CN110699561B - Method for producing high-purity metal vanadium by adopting directional solidification - Google Patents
Method for producing high-purity metal vanadium by adopting directional solidification Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 79
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 238000007711 solidification Methods 0.000 title claims abstract description 59
- 230000008023 solidification Effects 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 30
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 29
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical group [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 230000006698 induction Effects 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种采用定向凝固生产高纯金属钒的方法，属于钒金属冶炼技术领域，包括以下步骤：将定向凝固炉升温至700～800℃，加入氧化钒进行熔化，待氧化钒熔化完全后，喂入镁铝合金丝，开始定向凝固，待氧化钒反应完全后，停止喂线、加热，待样品冷却至室温后，分离得到钒粗品，将钒粗品破碎后用稀盐酸浸出即得高纯金属钒。本发明以氧化钒为原料，镁铝合金Mg4Al3为还原剂，降低了反应温度，显著降低了能耗；并且生产和分离过程同时进行，减少了工序，提高了生产效率；制备得到的金属钒纯度高于98％。The invention discloses a method for producing high-purity metal vanadium by directional solidification, belonging to the technical field of vanadium metal smelting. Then, feed magnesium-aluminum alloy wire to start directional solidification. After the reaction of vanadium oxide is complete, stop wire feeding and heating. After the sample is cooled to room temperature, the crude vanadium product is obtained by separation. Pure metal vanadium. The invention uses vanadium oxide as raw material and magnesium-aluminum alloy Mg 4 Al 3 as reducing agent, which reduces the reaction temperature and significantly reduces energy consumption; and the production and separation processes are carried out simultaneously, which reduces the number of procedures and improves the production efficiency; Metal vanadium purity is higher than 98%.
Description
技术领域technical field
本发明属于钒金属冶炼技术领域，具体涉及一种采用定向凝固生产高纯金属钒的方法。The invention belongs to the technical field of vanadium metal smelting, and in particular relates to a method for producing high-purity metal vanadium by directional solidification.
背景技术Background technique
钒是一种银灰色有光泽的金属，密度6.1g/cm3,熔点1890℃，沸点3000℃，在地壳中的总含量排在金属的第22位，是一种高熔点稀有金属，主要和其他一些金属矿共生，至今没有发现独立的钒矿。钒作为非常宝贵的战略性资源，广泛应用于汽车、航空航天、铁路、桥梁、聚变反应堆容器等领域。Vanadium is a silver-gray lustrous metal with a density of 6.1g/cm 3 , a melting point of 1890°C and a boiling point of 3000°C. The total content in the earth's crust ranks 22nd among metals. It is a rare metal with a high melting point. Some other metal mines coexist, and no independent vanadium mine has been found so far. As a very valuable strategic resource, vanadium is widely used in automobiles, aerospace, railways, bridges, fusion reactor vessels and other fields.
目前金属钒的生产方法主要有：真空碳热还原法、硅热还原法、氮化钒的热分解法、分步还原法、金属热还原法等。其中金属热还原法因为反应本身会产生大量热量，需要的起始温度低，产品纯度高等优点，受到了广泛关注。金属热还原氧化物的反应是基本的置换反应，选择还原剂金属的原则是它的氧化物标准形成自由焓要比被还原金属氧化物的低，适合用于氧化物还原的元素有硅、镁、铝和钙。锂和铍的氧化物标准形成自由焓虽然很低，但金属锂和铍的制备比较困难，用其做金属还原剂费用会相当高。硅因为具有形成稳定金属硅化物的强烈倾向，且硅的去除问题不易解决，所以在大多数情况下硅并不是理想的还原剂。由于氧化镁具有很高的熔点，镁和金属氧化物反应放出的热量一般不足以生成固态金属；同时，由于镁与钙和铝相比会在较低的温度沸腾，必须使用密闭容器来防止镁的损失，就更限制了镁热还原法的使用范围。钙热还原法与铝热还原法相比，现已不占优势，主要原因有二：第一，反应需在密闭容器中进行，在扩大规模上有其内在的限制；第二，与铝相比，纯净状态的钙的费用比较贵。铝热法生产纯金属钒一般先使钒氧化物经铝热还原生成钒铝合金，还原反应可选择在敞开的耐热容器内进行，然后钒铝合金再经高温真空脱除铝和电子束熔炼脱除其它残余杂质而得到纯金属钒，但是真空脱铝的过程需要耗费大量的能量。At present, the production methods of metal vanadium mainly include: vacuum carbothermal reduction method, silicon thermal reduction method, thermal decomposition method of vanadium nitride, step reduction method, metal thermal reduction method, etc. Among them, the metallothermic reduction method has received extensive attention because of the advantages of the reaction itself generating a large amount of heat, the required starting temperature being low, and the product purity being high. The reaction of metallothermic reduction of oxides is a basic replacement reaction. The principle of selecting a reducing agent metal is that its standard free enthalpy of oxide formation is lower than that of the reduced metal oxide. The elements suitable for oxide reduction are silicon and magnesium. , aluminum and calcium. Although the standard free enthalpy of formation of oxides of lithium and beryllium is very low, the preparation of metal lithium and beryllium is relatively difficult, and the cost of using them as metal reducing agents will be quite high. Silicon is not an ideal reducing agent in most cases because of its strong tendency to form stable metal silicides, and the problem of silicon removal is not easy to solve. Due to the high melting point of magnesium oxide, the heat released by the reaction of magnesium and metal oxides is generally insufficient to form solid metals; at the same time, since magnesium boils at a lower temperature than calcium and aluminum, closed containers must be used to prevent magnesium The loss of magnesium thermal reduction method limits the scope of application. Compared with the aluminothermic reduction method, the calcium thermal reduction method is no longer dominant. There are two main reasons: first, the reaction needs to be carried out in a closed container, which has inherent limitations in expanding the scale; second, compared with aluminum , the cost of pure calcium is more expensive. In the production of pure metal vanadium by aluminothermic method, vanadium oxide is generally reduced by aluminothermic to form vanadium-aluminum alloy. Pure metal vanadium is obtained by removing other residual impurities, but the process of vacuum dealumination requires a lot of energy.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种采用定向凝固生产高纯金属钒的方法，包括以下步骤：The object of the present invention is to provide a kind of method that adopts directional solidification to produce high-purity metal vanadium, comprises the following steps:
将定向凝固炉升温至700～800℃，加入氧化钒进行熔化，待氧化钒熔化完全后，喂入镁铝合金丝，开始定向凝固，待氧化钒反应完全后，停止喂线、加热，待样品冷却至室温后，分离得到钒粗品，将钒粗品破碎后用稀盐酸浸出即得高纯金属钒。The directional solidification furnace is heated to 700-800℃, and vanadium oxide is added for melting. After the vanadium oxide is completely melted, the magnesium-aluminum alloy wire is fed to start directional solidification. After the reaction of the vanadium oxide is complete, the wire feeding and heating are stopped. After cooling to room temperature, the crude vanadium product is separated and obtained, and the crude vanadium product is crushed and leached with dilute hydrochloric acid to obtain high-purity metal vanadium.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述氧化钒为三氧化二钒和/或五氧化二钒；所述定向凝固炉内的保护气体为氩气。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the vanadium oxide is vanadium trioxide and/or vanadium pentoxide; and the protective gas in the directional solidification furnace is argon.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述定向凝固炉的温度为750～800℃；优选的，所述定向凝固炉的温度为750℃。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the temperature of the directional solidification furnace is 750-800°C; preferably, the temperature of the directional solidification furnace is 750°C.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述镁铝合金丝中铝的重量百分数为40％～60％；优选的，所述镁铝合金丝为Mg4Al3合金丝，直径为3mm，密度为2.1g/cm3，线密度为0.148g/cm。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the weight percentage of aluminum in the magnesium-aluminum alloy wire is 40% to 60%; preferably, the magnesium-aluminum alloy wire is a Mg 4 Al 3 alloy wire, The diameter was 3 mm, the density was 2.1 g/cm 3 , and the linear density was 0.148 g/cm.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述镁铝合金丝的喂线速度为0.4～0.5cm/min；优选的，所述镁铝合金丝的喂线速度为0.43cm/min。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the feeding speed of the magnesium-aluminum alloy wire is 0.4-0.5 cm/min; preferably, the feeding speed of the magnesium-aluminum alloy wire is 0.43 cm/min. min.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述镁铝合金丝的喂线时间为2～6h。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the feeding time of the magnesium-aluminum alloy wire is 2-6 hours.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述镁铝合金丝的喂线时间为2.2～3.6h。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the wire feeding time of the magnesium-aluminum alloy wire is 2.2-3.6 hours.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述三氧化二钒与镁铝合金丝的反应时间为2.2～2.6h，所述五氧化二钒与镁铝合金丝的反应时间为3～3.6h。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the reaction time of the vanadium trioxide and the magnesium-aluminum alloy wire is 2.2 to 2.6h, and the reaction time of the vanadium pentoxide and the magnesium-aluminum alloy wire is 3～3.6h.
其中，上述的采用定向凝固生产高纯金属钒的方法，其特征在于：所述定向凝固的速度为10～20mm/h；优选的，所述定向凝固的速度为10mm/h；所述凝固后得到的合金圆柱棒坯的直径为20～30mm；优选为24mm。Wherein, the above-mentioned method for producing high-purity metal vanadium by directional solidification is characterized in that: the speed of the directional solidification is 10-20 mm/h; preferably, the speed of the directional solidification is 10 mm/h; The diameter of the obtained alloy cylindrical billet is 20-30 mm; preferably 24 mm.
其中，上述的采用定向凝固生产高纯金属钒的方法，所述分离是指通过观察样品底部钒的高度后，从样品上将钒粗品切割分离；所述破碎是指将钒粗品破碎至80-150目；所述稀硫酸的浓度为5～8mol/L。Wherein, in the above-mentioned method for producing high-purity metal vanadium by directional solidification, the separation refers to cutting and separating the crude vanadium product from the sample after observing the height of vanadium at the bottom of the sample; the crushing refers to crushing the crude vanadium product to 80-80 150 mesh; the concentration of the dilute sulfuric acid is 5-8 mol/L.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明以氧化钒为原料，镁铝合金Mg4Al3为还原剂，降低了反应温度，显著降低了能耗；并且生产和分离过程同时进行，减少了工序，提高了生产效率；制备得到的金属钒纯度高于98％。The invention uses vanadium oxide as raw material and magnesium-aluminum alloy Mg 4 Al 3 as reducing agent, which reduces the reaction temperature and significantly reduces energy consumption; and the production and separation processes are carried out simultaneously, which reduces the number of procedures and improves the production efficiency; Metal vanadium purity is higher than 98%.
具体实施方式Detailed ways
具体的，一种采用定向凝固生产高纯金属钒的方法，包括以下步骤：Specifically, a method for producing high-purity metal vanadium by directional solidification, comprising the following steps:
将定向凝固炉升温至700～800℃，加入氧化钒进行熔化，待氧化钒熔化完全后，喂入镁铝合金丝，开始定向凝固，待氧化钒反应完全后，停止喂线、加热，待样品冷却至室温后，分离得到钒粗品，将钒粗品破碎后用稀盐酸浸出即得高纯金属钒。The directional solidification furnace is heated to 700-800℃, and vanadium oxide is added for melting. After the vanadium oxide is completely melted, the magnesium-aluminum alloy wire is fed to start directional solidification. After the reaction of the vanadium oxide is complete, the wire feeding and heating are stopped. After cooling to room temperature, the crude vanadium product is separated and obtained, and the crude vanadium product is crushed and leached with dilute hydrochloric acid to obtain high-purity metal vanadium.
本发明的方法中，若反应温度过低，V2O5还未熔化或者粘度太大，将导致产率降低；若反应温度过高，将导致能量的损耗，另外由于反应大量放热，如果反应温度过高还可能导致镁的挥发；因此，本发明将反应温度设置为700～800℃。为了使制备得到的金属钒的纯度更高，本发明将反应温度设置为750～800℃。由于温度太高对金属钒纯度提升不明显，综合能耗考虑，本发明将反应温度设置为750℃。In the method of the present invention, if the reaction temperature is too low, V 2 O 5 has not been melted or the viscosity is too large, the yield will be reduced; if the reaction temperature is too high, energy loss will be caused. Too high reaction temperature may also lead to volatilization of magnesium; therefore, the present invention sets the reaction temperature to 700-800°C. In order to increase the purity of the prepared metal vanadium, the present invention sets the reaction temperature to 750-800°C. Because the temperature is too high, the improvement of the purity of vanadium metal is not obvious, and considering the comprehensive energy consumption, the present invention sets the reaction temperature to 750°C.
本发明所用的镁铝合金中，如果铝的含量过高，将导致局部反应温度过高，易生成α-Al2O3，如果α-Al2O3混入钒中不利于分离；如果铝的含量过低，由于局部反应温度可能大于镁的沸点，将导致高含量的镁容易挥发，造成镁的损失。因此，本发明将镁铝合金丝中铝的重量百分数为40％～60％；优选的，所述镁铝合金丝为Mg4Al3合金丝，直径为3mm，密度为2.1g/cm3，线密度为0.148g/cm。In the magnesium-aluminum alloy used in the present invention, if the content of aluminum is too high, the local reaction temperature will be too high, and α-Al 2 O 3 is easily formed. If α-Al 2 O 3 is mixed into vanadium, it is not conducive to separation; If the content is too low, since the local reaction temperature may be higher than the boiling point of magnesium, the high content of magnesium will be easily volatilized, resulting in the loss of magnesium. Therefore, in the present invention, the weight percentage of aluminum in the magnesium - aluminum alloy wire is 40% to 60% ; The linear density was 0.148 g/cm.
本发明的方法中，若Mg4Al3的喂线速度过快，将导致反应过于剧烈，产热太多，还将导致最后喂线总量增大，多加入的Al将和V形成合金，难以分离；若喂线速度过慢，将导致生产效率降低，严重时甚至导致V2O5沉积；因此，本发明将Mg4Al3的喂线速度设置为0.4～0.5cm/min；优选的，所述Mg4Al3的喂线速度为0.43cm/min。In the method of the present invention, if the wire feeding speed of Mg 4 Al 3 is too fast, the reaction will be too violent, the heat generation will be too much, and the total amount of the final wire feeding will also increase, and the added Al will form an alloy with V, It is difficult to separate; if the feed line speed is too slow, the production efficiency will be reduced, and even lead to V 2 O 5 deposition in severe cases; therefore, the present invention sets the feed line speed of Mg 4 Al 3 to 0.4-0.5cm/min; , the feed line speed of the Mg 4 Al 3 is 0.43cm/min.
本发明的方法中，定向凝固的速度太慢，将降低生产效率，延长生产时间，造成不必要的能耗消费；如果定向凝固的速度太快，将导致镁铝合金与氧化钒的反应增快，导致局部温度过高，镁挥发量增加，同时易生成难溶于酸的α-Al2O3。因此，本发明将定向凝固的速度为10～20mm/h；优选的，所述定向凝固的速度为10mm/h。In the method of the present invention, the speed of directional solidification is too slow, which will reduce production efficiency, prolong production time, and cause unnecessary energy consumption; if the speed of directional solidification is too fast, the reaction between magnesium-aluminum alloy and vanadium oxide will be accelerated. , resulting in high local temperature, increased volatilization of magnesium, and easy to generate α-Al 2 O 3 that is insoluble in acid. Therefore, in the present invention, the speed of directional solidification is 10-20 mm/h; preferably, the speed of directional solidification is 10 mm/h.
本发明方法制备得到的金属钒的纯度分析可采用YB/T 5328-2009中的方法，还可以采用YB/T 4218-2010中的方法。The purity analysis of the metal vanadium prepared by the method of the present invention can adopt the method in YB/T 5328-2009, and can also adopt the method in YB/T 4218-2010.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。The specific embodiments of the present invention will be further described below with reference to the examples, but the present invention is not limited to the scope of the described examples.
以下实施例中所使用的Mg4Al3丝的丝直径为3mm，密度为2.1g/cm3，线密度为0.148g/cm，是由冀盛牌镁铝合金粉熔融拉丝制成，其中，镁铝合金粉购自河北冀盛铝粉有限公司，然后由中铝集团西北铝加工公司代加工拉丝制成，加工工艺参数：挤压温度350℃，模具预热温度350℃，挤压速度15mm/s，模具出口直径3mm。The Mg 4 Al 3 wire used in the following examples has a wire diameter of 3 mm, a density of 2.1 g/cm 3 and a linear density of 0.148 g/cm . Magnesium-aluminum alloy powder was purchased from Hebei Jisheng Aluminum Powder Co., Ltd., and then processed and drawn by Northwest Aluminum Processing Company of Chinalco Group. Processing parameters: extrusion temperature 350 ℃, mold preheating temperature 350 ℃, extrusion speed 15mm /s, the diameter of the die outlet is 3mm.
以下实施例所使用的感应加热炉的加热圈设有上下移动的功能，当加热圈上移时，下方未加热的部分相当于直接空冷，具有相当大的温度梯度，能够实现定向凝固的功能。The heating ring of the induction heating furnace used in the following embodiments has the function of moving up and down. When the heating ring moves upward, the unheated part below is equivalent to direct air cooling, has a considerable temperature gradient, and can achieve the function of directional solidification.
实施例1Example 1
(1)选取V2O5 20g为钒原料，Mg4Al3丝为还原剂。(1) Select V 2 O 5 20g as vanadium raw material, and Mg 4 Al 3 wire as reducing agent.
(2)首先将V2O5放入石墨坩埚中，再将坩埚放入感应加热炉中。(2) Put V 2 O 5 into the graphite crucible first, and then put the crucible into the induction heating furnace.
(3)通入氩气作为保护气氛，升温至800℃。(3) Pour argon gas as a protective atmosphere, and raise the temperature to 800°C.
(4)待到V2O5熔化完全，以0.43cm/min喂入镁铝合金丝，开始定向凝固，速率为10mm/h，所述凝固后得到的合金圆柱棒坯的直径为24mm。(4) After the V 2 O 5 was completely melted, the magnesium-aluminum alloy wire was fed at 0.43 cm/min to start directional solidification at a rate of 10 mm/h, and the diameter of the alloy cylindrical billet obtained after the solidification was 24 mm.
(5)3h后，停止喂线，然后停止加热。(5) After 3h, stop feeding the thread, and then stop heating.
(6)待样品冷却至室温，将其沿纵向中心线切成两半，通过颜色观察底部钒的高度。(6) After the sample is cooled to room temperature, it is cut in half along the longitudinal center line, and the height of the vanadium at the bottom is observed by color.
(7)沿(6)中高度横向切割样品，将含钒的部分分离出来。(7) Cut the sample transversely along the height in (6) to separate out the vanadium-containing portion.
(8)将分离出来的金属破碎至颗粒状(80-150目)，用6mol/L的HCl分两次在室温下浸出，单次使用80mL，浸出时间为1h，浸出结束后过滤、干燥，得到高纯金属钒。(8) Crushing the separated metal to granular (80-150 mesh), leaching with 6mol/L HCl twice at room temperature, using 80mL for a single time, leaching time is 1h, filtering and drying after leaching, Obtain high-purity metal vanadium.
(9)用标准YB/T 5328-2009中的方法检测全钒量，折算纯度为98.6％。(9) The total vanadium content is detected by the method in the standard YB/T 5328-2009, and the converted purity is 98.6%.
实施例2Example 2
(1)选取V2O5 20g为钒原料，Mg4Al3丝为还原剂。(1) Select V 2 O 5 20g as vanadium raw material, and Mg 4 Al 3 wire as reducing agent.
(2)首先将V2O5放入坩埚中，再将坩埚放入感应加热炉中。(2) Put V 2 O 5 into the crucible first, and then put the crucible into the induction heating furnace.
(3)通入氩气作为保护气氛，升温至750℃。(3) Pour argon gas as a protective atmosphere, and raise the temperature to 750°C.
(4)待到V2O5熔化完全，以0.43cm/min喂入镁铝合金丝，开始定向凝固，速率为10mm/h，所述凝固后得到的合金圆柱棒坯的直径为24mm。(4) After the V 2 O 5 was completely melted, the magnesium-aluminum alloy wire was fed at 0.43 cm/min to start directional solidification at a rate of 10 mm/h, and the diameter of the alloy cylindrical billet obtained after the solidification was 24 mm.
(5)3h后，停止喂线，然后停止加热。(5) After 3h, stop feeding the thread, and then stop heating.
(6)待样品冷却至室温，将其沿纵向中心线切成两半，通过颜色观察底部钒的高度。(6) After the sample is cooled to room temperature, it is cut in half along the longitudinal center line, and the height of the vanadium at the bottom is observed by color.
(7)沿(6)中高度横向切割样品，将含钒的部分分离出来。(7) Cut the sample transversely along the height in (6) to separate out the vanadium-containing portion.
(8)将分离出来的金属破碎至颗粒状(80-150目)，用6mol/L HCl分两次在室温下浸出，单次使用80mL，浸出时间为1h，浸出结束后过滤、干燥，得到高纯金属钒。(8) Crushing the separated metal to granular (80-150 mesh), leaching with 6mol/L HCl twice at room temperature, using 80mL for a single time, leaching time is 1h, filtering and drying after leaching to obtain High-purity metal vanadium.
(9)用标准YB/T 5328-2009中的方法检测全钒量，折算纯度为98.4％。(9) The total vanadium content is detected by the method in the standard YB/T 5328-2009, and the converted purity is 98.4%.
实施例3Example 3
(1)选取V2O5 20g为钒原料，Mg4Al3丝为还原剂。(1) Select V 2 O 5 20g as vanadium raw material, and Mg 4 Al 3 wire as reducing agent.
(2)首先将V2O5放入坩埚中，再将坩埚放入感应加热炉中。(2) Put V 2 O 5 into the crucible first, and then put the crucible into the induction heating furnace.
(3)通入氩气作为保护气氛，升温至700℃。(3) Introduce argon gas as a protective atmosphere, and raise the temperature to 700°C.
(4)待到V2O5熔化完全，以0.43cm/min喂入镁铝合金丝，开始定向凝固，速率为10mm/h，所述凝固后得到的合金圆柱棒坯的直径为24mm。(4) After the V 2 O 5 was completely melted, the magnesium-aluminum alloy wire was fed at 0.43 cm/min to start directional solidification at a rate of 10 mm/h, and the diameter of the alloy cylindrical billet obtained after the solidification was 24 mm.
(5)3h后，停止喂线，然后停止加热。(5) After 3h, stop feeding the thread, and then stop heating.
(6)待样品冷却至室温，将其沿纵向中心线切成两半，通过颜色观察底部钒的高度。(6) After the sample is cooled to room temperature, it is cut in half along the longitudinal center line, and the height of the vanadium at the bottom is observed by color.
(7)沿(6)中高度横向切割样品，将含钒的部分分离出来。(7) Cut the sample transversely along the height in (6) to separate out the vanadium-containing portion.
(8)将分离出来的金属破碎至颗粒状(80-150目)，用6mol/L HCl分两次在室温下浸出，单次使用80mL，浸出时间为1h，浸出结束后过滤、干燥，得到高纯金属钒。(8) Crushing the separated metal to granular (80-150 mesh), leaching with 6mol/L HCl twice at room temperature, using 80mL for a single time, leaching time is 1h, filtering and drying after leaching to obtain High-purity metal vanadium.
(9)用标准YB/T 5328-2009中的方法检测全钒量，折算纯度为90.2％。(9) The total vanadium content is detected by the method in the standard YB/T 5328-2009, and the converted purity is 90.2%.
对比例1Comparative Example 1
(1)选取V2O5 20g为钒原料，铝丝为还原剂。(1) V 2 O 5 20g is selected as vanadium raw material, and aluminum wire is used as reducing agent.
(2)首先将V2O5放入坩埚中，再将坩埚放入感应加热炉中。(2) Put V 2 O 5 into the crucible first, and then put the crucible into the induction heating furnace.
(3)通入氩气作为保护气氛，升温至750℃。(3) Pour argon gas as a protective atmosphere, and raise the temperature to 750°C.
(4)待到V2O5熔化完全，以0.43cm/min喂入铝丝，同时开始定向凝固，速率为10mm/h，所述凝固后得到的合金圆柱棒坯的直径为24mm。(4) When the V 2 O 5 is completely melted, the aluminum wire is fed at 0.43 cm/min, and the directional solidification is started at the same time, and the rate is 10 mm/h, and the diameter of the alloy cylindrical billet obtained after the solidification is 24 mm.
(5)3h后，停止喂线，然后停止加热。(5) After 3h, stop feeding the thread, and then stop heating.
(6)待样品冷却至室温，将其沿纵向中心线切成两半，通过颜色观察底部钒的高度。(6) After the sample is cooled to room temperature, it is cut in half along the longitudinal center line, and the height of the vanadium at the bottom is observed by color.
(7)沿(6)中高度横向切割样品，将含钒的部分分离出来。(7) Cut the sample transversely along the height in (6) to separate out the vanadium-containing portion.
(8)将分离出来的金属破碎至颗粒状(80-150目)，用6mol/L HCl分两次在室温下浸出，单次使用80mL，浸出时间为1h，浸出结束后过滤、干燥，得到高纯金属钒。(8) Crushing the separated metal to granular (80-150 mesh), leaching with 6mol/L HCl twice at room temperature, using 80mL for a single time, leaching time is 1h, filtering and drying after leaching to obtain High-purity metal vanadium.
(9)标准YB/T 5328-2009中的方法检测全钒量，折算纯度为61.2％，这是因为大量α-Al2O3与钒混合在一起，无法被酸溶解。(9) The method in the standard YB/T 5328-2009 detects the total vanadium content, and the converted purity is 61.2%. This is because a large amount of α-Al 2 O 3 is mixed with vanadium and cannot be dissolved by acid.
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Granted publication date: 20201225 |