CN1283842C - Metal ceramic inert anode for molten salt electrolysis and preparation method thereof - Google Patents
Metal ceramic inert anode for molten salt electrolysis and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an electrode for extracting nonferrous metals by a molten salt electrolysis method, in particular to a metal ceramic inert anode and a preparation method thereof. The method is characterized in that: firstly, 0.01 to 100 percent of SnO2、0～99%AB2O4、0～30%MxOyPreparation of SnO2-AB2O4-MxOyCeramic powder, AB2O4Is a composite oxide having a spinel structure; then taking ceramic phase as 50-99% SnO2-AB2O4-MxOyThe metal phase of the ceramic powder is 1-50% of Ni-Cu-X alloy powder or metal powder with corresponding contents of Ni, Cu and X to prepare the metal ceramic inert anode. The invention improves the conductivity and corrosion resistance of the ceramic phase and the wettability of the metal relative to the ceramic phase, so that the metal phase does not overflow and is uniformly distributed in the sintering process of the metal ceramic inert anode, and the densification effect of the material is achieved; the oxidation of the metal phase and the dissociation or reduction of the ceramic phase are avoided, and the metal ceramic inert anode material with the target phase and good performance is obtained.
Description
Technical field:
The present invention extracts with the fused salt electrolysis process of non-ferrous metal (Al, rare earth and refractory metal etc.) and uses electrode relevant, particularly cermet inert anode and preparation method thereof.
Background technology:
The high temperature fused salt electrolysis process has proposed strict requirement to inert anode material, mainly comprises: can tolerate electrolytical corrosion, solubleness is little; Can tolerate the erosion effect of oozing of high temperature nascent oxygen; Good electrical conductivity is arranged; The physical strength height, heat-shock resistance is strong, is difficult for embrittlement; Easily machine-shaping is easy to be connected with metal guide rod etc.The inert anode material that patent documentation is reported mainly contains metal oxide ceramic, alloy anode and sintering metal three classes.Wherein, sintering metal has been taken into account the advantages such as satisfactory electrical conductivity of the strong corrosion resistant and the metal of metal oxide ceramic, and heat-shock resistance is poor, poorly conductive (ceramic phase matrix NiFe commonly used but exist
2O
4Electroconductibility relatively poor), be connected difficulty with metal guide rod, be difficult to problem such as maximization; In addition, in the material preparation process,,, be difficult to realize the densification of material so the less stable in ceramic matrix takes place by metallographic phase overflow and skewness easily because metallographic phase (as Cu) is relatively poor to the wettability of ceramic matrix; The disassociation of the oxidation of metallographic phase and ceramic phase takes place easily in the material sintering process or be reduced; Cause the oxidation and the selectivity corrosion of metallographic phase under the electrolysis working conditions easily, bring the slag that falls of ceramic phase to come off simultaneously.
Summary of the invention:
At the problems referred to above of cermet inert anode, adopt the prepared cermet inert anode of the present invention, be substituted with the existing deflection type anode that the non-ferrous metal fused salt electrolysis process is produced, realize the less energy-consumption of production process, pollution-free, targets such as low cost.
Metal ceramic inert anode for molten salt electrolysis of the present invention is with composite oxides SnO
2-AB
2O
4Be the ceramic phase matrix, the Ni-Cu alloy is the metallographic phase matrix, mixes respectively with the oxide M of different content
xO
yWith metal x and dispersion agent and binding agent, through colding pressing-cermet inert anode of sintering process preparation.It is characterized in that:
1. prepare cermet inert anode SnO
2-AB
2O
4-M
xO
yThe composition of raw materials of ceramic powder (in the quality percentage composition): 0.01～100%SnO
2, 0～99%AB
2O
4, 0～30%M
xO
yAB
2O
4For having the composite oxides of spinel structure; Wherein
A can be Ni, Mg, Co, Zn, Cu, at least a among Li and the Fe;
B can be Fe, Al, Co, Mn, at least a among Cr and the Ge;
M is Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir, Co, Ni, Fe, Al, Sn, Nb, Ta, Cr, Mo, W, Sb, V, Mb, at least a in Hf and the rare earth element;
2. the composition of raw materials (in the quality percentage composition) for preparing cermet inert anode: ceramic phase is 50～99%SnO
2-AB
2O
4-M
xO
yCeramic powder, metallographic phase are the Ni of 1～50%Ni-Cu-X powdered alloy or corresponding content, the metal-powder of Cu and X; Wherein
The quality percentage composition of the various constituent elements of metallographic phase is: 0.1～99.9%Ni, 0.1～99.9%Cu, 0～30%X; X is Co, Cr, Fe, Ag, Pt, at least a among the Au; Preferable alloy contains Ni, Cu in mutually at least;
3. dispersion agent is a water, alcohol, the adjacent dioctyl phthalate of benzene, oleic acid, ammonia salts solution, polyacrylamide solution, fish oil, o-butyl-2 salt, polyacrylic ester, at least a in the poly amic acid.
4. binding agent is a polyvinyl alcohol, carboxymethyl cellulose, hydroxy propyl cellulose, acrylic resin solution, sulfite solution, gelatin, polyoxyethylene glycol, polyethylene butyl ester, polyethylene ethyl ester, polyvinyl alcohol, at least a in the polyacrylic acid.
The metal ceramic inert anode for molten salt electrolysis preparation method is characterized in that: at first prepare ceramics powder and comply with, with SnO
2With AB
2O
4And M
xO
yRaw material, dispersion agent press proportion ingredient, calcined behind the ball mill mixing 5～15 hours, calcining temperature is 650～1350 ℃; AB wherein
2O
4And M
xO
yRaw material directly add with the oxide form of respective element A, B and M, perhaps carbonate, nitrate or other salt forms with respective element adds, add-on is respectively in the corresponding oxide equivalents of elements A, B and M;
Prepare cermet inert anode then, after ceramic phase and metallographic phase powder stock are pressed proportion ingredient, add dispersion agent and binding agent and carry out ball mill mixing, after oven dry removes fluid additive, adopt mold pressing or cast-isostatic cool pressing method to obtain the sintering metal green compact at 100～400MPa compacted under, at 1000～1500 ℃ of oxygen partial pressure sintering green compact that descend and control in the sintering atmosphere, obtain cermet inert anode.
Advantage of the present invention and positively effect show:
The ceramic matrix of the cermet inert anode that the present invention proposes adopts metal oxide M
xO
yAdulterated strong corrosion resistant SnO
2-AB
2O
4Compound oxidate ceramic improves its conductivity in the potential resistance to electrolyte contamination corrosive power that keeps ceramic phase;
Add dispersion agent and binding agent simultaneously in the ball-milling processing process of sintering metal powder raw material, it is good and be convenient to the metal-ceramic mixed powder raw material of green compact moulding to obtain reasonable particle size, sintering character;
Ceramic-metallic metallographic phase is Ni, Cu, X metal-powder or Ni-Cu-X powdered alloy, has improved the wettability of metallographic phase to ceramic phase, makes in the cermet inert anode sintering process metallographic phase not overflow and is evenly distributed, and has reached material densification effect;
In the material sintering process, the oxygen partial pressure of control in the sintering atmosphere avoided the disassociation of the oxidation of metallographic phase and ceramic phase or has been reduced, and obtains having target compound mutually and the cermet inert anode material of superperformance.
Description of drawings:
Fig. 1: cermet inert anode SnO
2-AB
2O
4-M
xO
yCeramic powder preparation technology.
Fig. 2: SnO
2-AB
2O
4-M
xO
yBase metal ceramic inert anode preparation technology.
Fig. 3: SnO
2-NiFe
2O
4The metallography microscope photo of/Ni-Cu-Co cermet inert anode.
Fig. 4: SnO
2-NiFe
2O
4-Sb
2O
3The metallography microscope photo of/Ni-Cu-Cr cermet inert anode.
Fig. 5: SnO
2-NiAl
2O
4The metallography microscope photo of-NiO/Ni-Cu-Ag cermet inert anode.
Embodiment:
Be described further below in conjunction with drawings and Examples:
Embodiment 1:
SnO
2-NiFe
2O
4/ Ni-Cu-Co cermet inert anode.
1. prepare ceramic powder, undertaken by the technical process of Fig. 1, with the industrial spirit of the adding of the raw material in the table 1 as dispersion agent, ball-milling processing 8 hours was calcined 8 hours down, is obtained the ceramic powder that median size is 3.31 μ m for 1200 ℃.The X-ray diffraction material phase analysis shows and contains SnO in the ceramic powder
2And NiFe
2O
4Two kinds of thing phases; The corrosion resistance nature of gained ceramic matrix is good, has semiconductor property under the electrolysis of aluminum temperature, is used as the powder stock of the ceramic matrix of cermet inert anode.
Table 1 cermet inert anode SnO
2-NiFe
2O
4The composition of raw materials example of ceramic powder
| Raw material | Quality percentage composition (%) |
| SnO 2 | 50.00 |
| F 2O 3 | 36.58 |
| NiO | 13.42 |
2. prepare cermet inert anode, technical process by Fig. 2 is carried out, with the raw material in the table 2 is dispersion agent with the industrial spirit, and polyvinyl alcohol is a binding agent, and ball-milling processing is after 8 hours, 80 ℃ of oven dry down, obtaining median size is the metal-ceramic mixed powder of 3.42 μ m, with the mixed powder compression molding, obtains the sintering metal green compact under 250MPa, the gained green compact 1250 ℃ of following sintering 4 hours, are adjusted oxygen partial pressure in the sintering atmosphere according to variation of temperature in the sintering process; Obtaining relative density after the cooling is 92.5%, has the be evenly distributed SnO of (the metallography microscope photo of seeing Fig. 3) of target compound phase composite and metallographic phase
2-NiFe
2O
4/ Ni-Cu-Co cermet inert anode.
Table 2 SnO
2-NiFe
2O
4The composition of raw materials example of/Cu-Ni-Co cermet inert anode
| Raw material | Quality percentage composition (%) |
| NiFe 2O 4-SnO 2Ceramic powder | 90 |
| The 80Ni-10Cu-10Co powdered alloy | 10 |
Embodiment 2:
SnO
2-NiFe
2O
4-Sb
2O
3/ Ni-Cu-Cr cermet inert anode
1. preparing ceramic powder, undertaken by Fig. 1 technical process, is dispersion agent with the industrial spirit with the raw material in the table 3, and ball-milling processing 8 hours was calcined 8 hours down, obtained the ceramic powder that median size is 3.11 μ m for 1200 ℃.The X-ray diffraction material phase analysis shows and mainly contains SnO in the ceramic powder
2And NiFe
2O
4Two-phase.The corrosion resistance nature of gained ceramic matrix is good, has semiconductor property under the electrolysis of aluminum temperature, and conductivity is good, as the ceramic powder raw material of cermet inert anode.
Table 3 cermet inert anode SnO
2-NiFe
2O
4-Sb
2O
3The composition of raw materials example of ceramic powder
| Raw material | Quality percentage composition (%) |
| SnO 2 | 48.00 |
| F 2O 3 | 36.58 |
| NiO | 13.42 |
| Sb 2O 3 | 2.00 |
2. preparing cermet inert anode, undertaken by Fig. 2 technical process, is dispersion agent with the industrial spirit with the raw material in the table 4, polyvinyl alcohol is a binding agent, after the ball-milling processing 8 hours, 80 ℃ of oven dry down obtain the metal that median size is 3.45 μ m-ceramic mixed powder; Under 250MPa, the mixed powder compression molding is obtained the sintering metal green compact.The gained green compact 1350 ℃ of following sintering 4 hours, are adjusted oxygen partial pressure in the sintering atmosphere according to variation of temperature in the sintering process; Obtaining relative density after the cooling is 95.5%, has the be evenly distributed SnO of (the metallography microscope photo of seeing Fig. 4 cermet inert anode) of target compound phase composite and metallographic phase
2-NiFe
2O
4-Sb
2O
3/ Ni-Cu-Cr cermet inert anode material.
Table 4 SnO
2-NiFe
2O
4-Sb
2O
3The composition of raw materials example of/Ni-Cu-Cr cermet inert anode
| Raw material | Quality percentage composition (%) |
| SnO 2-NiFe 2O 4-Sb 2O 3Ceramic powder | 90 |
| The 85Ni-10Cu-5Cr powdered alloy | 10 |
Embodiment 3:
SnO
2-NiAl
2O
4-CuO/Ni-Cu-Ag cermet inert anode
1. preparing ceramic powder, undertaken by Fig. 1 technical process, is dispersion agent with the industrial spirit with the raw material in the table 5, and ball-milling processing 8 hours was calcined 8 hours down, obtained the ceramic powder of 4.11 μ m for 1300 ℃.The X-ray diffraction material phase analysis shows and mainly contains SnO in the ceramic powder
2And NiAl
2O
4Two-phase.The corrosion resistance nature of gained ceramic matrix is good, has semiconductor property under the electrolysis of aluminum temperature, can be used as the ceramic powder raw material of cermet inert anode.
Table 5 cermet inert anode SnO
2-NiAl
2O
4The composition of raw materials example of-CuO ceramic powder
| Raw material | Quality percentage composition (%) |
| SnO 2 | 50.00 |
| Al 2O 3 | 27.71 |
| NiO | 20.29 |
| CuO | 2.00 |
2. preparing cermet inert anode, undertaken by Fig. 2 technical process, is dispersion agent with the industrial spirit with the raw material in the table 6, polyvinyl alcohol is a binding agent, after the ball-milling processing 8 hours, 80 ℃ of oven dry down obtain the metal that median size is 3.68 μ m-ceramic mixed powder; Under 200MPa, the mixed powder compression molding is obtained the sintering metal green compact; The gained green compact 1350 ℃ of following sintering 4 hours, are adjusted oxygen partial pressure in the sintering atmosphere according to variation of temperature in the sintering process; Obtaining relative density after the cooling is 97.12%, has the be evenly distributed SnO of (the metallography microscope photo of seeing Fig. 5 cermet inert anode) of target compound phase composite and metallographic phase
2-NiAl
2O
4-CuO/Ni-Cu-Ag cermet inert anode material.
Table 6 SnO
2-NiAl
2O
4The composition of raw materials example of-CuO/Ni-Cu-Ag cermet inert anode
| Raw material | Quality percentage composition (%) |
| SnO 2-NiAl 2O 4-CuO | 90 |
| The 65Ni-30Cu-5Ag powdered alloy | 10 |
Claims (2)
1. fused salt electrolysis SnO
2-NiFe
2O
4/ Ni-Cu-Co cermet inert anode is characterized in that:
1. the composition of raw materials of ceramic powder is by the quality percentage composition, for:
SnO
2 50.00％
F
2O
3 36.58％
NiO 13.42％
2. the composition of raw materials of cermet inert anode is by the quality percentage composition, for:
NiFe
2O
4-SnO
2Ceramic powder 90%
80Ni-10Cu-10Co powdered alloy 10%
2. fused salt electrolysis SnO
2-NiFe
2O
4The preparation method of/Ni-Cu-Co cermet inert anode is characterized in that:
1. prepare ceramic powder, with the industrial spirit of the adding of the raw material in the table 1 as dispersion agent, ball-milling processing 8 hours was calcined 8 hours down, is obtained the ceramic powder that median size is 3.31 μ m for 1200 ℃;
2. preparing cermet inert anode, is dispersion agent with the industrial spirit with the raw material in the table 2, and polyvinyl alcohol is a binding agent, and ball-milling processing was dried down for 80 ℃ after 8 hours, and obtaining median size is the metal-ceramic mixed powder of 3.42 μ m; Under 250MPa,, obtain the sintering metal green compact, with the gained green compact with the mixed powder compression molding; 1250 ℃ of following sintering 4 hours, adjust oxygen partial pressure in the sintering atmosphere according to variation of temperature in the sintering process; Obtaining relative density after the cooling is 92.5%, has the SnO that target compound phase composite and metallographic phase are evenly distributed
2-NiFe
2O
4/ Ni-Cu-Co cermet inert anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03136924 CN1283842C (en) | 2003-05-22 | 2003-05-22 | Metal ceramic inert anode for molten salt electrolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03136924 CN1283842C (en) | 2003-05-22 | 2003-05-22 | Metal ceramic inert anode for molten salt electrolysis and preparation method thereof |
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| Publication Number | Publication Date |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100392154C (en) * | 2005-03-10 | 2008-06-04 | 中南大学 | Protection means used for calcination starting or preheating exchanging inert anode for electrolysis of aluminium |
| CN101935852A (en) * | 2010-09-30 | 2011-01-05 | 中南大学 | Inertial electrode low-temperature aluminium electrolytic cell |
| CN102010193A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof |
| CN102732769B (en) * | 2012-07-17 | 2013-11-20 | 中南大学 | Nickel ferrite-copper metal ceramic inert anode material and preparation method |
| CN103668343B (en) * | 2013-12-03 | 2016-08-17 | 中南大学 | A kind of method improving conductivity of inert anode surface compact layer of metal ceramic |
| CN103922774A (en) * | 2014-03-07 | 2014-07-16 | 中南大学 | Micron-sized cermet precursor granules with micro/nano structure and preparation method thereof |
| CN107604387A (en) * | 2017-08-10 | 2018-01-19 | 中国铝业股份有限公司 | A kind of ceramal anode material and preparation method thereof |
| CN113215429A (en) * | 2021-04-30 | 2021-08-06 | 中南大学 | Preparation method of high-density metal ceramic inert anode material for aluminum electrolysis |
| CN113249755B (en) * | 2021-05-12 | 2023-05-02 | 郑州大学 | Inert anode material and preparation method and application thereof |
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