EP2397579A1 - Elektrode für die elektrolytische Chlorgewinnung - Google Patents

Elektrode für die elektrolytische Chlorgewinnung Download PDF

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Publication number
EP2397579A1
EP2397579A1 EP11170272A EP11170272A EP2397579A1 EP 2397579 A1 EP2397579 A1 EP 2397579A1 EP 11170272 A EP11170272 A EP 11170272A EP 11170272 A EP11170272 A EP 11170272A EP 2397579 A1 EP2397579 A1 EP 2397579A1
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EP
European Patent Office
Prior art keywords
noble metal
titanium
electrode
anatase
oxide
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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.)
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Application number
EP11170272A
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German (de)
English (en)
French (fr)
Inventor
Ruiyong Chen
Vinh Trieu
Harald Natter
Rolf Hempelmann
Andreas Bulan
Jürgen KINTRUP
Rainer Weber
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Bayer Intellectual Property GmbH
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Bayer MaterialScience AG
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Publication of EP2397579A1 publication Critical patent/EP2397579A1/de
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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
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds 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
    • 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
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the invention is based on known electrodes, at least consisting of an electrically conductive substrate based on a valve metal and an electrocatalytically active coating of a noble metal oxide or Edelmetalloxidgemischs and titanium oxide.
  • thermodynamic stability of the structure ie, the binding behavior of the MO 6 octahedra of Ru and Ti, depends on the surface free energy of the nanoparticles which is influenced by the surface chemistry (oxide and hydroxide formation, water adsorption) ( Nano Letter 5, 1261 (2005 )).
  • surface chemistry oxide and hydroxide formation, water adsorption
  • the thermally induced crystallization of amorphous phases under oxidizing conditions leads to a coating structure with a predominant rutile phase.
  • the invention relates to the production of an electrodeposition coating for electrolytic chlorine, which consists of a noble metal oxide and an anatase-rutile titanium oxide with a certainêtanatasanteil.
  • a particular electrode is characterized in that the coating has a proportion of anatase structure, characterized in that in each case after deduction of a linear background, the peak height of the most intense anatase reflex (Reflex (101)) in the X-ray diffractogram (radiation Cu ⁇ ) at least 60% of Height of the most intense rutile reflex (reflex (110)) in the X-ray diffractogram.
  • the targeted adjustment of the composition and the influence of the microstructure on the electrode coating is achieved, for example, by a two-stage process. In this case, a thermally stabilized and amorphous educt phase, which is produced in a sol-gel process, is first crystallized in a solvothermal treatment and then with a thermal after-treatment.
  • a material with an anatase structure is understood here simply as a material having a structure of the anatase structure type.
  • a solvothermal treatment in the sense of the invention is understood to mean a treatment at elevated pressure relative to the ambient pressure and elevated temperature relative to room temperature.
  • the described process control achieves a coating with a higher anatase content, which leads to a direct increase in efficiency in the extraction of chlorine.
  • a solvothermal process with a process temperature of at most 250 ° C., preferably 100 to 250 ° C. and a process pressure of 1 to 10 MPa, has proven suitable for the crystallization of an amorphous educt mixture.
  • the invention relates to an electrode, at least consisting of an electrically conductive substrate based on a valve metal, in particular a metal of titanium, tantalum, niobium or an alloy of these metals, with a major constituent of titanium, tantalum or niobium and an electrocatalytically active coating with up to 40 mol% of a noble metal oxide or Edelmetalloxidgemischs and at least 6 mol% of titanium oxide, characterized in that the coating has a minimum proportion of oxides with anatase structure, which is determined by the ratio of the signal height of the most intense anatase reflex (101) in the X-ray diffractogram ( Radiation CuK ⁇ ) to the signal level of the most intense rutile reflection (110) in each case after subtraction of a linear background in the same diffractogram, wherein the ratio has a value of at least 0.6, preferably at least 1.
  • the noble metal oxide selected is an oxide of one or more metals from the group of ruthenium, iridium, platinum, gold, rhodium, palladium, silver, rhenium. Oxides of ruthenium or iridium are particularly preferred as the noble metal oxide.
  • the electrocatalytically active layer preferably has 10 to 50 mol% of the noble metal oxide or noble metal oxide mixture, more preferably 15 to 50 mol%.
  • the proportion of the titanium oxide component in a preferred embodiment of the electrode is 50 to 90 mol%, particularly preferably 50 to 85 mol%.
  • the invention further provides a process for producing an electrode having an electrocatalytically active coating on an electrically conductive substrate, in particular a new electrode described above, comprising the steps:
  • a soluble titanium compound in particular Ti (iOPr) 4 in organic and / or aqueous solution
  • electrocatalytically active layers consisting of a 15-40 mol% noble metal component (eg RuO 2 or RuO 2 / IrO 2 mixtures) and a TiO 2 phase having a predominantly anatase structure can be produced by the process according to the invention.
  • a 15-40 mol% noble metal component eg RuO 2 or RuO 2 / IrO 2 mixtures
  • TiO 2 phase having a predominantly anatase structure can be produced by the process according to the invention.
  • a major proportion of anatase structure is present when, after subtracting a linear background, the height of the most intense reflex of the anatase structure (Reflex (101)) in the X-ray diffraction divided by the height of the most intense reflection of the rutile structure (Reflex (110)) is a value of greater than or equal to 0.6.
  • the coating solutions are obtained, for example, via a sol-gel process, preference being given to using as precursor salts chlorides, nitrates, alkoxides or acetylacetonates of the abovementioned noble metals which are dissolved in a solvent from the series of C 1 to C 8 alcohols, in particular methanol, n -Propanol, i-propanol, n-butanol or t-butanol are dissolved under stirring and sonication.
  • complexing agents such as acetylacetone or 4-hydroxy-4-methyl-2-pentanone are added.
  • the coating solution prepared in this way is used for the coating of electronically conductive materials such as titanium, tantalum and niobium or their alloys. These materials can be in different geometries z.
  • B sheets; Wires or nets are present
  • a mechanical, chemical or electrochemical treatment of the substrates may be necessary to remove any oxide layers present and to achieve a mechanical adhesion of the coating by increasing the substrate surface.
  • methods such as dripping, spin-coating, spraying, dipping or brushing can be used.
  • the resulting layer is air dried and then thermally stabilized at 100-250 ° C. Thicker layers can be obtained by repeating the steps previously described several times. After thermal stabilization, the coatings exhibit an amorphous structure which is crystallized by the process of the present invention.
  • the solvothermal process is carried out, for example, in a steel cylinder which can be sealed and heated.
  • the necessary process pressure is achieved by an evaporable liquid, which is located in a Tefloncommun inside the steel cylinder.
  • the sample itself hangs or lies in a glass vessel, which is in Tefloncred.
  • the process pressure can be adjusted by the amount of liquid and by the applied temperature.
  • liquids water, solvents or dilute sol solutions may be used
  • the closed steel cylinder is heated to 150 - 200 ° C at a rate of 10 ° / min for a period of 3-24 hours. This creates a pressure of 1-10 MPa inside the steel cylinder.
  • a thermal after-treatment for 1-2 hours at more than 300 ° C, preferably 400 to 600 ° C, preferably at 450 ° C to 550 ° C instead.
  • electrochemical tests eg cyclic voltammetry
  • electrochemical tests for the characterization of the chlorine evolution can be carried out with the aid of the resulting electrode.
  • the thermal aftertreatment significantly improves the performance of such electrodes over known electrodes.
  • the samples with solvothermal pretreatment have a significantly higher electrocatalytic activity compared to purely thermally treated samples.
  • Another object of the invention is the use of the electrode according to the invention as an anode in electrolyzers for the electrolysis of (aqueous) sodium chloride or hydrogen chloride solutions for the electrochemical production of chlorine.
  • the invention furthermore relates to an electrolyzer for the electrolysis of solutions containing sodium chloride or hydrogen chloride, characterized in that an electrode according to the invention is provided as the anode.
  • FIG. 1 shows an X-ray diffractogram of the solvothermal pretreated sample of Example 1
  • Titanium discs 15 mm in diameter (thickness: 2 mm) are sandblasted and then etched in 10% oxalic acid at 80 ° C for 2 hours. Thereafter, the platelets are removed from the acid and washed with 2-propanol. The drying process takes place in a stream of nitrogen.
  • solution A 168.5 mg RuCl 3 .xH 2 O (36% Ru) are dissolved in 6 ml 2-propanol and stirred for 12 hours.
  • Solution B is prepared from 333.1 ⁇ L of Ti (i-OPr) 4 and 561.5 ⁇ of 4-hydroxy-4-methyl-2-pentanone previously dissolved in 7.52 mL of 2-propanol.
  • the solvothermal treatment is carried out in the steel autoclave described above with a 250 ml Teflon insert filled with 30 ml of coating solution (37.5 mmol).
  • the coated sample is placed in a glass jar, which is placed in the Teflon insert.
  • the sealed autoclave is heated at a heating rate of 10 ° C / min to 150 ° C and left at this temperature for 24 hours.
  • the coated substrate is thermally post-treated at 450 ° C. in air for 1 hour.
  • the control sample without solvothermal pretreatment is thermally treated at 450 ° C in air for only one hour.
  • Fig. 1 shows the X-ray diffractogram of a sample with solvothermal pretreatment. It can be seen that predominantly anatase structure is present in the coating. After subtracting a linear background, the ratio of the height of the most intense reflex of the anatase structure (Reflex (101)) in the X-ray diffractogram to the height of the most intense reflex of the rutile structure (Reflex (110)) is 3.96. Without solvothermal pretreatment, only the rutile phase occurs.
  • the electrocatalytic activity for chlorine evolution was investigated by chronoamperometry (reference electrode: Ag / AgCl, 3.5 mo1 / 1 NaCl, pH: 3, T: 25 ° C). A current density of 1 kA / m 2 was applied and the potential was determined. For the solvothermal pretreated sample, a potential of 1.18 V results and for the purely thermally treated sample has a potential of 1.32 V.
  • the titanium substrates are treated as described in Example 1.
  • solution A 105.3 mg of RuCl 3 H 2 O (36% Ru) are dissolved in 488 ml of 2-propanol and stirred for 12 hours.
  • Solution B is prepared from 333.1 Ti (i-OPr) 4 and 561.5 ⁇ l of 4-hydroxy-4-methyl-2-pentanone previously dissolved in 7.52 ml of 2-propanol. For homogenization, it is stirred for 30 minutes. Solutions A and B are combined under ultrasound. This creates a transparent solution. For hydrolysis, 12.9 ⁇ l acetic acid and 27 ⁇ l deionized water are then added. The resulting mixture is stirred for 12 hours at room temperature.
  • this mixture Before this mixture can be used as a coating solution, it is diluted with 26.67 ml of 2-propanol. 50 ⁇ l of this solution are dropped onto the titanium platelets described above and then dried in air. This process is repeated 24 times, with thermal stabilization being carried out at 100 ° C. for 10 minutes after every fourth application. This results in an amorphous coating having a chemical composition of 25 mol% RuO 2 and 75 mol% TiO 2 . This corresponds to a ruthenium loading of 6.4 g / m 2 .
  • the solvothermal pretreatment and the thermal aftertreatment are carried out as described in Example 1.
  • the control sample without solvothermal pretreatment is thermally treated at 450 ° C in air for only one hour.
  • the phase analysis is carried out by means of X-ray diffractometry.
  • the ratio of the height of the most intense reflex of the anatase structure (Reflex (101)) in the X-ray diffractogram to the height of the most intense reflex of the rutile structure (Reflex (110)) is 1.81.
  • the electrocatalytic activity for chlorine evolution was examined by chronoamperometry (reference electrode: Ag / AgCl, 3.5 mol / 1 NaCl, pH: 3, T: 25 ° C). A current density of 1 kA / m 2 was applied and the potential determined. For the solvothermal pretreated sample a potential of 1.23 V results and for the purely thermally treated sample a potential of 1.42 V.
  • the titanium substrates are treated as described in Example 1.
  • solution A 105.3 mg of RuCl 3 -xH 2 O (36% Ru) are dissolved in 4.88 ml of 2-propanol and, for 12 hours, solution B is prepared from 333.1 Ti (i-OPr ) 4 and 561.5 ⁇ 1 of 4-hydroxy-4-methyl-2-pentanone previously dissolved in 7.52 ml of 2-propanol.
  • solution B is prepared from 333.1 Ti (i-OPr ) 4 and 561.5 ⁇ 1 of 4-hydroxy-4-methyl-2-pentanone previously dissolved in 7.52 ml of 2-propanol.
  • Solutions A and B are combined under ultrasound. This creates a transparent solution.
  • 12.9 ⁇ l acetic acid and 27 ⁇ l deionized water are added. The resulting mixture is stirred for 12 hours at rum temperature.
  • this mixture Before this mixture can be used as a coating solution, it is diluted with 26.67 ml of 2-propanol. 50 ⁇ l of this solution are dropped onto the titanium platelets described above and then dried in air. This process is repeated 24 times with thermal stabilization at 250 ° C for 10 minutes after every fourth application. This results in an amorphous coating having a chemical composition of 25 mol% RuO 2 and 75 mol% TiO 2 . This corresponds to a ruthenium loading of 6.4 g / m 2 .
  • the solvothermal treatment is carried out as described in Example 1, in a steel autoclave with a 250 ml Teflon insert, which is filled with 30 ml of coating solution (37.5 mmol).
  • the coated sample is placed in a glass jar, which is placed in the Teflon insert.
  • the coated substrate is thermally post-treated for one hour at 450 ° C. in air.
  • the control sample without solvothermal pretreatment is thermally treated at 450 ° C in air for only one hour.
  • the phase analysis is carried out by means of X-ray diffractometry.
  • the X-ray diffractogram of a sample without solvothermal pretreatment shows that only one rutile phase is present.
  • the electrocatalytic activity for chlorine evolution was examined by chronoamperometry (reference electrode: Ag / AgCl, 3.5 mol / l NaCl, pH: 3, T: 25 ° C). A current density of 1 kA / m 2 was applied and the potential was determined. For the solvothermal pretreated Sample results in a potential of 1.32 V and for the purely thermally treated sample has a potential of 1.41 V.
  • the titanium substrates are treated as described in Example 1.
  • solution A 63.2 mg RuCl 3 -xH 2 O (36% Ru) are dissolved in 1.26 ml 2-propanol and stirred for 12 hours.
  • Solution B is prepared from 377.5 ml of Ti (i-OPr) 4 and 561.5 ⁇ l of 4-hydroxy-4-methyl-2-pentanone previously dissolved in 11.1 ml of 2-propanol. For homogenization, it is stirred for 30 minutes. Solutions A and B are combined under ultrasound. This creates a transparent solution. For hydrolysis, 12.9 ⁇ l acetic acid and 27 ⁇ l deionized water are then added. The resulting mixture is stirred for 12 hours at room temperature.
  • this mixture Before this mixture is used as a coating solution, it is diluted with 26.67 ml of 2-propanol. 50 ⁇ l of this solution are dropped onto the titanium platelets described above and then dried in air. This process is repeated 8 times, with thermal stabilization at 200 ° C for 10 minutes after each application. This results in an amorphous coating having a chemical composition of 15 mol% RuO 2 and 85 mol% TiO 2 . This corresponds to a ruthenium loading of 3.86 g / m 2 .
  • the solvothermal treatment is carried out as described in Example 1 in a steel autoclave with a 250 ml Teflon insert, which is filled with 30 ml of coating solution (37.5 mmol).
  • the coated sample is placed in a glass jar, which is placed in the Teflon insert.
  • the sealed autoclave is heated at a heating rate of 10 ° C / min to 150 ° C and left at this temperature for 3 hours.
  • the coated substrate is thermally treated for 10 minutes at 250, 300, 350, 400 and 450 ° C in air. From the X-ray diffractogram of the sample it can be seen that a rutile / anatase mixture with a high content of rutile phase is present.
  • the ratio of the height of the most intense reflex of the anatase structure (reflex (101)) in the X-ray diffractogram to the height of the most intense reflex of the rutile structure (reflex (110)) is 0.10.
  • the electrocatalytic activity for chlorine evolution was investigated by chronoamperometry (reference electrode: Ag / AgCl, 3.5 mol / 1 NaCl, pH: 3, T: 25 ° C.). A current density of 1 kA / m 2 was applied and the potential was determined. A potential of 1.27 V was determined.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Catalysts (AREA)
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EP11170272A 2010-06-21 2011-06-17 Elektrode für die elektrolytische Chlorgewinnung Withdrawn EP2397579A1 (de)

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DE102010030293A DE102010030293A1 (de) 2010-06-21 2010-06-21 Elektrode für die elektrolytische Chlorgewinnung

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US (1) US8430997B2 (zh)
EP (1) EP2397579A1 (zh)
JP (1) JP2012007238A (zh)
KR (1) KR20110139126A (zh)
CN (1) CN102286756A (zh)
BR (1) BRPI1102666A2 (zh)
DE (1) DE102010030293A1 (zh)

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CN105734654A (zh) * 2014-12-11 2016-07-06 苏州吉岛电极科技有限公司 一种阳极制备方法
KR102260891B1 (ko) * 2016-11-29 2021-06-07 주식회사 엘지화학 전기 분해용 전극 및 전기 분해용 전극의 제조방법
KR20190022333A (ko) * 2017-08-23 2019-03-06 주식회사 엘지화학 전기분해용 양극 및 이의 제조방법
KR20190037518A (ko) 2017-09-29 2019-04-08 주식회사 엘지화학 전기분해 전극의 제조방법
KR102358447B1 (ko) 2017-09-29 2022-02-04 주식회사 엘지화학 전기분해 양극용 코팅액 조성물
CN108048862B (zh) * 2017-11-16 2020-04-28 江苏安凯特科技股份有限公司 一种析氯用阳极及其制备方法

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KR20110139126A (ko) 2011-12-28
BRPI1102666A2 (pt) 2012-11-06
US20110308939A1 (en) 2011-12-22
DE102010030293A1 (de) 2011-12-22
CN102286756A (zh) 2011-12-21
US8430997B2 (en) 2013-04-30
JP2012007238A (ja) 2012-01-12

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