CN104328278A - Slagging agent produced by high-purity vanadium-aluminium alloy and production method - Google Patents
Slagging agent produced by high-purity vanadium-aluminium alloy and production method Download PDFInfo
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- CN104328278A CN104328278A CN201410547931.3A CN201410547931A CN104328278A CN 104328278 A CN104328278 A CN 104328278A CN 201410547931 A CN201410547931 A CN 201410547931A CN 104328278 A CN104328278 A CN 104328278A
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Abstract
The invention discloses a slagging agent produced by a high-purity vanadium-aluminium alloy and a production method, and the slagging agent is high purity calcium vanadate. The method employs the calcium vanadate synthesized by a chemical method to substitute traditional lime and fluorite for being as the slagging agent, impurity content can be effectively reduced during an impurities removal process, compared with reagent grade lime and fluorite, the impurity content can be reduced by one magnitude order. According to the invention, the introduction of impurity can be effectively reduced, quality stabilization and control requirement of the vanadium-aluminium alloy product with high-purity can be satisfied, product purity can be effectively increased, calcium vanadate can be taken as a vanadium product, and can be taken as the slagging agent, cost of the slagging agent can be omitted, calcium vanadate also can substitute vanadium oxide in the reaction, and operation cost of vanadic anhydride can be reduced; when fluorite is taken as the slagging agent, fluoride can be generated during the reaction, so that environment pollution is generated, when the calcium vanadate is employed as the slagging agent, the product is only calcium aluminate which is in the slag, and no harmful fluoride is generated.
Description
Technical field
The invention belongs to vanadium alloy production field, the slag former that especially a kind of high purity vananum is produced and production method.
Background technology
Vananum is the important alloy element of one producing aviation-grade titanium alloy material, in titanium alloy is produced, have important application.Require very harsh to the impurity of adding material in aviation-grade titanium alloy material is produced, therefore the production of high purity vananum is imperative.Current vananum there is no unified standard, substantially using the standard of German GFE company vananum as aerospace vananum standard, specify in this standard that impurity element wherein should control: B≤0.003, C≤0.10, Cr≤0.10, Cu≤0.05, Fe≤0.4, Mg≤0.25, Mn≤0.05, Mo≤0.15, Ni≤0.05, P≤0.03, Pb≤0.10, S≤0.02, Si≤0.35, W≤0.015, Y≤0.003, H≤0.01, N≤0.04, O≤0.1, prepare and thisly can be applicable to aerospace high purity vanadium aluminium alloy there is good prospect.
Current industry routine produces the technical process of vananum as shown in Figure 1, during production, Vanadium Pentoxide in FLAKES (can mix part vanadous oxide), aluminum shot (powder) and slag former are mixed post-drying in proportion, put into Reaktionsofen, thermite reaction is caused with the magnesium ribbon igniting of lighting after adding starting mix, react complete after cooling, slag aluminium is separated and obtains vananum.At present no matter this technological process of production is at home or in the world, all there is no improvement project and proposes; Therefore the scheme of vananum purity is improved by production control technical process, unrealistic at present.
Application number be 201110095229.4 patent provide a kind of production method of vanadium-aluminium alloy, the method adopts the vanadium oxide of 99.5wt% and the aluminium powder of 99.7% to make raw material, after vanadium oxide and aluminium powder are mixed in proportion, with analytical pure barium peroxide, Potcrate for starting mix, be placed on reactant after barium peroxide, Potcrate being added the mixing of a small amount of aluminium powder, ignite starting mix initiation reaction with the magnesium ribbon lighted.
Application number be 201110107994.3 patent provide a kind of method for optimizing preparation process of vanadium-aluminum alloy, the method mixes in proportion by after vanadium oxide, aluminium powder, fluorite and lime fragmentation, the lime amount of allocating into accounts for 16% ~ 23% of aluminium powder, the fluorite amount of allocating into accounts for the 10%-15% of aluminium powder, smelts after the material of mixing is put into smelting furnace tamping.
Can be found out by above patent, conventional vananum smelting process needs to adopt lime and fluorite to cook slag former, makes starting mix, with magnesium ribbon ignition reaction with barium peroxide, Potcrate etc.In ordinary method, slag former is natural mineral, foreign matter content is wherein higher, and adopts barium peroxide, Potcrate etc. to make starting mix, with the way of magnesium ribbon ignition reaction, also can be introduced in the impurity such as K, Ba, the Mg that must be strict with in vananum, the production sending out aluminium alloy is produced a very large impact.
In current vananum production, aluminium and vanadium oxide are all the high purity products adopted, and its impurity level brought into is less, but also needs using Potcrate, barium peroxide etc. as starting mix, makes slag former with the conventional material such as unslaked lime or fluorite.As unslaked lime and the fluorite of slag former, every stove add-on is 12% ~ 22% of Vanadium Pentoxide in FLAKES add-on, add-on is larger, because slag former is natural or dressing product, foreign matter content wherein often has larger fluctuation because of the place of production and ore-dressing technique difference, and the impact of impurity wherein on vananum quality is larger.
In metallurgy lime standard, top-quality superfine lime composition is CaO>=92.0%, MgO% < 5.0, SiO
2≤ 1.5%, S≤0.020%, igloss≤2%, activity degree (4mol/mL, 40 ± 1 DEG C, 10min)>=360; CaF in fluorite standard
2>=97.0, SiO
2≤ 2.5, S, P do not do requirement, moisture≤5.0%; But for Si element, even superfine lime, Si content wherein also reaches 1.5%, and in the fluorite fine powder that in fluorite, quality is higher, Si content also reaches 2.5%.And to the most elements not requirement required in vananum in standard, these elements are very large to the quality influence of vananum.Metallurgical grade lime and fluorite are not suitable for producing highly purified vananum,
When current production meets the high purity vananum of German GFE company standard, slag former is all the analytical pure fluorite or unslaked lime that adopt, this kind of grade product expensive, the price of fluorite can reach more than 30000 yuan/ton, substantially increases the production cost of vananum.
Summary of the invention
The technical problem to be solved in the present invention is to provide the slag former that a kind of price is low, introduce the few high purity vananum production of impurity; Present invention also offers the production method that a kind of high purity vananum is produced.
For solving the problems of the technologies described above, the technical solution used in the present invention is: described slag former is high-purity calcium vanadate.
Calcium vanadate of the present invention is one or more in metavanadic acid calcium, pyrovanadic acid calcium, positive calcium vanadate.
The mass ratio that adds of high-purity calcium vanadate of the present invention is: calcium vanadate: Vanadium Pentoxide in FLAKES=1:0.3 ~ 1:3.5.
The inventive method the igniting of vanadium oxide, aluminium and slag former is caused thermite reaction form, and it adopts above-mentioned slag former.
Igniting described in the inventive method adopts the reaction of high-temperature electric arc electroinitiation.
Aluminium described in the inventive method adopts the aluminium ingot of 99.85wt% or 99.9wt%, and vanadium oxide adopts high purity vanadium.
Calcium vanadate is the one in vanadium product, is divided into metavanadic acid calcium (CaOV
2o
5), pyrovanadic acid calcium (2CaOV
2o
5), positive calcium vanadate (3CaOV
2o
5), can find out in calcium vanadate that the ratio being equivalent to calcium oxide and Vanadium Pentoxide in FLAKES is 1:1 ~ 3:1.Calcium vanadate can react obtained by ammonium vanadate (sodium) solution and milk of lime, and by the removal of impurities of ammonium vanadate (sodium) solution, obtain milk of lime after unslaked lime hydrolysis, filtration, the foreign matter contents such as Si wherein can reduce greatly, can obtain highly purified calcium vanadate product after reaction.For the calcium vanadate composition that certain unit adopts above-mentioned chemical method to prepare, wherein the mass percentage of main component is: Al 0.063%, Ca 34.82%, Cr 0.068%, Fe 0.088%, Mg 0.24%, Na 0.12%, P 0.064%, Si 0.16%, Ti 0.0095%, V 22.53%; Can find out that wherein impurity is well below the foreign matter content in the slag former such as metallurgy lime and fluorite.
Attachedly Figure 2 shows that CaO-Al during slag mutually when making slag former with calcium oxide
2o
3phasor, as seen from the figure along with the increase of CaO ratio in slag, the temperature of solidification of slag declines gradually, when the calcium oxide content added reaches 49% of the quantity of slag, the fusing point of slag can reach minimum 1395 DEG C, continues the add-on increasing calcium oxide, and slag melting starts again to raise.In reaction process, slag temperature generally can reach more than 1800 DEG C, can meet smelting requirements when therefore the add-on of calcium oxide accounts for 20% ~ 49% of the quantity of slag.In addition, under the prerequisite meeting smelting requirements, should reduce the add-on of calcium oxide, general calcium oxide is 0.12 ~ 0.22:1 with the add-on ratio of Vanadium Pentoxide in FLAKES as far as possible.Therefore add calcium vanadate in proportion when smelting vananum and can complete full up sufficient slag making requirement.Because calcium vanadate directly can be obtained by vanadium liquid, comparatively Vanadium Pentoxide in FLAKES production stage is less, also can be used as vanadium raw materials and slag former, therefore not only can stop the introducing of impurity from source, also can reduce production cost.
The beneficial effect adopting technique scheme to produce is: (1) improving product purity: the calcium vanadate that the present invention adopts chemical method to synthesize replaces traditional lime, fluorite as slag former, due in its production process through dedoping step, effectively can reduce foreign matter content wherein, even if compared with SILVER REAGENT lime, fluorite, foreign matter content wherein also can reduce an order of magnitude.Therefore, the application can reduce the introducing of impurity effectively, meets steady quality and the control overflow of highly purified vananum product, and then improving product purity effectively.
(2) production cost is reduced: calcium vanadate, as vanadium product, not only as slag former, saves slag former cost, also can vanadium oxide in surrogate response, Vanadium Pentoxide in FLAKES process cost 2000 ~ 2500 yuan/ton can be reduced.
(3) environmental protection is of value to: when adopting fluorite to make slag former, reaction can produce some fluorochemicals etc. and cause environmental pollution, and causes corrosion to factory building, equipment etc.And adopting calcium vanadate as after slag former, product only has calcium aluminate, all in slag, does not produce harmful fluorochemical.
(4) the present invention does not use the starting mix such as Potcrate, barium peroxide, ignites without magnesium ribbon yet, during the high-temperature electric arc electroinitiation directly adopting electrode to produce, further can reduce the introducing of impurity, thus further improving product purity.Equally, when aluminium and vanadium oxide employing high pure raw material, can same improving product purity.
In sum, the present invention has that impurity is introduced less, product purity is high, raw materials for production and cost low, product cost is low, the feature of energy-conserving and environment-protective, operational safety.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is the conventional process flow sheet producing vananum;
Fig. 2 is conventional production slag middle CaO-Al mutually
2o
3phasor.
Embodiment
Aluminum shot in following embodiment adopts the ingredient standard of 99.85% or 99.9% aluminium ingot shown in table 1; Adopt the Vanadium Pentoxide in FLAKES ingredient standard shown in table 2.Certainly, the impurity component in aluminium ingot and Vanadium Pentoxide in FLAKES is more few better.
Table 1 aluminium ingot ingredient standard
Table 2 Vanadium Pentoxide in FLAKES ingredient standard
Embodiment 1: this high purity production method of vanadium-aluminium alloy adopts following slag former and production technique.
After 1667kg metavanadic acid calcium is mixed with 500kg Vanadium Pentoxide in FLAKES (mass ratio 1:0.3) and 1183kg aluminum shot (powder) drop into Reaktionsofen (device), thermite reaction is carried out after igniting, cool after completion of the reaction, after being separated with vananum by slag, after polishing, fragmentation, sorting, obtain 85 vananum.The composition (weight) of gained vananum is: V 86.32%, Al 12.98%, N 0.0004%, O 0.05%, C 0.10%, S 0.004%, Cr 0.071%, Fe 0.251%, Mg 0.012%, Mn 0.019%, P 0.03%, Si 0.097%.
Embodiment 2: this high purity production method of vanadium-aluminium alloy adopts following slag former and production technique.
After 590kg pyrovanadic acid calcium is mixed with 1500kg Vanadium Pentoxide in FLAKES (mass ratio 1:2.55) and 1243kg aluminum shot (powder) drop into Reaktionsofen (device), thermite reaction is carried out after igniting, cool after completion of the reaction, after being separated with vananum by slag, after polishing, fragmentation, sorting, obtain 85 vananum.The composition of gained vananum is: V 89.23%, Al 10.21%, N 0.0005%, O 0.045%, C 0.009%, S 0.005%, Cr 0.070%, Fe 0.241%, Mg 0.010%, Mn 0.020%, P 0.025%, Si 0.095%.
Embodiment 3: this high purity production method of vanadium-aluminium alloy adopts following slag former and production technique.
After positive for 460kg calcium vanadate is mixed with 1633kg Vanadium Pentoxide in FLAKES (mass ratio 1:3.5) and 1248kg aluminum shot (powder) drop into Reaktionsofen (device), thermite reaction is carried out after igniting, cool after completion of the reaction, after being separated with vananum by slag, after polishing, fragmentation, sorting, obtain 85 vananum.The composition of gained vananum is: V 89.02%, Al 10.47%, N 0.0005%, O 0.035%, C 0.095%, S 0.005%, Cr 0.069%, Fe 0.228%, Mg 0.012%, Mn 0.017%, P 0.028%, Si 0.087%.
Claims (8)
1. a slag former for high purity vananum production, is characterized in that: described slag former is high-purity calcium vanadate.
2. the slag former of high purity vananum production according to claim 1, is characterized in that: described calcium vanadate is one or more in metavanadic acid calcium, pyrovanadic acid calcium, positive calcium vanadate.
3. the slag former of high purity vananum production according to claim 1 and 2, it is characterized in that, the mass ratio that adds of described high-purity calcium vanadate is: calcium vanadate: Vanadium Pentoxide in FLAKES=1:0.3-1:3.5.
4. a production method for high purity vananum, the igniting of vanadium oxide, aluminium and slag former is caused thermite reaction and forms by it, it is characterized in that: the high-purity calcium vanadate of described slag former.
5. the production method of high purity vananum according to claim 4, is characterized in that: described calcium vanadate is one or more in metavanadic acid calcium, pyrovanadic acid calcium, positive calcium vanadate.
6. the production method of high purity vananum according to claim 4, is characterized in that: the mass ratio that adds of described high-purity calcium vanadate is: calcium vanadate: Vanadium Pentoxide in FLAKES=1:0.3 ~ 1:3.5.
7. the production method of the high purity vananum according to claim 4,5 or 6, is characterized in that: described igniting adopts the reaction of high-temperature electric arc electroinitiation.
8. the production method of the high purity vananum according to claim 4,5 or 6, is characterized in that: described aluminium adopts the aluminium ingot of 99.85wt% or 99.9wt%, and vanadium oxide adopts high purity vanadium.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106541335A (en) * | 2016-10-08 | 2017-03-29 | 河钢股份有限公司承德分公司 | The method for removing the oxide-film and alloy slag inclusion on vananum surface |
| CN107267780A (en) * | 2017-08-08 | 2017-10-20 | 河钢股份有限公司承德分公司 | A kind of production method of vananum |
| CN110819834A (en) * | 2019-11-20 | 2020-02-21 | 河钢股份有限公司承德分公司 | Preparation method of vanadium-aluminum alloy and reactor |
| CN112609097A (en) * | 2020-11-20 | 2021-04-06 | 河钢承德钒钛新材料有限公司 | Method for preparing vanadium-aluminum alloy by using calcium vanadate |
| CN116574952A (en) * | 2023-03-13 | 2023-08-11 | 国瑞科创稀土功能材料(赣州)有限公司 | V-Al-RE intermediate alloy and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106541335A (en) * | 2016-10-08 | 2017-03-29 | 河钢股份有限公司承德分公司 | The method for removing the oxide-film and alloy slag inclusion on vananum surface |
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| CN110819834A (en) * | 2019-11-20 | 2020-02-21 | 河钢股份有限公司承德分公司 | Preparation method of vanadium-aluminum alloy and reactor |
| CN112609097A (en) * | 2020-11-20 | 2021-04-06 | 河钢承德钒钛新材料有限公司 | Method for preparing vanadium-aluminum alloy by using calcium vanadate |
| CN116574952A (en) * | 2023-03-13 | 2023-08-11 | 国瑞科创稀土功能材料(赣州)有限公司 | V-Al-RE intermediate alloy and preparation method thereof |
| CN116574952B (en) * | 2023-03-13 | 2024-01-16 | 国瑞科创稀土功能材料(赣州)有限公司 | V-Al-RE intermediate alloy and preparation method thereof |
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