CN1295379C - Inactive anode for aluminium electrolysis - Google Patents

Inactive anode for aluminium electrolysis Download PDF

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Publication number
CN1295379C
CN1295379C CNB2003101104974A CN200310110497A CN1295379C CN 1295379 C CN1295379 C CN 1295379C CN B2003101104974 A CNB2003101104974 A CN B2003101104974A CN 200310110497 A CN200310110497 A CN 200310110497A CN 1295379 C CN1295379 C CN 1295379C
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China
Prior art keywords
electrode
connecting rod
wall
inert anode
union lever
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Expired - Fee Related
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CNB2003101104974A
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Chinese (zh)
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CN1614097A (en
Inventor
周科朝
李志友
张雷
张晓勇
李劼
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Central South University
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Central South University
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Abstract

The present invention relates to an inert anode for aluminium electrolysis, which is arranged in an aluminium electrolytic tank and comprises a cup-shaped outer wall 1 and a connecting rod 2, wherein the connecting rod 2 which is arranged at a centre position is connected with the metallic electrode of the electrolytic tank, and a cavity in the shape of a circular arc is formed between the outer wall 1 and the connecting rod 2. The working surface and the molten salt electrolyte contacting part of the inert anode of the present invention adopt corrosion-resistant ceramic material or cermet material, the purity of electrolytic aluminum can be guaranteed, carbon resource is saved, and no harmful gas is discharged; the connecting rod adopts a gradient transition technique, so the abrupt change of the physical parameters of materials caused by the abrupt change of substances and high thermal stress caused by the abrupt change of the physical parameter of the materials are avoided, the problem that the connecting part between the metallic electrodes and electrodes has low binding strength and is easy to be cracked is avoided, and the service life of the electrodes is prolonged.

Description

A kind of used for aluminium electrolysis inert anode
Technical field
The present invention relates to the electrode that a kind of Aluminum Electrolysis Production is used.
Background technology
Adopt carbon anode as electrolysis electrode in the existing aluminum electrolysis industry, charcoal is consumed in electrolytic process and generates CO and CO 2, also, cause environmental pollution with the generation of obnoxious flavoures such as carbon fluoride, carbonitride, according to statistics, one ton of electrolytic aluminum of every production need consume 0.5～0.6 ton high quality carbon.Because carbon anode constantly consumes,, be unfavorable for the stable of production technique simultaneously in electrolytic process, also increased the complicacy of electrolyzer system control so need dynamically adjust the interpole gap of electrode.In order to address the above problem, the material that the electrolytic aluminum inert anode is adopted mainly contains metal and alloy, pottery, sintering metal three major types.Though metal and alloy type material have good electroconductibility and mechanical property, the deficiency of ubiquity poor corrosion resistance in the ionogen melting salt causes the corrosion dissolution of electrode self, and this has reduced the purity of electrolytic aluminum product; Ceramic-like materials has excellent corrosion resisting performance, but its conductivity and thermal shock resistance are poor, also is difficult to be connected with the metal electrode guide rod of electrolyzer; Sintering metal class material then combines some advantage of metal and stupalith, but metallographic phase content is when high, the poor corrosion resistance of material; When metallographic phase content hangs down,, need to solve the problem that is connected with the metal electrode guide rod though guaranteed the erosion resistance of material.
Summary of the invention
In order to solve the connectivity problem of metal electrode guide rod and inert anode, take into account the adjustability of electrode face distribution of current and the surface radiating that reduces electrode, special proposition the present invention.
Aluminium cell inert anode of the present invention comprises cup-shaped outer wall 1, is in the union lever 2 that the central position is connected with the electrolyzer metal electrode, and a circular-arc cavity is arranged between outer wall 1 and union lever 2.
Cup-shaped outer wall 1 is with NiFe 2O 4, ZnFe 2O 4, (Zn xNi 1-x) Fe 2O 4, CuFe 2O 4, CuAl 2O 4, NiAl 2O 4, (Cu xNi 1-x) Al 2O 4In one or more oxide ceramics be main body, add part NiO, SnO 2, ZrO 2, Nb 2O 5, Ta 2O 5The dense sintering body that one or more components among in the pottery one or more and Cu, Fe, Ni, Al, Zn, Sn, Ti, Ag, Au, the Pt are formed.Union lever 2 is with NiFe 2O 4, ZnFe 2O 4, (Zn xNi 1-x) Fe 2O 4, CuFe 2O 4, CuAl 2O 4, NiAl 2O 4, (Cu xNi 1-x) Al 2O 4In one or more oxide ceramics be main body, also can add SiC, TiC, Al 2O 3, SiO 2One or more of pottery; Metallographic phase then is made up of among Cu, Ni, Fe, Al, Zn, Sn, the Ti one or more.
Union lever 2 is the sintering metal rods that change with metallographic phase and ceramic phase constituent element component gradient, and the composition of the end that wherein links to each other with the noble electrode base and the composition of noble electrode are consistent, and the end that links to each other with the electrolyzer metal electrode is rich metallographic phase.The rich metallographic phase end of union lever 2 can directly connect with electrolyzer metal electrode guide rod, also can imbed the metal electrode guide rod therein.
The present invention can fill Al in cavity 2O 3The surface radiating that keeps the relatively stable of electrode temperature and minimizing electrode Deng material.
The preparation of electrode adopts technologies such as compression moulding and atmosphere sintering to finish.The first quantitative various pre-mixing powder of packing into step by step in ready-formed rubber or latex die sleeve adopts isostatic cool pressing technology (CIP) to suppress electrode blank; Through after the suitable machining, the counter electrode blank carries out high temperature sintering in the nitrogen of controlling oxygen partial pressure or argon gas atmosphere; Precision work is carried out on last counter electrode surface.
Its working face of inert anode of the present invention and adopted corrosion resistant pottery or cermet material with the molten salt electrolyte contact part, consumable or consumable are very not little in electrolytic process, both can guarantee the purity of electrolytic aluminum, saved carbon resource again, and there is not bad gas purging, reduce the cost of electrolytic aluminum on the one hand, avoided environmental pollution on the other hand; The union lever that links to each other with the electrolyzer metal electrode adopts the gradient transition technology, the sudden change of the material property parameter (as thermal expansivity, specific conductivity etc.) brought because of material sudden change and the high thermal stress that causes have thus been avoided, avoid metal electrode and electrode connecting portion branch bonding strength to hang down problem easy to crack simultaneously, prolonged the work-ing life of electrode; Between outer wall and union lever, adopt cavity to reduce the substance and the electrode cost of electrode, help keeping the stable of electrolyzer temperature and cutting down the consumption of energy.The preparation of electrode adopts Soft Roll cover isostatic cool pressing technology (CIP) once to finish the moulding of electrode blank, and the sintering under the employing controlled atmosphere once just can be realized the densification of electrode blank, has shortened the electrode preparation cycle.
Description of drawings
Fig. 1: inert anode schematic cross-section;
Fig. 2: inert anode union lever metallographic phase and ceramic phase constituent element component gradient change synoptic diagram.
a.NiFe 2O 4-80(Cu-75Fe-5Ni)
b.NiFe 2O 4-60(Cu-70Fe-5Ni)
c.NiFe 2O 4-46(Cu-60Fe-5Ni)
d.NiFe 2O 4-35(Cu-50Fe-5Ni)
e.NiFe 2O 4-27(Cu-40Fe-5Ni)
f.NiFe 2O 4-20(Cu-35Fe-5Ni)
g.NiFe 2O 4-15(Cu-20Fe-5Ni)
h.NiFe 2O 4-10(Cu-4Ni)
Embodiment
1. one kind with NiFe 2O 4-NiO is that corrosion-resistant ceramic phase component, Cu-Ni-Fe are the small-sized electrode of metallographic phase component.
A＞composition:
The corrosion-resistant ceramic phase component is NiFe 2O 4-NiO, the metallographic phase component is Cu-Ni-Fe.The material component of cup-shaped outer wall 1 is (NiFe 2O 4-NiO)-10 (Cu-5Ni) (numeral is a mass percent, down together).The composition profiles of gradient rod 2 as shown in Figure 2.
B＞preparation process
1＞. the preparation of ceramics powder: with Fe 2O 3With NiO be raw material, be NiFe by reaction product 2O 4Or NiFe 2O 4-5NiO takes by weighing raw material and a certain amount of water, pours ball material mass ratio in the lump into and be rolling ball milling 2～4h in about 8: 1 the ball milling bucket.Pour out raw material compound and abrading-ball, after 80～100 ℃ of dryings remove moisture content, sift out abrading-ball, exsiccant raw material compound is put into ceramic crucible, be warming up to 1200 ℃ with stove in atmosphere, behind the insulation 4h, stove is chilled to room temperature.Repeat above-mentioned wet-milling, drying, screening process, obtain ceramic powder.
2＞. batch mixing: take by weighing pottery and metal-powder by required composition proportion, add an amount of polyvinyl alcohol water solution, repeat wet-milling, drying, the screening process described in a, obtain mixed powder.
3＞. dress mould: (similar Fig. 1 of the shape of rubber moulding in the latex mould of A and the sealing of B end, die wall thick 2～4mm), fill earlier 2 each layers of part one by one, recharge 1 part, shake reality while filling, control the height and the final packing height of 1 part of 2 each layers of part well, fill in rubber plug and with iron wire with it in rubber moulding bundle jail.
4＞. cold isostatic compaction: slowly be forced into 100～200Mpa, behind pressurize 2～5min, slowly release proposes rubber moulding, takes out the electrode pressed compact.
5＞. sintering densification: pressed compact is put into the high-temperature atmosphere sintering oven after machining, in the atmosphere of argon gas or nitrogen that flows, and temperature programming to 400～450 ℃, insulation 4～6h.Seal High Temperature Furnaces Heating Apparatus then, be heated to 1200～1300 ℃, behind insulation 4～8h, stove is chilled to room temperature.

Claims (2)

1. used for aluminium electrolysis inert anode, it is characterized in that: comprise the cup-shaped outer wall, be in the union lever that the central position is connected with the electrolyzer metal electrode, a circular-arc cavity is arranged between outer wall and union lever, the cup-shaped outer wall is with NiFe 2O 4, ZnFe 2O 4, (Zn xNi 1-x) Fe 2O 4, CuFe 2O 4, CuAl 2O 4, NiAl 2O 4, (Cu xNi 1-x) Al 2O 4In one or more oxide ceramics be main body, add NiO, SnO 2, ZrO 2, Nb 2O 5, Ta 2O 5The dense sintering body that one or more components among in the pottery one or more and Cu, Fe, Ni, Al, Zn, Sn, Ti, Ag, Au, the Pt are formed; Union lever is with NiFe 2O 4, ZnFe 2O 4, (Zn xNi 1-x) Fe 2O 4, CuFe 2O 4, CuAl 2O 4, NiAl 2O 4, (Cu xNi 1-x) Al 2O 4In one or more oxide ceramics be main body, add SiC, TiC, Al 2O 3, SiO 2One or more of pottery; Metallographic phase then is made up of among Cu, Ni, Fe, Al, Zn, Sn, the Ti one or more.
2. inert anode according to claim 1, it is characterized in that: union lever is the sintering metal rod that changes with metallographic phase and ceramic phase constituent element component gradient, the composition of an end of wherein linking to each other with the noble electrode base is consistent with the composition of noble electrode, and linking to each other with the electrolyzer metal electrode, to hold be rich metallographic phase.
CNB2003101104974A 2003-11-04 2003-11-04 Inactive anode for aluminium electrolysis Expired - Fee Related CN1295379C (en)

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Application Number Priority Date Filing Date Title
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CN1295379C true CN1295379C (en) 2007-01-17

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102732769B (en) * 2012-07-17 2013-11-20 中南大学 Nickel ferrite-copper metal ceramic inert anode material and preparation method
WO2014022394A1 (en) * 2012-08-01 2014-02-06 Alcoa Inc. Inert electrodes with low voltage drop and methods of making the same
CN103820817A (en) * 2014-01-17 2014-05-28 饶云福 Inner-cooling inert anode for electrolytic aluminum
CN113249755B (en) * 2021-05-12 2023-05-02 郑州大学 Inert anode material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6332969B1 (en) * 1997-06-26 2001-12-25 Alcoa Inc. Inert electrode containing metal oxides, copper and noble metal
CN1384891A (en) * 1999-10-27 2002-12-11 阿尔科公司 Cermet inert anode for use in electrolytic production of metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6332969B1 (en) * 1997-06-26 2001-12-25 Alcoa Inc. Inert electrode containing metal oxides, copper and noble metal
CN1384891A (en) * 1999-10-27 2002-12-11 阿尔科公司 Cermet inert anode for use in electrolytic production of metals

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