CN101844926A - Pelleting method of titanium diboride powder - Google Patents
Pelleting method of titanium diboride powder Download PDFInfo
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Abstract
The invention provides a pelleting method of titanium diboride powder, which is suitable for preparing high-content high-strength large TiB2 particles for the wettable cathode of an aluminium electrolysis cell and is especially suitable for preparing the high-content high-strength large TiB2 particles for the wettable cathode of a deflector-type aluminium electrolysis cell. The method is characterized in that the high-content high-strength TiB2 particles are prepared by carrying out processes of kneading, shaping, roasting, crushing, sieving and the like on the titanium diboride powder as the main aggregate by adopting an organic binder or inorganic binder or a compound binder of the organic binder or the inorganic binder. The method has simple preparation process, controllable granularity and convenient application. The TiB2 particles prepared by the invention has the TiB2 content of 70-95 percent, the strength of 30-60MPa, and the resistivity of 0.5-40 muomega.m, and moreover, the TiB2 particles have small deformation and strong high temperature melt penetration resistance, can be completely wetted with aluminium liquid, realizes aluminium electrolysis production energy saving, prolongs the service life of the cathode of the aluminium electrolysis cell and reduces the aluminium electrolysis production cost.
Description
Technical field
The present invention relates to technical field of aluminum electrolysis, be particularly suitable for aluminium cell wettability negative electrode TiB2 (TiB
2) the particulate prilling process.
Technical background
Hall-Ai Lute aluminium metallurgy method is the unique method of industrial aluminium metallurgy in the worldwide from 1886 so far always, but its power consumption height, the negative electrode Years Of Service is not long, and electrolyzer is short work-ing life, thereby causes the aluminium production cost too high.Studies show that TiB
2The wettability cathode technique is the existing high temperature fused salt electrolysis legal system aluminium of innovation, realizes one of energy-conservation gordian technique significantly.
Current, TiB
2The application form of wettability negative electrode is more, by contrast, and TiB
2-C composite cathode material have bonding strength height, life-span long, be easy to characteristics such as maximization, performance is more excellent, is one of the most potential wettability cathode material.And existing TiB
2The preparation method mainly contains from spreading method and carbothermic method, and its finished product are TiB
2Powder, general granularity is 1-100 μ m, is difficult to prepare the TiB of various volume particle sizes
2Particle.Therefore, present TiB
2-C composite cathode technology of preparing can only adopt fine-grained TiB
2Powder is as the source of titanium boride, because fine powder is too much, tiny crack appears in negative electrode easily behind the shaping and roasting, causes negative electrode intensity and corrosion resistance nature not to reach requirement, influences its work-ing life.For avoiding the appearance of composite cathode material crackle, improve material mechanical property and and high base strength, must reduce TiB
2The consumption of powder.Yet titanium boride content can not get effective raising in the composite cathode material, causes performances such as composite cathode and molten aluminum liquid wettability can't reach desirable requirement, is difficult to realize real water conservancy diversion negative electrode, and sodium and ionogen corrode big to the infiltration of composite cathode.
At TiB
2Propose TiB in the problem that-C composite cathode material too much causes because of fine powder material, patent (No.200710192546.1)
2-C composite cathode aggregate carries out grain size distribution, can fundamentally solve above-mentioned drawback.From the angle of grain size distribution, adopt macrobead carbon aggregate cheap and easy to get to substitute TiB
2It is feasible that particle carries out grain size distribution, but at TiB
2The lip-deep macrobead carbon of-C composite cathode aggregate is because of poor with aluminum-liquid wetting, and influences the wettability between whole cathode material surface and the aluminium liquid, can't realize real wettability water conservancy diversion negative electrode.Above-mentioned showing, adopt TiB
2Particle is to TiB
2It is the effective way that realizes real wettability long life cathode that-C composite cathode aggregate carries out grain size distribution.Therefore, TiB
2The powder agglomeration technique is prepared sizes grating TiB
2The key of-C wettability composite cathode material.
Summary of the invention
At existing TiB
2-C composite cathode preparation and the deficiency that performance exists the invention provides that a kind of cost is low, intensity is big, anti-sodium perviousness strong, good conductivity, fully and the high-content TiB of aluminum-liquid wetting
2The particulate preparation method is in the hope of obtaining high-quality TiB
2-C composite cathode.
Technical solution of the present invention is as follows:
A kind of TiB
2The powder prilling process is characterized in that, may further comprise the steps:
Step 1: binding agent, aggregate, charcoal fiber and organic solvent are mixed, and the mass ratio of each component is: aggregate: 80-95%; Binding agent 5-20%; Carbon fiber 0-3.0%; Organic solvent 0-5.0%;
Step 2: mix the moulding of kneading: the mixture of step 1 gained is mixed the moulding of kneading, make the moulding product;
Step 3: roasting:, make roasting product with the roasting under 900 ℃ of-1400 ℃ of temperature condition of moulding product;
Step 4: broken and screening:, obtain TiB with screening again after the roasting product fragmentation
2Particle.
Described binding agent is organic binder bond, mineral binder bond or by the compound binding agent of organic binder bond and the compound preparation of mineral binder bond, and described organic binder bond is one or more the mixture in coal-tar pitch, petroleum pitch, Resins, epoxy, furane resin, polyimide resin, resol, carbolineum and the coal tar; Described mineral binder bond is the mixture of any one or multiple composition in alumina sol, magnesium oxide colloidal sol, silica sol, the silicon carbide colloidal sol.
Described aggregate is by TiB
2Powder or TiB
2Powder and carbonaceous aggregate mix to be formed, wherein TiB
2Powder accounts for the 85-100% of total aggregate, and the carbonaceous aggregate accounts for 0-15%.
Described carbonaceous aggregate is forged at least a composition in hard coal, metallurgical coke, needle coke, the carbon fiber powder by refinery coke, Graphite Powder 99, pitch coke, electric calcined anthracite, gas.
Described organic solvent is at least a formulated by in ethanol, ethyl acetate, the acetone.
Coal-tar pitch in the described binding agent, petroleum pitch, furane resin, polyimide resin, resol mix with aggregate, charcoal fibre fractionation with the pressed powder form, or mix with aggregate, charcoal fibre fractionation after adopting organic solvent dissolution to become liquid form, or mix and pinch with molten state form and aggregate, charcoal fibre fractionation.
Moulding process in the step 2 is to adopt vibratory compaction or compression molding, and the pressure magnitude range is: 0.5-10MPa (vibratory compaction), 50-180MPa (compression molding).
Described roasting process is: the speed with 8-15 ℃/h during beginning is warming up to 600 ℃, then with the speed of 15-25 ℃/h to 900-1400 ℃, insulation 6-15h is cooled to 600 ℃ with 30-40 ℃/h again, cools to room temperature then with the furnace.
Shattering process in the step 4 is carried out for adopting in jaw crusher, impact breaker, hammer mill, combined type crusher, impingement crusher, the cone crusher one or more.
The technical parameter explanation:
(1) forming pressure: 0.5-10MPa (vibratory compaction), 50-180MPa (compression molding).Pressure is crossed conference cracks the moulding product, and the too small moulding product density that then can cause is little, and intensity is low.
(2) heat-up rate: be lower than 600 ℃: 8-15 ℃/h; Be higher than 600 ℃: 15-25 ℃/h; Speed of cooling: 30-40 ℃/h is cooled to 600 ℃, cools to room temperature then with the furnace.When being lower than 600 ℃, the too fast meeting of heat-up rate causes a large amount of binding agent volatile matters to overflow, and increases the sample porosity, reduces sample intensity; After being higher than 600 ℃, heat-up rate can be fast slightly, because should mainly be the binding agent carbonization process in the stage; Cooling rate equally can not be too fast, can cause sample crackle or fracture to occur too soon; Intensification and cooling rate all can not be slow excessively, in order to avoid cause waste of energy.
(3) maturing temperature: 900 ℃-1400 ℃.Maturing temperature is too high to the equipment requirements height, and cost is increased; Maturing temperature is low excessively to cause sample roasting degree not enough, and performance can not reach requirement.
Advantage of the present invention:
The present invention by the roasting crush method to TiB
2Powder carries out granulation, and technology is simple, cost is low, easy to operate, gained TiB
2Granule strength is big, TiB
2Content height, anti-sodium perviousness are strong, good conductivity, with aluminium liquid complete wetting.The present invention proposes first to electrolysis of aluminum wettability negative electrode TiB
2Powder carries out granulation, has broken composite cathode raw material TiB
2The situation of having only powder, the grain size distribution that can be large size composite cathode aggregate provides the TiB of controllable granularity
2Particle.Adopt this TiB
2The composite cathode material of granules preparation has overcome because of TiB
2Powder too much and a large amount of crackles that occur, the volume density of whole cathode material is big, porosity is little, TiB
2The content height, thus can with aluminium liquid complete wetting, potential resistance to electrolyte contamination and sodium perviousness are strong, and thermal shock resistance is good, long service life.
Preparation technology of the present invention is simple, controllable granularity, application are convenient.The TiB of the present invention's preparation
2Particle, TiB
2Content can reach 70%-95%, intensity reach 30-60MPa, resistivity be 0.5-40 μ Ω m and be out of shape little, high temperature resistant melt penetrating quality strong and can with aluminium liquid complete wetting, can be used for the used for aluminium electrolysis wettability TiB of processability excellence
2Cathode material realizes that Aluminium Electrolysis is energy-conservation, improves the work-ing life of aluminium electrolytic cell cathode, reduces the Aluminium Electrolysis cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below with reference to figure and specific implementation process the present invention is described in further details:
Embodiment 1:
Granulating formula: aggregate 80% (TiB wherein
2Powder: 85%, refinery coke: 15%); Coal-tar pitch: 20%.
By above-mentioned dosage weighing, in kneading machine, mix and pinch, treat mixing after, at 180MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 900 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2(TiB is looked required in the selection of sieve to particle during screening
2Particulate globule size and deciding generally selects for use desired particle size up and down to the sieve of equidistant order number (as table 1).As: now need granularity to be about the TiB of 1000 μ m
2Particle, then can select 14 and 18 or 12 and 20 two kind of sieve crushed particles is sieved, obtain desired particle size TiB
2Particle.All the other embodiment screening processes and present embodiment same treatment).This TiB
2Particle volume density is 2.20g/cm
3, porosity is 19.5%, and ultimate compression strength is 32MPa, and resistivity is 35 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 2
Granulating formula: aggregate 80% (TiB wherein
2Powder: 100%, refinery coke: 0%); Coal-tar pitch: 20%.
By above-mentioned dosage weighing, pitch is heated to molten state, mix with aggregate then and pinch, treat mixing after, at 180MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 900 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.23g/cm
3, porosity is 17.0%, and ultimate compression strength is 35MPa, and resistivity is 25 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 3
Granulating formula: aggregate 80% (TiB wherein
2Powder: 85%, refinery coke: 15%); Coal-tar pitch+Resins, epoxy: 20%.
By above-mentioned dosage weighing, utilize acetone that Resins, epoxy is dissolved, mix with pitch and aggregate then, treat mixing after, at 180MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 900 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.18g/cm
3, porosity is 20.1%, and ultimate compression strength is 30MPa, and resistivity is 28 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 4
Granulating formula: aggregate 95% (TiB wherein
2Powder: 90%, refinery coke: 10%); Aluminum oxide is molten: 5%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 180MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1200 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.70g/cm
3, porosity is 19.5%, and ultimate compression strength is 34MPa, and resistivity is 40 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 5
Granulating formula: aggregate 90% (TiB wherein
2Powder: 90%, refinery coke: 10%); Alumina sol+pitch: 10%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 50MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1200 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.50g/cm
3, porosity is 17.5%, and ultimate compression strength is 30MPa, and resistivity is 38 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 6
Granulating formula: aggregate 90% (TiB wherein
2Powder: 90%, refinery coke: 10%); Alumina sol: 10%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 120MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1400 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize hammer mill to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.80g/cm
3, porosity is 16.2%, and ultimate compression strength is 34MPa, and resistivity is 1.5 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 7
Granulating formula: aggregate 90% (TiB wherein
2Powder: 90%, refinery coke: 10%); Alumina sol: 10%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 120MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1400 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize impact breaker+hammer mill to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.80g/cm
3, porosity is 16.2%, and ultimate compression strength is 34MPa, and resistivity is 1.5 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 8
Granulating formula: aggregate 90% (TiB wherein
2Powder: 90%, refinery coke: 10%); Alumina sol: 10%; Carbon fiber: 2.0%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 120MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1400 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.81g/cm
3, porosity is 18.3%, and ultimate compression strength is 55MPa, and resistivity is 1.2 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Embodiment 9
Granulating formula: aggregate 90% (TiB wherein
2Powder: 100%, refinery coke: 0%); Alumina sol: 10%; Carbon fiber: 2.0%.
By above-mentioned dosage weighing, in kneading machine, mix, treat mixing after, at 120MPa forming pressure compacted under.The moulding product are buried with coke, it is carried out roasting, heat up at a slow speed during beginning (8-15 ℃/h) to 600 ℃, be rapidly heated relatively then (15-25 ℃/h) to 1400 ℃, insulation 6-15h, cooling is (30-40 ℃/h) to 600 ℃, cool to room temperature then with the furnace fast.Utilize jaw crusher to the roasting product fragmentation, screening obtains varigrained high-content TiB
2Particle.This TiB
2Particle volume density is 2.90g/cm
3, porosity is 17.5%, and ultimate compression strength is 60MPa, and resistivity is 0.5 μ Ω m, and with aluminium liquid complete wetting, flawless, thermal shock resistance is good, long service life.
Table 1: sieve mesh numerical table
| The mesh number | ??μm | The mesh number | ??μm | The mesh number | ??μm | The mesh number | ??μm |
| ??2 | ??8000 | ??28 | ??600 | ??100 | ??150 | ??250 | ??58 |
| ??3 | ??6700 | ??30 | ??550 | ??115 | ??125 | ??270 | ??53 |
| ??4 | ??4750 | ??32 | ??500 | ??120 | ??120 | ??300 | ??48 |
| ??5 | ??4000 | ??35 | ??425 | ??125 | ??115 | ??325 | ??45 |
| ??6 | ??3350 | ??40 | ??380 | ??130 | ??113 | ??400 | ??38 |
| ??7 | ??2800 | ??42 | ??355 | ??140 | ??109 | ??500 | ??25 |
| ??8 | ??2360 | ??45 | ??325 | ??150 | ??106 | ??600 | ??23 |
| ??10 | ??1700 | ??48 | ??300 | ??160 | ??96 | ??800 | ??18 |
| ??12 | ??1400 | ??50 | ??270 | ??170 | ??90 | ??1000 | ??13 |
| ??14 | ??1180 | ??60 | ??250 | ??175 | ??86 | ??1340 | ??10 |
| ??16 | ??1000 | ??65 | ??230 | ??180 | ??80 | ??2000 | ??6.5 |
| ??18 | ??880 | ??70 | ??212 | ??200 | ??75 | ??5000 | ??2.6 |
| ??20 | ??830 | ??80 | ??180 | ??230 | ??62 | ??8000 | ??1.6 |
| ??24 | ??700 | ??90 | ??160 | ??240 | ??61 | ??10000 | ??1.3 |
Claims (9)
1. TiB
2The powder prilling process is characterized in that, may further comprise the steps:
Step 1: binding agent, aggregate, charcoal fiber and organic solvent are mixed, and the mass ratio of each component is: aggregate: 80-95%; Binding agent 5-20%; Carbon fiber 0-3.0%; Organic solvent 0-5.0%;
Step 2: mix the moulding of kneading: the mixture of step 1 gained is mixed the moulding of kneading, make the moulding product;
Step 3: roasting:, make roasting product with the roasting under 900 ℃ of-1400 ℃ of temperature condition of moulding product;
Step 4: broken and screening:, obtain the TiB2 particle with screening again after the roasting product fragmentation.
2. TiB according to claim 1
2The powder prilling process, it is characterized in that, described binding agent is organic binder bond, mineral binder bond or by the compound binding agent of organic binder bond and the compound preparation of mineral binder bond, and described organic binder bond is one or more the mixture in coal-tar pitch, petroleum pitch, Resins, epoxy, furane resin, polyimide resin, resol, carbolineum and the coal tar; Described mineral binder bond is the mixture of any one or multiple composition in alumina sol, magnesium oxide colloidal sol, silica sol, the silicon carbide colloidal sol.
3. TiB according to claim 1
2The powder prilling process is characterized in that, described aggregate is by TiB
2Powder or TiB
2Powder and carbonaceous aggregate mix to be formed, wherein TiB
2Powder accounts for the 85-100% of total aggregate, and the carbonaceous aggregate accounts for 0-15%.
4. TiB according to claim 3
2The powder prilling process is characterized in that, described carbonaceous aggregate is forged at least a composition in hard coal, metallurgical coke, needle coke, the carbon fiber powder by refinery coke, Graphite Powder 99, pitch coke, electric calcined anthracite, gas.
5. TiB according to claim 1
2The powder prilling process is characterized in that, described organic solvent is at least a formulated by in ethanol, ethyl acetate, the acetone.
6. TiB according to claim 2
2The powder prilling process, it is characterized in that, coal-tar pitch in the described binding agent, petroleum pitch, furane resin, polyimide resin, resol mix with aggregate, charcoal fibre fractionation with the pressed powder form, or mix with aggregate, charcoal fibre fractionation after adopting organic solvent dissolution to become liquid form, or mix and pinch with molten state form and aggregate, charcoal fibre fractionation.
7. TiB according to claim 1
2The powder prilling process is characterized in that, the moulding process in the step 2 is to adopt vibratory compaction or compression molding, and for vibratory compaction, the pressure magnitude range is: 0.5-10MPa, for compression molding, the pressure magnitude range is 50-180MPa.
8. TiB according to claim 1
2The powder prilling process is characterized in that, described roasting process is: the speed with 8-15 ℃/h during beginning is warming up to 600 ℃, then with the speed of 15-25 ℃/h to 900-1400 ℃, insulation 6-15h is cooled to 600 ℃ with 30-40 ℃/h again, cools to room temperature then with the furnace.
9. according to each described TiB of claim 1-8
2The powder prilling process is characterized in that, the shattering process in the step 4 is carried out for adopting in jaw crusher, impact breaker, hammer mill, combined type crusher, impingement crusher, the cone crusher one or more.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010206A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Titanium boride composite material for aluminum electrolysis and preparation method thereof |
| CN102051060A (en) * | 2010-11-23 | 2011-05-11 | 中南大学 | Inorganic modified coal pitch and preparation method thereof |
| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
| CN102531657A (en) * | 2012-01-05 | 2012-07-04 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN102744410A (en) * | 2012-04-27 | 2012-10-24 | 中国铝业股份有限公司 | Method for preparing TiB2 layer of cathode for aluminum electrolytic bath |
| CN103194101A (en) * | 2013-03-27 | 2013-07-10 | 江苏联合金陶特种材料科技有限公司 | Titanium boride-based coating composite material for aluminum electrolysis, preparation method and coating method thereof |
| CN103429791A (en) * | 2011-02-11 | 2013-12-04 | 西格里碳素欧洲公司 | Surface-profiled cathode block containing hard material |
| CN103748057A (en) * | 2011-08-23 | 2014-04-23 | Esk陶瓷有限及两合公司 | Titanium diboride granules as erosion protection for cathodes |
| CN106082220A (en) * | 2016-05-31 | 2016-11-09 | 神雾环保技术股份有限公司 | Compound binding agent, the mixture pelletizing comprising it and preparation method thereof |
| CN107364866A (en) * | 2017-06-28 | 2017-11-21 | 大连华锐重工集团股份有限公司 | A kind of low-order coal prepares the method and compound binding agent of calcium carbide furnace charge |
| CN107382353A (en) * | 2017-08-10 | 2017-11-24 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method of fibre reinforced titanium diboride based composites |
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| 《中南工业大学学报（自然科学版）》 20030228 李庆余等 中低温烧结铝电解用TiB2-碳素复合阴极材料 第24-27页 1-9 第34卷, 第1期 * |
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| CN102051060B (en) * | 2010-11-23 | 2012-04-25 | 中南大学 | Inorganic modified coal pitch and preparation method thereof |
| CN102010206A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Titanium boride composite material for aluminum electrolysis and preparation method thereof |
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| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
| CN102531657B (en) * | 2012-01-05 | 2013-11-20 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN102531657A (en) * | 2012-01-05 | 2012-07-04 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN102744410A (en) * | 2012-04-27 | 2012-10-24 | 中国铝业股份有限公司 | Method for preparing TiB2 layer of cathode for aluminum electrolytic bath |
| CN103194101A (en) * | 2013-03-27 | 2013-07-10 | 江苏联合金陶特种材料科技有限公司 | Titanium boride-based coating composite material for aluminum electrolysis, preparation method and coating method thereof |
| CN103194101B (en) * | 2013-03-27 | 2016-03-09 | 江苏联合金陶特种材料科技有限公司 | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method |
| CN106082220A (en) * | 2016-05-31 | 2016-11-09 | 神雾环保技术股份有限公司 | Compound binding agent, the mixture pelletizing comprising it and preparation method thereof |
| CN107364866A (en) * | 2017-06-28 | 2017-11-21 | 大连华锐重工集团股份有限公司 | A kind of low-order coal prepares the method and compound binding agent of calcium carbide furnace charge |
| CN107382353A (en) * | 2017-08-10 | 2017-11-24 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method of fibre reinforced titanium diboride based composites |
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