CN1029412C - Carbon heating process for producing ferroboron from premade boron coke - Google Patents
Carbon heating process for producing ferroboron from premade boron coke Download PDFInfo
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- CN1029412C CN1029412C CN 93108638 CN93108638A CN1029412C CN 1029412 C CN1029412 C CN 1029412C CN 93108638 CN93108638 CN 93108638 CN 93108638 A CN93108638 A CN 93108638A CN 1029412 C CN1029412 C CN 1029412C
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Abstract
The present invention relates to a technique for producing ferroboron from preformed boron coke by a carbon-thermic reduction method, which comprises: the mixed raw material composed of boron oxide or boric acid and charcoal is heated to produce boron coke used as the raw material for the smelting; after being crushed, the boron coke is mixed with iron dust or iron oxide and a furnace material loosening agent (for example charcoal and carbohydrate) and then added to the electric furnace; the materials are smelted for some time to produce the required ferroboron. The low-aluminum ferroboron produced by the technique of the present invention not only meets the requirements for the production in the amorphous state, but also has the advantages of convenient control and wide requirement range for raw materials; the present invention greatly prolongs the furnace life, basically eliminates the rise phenomenon of the furnace bottom and is suitable for large-scale continuous production.
Description
The carbothermy that the present invention relates to a kind of prefabricated boron Jiao is produced ferro-boron technology, relates to the manufacturing field of ferro-boron in the metallurgy industry, is to produce the low technologic a kind of improvement project of aluminium ferro-boron.
Low aluminium ferro-boron is an important boron raw material of producing amorphous alloy, and the ferro-boron that traditional thermite process production technique is produced can not finely satisfy the requirement that non-crystalline state is produced, because undesirable aluminium foreign matter content is too high in the ferro-boron, and the production cost costliness.For reducing production costs, reduce the content of aluminium and other harmful elements, be badly in need of the high and cheap ferro-boron manufacturing process of exploitation boron content.
The late nineteen eighties, the iron alloy enterprise of many countries and scientific research institution have carried out a large amount of research to this class technology, and electric furnace carbothermy technology wherein is low with its cost, and the characteristics that aluminium content is low in the product are particularly noticeable, become hot of research and development.
Carbothermy is smelted ferro-boron, and the boric acid in the raw material can melt when going into the stove heating because of fusing point low (450 ℃), thereby produces " separation " phenomenon with other raw materials, has a strong impact on reaction effect.Invented at this problem U.S. connection letter Allied Corporation and to have made ball post-heating agglomerating raw material treatment process (United States Patent (USP) 4486226, European patent 0146947) in advance, its method is with the boron raw material, iron or ferric oxide, charcoal or carbohydrate, and as the sugared mixed pelletizing post-heating sintering of making the ball binding agent, add in the electric furnace then and smelt, according to the data record, the product boron-containing quantity is 13.6-15.4%, boron rate of recovery 69-86%, it is not high that it exists boron content, the problem that alloy recovery is not high.
The scheme that is smelted into ferro-boron with boric acid, ferric oxide, charcoal and wooden mixture in the direct current submerged arc furnace introduced in the 43rd page of " carbothermy is produced the optimum parameter of ferro-boron " literary composition of the fifth phase in 1992 " iron alloy " magazine, the alloy boracic 18-20% of its production, the boron rate of recovery is 95%, but it exists furnace life short (2-3 month), production status problem of unstable.
The objective of the invention is to relate to a kind of scheme of producing ferro-boron technology, it can make product have high and stable boron content, and the rate of recovery of boron reaches more than 95%, can improve industrial stability again on the basis that does not increase industrial cost, prolongs furnace life.
Carbothermy is smelted the following problem of ferro-boron ubiquity: (1) " separation " phenomenon.Because boric acid fusing point low (450 ℃) is smelted the at first fusing of being heated, from furnace charge, separate, destroyed the homogeneity of reactant, boron content, the rate of recovery all are affected; (2) furnace charge lacks suitable sponginess, and furnace charge is too loose, and a large amount of boron vapours are escaped in the flue, reduces the boron dividing potential drop of reaction zone greatly, and the rate of recovery of boron-containing quantity and boron is descended; Otherwise the furnace charge sedimentation is not enough, and reaction generates CO gas can not be got rid of smoothly, and reaction is suppressed, and influences production effect too; (3) furnace bottom rising is fast.This mainly is that the accumulation of superfluous charcoal causes in reacting.
In order to overcome the above problems, the present invention has taked following measure: (1) at first is blended in heat-agglomerating in the rotary kiln with the oxide compound of boron or the part of boric acid and carbon support, the middle furnace charge of the sintering after product can obtain loosening after fragmentation, porous-boron Jiao.Because the oxide compound of boron combines with carbon support is even among boron Jiao, can avoid " separation phenomenon ", and improve the homogeneity of furnace charge, help the local surplus of anti-blocking and cause furnace bottom rising; (2) add in the stove with boron Jiao, iron filings and carbon support compound, ratio is pressed the chemical reaction amount and is calculated, (actual process correction in addition), the 30-40%(weight ratio of carbon support amount wherein) selected carbohydrate for use with suitable loose character, best is that rice husk or granularity are the wood sawdust of 1-3mm, and all the other carbon supports are charcoal preferably.Height of furnace charge is remained on the 500-1000mm scope (look the stove watt level, be generally 1000KVA-3000KVA), after pyrotic smelting, regularly open the stove eye, just can obtain boron-containing quantity in the 20-23%(weight ratio) ferro-boron, because do not have aluminium in the raw material, the Aluminum in Alloy impurity element concentration can be controlled at the 0.05%(weight ratio) below, the rate of recovery also obviously improves, after the installation furnace gas escaped the boron oxide retrieving arrangement, the utilization of boron can reach more than 95% in the whole technology.
Fig. 1 is a process flow diagram of the present invention.
Specifically describe technology of the present invention as follows by reference to the accompanying drawings:
Heat-agglomerating after preferably charcoal (2) (size of charcoal is between 10-30mm) mixes with carbon carrier with the oxide of boron or boric acid (1), sintering is finished in rotary kiln (7), the material bed tempertaure is between 450-800 ℃, adjusting the rotary kiln rotating speed had both made sintering thorough, guarantee that again charcoal scaling loss amount is minimum, be generally per minute 1-2 week, sintering time 3-10 minute. The sintering afterproduct is by B2O
3With the loose porous shape object that charcoal is combined into, be cooled to room temperature be broken into the 50-100mm size fragment boron Jiao (3). Boron raw material (1) was 3: 1 to 6: 1 with the proportion scale of charcoal (2) when sintering boron was burnt, and this ratio can realize charcoal and B2O
3The most uniform combination, and need not add other adhesive such as syrup etc.
Iron filings (4), boron Jiao (3), carbon carrier preferably charcoal (5) and furnace charge raising agent preferably rice husk or granularity are the wood sawdust (6) of 1-3mm, be mixed to join in the reaction zone (9) of burried arc furnace or electric arc furnaces (8), be heated to about 1600 ℃, following reaction taken place:
B
2O
3+3C＝2〔B〕+3CO↑
When the gas of the boracic that generates when reaction rises to and runs into the fused molten iron in the loose furnace charge, will be absorbed by molten iron and form ferro-boron.
From the following formula reaction as can be known, the smooth discharge of the CO gas that reaction generates helps molecular balance to carry out to positive dirction, helps to strengthen the boron dividing potential drop of reaction zone, thereby improves the boron-containing quantity of ferro-boron, therefore should make furnace charge keep loose, good permeability.Furnace charge must have certain gas-permeable resistance again keeping this boron dividing potential drop on the other hand, and makes boron vapour be dripped absorption by the molten iron in the furnace charge fully, so furnace charge also must guarantee certain thickness and porous strainability.Adopted the raising agent of carbohydrate in the furnace charge, preferably adopting rice husk or granularity is the wood sawdust of 1-3mm for this reason, and its ratio accounts for the 30-40% of Restore All agent, and corresponding furnace charge layer thickness is controlled at the 500-1000mm scope.During heating, this raising agent also will be carbonized, and a part that becomes reductive agent is participated in reaction.Through after the smelting of certain hour, can regularly obtain low aluminium ferro-boron from fire door.The boron-containing quantity of ferro-boron reaches the 20-23%(weight ratio), aluminium content is lower than the 0.05%(weight ratio), comprehensive recovery can reach more than 95%.
Use the low aluminium ferro-boron of explained hereafter of the present invention can not only satisfy the requirement that non-crystalline state is produced, and control easy, the ingredient requirement wide ranges, furnace life also prolongs greatly, has eliminated the furnace bottom rising phenomenon basically, is fit to large scale continuous prod.
Below provide and implement two examples of the present invention, but the scope of the invention is not subjected to this example restriction.
Example one, industrial boric acid (is contained 99% H
3BO
3) with lumpiness be that the granule charcoal of 10-20mm joins in the rotary kiln with 100: 20 ratios, the rotary kiln rotating speed is 1.0 cycle per minutes, 500 ℃ of material bed tempertaures, sintering time is 5 minutes, the sinter of generation is broken into boron Jiao of 50-100mm after cooling; With boron Jiao, iron filings, charcoal, rice husk with 100: 94: 21: 40 mixed, add in the three-phase submerged arc furnace, guarantee that the stock column height is 650mm.The electric current of controlling every phase electrode is 7000A, after 8 hours, obtains the ferro-boron (being weight ratio) of following specification:
Boron % carbon % aluminium % sulphur % phosphorus % iron %
22 2.20 0.03＜0.01＜0.02 all the other
The burnt method for making of example two, boron is with example one, with boron Jiao, iron filings, charcoal, sawdust with 100: 94: 21: 40 mixed, join and exchange in the submerged arc furnace, making the stock column height is 600mm.Controlling every phase electrode current is 7000A, after 8 hours, obtains the ferro-boron (being weight ratio) of following specification:
Boron % carbon % aluminium % sulphur % phosphorus % iron %
20 0.25 0.03＜0.01＜0.02 all the other
More than two routine smelting recoveries all between 70-86%, the meter measure that is recycled, comprehensive recovery is all more than 95%.
Claims (2)
1, a kind of technology of carbothermy refining ferro-boron is characterized in that:
A, boron Jiao's the manufacturing raw material boric acid or the proportion scale of boron oxide and charcoal are between 6: 1 to 3: 1, and at the rotary kiln internal heating, the Heating temperature of rotary kiln is 450 ℃ to 800 ℃ with mixing raw material, produce boron Jiao as raw materials for metallurgy;
B, boron Jiao are after fragmentation, be mixed to join in the electric furnace with the porousness furnace charge raising agent of iron filings or ferric oxide, charcoal and carbohydrate, it is the wood sawdust of 1-3mm that the porousness furnace charge raising agent of carbohydrate adopts rice husk or diameter, the furnace charge raising agent accounts for the 30-40% (weight ratio) of Restore All dosage, the stock column height concrete scope of furnace charge in electric furnace is 500-1000mm, after the heating melting, produce required ferro-boron.
2, carbothermy according to claim 1 is smelted the technology of ferro-boron, and it is characterized in that: electric melting furnace is submerged arc furnace or electric arc furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93108638 CN1029412C (en) | 1993-07-17 | 1993-07-17 | Carbon heating process for producing ferroboron from premade boron coke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93108638 CN1029412C (en) | 1993-07-17 | 1993-07-17 | Carbon heating process for producing ferroboron from premade boron coke |
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| Publication Number | Publication Date |
|---|---|
| CN1083125A CN1083125A (en) | 1994-03-02 |
| CN1029412C true CN1029412C (en) | 1995-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93108638 Expired - Fee Related CN1029412C (en) | 1993-07-17 | 1993-07-17 | Carbon heating process for producing ferroboron from premade boron coke |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296506C (en) * | 2004-02-20 | 2007-01-24 | 黄湛良 | Ferro-aluminium-boron alloy and its production method |
| CN100451155C (en) * | 2002-03-28 | 2009-01-14 | 新日本制铁株式会社 | High-purity ferroboron |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286998C (en) | 2002-03-28 | 2006-11-29 | 新日本制铁株式会社 | High-purity ferroboron, a mother alloy for iron-base amorphous alloy, an iron-base amorphous alloy, and methods for producing the same |
| CN105238990B (en) * | 2015-11-12 | 2017-11-10 | 中冶东方工程技术有限公司 | A kind of borosilicate ferroalloy and its production method |
| CN106853533B (en) * | 2015-12-09 | 2018-07-27 | 苏州纳朴材料科技有限公司 | A method of preparing high-purity ferro-boron superfine powder |
| CN113528984A (en) * | 2021-01-15 | 2021-10-22 | 武汉科技大学 | FeSiPC amorphous soft magnetic alloy and preparation method thereof |
| CN116904839B (en) * | 2023-09-12 | 2023-11-24 | 内蒙古永磊材料科技有限公司 | High-purity ferroboron and preparation method thereof |
-
1993
- 1993-07-17 CN CN 93108638 patent/CN1029412C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451155C (en) * | 2002-03-28 | 2009-01-14 | 新日本制铁株式会社 | High-purity ferroboron |
| CN1296506C (en) * | 2004-02-20 | 2007-01-24 | 黄湛良 | Ferro-aluminium-boron alloy and its production method |
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| Publication number | Publication date |
|---|---|
| CN1083125A (en) | 1994-03-02 |
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