EP0745701A1 - Procédé de régénération de diaphragmes en matière synthétiques - Google Patents

Procédé de régénération de diaphragmes en matière synthétiques Download PDF

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Publication number
EP0745701A1
EP0745701A1 EP96108246A EP96108246A EP0745701A1 EP 0745701 A1 EP0745701 A1 EP 0745701A1 EP 96108246 A EP96108246 A EP 96108246A EP 96108246 A EP96108246 A EP 96108246A EP 0745701 A1 EP0745701 A1 EP 0745701A1
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EP
European Patent Office
Prior art keywords
weight
diaphragm
corrosion inhibitor
mineral acid
pref
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.)
Granted
Application number
EP96108246A
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German (de)
English (en)
Other versions
EP0745701B1 (fr
Inventor
Rudi Dr. Kröner
Bernd Dr. Leutner
Hans-Michael Dr. Schneider
Holger Dr. Friedrich
Kurt Hecky
Dieter Dr. Schläfer
Wolfgang Dr. Steiner
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0745701A1 publication Critical patent/EP0745701A1/fr
Application granted granted Critical
Publication of EP0745701B1 publication Critical patent/EP0745701B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25B13/00—Diaphragms; Spacing elements
    • 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
    • C25B15/00—Operating or servicing cells

Definitions

  • the present invention relates to a method for the regeneration of plastic diaphragms, in particular for the regeneration of plastic diaphragms from chloralkali electrolysis.
  • the diaphragm method uses electrolysis cells that use a cathode grid made of iron, on which the diaphragm material e.g. has been applied by vacuum deposition.
  • dimensionally stable anodes DSA
  • the anode which are, for example, expanded metal meshes made of titanium, which are coated with ruthenium oxide / titanium oxide.
  • the anodes are expanded in order to keep the distance between the anode and cathode and thus the ohmic voltage drop as small as possible.
  • the diaphragm process uses diaphragms made of different materials, such as asbestos. More recently, plastic diaphragms have also been used, which are produced by vacuum deposition of a fiber material and subsequent sintering.
  • the fiber material can consist, for example, of PTFE fibers with embedded and adhering ZrO 2 particles. Examples of such a fiber material are Polyramix® fibers (Oxytech) and Tephram® fibers (PPG Industries, Inc.).
  • plastic diaphragms can be operated much longer.
  • an asbestos diaphragm typically has a service life of approximately 4,000 to 10,000 operating hours and is then replaced, plastic diaphragms can be used over a period of approximately 17,000 to 26,000 operating hours.
  • DE 19 56 291 proposes to remove blockages from diaphragms by rinsing the diaphragm with hydroxypolycarboxylic acids, such as citric acid, gluconic acid, etc. Although this method is also suitable for partially removing superficial deposits from iron oxides, it is not possible in this way to remove iron oxide penetrations in plastic diaphragms.
  • Japanese patent application JP 60077985 in which a method for cleaning electrolytic cells of the diaphragm type, which are used in particular for the production of hydrogen from alkalis, with mixtures of acids and surfactants, is described, can only be used for cleaning an expanded asbestos diaphragm, since here too the corrosion of the iron and titanium parts cannot be avoided.
  • German Offenlegungsschrift 15 67 962 describes a method for regenerating an asbestos diaphragm in which a corrosion inhibitor is used to protect the iron parts. Even with this method, only superficial deposits can be removed, while the diaphragm cannot be removed. Since asbestos as a material is not stable under strongly acidic conditions, the corrosion inhibitors proposed in the published patent application are also not sufficient to protect the cathode when regenerating a plastic diaphragm. In addition, titanium corrosion cannot be prevented by this method.
  • EDTA ethylenediamine tetraacetic acid
  • the proposed complexing agents are comparatively expensive compounds.
  • the rinsing solution obtained when cleaning the diaphragm cannot go untreated due to the complexing agents it contains Waste water are given, so that additional costs for the elaborate disposal are incurred.
  • the cell's plastic diaphragm is usually completely removed and replaced by a new one in order to regenerate it. This procedure is cost-intensive, since the new equipment of the cell requires extensive work and the new diaphragm material required for this is very expensive. There are also landfill costs for the material that has become unusable. A cleaning of the plastic diaphragm must completely remove the iron impurities, otherwise the hydrogen concentration in the chlorine cannot drop permanently after regeneration. Since the aged iron oxides in particular are very stubbornly adhering and difficult to dissolve deposits and growths, the use of agents is necessary which, on the other hand, can lead to corrosion of iron and titanium parts in the cell.
  • the object of the present invention is therefore to provide a method for the regeneration of plastic diaphragms, in which deposits and / or growths on or in the plastic diaphragm can be removed economically, in particular without significantly corroding iron and / or titanium components and without being difficult residues to be disposed arise. According to the present invention, this object is achieved by the subjects defined in the independent patent claims; advantageous further developments are listed in the subclaims.
  • this object is achieved by a process for the regeneration of plastic diaphragms, in which a mineral acid solution is mixed with a corrosion inhibitor, and the mixture thus obtained at a temperature of about 30 to 110 ° C, preferably 40 to 80 ° C, in particular 50 to 70 ° C, about 0.1 to 84 hours, preferably 1 to 72 hours, in particular 2 to 24 hours, is passed through the plastic diaphragm.
  • a process for the regeneration of plastic diaphragms in which a mineral acid solution is mixed with a corrosion inhibitor, and the mixture thus obtained at a temperature of about 30 to 110 ° C, preferably 40 to 80 ° C, in particular 50 to 70 ° C, about 0.1 to 84 hours, preferably 1 to 72 hours, in particular 2 to 24 hours, is passed through the plastic diaphragm.
  • a method is preferably provided in which the mineral acid solution is used in a concentration of 0.3 to 20% by weight, in particular 2 to 10% by weight.
  • Particularly preferred is the use of an acid which consists at least partially, preferably exclusively of hydrochloric acid, as the mineral acid.
  • hydrochloric acid prevents foreign ions from entering the cell, which would then have to be removed by lengthy rinsing.
  • another mineral acid for example sulfuric acid, would of course also be suitable for carrying out the cleaning.
  • the mineral acid solution contains up to 250 g / l sodium chloride.
  • the cleaning effect of this mixture is increased by the addition of sodium chloride.
  • sodium chloride For example, with the addition of NaCl, it is possible to reduce the concentration of hydrochloric acid (eg from 9% to 2%), although the solution still has a sufficient cleaning effect.
  • 0.005 to 5% by weight, preferably 0.05 to 0.5% by weight, of corrosion inhibitor is provided in the mixture of the mineral acid solution with the corrosion inhibitor, the percentages by weight relating to the mixture of the mineral acid solution refer to the corrosion inhibitor as 100 wt .-%. This dosage of the corrosion inhibitor leads to protection of the iron parts in the electrolysis cell.
  • a corrosion inhibitor which contains at least one alkynol.
  • a corrosion inhibitor which contains at least one alkynol and is preferably mixed with 1 to 25% by weight of an amine and / or 0.1 to 3% by weight of a surfactant can also preferably be used, the percentages by weight relating to the corrosion inhibitor 100% by weight.
  • alkynols can, for example, alkynediols such as butynediol, 3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol , or also be propargyl alcohol or hexinol (3-hexin-2-ol) or ethynylcyclohexanol.
  • Amines such as hexamethylenetetramine, ethylhexylamine, diethylhexylamine or other primary, secondary or tertiary amines can be added to these alkinols.
  • the alkynols act as a monomer for the formation of a corrosion-inhibiting coating on the iron parts that are to be protected.
  • a surfactant which contains a quaternary ammonium compound.
  • Organic ammonium compounds with quaternary nitrogen atoms can include, for example, quaternary ammonium compounds with in particular long alkyl chains, such as, for example, distearyldimethylammonium chloride (DSDMA), Protectol KLC 80® or Protectol KLC 50® (BASF) or Pluradyne CI 1066® (BASF Corp.).
  • Particularly preferred mixtures of alkynols with amines and / or quaternary ammonium compounds include about 98% butynediol and 2% hexamethylenetetramine or, for example, about 97.8% butynediol plus about 2% hexamethylenetetramine plus about 0.2% Protectol KLC 50®.
  • the mineral acid solution contains about 500 to 5000 ppm copper or iron salts.
  • Water-soluble Fe III or Cu II salts are preferably added to the mixture of the mineral acid solution and the corrosion inhibitor. This can be achieved, for example, by additionally adding, for example, iron chloride to the mixture of the mineral acid solution with the corrosion inhibitor, or by pumping the mixture of the mineral acid solution with the corrosion inhibitor through the diaphragm in a circle.
  • the iron-containing deposits detached from the diaphragm thereby provide Fe 3+ compounds, which then act as a corrosion inhibitor with respect to the titanium, of which the anodes in particular have larger proportions in uncoated form.
  • Another advantageous method of the present invention provides that the diaphragm is additionally rinsed, in particular rinsed, with water and / or a sodium chloride solution.
  • the water used is preferably pure water.
  • a sodium chloride solution is advantageously used for this rinsing, since in this case there is no risk of uncontrolled dilution by residual water when fresh brine is subsequently poured into the cell.
  • the cell is filled with fresh brine anyway.
  • alkyne monools in particular propargyl alcohol or ethynylcyclohexanol
  • alkynols are preferably also used as alkynols, an alkynol preferably being used in a concentration greater than 30% by weight, typically in a concentration greater than 80% by weight.
  • the percentage by weight here relates to the total alkynols used as 100% by weight.
  • These corrosion inhibitors are more effective in preventing iron corrosion. They can preferably be used where cells are used in which anodes are provided which are completely coated with a ruthenium-titanium oxide layer. In this case, the addition of iron salts can also be dispensed with.
  • Effective corrosion inhibitors are mixtures which contain alkyne monools, for example propargyl alcohol or ethynylcyclohexanol, as the main component. These corrosion inhibitors are particularly suitable for use in mixtures that do not have dissolved iron salts.
  • the mixture of mineral acid solution with the corrosion inhibitor should only be used once in this case.
  • a preferred mixture for inhibiting iron corrosion includes, for example, a mixture of about 2% Protectol KLC 80®, about 1% ethinylcyclohexanol, about 8% ethylhexylamine or diethylhexylamine, and about 89% propargyl alcohol.
  • Another advantageous mixture comprises approximately 2% Pluradyne CI 1066® and approximately 98% propargyl alcohol.
  • the mixture is passed through an electrolytic cell without prior removal of the diaphragm and electrode. In this way it is possible to regenerate the diaphragm without having to remove the diaphragm. Such in-situ cleaning of the diaphragm saves time, costs and labor. A complex removal of the diaphragm from the cell and detachment of the diaphragm material is therefore no longer necessary.
  • an advantageous method according to the present invention for the regeneration of plastic diaphragms can be provided, a method as described above being used several times in succession or at least two methods as described above in succession.
  • the diaphragms with different mixtures of mineral acid solutions with different corrosion inhibitors can be used in succession at different temperatures for a different length of time, whereby the advantages of the individual process parameters can be combined in such a way that the optimum for the present contamination Combination of individual processes and process parameters is provided.
  • the individual processes or process steps can also be separated from one another by rinsing the diaphragm with a rinsing solution, in particular with pure water or a sodium chloride solution.
  • a chlor-alkali cell eg a monopolar cell from Diamond Shamrock
  • anode gas of which a high hydrogen concentration (> 4% by volume) had been measured was switched off and the solution therein was drained off.
  • An 8% hydrochloric acid which contains 0.2% by weight of Korantin BH® (corrosion inhibitor from BASF AG based on butynediol and hexamethylenetetramine) was then preheated to 40 ° C. and pumped into the cell on the anode side. After the cell was completely filled, further solution was pumped in and removed on the cathode side and returned to the reservoir. This process was continued for 24 hours while maintaining the temperature of the hydrochloric acid at 50 ° C.
  • Pieces of titanium electrodes immersed in the mixture of hydrochloric acid and the corrosion inhibitor showed no weight loss. Also immersed pieces of ice cathodes showed a weight loss of approx. 1% after 24 hours.
  • a cell in the chlor-alkali electrolysis was switched off and the solution therein was drained off.
  • the diaphragm was then rinsed at 70 ° C. for 2 hours with an aqueous solution of approximately 2% hydrochloric acid, approximately 250 g / l sodium chloride, approximately 0.5% Korantin BH and approximately 0.1% Fe 3+ ions.
  • the diaphragm was then rinsed with pure water for about an hour.
  • the weight loss of the iron cathode was between 0.5 and 1.5% by weight, and the titanium corrosion was less than 0.02% weight loss.
  • the iron-containing deposits were completely, i.e. over 98% removed from the diaphragm.
  • the solution contained therein was drained from a switched off chlor-alkali electrolysis cell. Thereupon the diaphragm was covered with an aqueous Solution containing about 8% hydrochloric acid, 0.5% Korantin BH® and about 0.1% Fe 3+ ions was rinsed at 70 ° C for about 2 hours. In a second step, the diaphragm was rinsed with an aqueous solution containing about 8% hydrochloric acid, about 0.5% Korantin BH® and about 0.1% Fe 3+ ions at 50 ° C for 24 hours. The diaphragm was then rinsed with pure water for about an hour.
  • the weight loss of the iron cathode was between 1 and 2% by weight and the titanium corrosion was less than 0.02% weight loss.
  • the iron-containing deposits were completely, i.e. over 98% removed from the diaphragm.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP96108246A 1995-05-31 1996-05-23 Procédé de régénération de diaphragmes en matière synthétiques Expired - Lifetime EP0745701B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19519921A DE19519921A1 (de) 1995-05-31 1995-05-31 Verfahren zur Regenerierung von Kunststoffdiaphragmen
DE19519921 1995-05-31

Publications (2)

Publication Number Publication Date
EP0745701A1 true EP0745701A1 (fr) 1996-12-04
EP0745701B1 EP0745701B1 (fr) 1998-12-09

Family

ID=7763296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96108246A Expired - Lifetime EP0745701B1 (fr) 1995-05-31 1996-05-23 Procédé de régénération de diaphragmes en matière synthétiques

Country Status (6)

Country Link
US (1) US5755951A (fr)
EP (1) EP0745701B1 (fr)
CN (1) CN1077609C (fr)
DE (2) DE19519921A1 (fr)
NO (1) NO962216L (fr)
PL (1) PL314547A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7255798B2 (en) * 2004-03-26 2007-08-14 Ion Power, Inc. Recycling of used perfluorosulfonic acid membranes
ITMI20131521A1 (it) 2013-09-16 2015-03-17 Industrie De Nora Spa Cella elettrolitica per produzione di soluzioni ossidanti
CN111403838B (zh) * 2019-12-23 2023-04-25 余姚市鑫和电池材料有限公司 一种退役动力锂电池隔膜纸回收再利用方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174269A (en) * 1978-06-21 1979-11-13 Ppg Industries, Inc. Method of treating electrodes
US4204921A (en) * 1979-03-19 1980-05-27 Basf Wyandotte Corporation Method for rejuvenating chlor-alkali cells
EP0694632A1 (fr) * 1994-07-28 1996-01-31 OxyTech Systems, Inc. Régénération d'un diaphragme de cellule d'électrolyse

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1309214A (en) * 1919-07-08 Hugh k
GB1468355A (en) * 1973-07-18 1977-03-23 Ici Ltd Making porous diaphragms in electrolytic cells
US3467586A (en) * 1965-04-12 1969-09-16 Hooker Chemical Corp Rejuvenation of diaphragms for chlor-alkali cells
US3630863A (en) * 1968-11-13 1971-12-28 Ppg Industries Inc Cell diaphragm treatment
US3988223A (en) * 1975-10-28 1976-10-26 Basf Wyandotte Corporation Unplugging of electrolysis diaphragms
SU739261A2 (ru) * 1977-05-23 1980-06-05 Кишиневский политехнический институт им.С.Лазо Вихревой усилитель
SU808561A1 (ru) * 1978-09-01 1981-02-28 Предприятие П/Я В-2287 Способ промывки диафрагмы
US4381230A (en) * 1981-06-22 1983-04-26 The Dow Chemical Company Operation and regeneration of permselective ion-exchange membranes in brine electrolysis cells
JPS6077985A (ja) * 1983-10-06 1985-05-02 Kao Corp 電解槽の洗浄方法および洗浄薬剤
US5133843A (en) * 1990-09-10 1992-07-28 The Dow Chemical Company Method for the recovery of metals from the membrane of electrochemical cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174269A (en) * 1978-06-21 1979-11-13 Ppg Industries, Inc. Method of treating electrodes
US4204921A (en) * 1979-03-19 1980-05-27 Basf Wyandotte Corporation Method for rejuvenating chlor-alkali cells
EP0694632A1 (fr) * 1994-07-28 1996-01-31 OxyTech Systems, Inc. Régénération d'un diaphragme de cellule d'électrolyse

Also Published As

Publication number Publication date
CN1147566A (zh) 1997-04-16
PL314547A1 (en) 1996-12-09
US5755951A (en) 1998-05-26
DE59600938D1 (de) 1999-01-21
CN1077609C (zh) 2002-01-09
NO962216L (no) 1996-12-02
DE19519921A1 (de) 1996-12-05
NO962216D0 (no) 1996-05-30
EP0745701B1 (fr) 1998-12-09

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