US3793164A - High current density brine electrolysis - Google Patents
High current density brine electrolysis Download PDFInfo
- Publication number
- US3793164A US3793164A US00352418A US3793164DA US3793164A US 3793164 A US3793164 A US 3793164A US 00352418 A US00352418 A US 00352418A US 3793164D A US3793164D A US 3793164DA US 3793164 A US3793164 A US 3793164A
- Authority
- US
- United States
- Prior art keywords
- percent
- oxide
- anode
- metal oxide
- titanium
- 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
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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
- 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
- ABSTRACT Described is a method of electrolyzing brine in a mercury cell, at applied current densities of at least 6 amperes per square inch, employing as the anode a titanium substrate bearing on at least a portion of the surface thereof a mixed oxide coating of from 30 to 90 percent stannic oxide, from 1.0 to 10 percent antimony oxide, from 1.0 to 50 percent of at least one platinum group metal oxide, and from 0.5 to 30 percent of a valve metal oxide selected from the group consisting of titanium and tantalum oxides.
- the apparatus employed for this purpose is quite expensive and a primary concern in commercial operation is to obtain the maximum amount of production per unit of floor space.
- One method of so doing is to increase the anode current density at which the cell operates.
- the maximum current density that could be employed without drastically reducing the useful life of the anode was on the order of 5.0 asi.
- the apparent cause of this passivation was brine depletion across the cell, oxygen evolution increasing with decreasing brine concentration.
- an improvement consists essentially of employing as the anode a titanium substrate bearing on at least a portion of the surface thereof a mixed oxide coating of from 30 to 90 percent by weight stannic oxide, from 1.0 to percent antimony oxide, calculated as Sb O from 1.0 to 50 percent of at least one platinum group metal oxide, and from 0.5 to 30 percent of a valve metal oxide selected from the group consisting of titanium and tantalum oxides, with the proviso that the mole ratio of tin to antimony oxides be between 85:15 and 95:5, and applying current to said anode at a rate of at least 6 amperes per square inch.
- valve metal oxide is TiO
- platinum group metal oxide is a combination of RuO,and IrO,.
- the mercury cells to which the practice of the present invention may be applied may be of the horizontal, vertical, or inclined plane type, all of which are well known to those skilled in the art. Such cells and their operation are described, for example, at Kirk-Othmer,
- Such cells operate on aqueous sodium chloride solutions having concentrations at or approaching saturation (brine), e.g., 325 grams per liter, although sea water has been successfully electrolyzed in some instances.
- concentrations at or approaching saturation e.g., 325 grams per liter
- the distance between the parallel anodes and mercury cathode of the cell is kept quite low, often on the order of 0.1 to 0.3 inch.
- Such cells are operated at temperatures up to the boiling point of brine and at sodium-mercury amalgam concentrations on the order of from 0.1 to 0.15 percent, the latter factor being controllable to some extent by regulating the mercury flow rate.
- Conventional operation is at anode current densities on the order of 3 to 4 asi and up to 6 asi.
- the amount of current supplied to the cell is at least 6 amperes per square inch of anode surface, preferably 6 to 10 asi.
- the brine becomes severely depleted during its passage from inlet to outlet thereby increasing the amount of oxygen evolved at the anode surface and normally contributing to the rapid passivation of same.
- the anode comprises a titanium substrate bearing on at least a portion of the surface thereof a mixed coating of the oxides of tin, antimony, at least one platinum group metal, and a valve metal selected from the group titanium and tantalum.
- Such anodes also exhibit a long life, i.e., a low platinum group metal wear-rate per ton of chlorine.
- the conductive substrate is generally titanium, although a more conductive material, such as copper or aluminum, bearing a surface of titanium may be employed. Additionally, layers on the substrate intermediate the titanium and the coating, such as those described in US Pat. No. 3,711,397, are contemplated.
- the configuration of the substrate may vary considerably but it is generally in the form of a sheet, particularly a foraminous sheet, such as expanded mesh.
- stannic oxide preferably present in the form of crystalline SnO and employed within the range of from 30 to 90, especially 30 to 50, percent by weight of the total coating composition.
- the antimony oxide component enters into the tin oxide crystal lattice, rendering same more electrically conductive.
- the antimony is present in an indeterminate oxide form owing to its entrance into the stannic oxide crystal lattice, it is expressed for convenience sake as Sb,O
- the antimony oxide is present within the range from 1.0 to 10, preferably 4.0 to 8.0, percent by weight.
- tin and antimony oxides are further qualified by the proviso that they be present, respectively, in the range, on a mole ratio basis, of 95:5 to :15, especially :10. In this fashion, there is ob tained the desired doping effect of the antimony on the tin oxide without the presence of an excess separate phase of antimony oxide.
- the third component of the mixed coating is at least one platinum group metal oxide, by which term it is intended to include the oxides of platinum, palladium, ruthenium, iridium, rhodium, and osmium, especially those of ruthenium and iridium. These platinum group metal oxides are present for the most part in their most acid.
- the concentration of the metals in thesolution 3 4 highly oxidized state and within the range of from 1.0 sition is incomplete, small amounts of salts may remain it 7 to 50, especially 20 to 40, percent by weight.
- An espewithout detrimental effect in the coating, for example, cially preferred anode is one the coating of which consmall amounts of chloride in the primarily oxide coattains a combination of RuO and IrO ing.
- the final component is a valve metal oxide selected
- titanium is present in the form of embodiments by which it maybe carried into effect, TiO and is essentially crystalline (rutile) in nature
- rutile essentially crystalline
- the following specific example is afforded.
- tantalum is em loyed, a generally amorphous tantalum oxide result: Therefore, although it is ex- 10 a a A e pressed as Ta 0 it is understood that mixtures of tan- Four anodes were prepared from the following Sohb talum oxides may in fact be present.
- Ta O is tions. preferred.
- valve metal oxide em- Anodel 50m1n butano1 125 gSnC]4.5H2O, 0.91 ployed are generally within the range of from 0.5 to 30 g s c and 1 g c 14 0 33% Ru) Percent y weight, especially 15 to 25 percent 15 Anode 2 45 ml ethanol, 5.0 g orthobutyl titanate,
- a preferred electrode comprises an expanded 1,1 g sbc1,, 15.1 g SnCl -5H O, and 7.6 g R1101, titanium metal substrate bearing a coating containing H 0 3 Ru). about 47 Percent t Percent z a p Anode 3 s0 ml n-butanol, 12.5 g SnCL'SH O, 0.91 cent Ru0 4.5 percent lrO and percent Ta Or- 20 g SbCI, 7.0 g orthobutyl titanate, and 1.1 g
- Anode 4 .45 1 ethanol, 45 g c H g s a the preferred method of preparing the multicomponent 15 1 g S ch-511 0, and 7.6 g Rucl 'xll O coating composition on the titanium substrate is by de- (38%R position from a solution of the appropriate thermo- 25
- it is deslr' solution by brush to a clean titanium metal mesh with able to paint or brush an acidified alcoholic solution of h i i i between h t, fi t t 110 C for 3 said salts onto the substrate, followed by drying at minutes f ll ed b 7 minutes t 500C C for from 3 to especially 5, minutes and
- These are employed as anodes in a horizontal merfinally by aking in an
- electrolyte is a 310 g/l brine solution having a pH be repeated any number of times until the desired coatwithin the range of 33-6 and a. temperature of about 70 ing thickness is obtained, for example, 6 to 10 coats.
- electrolysis The preferred solvents for the thermally decomposable 35 is continued. at 6 amperes per square inch for 500 salts arethe lower alkanols such as ethanol, propanol, hours, the loss being determined by weight differential.
- Valve metal OXlde elected salts of the remaining materials, although it is generally from a group consisting of tltahlum and tantalum believed that preformed valve'metal oxides should not ides, with the Proviso that the mole ratio of tin to antibe employed nor should separately preformed tin and molly oxides is between 85115 and 9515; na pp y hg antimony oxides be used. Further, if thermal decompoa ijlii ii jfisl5WPPYB From the table, it is evident that Anode 1, without square inch.
- metal oxide is Ta O and is present within the range of 15 to 25 percent.
- the coating contains from 30 to 50 percent SnO 4 to 8 percent antimony oxide, 20 to 40 percent of at least one platinum metal oxide, and 15 to 25 percent Ta O
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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)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35241873A | 1973-04-19 | 1973-04-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3793164A true US3793164A (en) | 1974-02-19 |
Family
ID=23385053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00352418A Expired - Lifetime US3793164A (en) | 1973-04-19 | 1973-04-19 | High current density brine electrolysis |
Country Status (7)
Country | Link |
---|---|
US (1) | US3793164A (de) |
JP (1) | JPS5011997A (de) |
BR (1) | BR7403074D0 (de) |
DE (1) | DE2418740A1 (de) |
GB (1) | GB1417950A (de) |
IT (1) | IT1005989B (de) |
SE (1) | SE7405202L (de) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3875043A (en) * | 1973-04-19 | 1975-04-01 | Electronor Corp | Electrodes with multicomponent coatings |
US3917518A (en) * | 1973-04-19 | 1975-11-04 | Diamond Shamrock Corp | Hypochlorite production |
FR2336976A1 (fr) * | 1975-12-29 | 1977-07-29 | Diamond Shamrock Corp | Electrode comprenant un substrat en metal valve, un revetement intermediaire semi-conducteur et un revetement superficiel de dioxyde de plomb |
US4057480A (en) * | 1973-05-25 | 1977-11-08 | Swiss Aluminium Ltd. | Inconsumable electrodes |
US4061558A (en) * | 1975-06-09 | 1977-12-06 | Tdk Electronics Co., Ltd. | Electrode |
US4213843A (en) * | 1978-03-24 | 1980-07-22 | Permelec Electrode Ltd. | Electrolysis electrodes and method of making same |
US4297421A (en) * | 1977-11-10 | 1981-10-27 | The International Nickel Co., Inc. | Battery and electrolytic cell electrodes |
EP0121694A1 (de) * | 1983-03-11 | 1984-10-17 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Katalysator zur Beschichtung von Anoden und Verfahren zu dessen Herstellung |
EP0153586A1 (de) * | 1984-01-31 | 1985-09-04 | TDK Corporation | Elektrode für Elektrolyse |
WO2002063068A2 (en) * | 2001-02-06 | 2002-08-15 | United States Filter Corporation | Electrode coating and its use in the production of chlorate |
EP2055806A1 (de) * | 2007-10-31 | 2009-05-06 | Daiki Ataka Engineering Co., Ltd. | Anode für elektrochemische Reaktion |
CN102517603A (zh) * | 2011-11-30 | 2012-06-27 | 浙江大学 | 一种钛基低贵重金属含量氧化物涂层阳极的制备方法 |
CN103981534A (zh) * | 2013-02-08 | 2014-08-13 | 拜耳材料科技股份有限公司 | 用于氯气制备的电催化剂,电极涂层和电极 |
CN104988535A (zh) * | 2015-05-22 | 2015-10-21 | 东南大学 | 一种混合金属氧化物涂层电极及其制备方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5263176A (en) * | 1975-11-20 | 1977-05-25 | Hodogaya Chem Co Ltd | Anode for electrolysis |
CA1094891A (en) * | 1976-03-15 | 1981-02-03 | Diamond Shamrock Corporation | Electrode coating method |
JPS5597486A (en) * | 1979-01-21 | 1980-07-24 | Tdk Corp | Electrode for electrolysis and its manufacture |
JPH0413881A (ja) * | 1990-05-02 | 1992-01-17 | Japan Carlit Co Ltd:The | フィルタープレス型複極式電解槽 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3491014A (en) * | 1969-01-16 | 1970-01-20 | Oronzio De Nora Impianti | Composite anodes |
US3627669A (en) * | 1968-12-13 | 1971-12-14 | Ici Ltd | Electrodes for electrochemical cells |
US3663280A (en) * | 1968-04-02 | 1972-05-16 | Ici Ltd | Electrodes for electrochemical processes |
US3671415A (en) * | 1969-09-02 | 1972-06-20 | Ici Ltd | Continuous lead-in core for an electrode assembly |
US3701724A (en) * | 1968-10-18 | 1972-10-31 | Ici Ltd | Electrodes for electrochemical processes |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1352872A (en) * | 1971-03-18 | 1974-05-15 | Ici Ltd | Electrodes for electrochemical processes |
JPS4735736A (de) * | 1971-03-22 | 1972-11-25 |
-
1973
- 1973-04-19 US US00352418A patent/US3793164A/en not_active Expired - Lifetime
-
1974
- 1974-04-17 BR BR3074/74A patent/BR7403074D0/pt unknown
- 1974-04-18 IT IT50462/74A patent/IT1005989B/it active
- 1974-04-18 GB GB1710774A patent/GB1417950A/en not_active Expired
- 1974-04-18 DE DE2418740A patent/DE2418740A1/de not_active Withdrawn
- 1974-04-18 SE SE7405202A patent/SE7405202L/sv unknown
- 1974-04-19 JP JP49043493A patent/JPS5011997A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3663280A (en) * | 1968-04-02 | 1972-05-16 | Ici Ltd | Electrodes for electrochemical processes |
US3701724A (en) * | 1968-10-18 | 1972-10-31 | Ici Ltd | Electrodes for electrochemical processes |
US3627669A (en) * | 1968-12-13 | 1971-12-14 | Ici Ltd | Electrodes for electrochemical cells |
US3491014A (en) * | 1969-01-16 | 1970-01-20 | Oronzio De Nora Impianti | Composite anodes |
US3671415A (en) * | 1969-09-02 | 1972-06-20 | Ici Ltd | Continuous lead-in core for an electrode assembly |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3875043A (en) * | 1973-04-19 | 1975-04-01 | Electronor Corp | Electrodes with multicomponent coatings |
US3917518A (en) * | 1973-04-19 | 1975-11-04 | Diamond Shamrock Corp | Hypochlorite production |
US4057480A (en) * | 1973-05-25 | 1977-11-08 | Swiss Aluminium Ltd. | Inconsumable electrodes |
US4061558A (en) * | 1975-06-09 | 1977-12-06 | Tdk Electronics Co., Ltd. | Electrode |
FR2336976A1 (fr) * | 1975-12-29 | 1977-07-29 | Diamond Shamrock Corp | Electrode comprenant un substrat en metal valve, un revetement intermediaire semi-conducteur et un revetement superficiel de dioxyde de plomb |
US4297421A (en) * | 1977-11-10 | 1981-10-27 | The International Nickel Co., Inc. | Battery and electrolytic cell electrodes |
US4213843A (en) * | 1978-03-24 | 1980-07-22 | Permelec Electrode Ltd. | Electrolysis electrodes and method of making same |
EP0121694A1 (de) * | 1983-03-11 | 1984-10-17 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Katalysator zur Beschichtung von Anoden und Verfahren zu dessen Herstellung |
US4513102A (en) * | 1983-03-11 | 1985-04-23 | Bbc Brown, Boveri & Company, Limited | Catalyst for coating anodes and a process for its preparation |
US4626334A (en) * | 1984-01-31 | 1986-12-02 | Tdk Corporation | Electrode for electrolysis |
EP0153586A1 (de) * | 1984-01-31 | 1985-09-04 | TDK Corporation | Elektrode für Elektrolyse |
WO2002063068A2 (en) * | 2001-02-06 | 2002-08-15 | United States Filter Corporation | Electrode coating and its use in the production of chlorate |
WO2002063068A3 (en) * | 2001-02-06 | 2003-02-27 | United States Filter Corp | Electrode coating and its use in the production of chlorate |
CN1541285B (zh) * | 2001-02-06 | 2010-06-09 | 西门子水技术控股公司 | 电极涂层及其使用和制备方法 |
EP2055806A1 (de) * | 2007-10-31 | 2009-05-06 | Daiki Ataka Engineering Co., Ltd. | Anode für elektrochemische Reaktion |
CN102517603A (zh) * | 2011-11-30 | 2012-06-27 | 浙江大学 | 一种钛基低贵重金属含量氧化物涂层阳极的制备方法 |
CN103981534A (zh) * | 2013-02-08 | 2014-08-13 | 拜耳材料科技股份有限公司 | 用于氯气制备的电催化剂,电极涂层和电极 |
US20140224666A1 (en) * | 2013-02-08 | 2014-08-14 | Nano-X-Gmbh | Electrocatalyst, electrode coating and electrode for the preparation of chlorine |
US9677183B2 (en) * | 2013-02-08 | 2017-06-13 | Covestro Deutschland Ag | Electrocatalyst, electrode coating and electrode for the preparation of chlorine |
CN104988535A (zh) * | 2015-05-22 | 2015-10-21 | 东南大学 | 一种混合金属氧化物涂层电极及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
BR7403074D0 (pt) | 1974-11-19 |
DE2418740A1 (de) | 1974-11-07 |
GB1417950A (en) | 1975-12-17 |
JPS5011997A (de) | 1975-02-06 |
SE7405202L (de) | 1974-10-21 |
IT1005989B (it) | 1976-09-30 |
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Legal Events
Date | Code | Title | Description |
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STCF | Information on status: patent grant |
Free format text: PATENTED FILE - (OLD CASE ADDED FOR FILE TRACKING PURPOSES) |
|
AS | Assignment |
Owner name: DIAMOND SHAMROCK CHEMICALS COMPANY Free format text: CHANGE OF NAME;ASSIGNOR:DIAMOND SHAMROCK CORPORATION CHANGED TO DIAMOND CHEMICALS COMPANY;REEL/FRAME:004197/0130 |
|
AS | Assignment |
Owner name: ELTECH SYSTEMS CORPORATION, 6100 GLADES ROAD, BOCA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DIAMOND SHAMROCK CORPORATION, 717 N. HARWOOD STREET, DALLAS, TX 75201;REEL/FRAME:004357/0479 Effective date: 19841024 |
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AS | Assignment |
Owner name: ELECTRODE CORPORATION, A CORP. OF DE, OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ELTECH SYSTEMS CORPORATION;REEL/FRAME:004976/0455 Effective date: 19881026 Owner name: ELECTRODE CORPORATION, 470 CENTER STREET, CHARDON, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:ELTECH SYSTEMS CORPORATION;REEL/FRAME:004976/0455 Effective date: 19881026 |