CN100457612C - Method for preparing fine grains of tantalum carbide - Google Patents
Method for preparing fine grains of tantalum carbide Download PDFInfo
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- CN100457612C CN100457612C CNB2006101660235A CN200610166023A CN100457612C CN 100457612 C CN100457612 C CN 100457612C CN B2006101660235 A CNB2006101660235 A CN B2006101660235A CN 200610166023 A CN200610166023 A CN 200610166023A CN 100457612 C CN100457612 C CN 100457612C
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Abstract
This invention provides a method for preparing TaC powder with fine particles. This method comprises: (1) decomposing crushed waste Ta-containing materials in a mixture of HF and H2SO4 at a solid/liquid volume ratio of 1:1.5; (2) adjusting the acidity of the Ta-containing supernatant to 8-10mol/L, heating to 80 deg.C, adding excess chemical pure AlCl3 and chemical pure tannic acid, and stirring to obtain Ta-tannate complex; (3) drying, placing in a vacuum furnace, heating to 1300-1400 deg.C, standing for 4-9 h, cooling and taking out to obtain TaC powder qualified in chemical composition; (4) ball-milling to obtain TaC power with fine particles less than or equal to 1.5 mum. The method utilizes waste Ta-containing electronic devices as raw materials to prepare TaC power with fine particles qualified for hard alloy production.
Description
Technical field
The present invention relates to the preparation method of tantalum carbide, especially the preparation of fine grains of tantalum carbide powder.
Background technology
TaC has obtained using widely as the additive of Wimet, and it mainly acts on is to improve the hot strength of Wimet and suppress growing up of WC grain.The traditional method of preparation TaC powder is with general T a
2O
5Mix with the solid carbon ball milling, form, obtain fine grain TaC powder through carbon tube furnace and the carbonization of vacuum oven secondary.But owing to adopt Ta
2O
5Be raw material, this method cost is higher.To contain tantalum product tailing and to contain useless tantalum such as tantalum waste electronic device be the feedstock production tantalum carbide if adopt, then need through over hydrogenation, fragmentation, dehydrogenation, join carbon, mixing, carbonization and other processes, the tantalum carbide granularity of preparation is generally about 6 microns, is difficult to satisfy the requirement of CEMENTED CARBIDE PRODUCTION.
Summary of the invention
The invention provides a kind of utilize useless tantalum for raw material, satisfy the method for CEMENTED CARBIDE PRODUCTION with fine particle TaC powder.
The method for preparing fine grains of tantalum carbide of the present invention may further comprise the steps successively:
(1) will contain the tantalum waste garrulous material and place decomposer, carry out 6 hours～9 hours decomposition, after decomposition is finished, leave standstill 2 hours～3 hours, upper strata tantalum clear liquid will be transferred in the storage tank through hydrofluoric acid and vitriolic mixing acid;
(2) add pure water and regulate the acidity of tantalum clear liquid in the storage tank to 8mol/L～10mol/L, feed water vapor the tantalum clear liquid is heated to 80 ℃, press the excessive chemical pure aluminum chloride of dosage adding that the useless tantalum of per kilogram adds 1 kilogram of chemical pure aluminum chloride, continuously stirring 9 minutes～12 minutes;
(3) contain the dosage adding chemical pure Weibull that the tantalum waste garrulous material adds 1.8～2.2 kilograms of chemical pure Weibull by per kilogram, continuously stirring stops heating and stirring after 9 minutes～12 minutes, leaves standstill and is cooled to room temperature;
(4) with pure water the resulting product of step 4 is washed, filters, place 100 ℃ baking oven to dry 6 hours～11 hours the tannin tantalum complex precipitation that obtains;
(5) the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1300 ℃～1400 ℃ insulations 4 hours～9 hours down, cool off then and came out of the stove in 12 hours～20 hours, obtain the satisfactory tantalum carbide powder of chemical ingredients;
(6) the tantalum carbide sphere of powder that obtains is galled broken, ratio of grinding media to material is 2: 1, and milling time 4 hours～8 hours obtains the fine grains of tantalum carbide of granularity≤1.5 micron.
The concentration of hydrofluoric acid is 55wt% described in the step (1), and vitriolic concentration is 93wt%, and hydrofluoric acid and vitriolic volume ratio are 4.6: 1～5.2: 1; The solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.
Described in the step (1) in the decomposition course every interval 1 hour stir 1 time.
Ultimate principle of the present invention is:
(1)Ta+14HF→2H
2TaF
7+5H
2↑
(2) in the presence of excessive aluminum chloride, fluorotantalic acid and Weibull reaction generate the Weibull complex compound sediment of tantalum.
Fluorotantalic acid+Weibull+aluminum chloride → hexafluoro aluminic acid+tannin tantalum complex+hydrochloric acid
(3)Ta+C→TaC
The method that the present invention adopts chemical dissolution, organism complexing to combine with vacuum metling, rationally select lysate and concentration/proportioning thereof, solid-to-liquid ratio and other processing parameters for use, the tantalum that will give up dissolving, complexing, obtain complex precipitate, and utilize complex compound to decomposite the very thin carbon of granularity and tantalum and with the particle uniform distribution of molecular level, carbonization at low temperature in vacuum oven obtains fine particle TaC, therefore TaC powder size≤1.5 μ m satisfy Wimet and ultra-fine cemented carbide fully and produce required.Utilization of the present invention simultaneously contains tantalum product tailing and is raw material with useless tantalums such as containing the tantalum waste electronic device, and cost is low.
Embodiment
Embodiment 1:
50Kg is contained the steel lining soft rubber decomposer that the tantalum waste garrulous material places Φ 1000 * 1500mm, adding concentration is respectively hydrofluoric acid and the sulfuric acid of 55wt%, 93wt%, hydrofluoric acid and vitriolic volume ratio are 5: 1, and the solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.Carry out 8 hours decomposition through hydrofluoric acid and vitriolic mixing acid, stirred 1 time in 1 hour at wherein every interval, after to be decomposed the finishing, left standstill 3 hours, and upper strata tantalum clear liquid is transferred in the storage tank; The acidity that adds tantalum clear liquid in the pure water adjusting storage tank feeds water vapor the tantalum clear liquid is heated to 80 ℃ to 9.5mol/L, adds chemical pure aluminum chloride 50Kg, and continuously stirring 12 minutes is sheltered fluorion; Add 100Kg chemical pure Weibull again, 12 minutes complex-precipitation tantalums of continuously stirring stop heating and stirring then, leave standstill and are cooled to room temperature.With pure water the tannin tantalum complex throw out that obtains is washed, filters in the baking oven that is placed on 100 ℃ and dried 11 hours; Then the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1380 ℃ and be incubated 8 hours down, cool off then and came out of the stove in 18 hours, obtain chemical ingredients tantalum carbide powder as shown in table 1.The tantalum carbide sphere of powder worn-off that obtains is broken, and ratio of grinding media to material is 2: 1, grinds 6 hours, obtains the fine grains of tantalum carbide of granularity (Fei Shi Fsss, down together) 1.4 μ m.
Embodiment 2:
20Kg is contained the steel lining soft rubber decomposer that the tantalum waste garrulous material places Φ 1000 * 1500mm, adding concentration is respectively hydrofluoric acid and the sulfuric acid of 55wt%, 93wt%, hydrofluoric acid and vitriolic volume ratio are 4.8: 1, and the solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.Carry out 7 hours decomposition through hydrofluoric acid and vitriolic mixing acid, stirred 1 time in 1 hour at wherein every interval, after to be decomposed the finishing, left standstill 2 hours, and upper strata tantalum clear liquid is transferred in the storage tank; The acidity that adds tantalum clear liquid in the pure water adjusting storage tank feeds water vapor the tantalum clear liquid is heated to 80 ℃ to 8mol/L, adds chemical pure aluminum chloride 20Kg, and continuously stirring 9 minutes is sheltered fluorion; Add 40Kg chemical pure Weibull again, 9 minutes complex-precipitation tantalums of continuously stirring stop heating and stirring then, leave standstill and are cooled to room temperature.With pure water with the tannin tantalum complex washing of precipitate that obtains, filtered in the baking oven that is placed on 100 ℃ oven dry 6 hours; Then the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1300 ℃ and be incubated 4 hours down, cool off then and came out of the stove in 12 hours, obtain chemical ingredients tantalum carbide powder as shown in table 1.The tantalum carbide sphere of powder worn-off that obtains is broken, and ratio of grinding media to material is 2: 1, grinds 4 hours, obtains the fine grains of tantalum carbide of granularity 1.21 μ m.
Embodiment 3:
60Kg is contained the steel lining soft rubber decomposer that the tantalum waste garrulous material places Ф 1000 * 1500mm, adding concentration is respectively hydrofluoric acid and the sulfuric acid of 55wt%, 93wt%, hydrofluoric acid and vitriolic volume ratio are 5.2: 1, and the solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.Carry out 9 hours decomposition through hydrofluoric acid and vitriolic mixing acid, stirred 1 time in 1 hour at wherein every interval, after to be decomposed the finishing, left standstill 3 hours, and upper strata tantalum clear liquid is transferred in the storage tank; The acidity that adds tantalum clear liquid in the pure water adjusting storage tank feeds water vapor the tantalum clear liquid is heated to 80 ℃ to 10mol/L, adds chemical pure aluminum chloride 60Kg, and continuously stirring 12 minutes is sheltered fluorion; Add 110Kg chemical pure Weibull again, 12 minutes complex-precipitation tantalums of continuously stirring stop heating and stirring then, leave standstill and are cooled to room temperature.With pure water with the tannin tantalum complex washing of precipitate that obtains, filtered in the baking oven that is placed on 100 ℃ oven dry 12 hours; Then the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1400 ℃ and be incubated 9 hours down, cool off then and came out of the stove in 20 hours, obtain chemical ingredients tantalum carbide powder as shown in table 1.The tantalum carbide sphere of powder worn-off that obtains is broken, and ratio of grinding media to material is 2: 1, grinds 8 hours, obtains the fine grains of tantalum carbide of granularity 1.35 μ m.
Embodiment 4:
30Kg is contained the steel lining soft rubber decomposer that the tantalum waste garrulous material places Ф 1000 * 1500mm, adding concentration is respectively hydrofluoric acid and the sulfuric acid of 55wt%, 93wt%, hydrofluoric acid and vitriolic volume ratio are 4.6: 1, and the solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.Carry out 6 hours decomposition through hydrofluoric acid and vitriolic mixing acid, stirred 1 time in 1 hour at wherein every interval, after to be decomposed the finishing, left standstill 2 hours, and upper strata tantalum clear liquid is transferred in the storage tank; The acidity that adds tantalum clear liquid in the pure water adjusting storage tank feeds water vapor the tantalum clear liquid is heated to 80 ℃ to 8.5mol/L, adds chemical pure aluminum chloride 30Kg, and continuously stirring 10 minutes is sheltered fluorion; Add 60Kg chemical pure Weibull again, 10 minutes complex-precipitation tantalums of continuously stirring stop heating and stirring then, leave standstill and are cooled to room temperature.With pure water the tannin tantalum complex precipitate product that obtains is washed, filters in the baking oven that is placed on 100 ℃ and dried 7 hours; Then the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1350 ℃ and be incubated 7 hours down, cool off then and came out of the stove in 14 hours, obtain chemical ingredients tantalum carbide powder as shown in table 1.The tantalum carbide sphere of powder worn-off that obtains is broken, and ratio of grinding media to material is 2: 1, grinds 6 hours, obtains the fine grains of tantalum carbide of granularity 1.3 μ m.
The performance index of table 1 fine particle TaC
| Chemical ingredients | C | O | N | Ca | Al | Fe | Mo | Na | Si | Cr | Fsss(μm) |
| Embodiment 1 | 6.21 | 0.35 | 0.023 | ＜0.01 | ＜0.01 | 0.053 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 1.40 |
| Embodiment 2 | 6.22 | 0.30 | 0.001 | ＜0.01 | ＜0.01 | 0.025 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 1.21 |
| Embodiment 3 | 6.20 | 0.25 | 0.003 | ＜0.01 | ＜0.01 | 0.030 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 1.35 |
| Embodiment 4 | 6.21 | 0.30 | 0.003 | ＜0.01 | ＜0.01 | 0.050 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | 1.30 |
Claims (3)
1, a kind of method for preparing fine grains of tantalum carbide may further comprise the steps successively:
(1) will contain the tantalum waste garrulous material and place decomposer, carry out 6 hours～9 hours decomposition, after decomposition is finished, leave standstill 2 hours～3 hours, upper strata tantalum clear liquid will be transferred in the storage tank through hydrofluoric acid and vitriolic mixing acid;
(2) add pure water and regulate the acidity of tantalum clear liquid in the storage tank to 8mol/L～10mol/L, feed water vapor the tantalum clear liquid is heated to 80 ℃, press the dosage adding chemical pure aluminum chloride that the useless tantalum of per kilogram adds 1 kilogram of chemical pure aluminum chloride, continuously stirring 9 minutes～12 minutes;
(3) contain the dosage adding chemical pure Weibull that the tantalum waste garrulous material adds 1.8～2.2 kilograms of chemical pure Weibull by per kilogram, continuously stirring stops heating and stirring after 9 minutes～12 minutes, leaves standstill and is cooled to room temperature;
(4) with pure water the resulting product of step 4 is washed, filters, place 100 ℃ baking oven to dry 6 hours～11 hours the tannin tantalum complex precipitation that obtains;
(5) the tannin tantalum complex of oven dry is packed in the vacuum oven, be warming up to 1300 ℃～1400 ℃ insulations 4 hours～9 hours down, cool off then and came out of the stove in 12 hours～20 hours, obtain the tantalum carbide powder;
(6) the tantalum carbide sphere of powder that obtains is galled broken, ratio of grinding media to material is 2: 1, and milling time 4 hours～8 hours obtains the tantalum carbide of granularity≤1.5 micron.
2, the method for preparing tantalum carbide according to claim 1 is characterized in that: the concentration of hydrofluoric acid is 55wt% described in the step (1), and vitriolic concentration is 93wt%, and hydrofluoric acid and vitriolic volume ratio are 4.6: 1～5.2: 1; The solid sour volume ratio that contains tantalum waste garrulous material and mixing acid is 1: 1.5.
3, the method for preparing tantalum carbide according to claim 1 is characterized in that: described in the step (1) in the decomposition course every interval 1 hour stir 1 time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101660235A CN100457612C (en) | 2006-12-31 | 2006-12-31 | Method for preparing fine grains of tantalum carbide |
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|---|---|---|---|
| CNB2006101660235A CN100457612C (en) | 2006-12-31 | 2006-12-31 | Method for preparing fine grains of tantalum carbide |
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| CN100457612C true CN100457612C (en) | 2009-02-04 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225764B (en) * | 2011-05-25 | 2013-02-13 | 山东理工大学 | Preparation method of tantalum carbide powder |
| CN102560127B (en) * | 2012-02-29 | 2013-05-08 | 江西景泰钽业有限公司 | Method for preparing ultrafine tantalum carbide from tantalum capacitor scraps |
| CN103482625B (en) * | 2012-06-14 | 2018-05-08 | 中国人民解放军63971部队 | A kind of preparation method of niobium carbide and carbonization tantalum electrode |
| CN112939569A (en) * | 2021-03-19 | 2021-06-11 | 哈尔滨化兴软控科技有限公司 | Method for recycling tantalum carbide crucible material for PVT (physical vapor transport) method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044222A (en) * | 1998-07-30 | 2000-02-15 | Mitsui Mining & Smelting Co Ltd | Production of tantalum carbide |
| JP2002316822A (en) * | 2001-04-19 | 2002-10-31 | Mitsui Mining & Smelting Co Ltd | Method for recovering tantalum/niobium from carbide- base raw material containing tantalum/niobium |
| EP1666413A1 (en) * | 2003-08-01 | 2006-06-07 | The New Industry Research Organization | Tantalum carbide, method for producing tantalum carbide, tantalum carbide wiring and tantalum carbide electrode |
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2006
- 2006-12-31 CN CNB2006101660235A patent/CN100457612C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044222A (en) * | 1998-07-30 | 2000-02-15 | Mitsui Mining & Smelting Co Ltd | Production of tantalum carbide |
| JP2002316822A (en) * | 2001-04-19 | 2002-10-31 | Mitsui Mining & Smelting Co Ltd | Method for recovering tantalum/niobium from carbide- base raw material containing tantalum/niobium |
| EP1666413A1 (en) * | 2003-08-01 | 2006-06-07 | The New Industry Research Organization | Tantalum carbide, method for producing tantalum carbide, tantalum carbide wiring and tantalum carbide electrode |
Non-Patent Citations (4)
| Title |
|---|
| 两次碳化法制取细颗粒碳化钽的工艺研究. 汤仁中.稀有金属与硬质合金，第140期. 2000 |
| 两次碳化法制取细颗粒碳化钽的工艺研究. 汤仁中.稀有金属与硬质合金，第140期. 2000 * |
| 液相先驱体转发法制备TaC抗烧蚀材料. 相华，徐永东，张立同，陈来飞.无机材料学报，第21卷第4期. 2006 |
| 液相先驱体转发法制备TaC抗烧蚀材料. 相华，徐永东，张立同，陈来飞.无机材料学报，第21卷第4期. 2006 * |
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