CN115786801B - Production method of low-impurity ferrovanadium alloy and ferrovanadium alloy without surface layer oxidation impurity - Google Patents
Production method of low-impurity ferrovanadium alloy and ferrovanadium alloy without surface layer oxidation impurity Download PDFInfo
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- CN115786801B CN115786801B CN202211485141.8A CN202211485141A CN115786801B CN 115786801 B CN115786801 B CN 115786801B CN 202211485141 A CN202211485141 A CN 202211485141A CN 115786801 B CN115786801 B CN 115786801B
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- 239000000956 alloy Substances 0.000 title claims abstract description 80
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 239000002344 surface layer Substances 0.000 title claims abstract description 43
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims description 34
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims description 26
- 239000012535 impurity Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000003647 oxidation Effects 0.000 title description 5
- 238000007254 oxidation reaction Methods 0.000 title description 5
- 238000005422 blasting Methods 0.000 claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 239000010410 layer Substances 0.000 claims abstract description 29
- 238000003723 Smelting Methods 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims 1
- 239000000314 lubricant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 229910002064 alloy oxide Inorganic materials 0.000 abstract description 2
- 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 description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 description 10
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The high-valence oxide on the surface layer of the alloy is removed through shot blasting, whether the oxide is removed or not is detected through detecting the oxygen content of the surface layer, the shot blasting is the treatment of the alloy with the granularity meeting the requirement and in the room temperature state after crushing, the surface of the alloy is bright silver after shot blasting, the valence state of the alloy is stable, and the alloy can not be oxidized any more; the impact of the crushing process on the alloy surface layer can not be detected, so the thickness of the alloy oxide layer is mastered by detecting the oxygen content of different thicknesses of the surface layer before shot blasting, thereby adjusting the shot blasting process, controlling the thickness of the shot blasting removal surface, further controlling the removal thickness of the oxide layer and ensuring the removal of the oxide layer.
Description
Technical Field
The invention relates to the technical field of preparation of ferrovanadium, in particular to a production method of low-impurity ferrovanadium and ferrovanadium without oxidation impurities on the surface layer.
Background
The ferrovanadium alloy is applied to an additive in roller production, and can improve the hardness and strength of the roller. In the vanadium iron alloy product, vanadium metal and iron metal exist in a simple substance eutectic state, two main metal elements in the vanadium iron alloy are controlled to exist in a simple substance state by controlling a smelting process, and the content of other elements meets the process requirement.
The melting point of the ferrovanadium alloy is lower with lower vanadium content, and particularly for 50 ferrovanadium, the melting point is 1400-1500 ℃. However, for manufacturers, after the ferrovanadium is smelted, the ferrovanadium is cooled to form a metal cake, and the metal cake can be discharged, and the alloy cake is crushed to a specified particle size, usually 10-15mm, after the metal cake is discharged. The surface temperature of the ferrovanadium alloy is 500-600 ℃ when the ferrovanadium alloy is cooled and discharged, and vanadium metal exposed to air is easily oxidized by the air at the temperature to form high-valence vanadium oxide; in addition, during crushing, when the alloy blocks are extruded and crushed by the teeth of the jaw crusher, the alloy surfaces and the sections are oxidized at the instant high temperature, the instant alloy temperature is very high (the reddening state is shown according to field observation), and the temperature is 500-600 ℃ at the moment, and high-valence vanadium oxides are formed due to oxidation and the oxidation colors of different valence states are shown. One skilled in the art can initially determine whether an oxide is present, or the composition of the oxide, based on color. The instant high temperature of the crushing can cause the surface of part of the alloy block to be in dark blue or black, wherein the dark blue is that tetravalent vanadium (VO 2) is formed on the surface of the alloy, the melting point is 1967 ℃, the black is that trivalent vanadium (V2O 3) is formed on the surface of the alloy, and the melting point is 2000 ℃. The melting point of the high-valence vanadium oxide is higher than that of the ferrovanadium alloy.
When the vanadium iron alloy is applied to the additive in the roller, if the content of the high-valence vanadium oxide in the vanadium iron alloy is higher, after the vanadium iron alloy is melted in the roller smelting preparation process, the high-valence vanadium oxide is difficult to be melted into molten steel due to the high melting point of the high-valence vanadium oxide, so that black spots (mixed with unmelted high-valence vanadium oxide impurity particles with high hardness) appear on the surface of the roller, and defects such as air holes, cracks or impurity particles appear on the surface of the roller formed in the later stage.
Disclosure of Invention
In view of the above, it is desirable to provide a method for producing low impurity ferrovanadium alloy, comprising the steps of:
raw material proportioning;
smelting: putting the mixed materials into a reaction furnace, igniting and smelting;
standing: after smelting, standing, settling and cooling alloy liquid;
discharging: after the alloy liquid is solidified into solid, pulling out the furnace body, and pulling out the alloy cake;
crushing: crushing the material cake by adopting a jaw crusher to form an alloy material block;
blasting: throwing the alloy material blocks into a shot blasting machine for shot blasting, wherein a shot blasting medium adopts aluminum shots and steel shots with the proportion of 2-3:7-8, and a surface oxide layer is removed to form the vanadium-iron alloy with a non-oxidized surface layer.
The beneficial effects are that: in the invention, the high-valence vanadium oxide is generated in the tapping and crushing processes after smelting, so that the generation of oxide cannot be controlled by controlling the early smelting and can only be realized by post-treatment, and the generation of high-valence vanadium oxide is generated on the surface layer contacted with air, so that the oxygen content of the whole alloy cannot represent or react with the high-valence oxide on the surface layer in the background technical problem and can only be controlled by treating the surface layer oxide. The high-valence oxide on the surface layer of the alloy is removed through shot blasting, whether the oxide is removed or not is detected through detecting the oxygen content of the surface layer, the shot blasting is the treatment of the alloy with the granularity meeting the requirement after crushing and in a room temperature state, the surface of the alloy is bright silver after shot blasting, and the valence state of the alloy is stable and cannot be oxidized any more.
The impact of the crushing process on the alloy surface layer can not be detected, so the thickness of the alloy oxide layer is mastered by detecting the oxygen content of different thicknesses of the surface layer before shot blasting, thereby adjusting the shot blasting process, controlling the thickness of the shot blasting removal surface, further controlling the removal thickness of the oxide layer and ensuring the removal of the oxide layer.
Drawings
FIG. 1 is a diagram showing the positions of an example alloy block 1mm, 2mm, 5mm from the surface layer. In the figure, 01 denotes a position 5mm from the surface layer, 02 denotes a position 2mm from the surface layer, and 03 denotes a position 1mm from the surface layer.
Detailed Description
The invention provides a production method of low-impurity ferrovanadium alloy, which comprises the following steps:
raw material ingredients (the following raw materials are weighed and configured according to the corresponding weight ratio, V2O5 is 40-50 parts, aluminum powder is 35-45 parts, caO is 4-6 parts, caF2 is 3-4 parts, and return furnace material is 6-7 parts);
smelting: putting the mixed materials into a reaction furnace, igniting and smelting;
standing: after smelting, the alloy liquid is stood, settled and cooled (at least 40 h);
discharging: after the alloy liquid is solidified into solid, pulling out the furnace body, and pulling out the alloy cake;
crushing: crushing the material cake by adopting a jaw crusher to form an alloy material block;
blasting: throwing the alloy material blocks into a shot blasting machine for shot blasting, wherein a shot blasting medium adopts aluminum shots and steel shots with the proportion of 2-3:7-8, and a surface oxide layer is removed to form the vanadium-iron alloy with a non-oxidized surface layer.
Further, the thickness of the surface oxide layer is detected before the shot blasting step, and the thickness of the surface oxide layer of the alloy is detected by adopting an oxygen content detection method.
Further, the thickness detection of the oxide layer on the surface layer is also arranged after the shot blasting step, and the oxygen content of the alloy surface layer is detected by adopting an oxygen content detection method.
Further, the oxygen content was less than 0.5% in the surface layer 2 mm.
Further, the granularity of the ferrovanadium alloy is 10-15mm, and the deviation of the oxygen content in the surface layer 2mm and the internal oxygen content is less than 0.03%.
Further, the ferrovanadium alloy comprises the following components in percentage by mass: v:48-52%, O less than or equal to 0.5% (the content of other elements is the same as that of national standard mark or not strictly controlled), wherein O less than or equal to 0.5% is within 2mm from the surface layer.
The method comprises the following steps: raw material proportioning, smelting, standing, tapping and crushing are all conventional operations in the field or are the existing operation steps of the applicant, and are not repeated here.
Example 1 crushing and shot blasting of 15+ -1 mm-sized ferrovanadium alloy material
(1) 2mm aluminum shots and 2mm steel shots are adopted to form shot blasting media according to the proportion of 3:7, and the shot blasting media are filled into a shot blasting machine;
(2) Throwing the alloy material formed after crushing into a shot blasting machine, controlling the speed 2900r/min of the shot blasting machine, the output power of a motor to be 11KW, the shot blasting amount to be 170Kg/min and the shot blasting speed>82m/s; the crawler belt transmission speed is 1000r/min, and the dedusting storm speed is 5000m 3 /h；
(3) The loading amount of the alloy block into the loading machine is 0.6m 3 ；
(4) Separating the shot-blasted alloy block from the shot-blasted medium, and detecting the performance of the finished product by the involution Jin Liaokuai. The test data are shown in Table 2.
Example 2
The process is the same as that of the embodiment 1, except that the (3) in the embodiment 1 is that a shot blasting medium is formed by adopting a 2mm aluminum shot and a 2mm steel shot according to the proportion of 2.5:7.5, and the shot blasting medium is filled into a shot blasting machine; and detecting the performance of the finished product. The test data are shown in Table 2.
Example 3
The process is the same as that of the embodiment 1, except that the (3) in the embodiment 1 is that a shot blasting medium is formed by adopting 2mm aluminum shots and 2mm steel shots according to the proportion of 2:8, and the shot blasting medium is filled into a shot blasting machine; and detecting the performance of the finished product. The test data are shown in Table 2.
Comparative example 1
The process is the same as that of the embodiment 1, except that the (3) in the embodiment 1 is that a shot blasting medium is formed by adopting 2mm aluminum shots and 2mm steel shots according to the proportion of 4:6, and the shot blasting medium is filled into a shot blasting machine; and detecting the performance of the finished product. The test data are shown in Table 2.
Comparative example 2
The process is the same as that of the embodiment 1, except that the (3) in the embodiment 1 is that a shot blasting medium is formed by adopting 2mm aluminum shots and 2mm steel shots according to the proportion of 1:9, and the shot blasting medium is filled into a shot blasting machine; and detecting the performance of the finished product. The test data are shown in Table 2.
Generally, for different alloys, the thickness of an oxide layer formed during crushing is also different, and the scheme is that after crushing, the thickness of the oxide layer is determined by detecting the oxygen content of a surface layer, and then the material and the proportion of a shot blasting material are determined according to the thickness of the oxide layer, so that a proper shot blasting process is determined for the V48-52 ferrovanadium alloy.
See table 1, fig. 1. Before shot blasting, taking the positions 1mm, 2mm and 3mm away from the surface layer, detecting the oxygen content higher, wherein the oxygen content at the positions 1mm and 2mm is higher than that at the position 5mm, forming high-valence vanadium oxide in the thickness of the surface layer, detecting the oxygen content at the position 3mm away from the surface layer, and detecting the oxygen content to be close to that at the position 5mm, thereby determining that the thickness of the oxide layer is about 2mm, measuring the oxygen content at the position 5mm away from the surface layer before or after shot blasting, wherein the position is basically the center position of the alloy block, and can represent the oxygen content of the alloy block. The above test also further verifies that the oxide described in the background art is an oxide layer formed by the contact of the instantaneous high temperature surface with air at the time of tapping or crushing. Therefore, after shot blasting, whether the oxide layer is removed completely after shot blasting can be detected by only detecting whether the oxygen content at the positions of 1mm and 2mm on the surface layer is close to the oxygen content at the position of 5mm. Moreover, the oxide layer can be removed only by blasting after crushing, for example, the oxide layer can not be removed from the surface layer of the crushed alloy quickly by blasting in other stages.
TABLE 1
TABLE 2
The data in examples 1, 2 and 3 show that the aluminum shot and the steel shot have proper proportion and stronger shot blasting strength, and after detection, the oxygen content in the depth of 1mm and 2mm is basically equal to the oxygen content in the depth of 5mm (namely, the inside of the alloy block), which indicates that the oxide layer on the surface layer is completely removed, the oxygen content on the surface layer is almost the same as the oxygen content in the inside of the alloy block, and the deviation is less than 0.03%. The color is the natural silver of the ferrovanadium alloy, and has no deep blue and black, and the oxide layer is completely removed, so that the shot blasting effect is good.
In comparative example 1, the aluminum pellet ratio was larger than that in examples 1, 2 and 3, the shot blasting strength was lowered, and after detection, the oxygen content was higher than that in the depth of 5mm in the depth of 1mm and 2mm, and it was apparent that the oxide layer was not removed cleanly due to the insufficient shot blasting strength due to the high aluminum pellet ratio.
In comparative example 2, the aluminum shot ratio was smaller than that in examples 1, 2 and 3, the shot blasting strength was remarkably enhanced, and after detection, the oxygen content in the depth of 1mm and 2mm was substantially leveled with the oxygen content in the depth of 5mm (i.e., the core of the alloy block), indicating that the surface oxide layer was removed cleanly, but after observation, the surface layer was gray black, indicating that the steel shot had polished the alloy surface layer to damage, or that the iron oxide in the steel shot adhered to the alloy surface layer, resulting in gray black. It can be seen that the ratio can remove the surface oxide layer, but the appearance cannot meet the process requirements.
After the shot blasting treatment is adopted in the embodiment, firstly, the silver, dark blue and black are avoided, the surface oxide is completely removed by observing the color change, and secondly, the oxygen content of the surface layer (1 mm and 2mm positions) is detected to be not more than 0.5%, the deviation from the core oxygen content of the alloy block is less than or equal to 0.03%, so that the oxide is completely removed, and the surface layer removal uniformity and consistency are good, so that the surface layer oxide is uniformly removed.
When alloy products are produced, no matter manufacturers sell the alloy products in a block shape or a granular shape, or users break the alloy with larger grain size to form smaller grains, the breaking process in the background technology exists, and oxides can be generated on the surface locally. The oxygen content in the alloy is controlled by alloy manufacturers, most of the oxygen content is controlled in the smelting process, surface oxide generated by crushing of the alloy cold material is unavoidable, and the oxide is a way for oxygenation during subsequent smelting or adding of the alloy material, so that the removal of the surface oxide is also a common technical difficulty in the field.
The foregoing disclosure is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the scope of the invention, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the invention as defined by the appended claims.
Claims (3)
1. A production method of low-impurity ferrovanadium alloy is characterized by comprising the following steps:
raw material proportioning: the following raw materials are weighed and configured according to the corresponding weight ratio, V2O5:40-50 parts of aluminum powder: 35-45 parts of CaO:4-6 parts of CaF2:3-4 parts of furnace return material: 6-7 parts of a lubricant;
smelting: putting the mixed materials prepared in the raw material proportioning step into a reaction furnace, and igniting and smelting;
standing: after smelting, standing, settling and cooling alloy liquid;
discharging: after the alloy liquid is solidified into solid, pulling out the furnace body, and pulling out the alloy cake;
crushing: crushing the material cake by adopting a jaw crusher to form an alloy material block;
blasting: throwing the alloy material blocks into a shot blasting machine for shot blasting, wherein a shot blasting medium adopts aluminum shots and steel shots with the proportion of 2-3:7-8, and a surface oxide layer is removed to form vanadium-iron alloy with a non-oxidized surface layer;
the low-impurity ferrovanadium alloy produced by the steps has the oxygen content less than or equal to 0.5 percent in the surface layer of 2 mm.
2. The method for producing a low impurity ferrovanadium alloy according to claim 1, wherein the thickness of the surface oxide layer of the alloy is detected by detecting the oxygen content by detecting the thickness of the surface oxide layer of the alloy by setting the thickness of the surface oxide layer before the shot blasting step.
3. The method for producing a low impurity ferrovanadium alloy according to claim 1, wherein the surface oxide layer thickness detection is further provided after the shot blasting step, and the oxygen content of the surface layer of the alloy is detected by an oxygen content detection method.
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|---|---|---|---|---|
| GB709869A (en) * | 1951-07-24 | 1954-06-02 | Fischer Ag Georg | Process for the surface treatment of light alloy components by abrasive blast |
| CN108300880A (en) * | 2018-02-02 | 2018-07-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium iron |
| CN109234533A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团钒钛资源股份有限公司 | Low-grade aluminum shot smelting ferrovanadium |
| CN113151730A (en) * | 2021-04-25 | 2021-07-23 | 攀钢集团北海特种铁合金有限公司 | External smelting method of ferrovanadium |
| CN113913677A (en) * | 2021-09-29 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | 50 ferrovanadium alloy and smelting method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099715B (en) * | 2017-06-13 | 2018-08-28 | 东北大学 | The method for preparing vanadium iron with wash heat refining based on the reduction of aluminothermy self- propagating gradient |
| CN109628731B (en) * | 2019-01-31 | 2020-09-04 | 河钢股份有限公司承德分公司 | Method for extracting and preparing vanadium and alloy powder by short-process treatment of vanadium-containing raw material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB709869A (en) * | 1951-07-24 | 1954-06-02 | Fischer Ag Georg | Process for the surface treatment of light alloy components by abrasive blast |
| CN108300880A (en) * | 2018-02-02 | 2018-07-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of vanadium iron |
| CN109234533A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团钒钛资源股份有限公司 | Low-grade aluminum shot smelting ferrovanadium |
| CN113151730A (en) * | 2021-04-25 | 2021-07-23 | 攀钢集团北海特种铁合金有限公司 | External smelting method of ferrovanadium |
| CN113913677A (en) * | 2021-09-29 | 2022-01-11 | 河钢承德钒钛新材料有限公司 | 50 ferrovanadium alloy and smelting method thereof |
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