the action of the Na ion on the anodic oxidation process. Therefore, the prevailing view has been that direct electrolysis for the production of sodium persulfate from sodium sulfate is technically impossible or uneconomical.
  • an ammonium persulfate solution is formed from ammonium bisulfate solution with current yields averaging 70 percent, plus hydrogen and oxygen.
  • the electrolytic cells used for this purpose require means at the cathode, such as an asbestos cord wrapping or the like, to combat the ad-diffusion of the anions so that the reduction of the persulfate ions may be limited or prevented.
  • a precipitation of (NH S O in this case is generally undesirable and leads to a considerable increase in the cell voltage and hence in the energy requirement.
  • the salt is separated by suitable separating units and then dried. Then it is reacted with sodium hydroxide or caustic soda solution in accordance with:
  • the invention provides a process for the direct electrolytic production of sodium persulfate suitable for use on a large commercial scale in which the product formed is recoverable without a thermal crystallization process, i.e., in which a major drawback of prior art processes is overcome.
  • the process of the invention comprises the direct electrolytic production by electrolyzing, at 0.3 to 1.2 A/cm 'a solution containing Na SO and H SO in such quantity that the solubility of the sodium peroxodisulfate that is formed will be less than 0.6 mole per liter and the concentration of Na SO and H SO is kept constant during the electrolysis.
  • a solution which contains 2.6 to 3.1 moles Na SO per liter and 2.8 to 3.5 moles l-I SO per liter.
  • Na S O has a solubility of 0.2 to 0.6 mole.
  • the feedstocks must be added constantly in such measure that the concentration of acid, sulfate and sodium ions will remain as constant as possible.
  • newly formed sodium persulfate immediately precipitates in crystallized form and is thus removed from any further reactions. It can best be separated continuously in a partial stream by means of suitable separating units. After washing and drying, a very pure salt is obtained.
  • the amounts of electrolyte used in an electrolysis apparatus are not to exceed approximately 200 liters per kA with reference to the installed current intensity.
  • the operating range is 80 to 160 l/kA.
  • the preferred anode material is pure platinum in the form of sheets, wires or bands, or in the form of a coating on suitable supports. These supports will also serve as a conductor of current to the platinum which alone has the electrochemical action.
  • the anodic current density necessary for the anodic oxidation of the hydrogen sulfate ion amounts to at least 0.3 A/cm it may be increased up to 1.2 A/cm if provision is made for sufficient cooling.
  • the electrolyte temperature may amount to as much as about 28C, or even more for short periods. The best yields are obtained if the temperature is not substantially more than 22C.
  • polarization-increasing compounds such as chloride, borate, cyanide, rhodanide, etc., is preferred for optimum results. If such compounds are added it is desirable to keep their concentration constant, too.
  • EXAMPLE 1 An electrolyte, consisting of 3.0 moles Na SO per liter, 3.3 moles of H SO per liter and 0.5 g NaCl 0.8 g NaCN per liter, was pumped by means of a pump (5) through the electrolysis cell l where the chemical process of Equation (5) took place, was separated in container (2) from the electrolysis gas mixture (3) and was recycled into container (4). From the latter a partial stream was fed to the saturation tank (6) where the raw materials (8) were continuously metered in at a rate corresponding to the electrochemical transformation.
  • the electrolysis was performed in a flow-through cell with a current density of 0.5 A/cm at a current drain of 60 A; the time of stay of the electrolyte in the cell was 0.37 seconds, and its temperature was C; the electrolyte volume was 8 liters. After about 6 hours of operating time, crystallized Na s 0 begain to pretion.
  • EXAMPLE 2 In the same system as described in Example 1, an electrolyte consisting of 2.8 moles of Na SO per liter, 3.1 moles of H SO per liter and 0.4 g of NaSCN per liter, was electrolyzed at 0.6 A/cm Steady current yields of about 60 percent were produced over the 6-day course of the experiment. The cell voltage was 5. 1 volts. This shows an electrolysis power requirement of about 1.9 kWh per kg of sodium persulfate.
  • Process for the direct electrolytic production of sodium peroxodisulfate from (sodium hydrogen sulfate) a solution containing Na SO and H SO which process comprises electrolyzing in a cell, at a current density of from 0.3 to 1.2 amperes per square centimeter, an electrolytic solution containing said Na SO and H SO in such quantity that the solubility of the sodium peroxodisulfate formed amounts to less than 0.6 mole per liter, and maintaining the concentration of Na SQ, and H 50 constant during the electrolysis.
  • perature of the electrolyte solution is maintained at below 28C.

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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)
US448610A 1973-09-18 1974-03-06 Process for the electrolytic production of sodium peroxodisulfate Expired - Lifetime US3915816A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2346945A DE2346945C3 (de) 1973-09-18 1973-09-18 Verfahren zur direkten elektrolytischen Herstellung von Natriumperoxodisulfat

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US3915816A true US3915816A (en) 1975-10-28

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US448610A Expired - Lifetime US3915816A (en) 1973-09-18 1974-03-06 Process for the electrolytic production of sodium peroxodisulfate

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US (1) US3915816A (ja)
JP (1) JPS5135588B2 (ja)
AU (1) AU497870B2 (ja)
BR (1) BR7407724D0 (ja)
DD (1) DD108962A5 (ja)
DE (1) DE2346945C3 (ja)
ES (1) ES422348A1 (ja)
FR (1) FR2243903B1 (ja)
GB (1) GB1473714A (ja)
IT (1) IT1020817B (ja)
NL (1) NL183414C (ja)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2757861A1 (de) * 1976-12-23 1978-06-29 Fmc Corp Verfahren zur herstellung von natriumperoxydisulfat
FR2375345A1 (fr) * 1976-12-23 1978-07-21 Fmc Corp Polariseur pour la production electrolytique de peroxydisulfates
US4144144A (en) * 1976-12-23 1979-03-13 Fmc Corporation Electrolytic production of sodium persulfate
US5082543A (en) * 1989-11-16 1992-01-21 Peroxid-Chemie Gmbh Filter press electrolysis cell
DE19530218A1 (de) * 1995-08-17 1997-02-20 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren zur kombinierten elektrochemischen Herstellung von Natriumperoxodisulfat und Natronlauge
US6168670B1 (en) * 1997-12-30 2001-01-02 Lpw-Blasberg Anlagen Gmbh Method of pickling articles of copper and metals less noble than copper
US6200454B1 (en) 1997-12-24 2001-03-13 Mitsubishi Gas Chemical Company, Inc. Process for producing sodium persulfate
US20010015322A1 (en) * 2000-02-23 2001-08-23 Kenichi Kimizuka Process for producing sodium persulfate
EP2546389A1 (de) 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Verfahren zur Herstellung eines Ammonium- oder Akalimetallperosodisulfats im ungeteilten Elektrolyseraum
WO2014009536A1 (de) 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Ungeteilte elektrolysezelle und deren verwendung
US9540740B2 (en) 2012-07-13 2017-01-10 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW416997B (en) * 1998-03-30 2001-01-01 Mitsubishi Gas Chemical Co Process for producing persulfate
JP4880865B2 (ja) * 2001-04-27 2012-02-22 アイレンブルガー エレクトロリーゼ− ウント ウムヴェルトテヒニク ゲゼルシャフト ミット ベシュレンクテル ハフツング 亜二チオン酸ナトリウム及びペルオキソ二硫酸ナトリウムを電気化学的に同時に製造する方法
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US880599A (en) * 1906-02-12 1908-03-03 Gustav Teichner Process for electrolytically producing persulfates.
US1059809A (en) * 1910-10-06 1913-04-22 Gustav Adolph Manufacture of persulfates.
US2281090A (en) * 1937-03-31 1942-04-28 Buffalo Electro Chem Co Electrolytic manufacture of potassium persulphate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE172508C (ja) *

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US880599A (en) * 1906-02-12 1908-03-03 Gustav Teichner Process for electrolytically producing persulfates.
US1059809A (en) * 1910-10-06 1913-04-22 Gustav Adolph Manufacture of persulfates.
US2281090A (en) * 1937-03-31 1942-04-28 Buffalo Electro Chem Co Electrolytic manufacture of potassium persulphate

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2757861A1 (de) * 1976-12-23 1978-06-29 Fmc Corp Verfahren zur herstellung von natriumperoxydisulfat
FR2375344A1 (fr) * 1976-12-23 1978-07-21 Fmc Corp Production electrolytique de persulfate de sodium
FR2375345A1 (fr) * 1976-12-23 1978-07-21 Fmc Corp Polariseur pour la production electrolytique de peroxydisulfates
US4127456A (en) * 1976-12-23 1978-11-28 Fmc Corporation Polarizer for the electrolytic production of peroxydisulfates
US4144144A (en) * 1976-12-23 1979-03-13 Fmc Corporation Electrolytic production of sodium persulfate
US5082543A (en) * 1989-11-16 1992-01-21 Peroxid-Chemie Gmbh Filter press electrolysis cell
DE19530218A1 (de) * 1995-08-17 1997-02-20 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren zur kombinierten elektrochemischen Herstellung von Natriumperoxodisulfat und Natronlauge
US6200454B1 (en) 1997-12-24 2001-03-13 Mitsubishi Gas Chemical Company, Inc. Process for producing sodium persulfate
US6168670B1 (en) * 1997-12-30 2001-01-02 Lpw-Blasberg Anlagen Gmbh Method of pickling articles of copper and metals less noble than copper
US20010015322A1 (en) * 2000-02-23 2001-08-23 Kenichi Kimizuka Process for producing sodium persulfate
EP2546389A1 (de) 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Verfahren zur Herstellung eines Ammonium- oder Akalimetallperosodisulfats im ungeteilten Elektrolyseraum
WO2013007816A2 (de) 2011-07-14 2013-01-17 United Initiators Gmbh & Co. Kg Ungeteilte elektrolysezelle und deren verwendung
US9556527B2 (en) 2011-07-14 2017-01-31 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use of the same
WO2014009536A1 (de) 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Ungeteilte elektrolysezelle und deren verwendung
US9540740B2 (en) 2012-07-13 2017-01-10 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use thereof

Also Published As

Publication number Publication date
DE2346945A1 (de) 1975-03-27
DD108962A5 (ja) 1974-10-12
ES422348A1 (es) 1976-04-01
NL183414C (nl) 1988-10-17
AU497870B2 (en) 1979-01-18
AU7303974A (en) 1976-03-11
IT1020817B (it) 1977-12-30
DE2346945B2 (de) 1976-12-09
JPS5056395A (ja) 1975-05-17
BR7407724D0 (pt) 1975-07-15
DE2346945C3 (de) 1982-05-19
FR2243903A1 (ja) 1975-04-11
NL7411926A (nl) 1975-03-20
GB1473714A (en) 1977-05-18
JPS5135588B2 (ja) 1976-10-04
FR2243903B1 (ja) 1977-09-16
NL183414B (nl) 1988-05-16

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