CN101608321A - A kind of aluminum electrolyzing cell used TiB 2The preparation method of/C gradient cathode material - Google Patents
A kind of aluminum electrolyzing cell used TiB 2The preparation method of/C gradient cathode material Download PDFInfo
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- CN101608321A CN101608321A CNA2009100122559A CN200910012255A CN101608321A CN 101608321 A CN101608321 A CN 101608321A CN A2009100122559 A CNA2009100122559 A CN A2009100122559A CN 200910012255 A CN200910012255 A CN 200910012255A CN 101608321 A CN101608321 A CN 101608321A
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Abstract
A kind of aluminum electrolyzing cell used TiB
2The preparation method of/C gradient cathode material belongs to the aluminum electrolysis technology field, and the raw material of employing is TiB
2, carbonaceous aggregate and binding agent, the process engineering continous batching, batch mixing, stone continuously, order is: by bottom to the top layer, TiB in each layering
2Content incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively; The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, naturally cool to normal temperature then, obtain product, the material micro components of the inventive method preparation becomes the gradient gradual change, can solve carbon element and TiB well
2The coating that causes of thermal mismatching problem such as easily peel off, and the anti-sodium erosion of this cathode material performance is strong, can significantly improve the life-span of current efficiency of aluminium cell and electrolyzer.
Description
Technical field
The invention belongs to the aluminum electrolysis technology field, be specifically related to the aluminium electrolytic cell cathode preparation methods.
Background technology
Hall-Ai Lute electrolytic process is produced aluminium and is had following shortcoming: 1. adopt the deflection type carbon annode to produce, the consumption of high quality carbon big (500～600kg/t-Al); 2. environmental pollution is serious, discharges a large amount of CO
2(1.17t/t-Al) and carcinogenic substance fluorocarbon etc.; 3. the aluminum-liquid wetting of negative electrode is poor, adopts high pole span operation, power consumption height (14000～15000kwh/t-Al) for fear of the fluctuation of aluminium liquid; 4. single chamber horizontal electrode, the production cost height, the productive rate of unit surface is low.Based on above reason, both at home and abroad the aluminium industry member is sent out a kind of novel aluminium cell of exhibition, and the characteristics of this aluminium cell are: become consumable carbon anodes and be expendable inert anode not; Become not into the wetting negative electrode of liquid aluminium is the wettability negative electrode, realize low pole span operation; The change single chamber is multicell, boosts productivity.The basis that novel electrolytic bath is achieved is the research success of inert anode and wettability negative electrode, has only both to share, and just might reduce pole span, stably manufactured makes power consumption reach 10000～11000kwh/t-Al, reaches to cut down the consumption of energy, decontamination, the target that reduces cost.At present, the aluminium industry member is all in the research and development that steps up inert anode and inertia wettability negative electrode, because the design of novel electrolytic bath and exploitation must be based upon on inert anode and the inertia wettability negative electrode both at home and abroad.Wherein inert anode material also is in laboratory stage at present, from big industrial applications one segment distance is arranged still.And the development of wettability negative electrode is very fast, and part is used industrial.
Inertia wettability negative electrode has the following advantages: because molten aluminum and this cathode surface can be wetting well, therefore need be in the layer of molten aluminum of preserving on the negative electrode about 20cm, only hang up the thick aluminium liquid film of one deck 3～5mm and can form smooth stable negative electrode, eliminated the huge interference of magnetic field thus to electrolysis production, and can significantly lower two interpolar distances, thereby saves energy significantly.The wettable negative electrode of ideal inertia must satisfy following some: by molten aluminum liquid wetting; Be insoluble in ionogen and the aluminium liquid, energy is high temperature resistant and the corrosion of fluoride molten salt and molten aluminium; Good electrical conductivity is arranged; High physical strength and thermal shock resistance are arranged; Machine-shaping easily, three-dimensional dimension is stable.The material that can satisfy the inert cathode requirement is few, mainly is that titanium in the fire-resistant hard metal material, zirconium compounds are more suitable, wherein especially with the TiB2 material for well.Studies show that: TiB
2TiB in the/C composite cathode material
2Content when 10～30% (massfractions), can quicken aluminium liquid and begin wetting speed; TiB
2When content was 40-70%, cathode material and aluminium liquid had good wettability; TiB
2Content is greater than 70% o'clock, material and aluminium liquid complete wetting.Work as TiB
2Content is 37% o'clock, satisfies the electrolysis of aluminum needs substantially.And the inertia wettability negative electrode of studying and using at present all exists the shortcoming that some are difficult to overcome, for example, since manufacture craft and cost, pure TiB
2The use of entity negative electrode is restricted.
Traditional TiB
2The coated cathode material is with pure TiB
2Be coated on the carbon block base body defective (as patent ZL02108199.9) such as because bonding force is not enough between coating and matrix, the use floating coat comes off seriously, lack work-ing life and the potential resistance to electrolyte contamination erosional competency is undesirable.Traditional TiB
2The composite layer cathode material is to contain TiB
2, the broken compound thickener of binding agent, graphite and carbon block base body by integral forming be prepared from (as patent: ZL200410100977.7, patent application: 200710192546.1).This cathode material exists matrix and TiB equally
2Thermal mismatch problem between the composite bed, in order to improve its work-ing life, it is very thick that composite bed need be done, TiB usually
2Content usually more than 60%～70%, cost is very high, and does not fundamentally solve carbon piece cathode material existing work-ing life short, ionogen and corrode problems such as serious.
At present, based on inertia wettability cathode material characteristics, successfully develop drainage type TiB
2/ C matrix material aluminium cell or guide flow type TiB
2The coated cathode aluminium cell (ZL03124435.1, ZL01248353.2, ZL200410023392.X, US6093304A, application number 200710192546.1, ZL2004101000977.7).Such electrolyzer direct current consumption has reduced more than 1000～2000kWh/t-Al.But the improved aluminium cell of this class is TiB
2Or TiB
2/ C composite cathode material be coated in the carbon block base body or with the carbon block base body by integral forming, but all be to adopt at TiB
2/ C coating-underlying structure, the bonding strength that exists coating is undesirable, because the difference of matrix and coated material thermal expansivity causes thermal stresses and causes coating cracking, phenomenon such as peels off, had a strong impact on the work-ing life of electrolyzer and the stability of electrolysis of aluminum operation, more can't satisfy the performance requriements of following novel aluminum cell the wettability cathode material.Chinese patent ZL200710010523.4, patent application 200810228017.7 disclose the lobed special-shaped electrolyzer in cathode block surface, and commerical test shows that this electrolyzer direct current consumption has reduced more than the 1000kWh/t-Al.Novel electrolytic bath after more than improving all can not fundamentally change existing bath life short, energy consumption is high and shortcoming such as negative electrode aluminum-liquid wetting difference.
Summary of the invention
Weak point at aluminum current electric tank cathode material and preparation method's existence the invention provides a kind of aluminum electrolyzing cell used TiB
2The preparation method of/C gradient cathode material is to solve carbon element and TiB
2The cathode material that causes of thermal mismatching in use coating problem, the life-span of improving the anti-sodium erosion of cathode material performance, current efficiency of aluminium cell and electrolyzer such as easily peel off.
The raw material that the inventive method adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 3.0 μ m～200 μ m, purity 〉=90%;
Binding agent is one or more the composition in coal-tar pitch, petroleum pitch, coal tar, Resins, epoxy, the furane resin.
Wherein, coal-tar pitch or petroleum pitch solid content are 55%～95% by mass percentage, and coal tar coking value≤50%, Resins, epoxy can be selected middle ring oxygen value (0.25～0.45) for use, as 6101,634; It is 4000～7000 that furane resin are selected molecular weight for use.If adopt the wherein composition of more than one materials, the material that is adopted can be with any than mixing.
The carbonaceous aggregate is one or more the composition in hard coal, refinery coke, metallurgical coke, graphite, natural graphite, the carbon fiber.
Wherein, hard coal is that electric calcined anthracite or gas are forged hard coal, carbon content 〉=90%; Refinery coke carbon content 〉=90%; Metallurgical coke content 〉=90%; The carbon content of graphite or natural graphite 〉=90%; Carbon fiber carbon content 〉=90%.
No matter adopt which kind of carbonaceous aggregate (mixtures of above-mentioned one or more), require carbon content 〉=90%, granularity is 3.0 μ m～200 μ m after grinding, and satisfies this requirement and gets final product.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
The inventive method adopts the above-mentioned raw materials continous batching, and the material for preparing each time is as a layering, and in each layering, the consumption of binding agent is TiB by mass percentage
2, carbonaceous aggregate and three kinds of raw material total amounts of binding agent 10%～20%, TiB by mass percentage
2Consumption be 0～90% of three kinds of raw material total amounts, the consumption of carbonaceous aggregate is 90%～0 of three kinds of raw material total amounts by mass percentage.TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content by first layering to last layering incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2Content by first layering to last layering variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Stratified quantity, each stratified thickness are decided according to the geometrical dimension of cathode material, desirable 6～50 layers of the number of plies, the desirable 20～200mm of each stratified thickness.
(2) batch mixing, stone;
The continuous batch mixing of the inventive method, stone.With first stratified TiB
2Did earlier mixed 30～60 minutes with the carbonaceous aggregate, add binding agent then, wet mixing 30～60 minutes, the wet mixing temperature is 140 ℃～170 ℃, is laid in then in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.
Require the order of batch mixing and stone to be: by bottom to uppermost top layer, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process can adopt mixer to finish according to the method described above.With first stratified TiB
2Put into dry-mixed machine with the carbonaceous aggregate and did earlier mixed 30～60 minutes, then with the TiB that mixes
2Put into the wet mixing machine with the carbonaceous aggregate, add binding agent, wet mixing 30～60 minutes, the wet mixing temperature is 140 ℃～170 ℃, and the material that wet mixing is intact is laid in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.Require the order of batch mixing and stone to be equally: by bottom to uppermost top layer, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process also can adopt continuous mixer according to above-mentioned do mix, wet mixing, stone method finish.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1100 ℃～1600 ℃, and sintering pressure is 2～40MPa, sintering time is 60 minutes～240 minutes, through hot pressed sintering, naturally cools to normal temperature then, obtain product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
The cathode material of the inventive method preparation is different from existing TiB
2The coated cathode material also is different from composite layer cathode carbon block of material, but a kind of TiB
2/ C gradient cathode material.This gradient cathode material does not have carbon block base body and TiB
2Coating (or TiB
2Composite bed) branch, TiB in the whole cathode material
2Content is graded by mass percentage from the bottom to the top layer, and according to the electrolysis of aluminum actual needs, the face that cathode material contacts with aluminium liquid is the top layer, only needs TiB
2Content gets final product between 40～70%.Therefore this cathode material does not exist TiB owing to be to adopt the gradient material Design Theory
2And also there is not conventional cathode material interface TiB in the thermal mismatch problem between the graphite carbon
2Coating (or TiB
2Composite bed) and defective such as the interface bond strength between the carbon piece is low, and its wetting effect height, can solve conventional cathode material work-ing life low, ionogen effectively and corrode defectives such as serious.
The present invention handles advantage in the interface problem with gradient material, be applied to improve the cathode material life-span in the aluminium electrolytic industry, broken through the pattern that in the past adopts coating-substrate, both reduced the cost of cell lining material, the work-ing life of having improved cathode material again simultaneously.Because the material micro components becomes the gradient gradual change, can solve carbon element and TiB well
2The material that causes of thermal mismatching in use coating problem such as easily peel off, and the anti-sodium erosion of this cathode material performance is strong, the life-span that can improve current efficiency of aluminium cell and electrolyzer.The inventive method is compared with traditional cathode material preparation method and is had the following advantages:
(1) the wettability cathode material working face performance characteristics of the inventive method preparation is greatly improved; with aluminium liquid complete wetting, can form the surfaces of aluminum liquid film, can effectively reduce pole span; improve the current efficiency of electrolyzer, can effectively protect cathode material by electrolytical erosion simultaneously.
(2) the present invention adopts pressing methods, and prepared gradient cathode material has advantages such as density height, good thermal shock, tensile strength, ultimate compression strength height and anti-sodium erosional competency are strong.
(3) cathode material of the inventive method preparation is a gradient material, has avoided TiB
2Thermal mismatch problem with composition such as graphite carbon does not also exist the interface in conjunction with problem, has therefore solved TiB
2Existing disbonding defectives such as coated cathode material.
(4) TiB in the cathode material
2Concentration gradients change, satisfying under the condition of service requirements, can effectively control TiB
2Consumption, reduce the cost of cathode material.
(5) the inventive method can be prepared large-sized wettability cathode material (according to the electrolyzer size, its three-dimensional dimension be 50mm～1000mm or more than), can satisfy the demand of modernized large-scale aluminum electrolytic cell anticathode material, for realizing that Aluminium Electrolysis provides possibility under the lower molecular ratio condition, prepared cathode material is particularly suitable for the lobed special-shaped electrolyzer in present state-of-the-art cathode block surface and uses.
(6) the present invention adopts the conceptual design of gradient material, and adopts hot-pressing sintering method to prepare moulding, efficiently solves poor, the TiB of simple carbon piece cathode material wettability
2Defectives such as the coated cathode material coating easily peels off, work-ing life is short.Adopt the gradient cathode material of the inventive method preparation, electrobath start initial stage negative electrode sodium absorbing capacity obviously reduces, and the potential resistance to electrolyte contamination erosional competency obviously strengthens, resistivity is low, and cathode drop obviously reduces, and bath voltage also obviously reduces, power consumption obviously reduces, and can make to improve bath life more than 1000 days.
Embodiment
Embodiment 1
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 100 μ m, purity 97%;
Binding agent is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. the coal tar of the petroleum pitch of the coal-tar pitch of solid content 65%, solid content 65%, coking value 45%, Resins, epoxy 6101 or molecular weight are a kind of in 4500 the furane resin;
2. the coal-tar pitch of Resins, epoxy 6101 and solid content 65% is by weight the composition that mixes gained at 1: 4;
3. molecular weight be 5000 furane resin with the petroleum pitch of solid content 55% by weight the composition that mixes gained at 1: 1;
4. the coal tar of coking value 40% and Resins, epoxy 6101 products are by weight the composition that mixes gained at 2: 1;
5. the furane resin of the coal tar of coking value 45%, Resins, epoxy 6101 products and molecular weight 5000 mixed the composition of gained by weight 1: 1: 1.
The carbonaceous aggregate is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. a kind of in hard coal, refinery coke, metallurgical coke, graphite, natural graphite or the carbon fiber;
2. electric calcined anthracite and graphite are by weight the composition that mixes gained at 1: 4;
3. refinery coke, metallurgical coke weight ratio are mixed the composition of gained at 1: 1;
4. gas is forged hard coal, natural graphite and carbon fiber mixed gained by weight 1: 4: 3 composition;
5. refinery coke, metallurgical coke, graphite and carbon fiber were by weight 1: 1: 3: 2 mix the composition of gained.
It is 100 μ m that above-mentioned carbonaceous aggregate requires through attrition process carbonaceous aggregate size; Carbon content 95%.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
According to the proportion ingredient of table 1, the number of plies is 6 layers, each stratified thickness 200mm.
(2) batch mixing, stone;
Require the order of batch mixing and stone to be: by 1 layer to 6 layers, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process adopts mixer to finish according to the method described above.With first stratified TiB
2Put into dry-mixed machine with the carbonaceous aggregate and do mixed 45min earlier, then with the TiB that mixes
2Put into the wet mixing machine with the carbonaceous aggregate, add binding agent, wet mixing 45min, the wet mixing temperature is 150 ℃, and the material that wet mixing is intact is laid in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1350 ℃, and sintering pressure is 25MPa, and sintering time is 150min, through hot pressed sintering, naturally cools to normal temperature then, obtains product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
This gradient cathode material densification is smooth, TiB
2Become graded, no interface exists between layer and the layer, surface and aluminium liquid complete wetting.Its porosity is 8%, and ultimate compression strength is 80MPa.This sample directly is put in 900 ℃ of aluminium liquid, takes out rapidly, repeatedly more than 30 times, specimen surface flawless, no obscission.
Table 1 embodiment 1 proportioning raw materials table
Embodiment 2
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 10 μ m, purity 95%;
Binding agent is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. the coal tar of the petroleum pitch of the coal-tar pitch of solid content 75%, solid content 75%, coking value 28% mixed the composition of gained by weight 1: 2: 3;
2. the coal-tar pitch of Resins, epoxy 634 products and solid content 75% is by weight the composition that mixes gained at 3: 4;
3. molecular weight be 6800 furane resin product with the petroleum pitch of solid content 85% by weight the composition that mixes gained at 3: 1;
4. the coal tar of coking value 28% and Resins, epoxy 634 products are by weight the composition that mixes gained at 5: 1;
5. the coal tar of coking value 45%, Resins, epoxy 634 products and molecular weight are 6800 furane resin product mixed gained by weight 1: 3: 5 composition.
The carbonaceous aggregate is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. hard coal, refinery coke, metallurgical coke and graphite were by weight 1: 2: 3: 4 mix the composition of gained;
2. electric calcined anthracite and graphite are by weight the composition that mixes gained at 3: 4;
3. refinery coke, metallurgical coke weight ratio are mixed the composition of gained at 1: 5;
4. gas is forged hard coal, natural graphite and carbon fiber mixed gained by weight 1: 2: 4 composition;
5. refinery coke, metallurgical coke, graphite and carbon fiber were by weight 1: 2: 3: 4 mix the composition of gained.
It is 10 μ m that above-mentioned carbonaceous aggregate requires through attrition process carbonaceous aggregate size, carbon content 96%.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
According to the proportion ingredient of table 2, the number of plies is 9 layers, each stratified thickness 20mm.
(2) batch mixing, stone;
Require the order of batch mixing and stone to be: by 1 layer to 9 layers, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process adopts continuous mixer to finish.With first stratified TiB
2Do mixed 30min, the TiB that is mixing then earlier with the carbonaceous aggregate
2With add binding agent in the carbonaceous aggregate, wet mixing 30min, the wet mixing temperature is 140 ℃, the material that wet mixing is intact is laid in the hot pressing die, carry out again after the same method second stratifiedly do to mix, wet mixing, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stacks layer by layer.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1100 ℃, and sintering pressure is 5MPa, and sintering time is 60min, through hot pressed sintering, naturally cools to normal temperature then, obtains product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
This gradient cathode material densification is smooth, TiB
2Become graded, no interface exists between layer and the layer, surface and aluminium liquid complete wetting.Its porosity is 7.5%, and ultimate compression strength is 85MPa.This sample directly is put in 900 ℃ of aluminium liquid, takes out rapidly, repeatedly more than 30 times, specimen surface flawless, no obscission.
Table 2 embodiment 2 proportioning raw materials tables
Embodiment 3
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 200 μ m, purity 97%;
Binding agent is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. the coal tar of the petroleum pitch of the coal-tar pitch of solid content 75%, solid content 75%, coking value 48%, Resins, epoxy 6101 and molecular weight be 7000 furane resin by weight 1: 1: 1: mix the composition of gained at 1: 1;
2. the petroleum pitch of Resins, epoxy 6101 products and solid content 90% is by weight the composition that mixes gained at 1: 6;
3. molecular weight be 7000 furane resin product with the petroleum pitch of solid content 75% by weight the composition that mixes gained at 1: 8;
4. the coal tar of coking value 48% and Resins, epoxy 634 products are by weight the composition that mixes gained at 10: 1;
5. the furane resin product of the coal tar of coking value 45%, Resins, epoxy 6101 products and molecular weight 6000 mixed the composition of gained by weight 1: 5: 10.
The carbonaceous aggregate is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. hard coal, refinery coke, metallurgical coke, graphite, natural graphite and carbon fiber were by weight 1: 1: 1: the composition of 1: 1: 1 mixing gained;
2. electric calcined anthracite and graphite are by weight the composition that mixes gained at 1: 10;
3. refinery coke, metallurgical coke mixed the composition of gained by weight 1: 6;
4. gas is forged hard coal, natural graphite and carbon fiber mixed gained by weight 10: 4: 3 composition;
5. refinery coke, metallurgical coke, graphite and carbon fiber were by weight 10: 5: 3: 2 mix the composition of gained.
It is 200 μ m that above-mentioned carbonaceous aggregate requires through attrition process carbonaceous aggregate size; Carbon content 98%.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
According to the proportion ingredient of table 3, the number of plies is 11 layers, each stratified thickness 60mm.
(2) batch mixing, stone;
Require the order of batch mixing and stone to be: by 1 layer to 11 layers, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively.
Blending process adopts mixer to finish according to the method described above.With first stratified TiB
2Put into dry-mixed machine with the carbonaceous aggregate and do mixed 60min earlier, then with the TiB that mixes
2Put into the wet mixing machine with the carbonaceous aggregate, add binding agent, wet mixing 60min, the wet mixing temperature is 170 ℃, and the material that wet mixing is intact is laid in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1600 ℃, and sintering pressure is 40MPa, and sintering time is 240min, through hot pressed sintering, naturally cools to normal temperature then, obtains product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
This gradient cathode material densification is smooth, TiB
2Become graded, no interface exists between layer and the layer, surface and aluminium liquid complete wetting.Its porosity is 10%, and ultimate compression strength is 82MPa.This sample directly is put into 900 ℃ this sample directly is put in the aluminium liquid, take out rapidly, 30 times repeatedly, specimen surface flawless, no obscission.
Table 3 embodiment 3 proportioning raw materials tables
Embodiment 4
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 150 μ m, purity 99%;
Binding agent is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. Resins, epoxy 6101 and molecular weight are 7000 furane resin mixed gained by weight 7: 3 composition;
2. the coal-tar pitch of Resins, epoxy 6101 products and solid content 65% is by weight the composition that mixes gained at 5: 2;
3. molecular weight be 4000 furane resin product with the petroleum pitch of solid content 80% by weight the composition that mixes gained at 6: 5;
4. the coal tar of coking value 40% and Resins, epoxy 6101 products are by weight the composition that mixes gained at 6: 5;
5. the coal tar of coking value 45%, Resins, epoxy 6101 products and furane resin (molecular weight 5000) product mixed the composition of gained by weight 8: 5: 1.
The carbonaceous aggregate is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. metallurgical coke, graphite, natural graphite and carbon fiber were by weight 1: 2: 3: 5 mix the composition of gained;
2. electric calcined anthracite and graphite are by weight the composition that mixes gained at 7: 4;
3. refinery coke, metallurgical coke mixed the composition of gained by weight 8: 1;
4. gas is forged hard coal, natural graphite and carbon fiber mixed gained by weight 7: 4: 3 composition;
5. refinery coke, metallurgical coke, graphite and carbon fiber were by weight 7: 5: 3: 2 mix the composition of gained.
It is 150 μ m that above-mentioned carbonaceous aggregate requires through attrition process carbonaceous aggregate size; Carbon content 99%.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
According to the proportion ingredient of table 4, the number of plies is 15 layers, each stratified thickness 50mm.
(2) batch mixing, stone;
Require the order of batch mixing and stone to be: by 1 layer to 15 layers, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process adopts mixer to finish according to the method described above.With first stratified TiB
2Put into dry-mixed machine with the carbonaceous aggregate and do mixed 40min earlier, then with the TiB that mixes
2Put into the wet mixing machine with the carbonaceous aggregate, add binding agent, wet mixing 40min, the wet mixing temperature is 155 ℃, and the material that wet mixing is intact is laid in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1400 ℃, and sintering pressure is 20MPa, and sintering time is 200min, through hot pressed sintering, naturally cools to normal temperature then, obtains product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
This gradient cathode material densification is smooth, TiB
2Become gradient to change continuously, no interface exists between layer and the layer, surface and aluminium liquid complete wetting.Its porosity is 9%, and ultimate compression strength is 83MPa.This sample directly is put in 900 ℃ of aluminium liquid, takes out rapidly, repeatedly more than 30 times, specimen surface flawless, no obscission.
Table 4 embodiment 4 proportioning raw materials tables
Embodiment 5
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent.
TiB wherein
2Granularity requirements be 50 μ m, purity 99%;
Binding agent is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. the coal tar of coking value 40%, Resins, epoxy 634 and molecular weight are the composition that 5000 furane resin weight ratio is mixed gained at 1: 3: 6;
2. the coal-tar pitch of Resins, epoxy 634 products and solid content 65% is by weight the composition that mixes gained at 9: 5;
3. molecular weight be 5000 furane resin product with the petroleum pitch of solid content 55% by weight the composition that mixes gained at 8: 1;
4. the coal tar of coking value 40% and Resins, epoxy 6101 is by weight the composition that mixes gained at 9: 1;
5. the coal tar of coking value 45%, Resins, epoxy 634 products and furane resin (molecular weight 5500) product mixed the composition of gained by weight 1: 5: 9.
The carbonaceous aggregate is selected following 1., 2., 3., 4. or 5. a kind of for use:
1. hard coal, refinery coke, natural graphite and carbon fiber were by weight 9: 5: 3: 2 mix the composition of gained;
2. electric calcined anthracite and graphite are by weight the composition that mixes gained at 1: 5;
3. refinery coke, metallurgical coke weight ratio are mixed the composition of gained at 1: 6;
4. gas is forged hard coal, natural graphite and carbon fiber mixed gained by weight 9: 4: 3 composition;
5. refinery coke, metallurgical coke, graphite and carbon fiber were by weight 10: 7: 3: 2 mix the composition of gained.
It is 50 μ m that above-mentioned carbonaceous aggregate requires through attrition process carbonaceous aggregate size; Carbon content 99%.
The present invention adopts hot pressing sintering method to prepare TiB
2/ C gradient cathode material, step is as follows.
(1) batching;
According to the proportion ingredient of table 5, the number of plies is 31 layers, each stratified thickness 30mm.
(2) batch mixing, stone;
Require the order of batch mixing and stone to be: by 1 layer to 31 layers, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively.
Blending process adopts mixer to finish according to the method described above.With first stratified TiB
2Put into dry-mixed machine with the carbonaceous aggregate and do mixed 35min earlier, then with the TiB that mixes
2Put into the wet mixing machine with the carbonaceous aggregate, add binding agent, wet mixing 45min, the wet mixing temperature is 145 ℃, and the material that wet mixing is intact is laid in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer.
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1200 ℃, and sintering pressure is 15MPa, and sintering time is 90min, through hot pressed sintering, naturally cools to normal temperature then, obtains product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
This gradient cathode material densification is smooth, TiB
2Become gradient to change continuously, no interface exists between layer and the layer, surface and aluminium liquid complete wetting.Its porosity is 8.5%, and ultimate compression strength is 88MPa.This sample directly is put in 900 ℃ of aluminium liquid, takes out rapidly repeatedly more than 30 times specimen surface flawless, no obscission.
Table 5 embodiment 5 proportioning raw materials tables
Claims (5)
1, a kind of aluminum electrolyzing cell used TiB
2The preparation method of/C gradient cathode material is characterized in that processing step is as follows:
(1) batching;
The raw material that adopts is TiB
2, carbonaceous aggregate and binding agent, continous batching, the material for preparing each time are as a layering, in each layering, the consumption of binding agent is 10%～20% of three kinds of raw material total amounts, TiB by mass percentage by mass percentage
2Consumption be 0～90% of three kinds of raw material total amounts, the consumption of carbonaceous aggregate is 90%～0 of three kinds of raw material total amounts by mass percentage, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content by first layering to last layering incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2Content by first layering to last layering variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively;
(2) batch mixing, stone;
Continuous batch mixing, stone are with first stratified TiB
2Did earlier mixed 30～60 minutes with the carbonaceous aggregate, add binding agent then, wet mixing 30～60 minutes, the wet mixing temperature is 140 ℃～170 ℃, is laid in then in the hot pressing die, carries out second stratified dried mixed, wet mixing after the same method again, then it is laid in first above layering, finish again according to this next until last stratified do mix, wet mixing, stone, each place Min layers is put into above the previous layering, stack layer by layer;
Require the order of batch mixing and stone to be: by bottom to uppermost top layer, TiB in each layering
2Different with the content of carbonaceous aggregate, TiB
2Content incremental variations successively, the variation and the content of carbonaceous aggregate successively decreases successively; Perhaps TiB
2The content variation of successively decreasing successively, and the content of carbonaceous aggregate incremental variations successively;
(3) hot pressed sintering;
The above-mentioned material of completing is layer by layer carried out hot pressed sintering in hot pressing die, sintering temperature is 1100 ℃～1600 ℃, and sintering pressure is 2～40MPa, sintering time is 60 minutes～240 minutes, through hot pressed sintering, naturally cools to normal temperature then, obtain product, promptly aluminum electrolyzing cell used TiB
2/ C gradient cathode material.
2, according to the described aluminum electrolyzing cell used TiB of claim 1
2The preparation method of/C gradient cathode material is characterized in that binding agent is one or more the composition in coal-tar pitch, petroleum pitch, coal tar, Resins, epoxy, the furane resin; The carbonaceous aggregate is one or more the composition in hard coal, refinery coke, metallurgical coke, graphite, natural graphite, the carbon fiber.
3, according to the described aluminum electrolyzing cell used TiB of claim 1
2The preparation method of/C gradient cathode material is characterized in that TiB
2Granularity requirements be 3.0 μ m～200 μ m, purity 〉=90%; The carbonaceous aggregate size is 3.0 μ m～200 μ m, carbon content 〉=90%.
4, according to the described aluminum electrolyzing cell used TiB of claim 2
2The preparation method of/C gradient cathode material is characterized in that coal-tar pitch or petroleum pitch solid content are 55%～95% by mass percentage; Coal tar coking value≤50%; The Resins, epoxy oxirane value is 0.25～0.45; The furane resin molecular weight is 4000～7000; Hard coal is that electric calcined anthracite or gas are forged hard coal, carbon content 〉=90%; Refinery coke carbon content 〉=90%; Metallurgical coke content 〉=90%; The carbon content of graphite or natural graphite 〉=90%; Carbon fiber carbon content 〉=90%.
5, according to the described aluminum electrolyzing cell used TiB of claim 1
2The preparation method of/C gradient cathode material is characterized in that stratified quantity is 6～50 layers, and each stratified thickness is 20～200mm.
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| CN102383147A (en) * | 2011-08-12 | 2012-03-21 | 福州赛瑞特新材料技术开发有限公司 | Sandwich biscuit type graphite/titanium diboride electrode and manufacturing method thereof |
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