CN101886203A - Silicon iron product with low content of nitrogen - Google Patents
Silicon iron product with low content of nitrogen Download PDFInfo
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- CN101886203A CN101886203A CN 201010211355 CN201010211355A CN101886203A CN 101886203 A CN101886203 A CN 101886203A CN 201010211355 CN201010211355 CN 201010211355 CN 201010211355 A CN201010211355 A CN 201010211355A CN 101886203 A CN101886203 A CN 101886203A
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Abstract
The invention relates to a silicon iron product with low content of nitrogen and a production method thereof. The product comprises the following components in percentage by weight: 74 to 80 percent of Si, 20-26 percent of Fe, less than or equal to 0.003 percent of N, less than or equal to 0.001 percent of Pb, less than or equal to 0.010 percent of Ti, less than or equal to 0.012 percent of C, less than or equal to 0.015 percent of Cr, less than or equal to 0.070 percent of Mn, and the balance of inevitable impurities. The production method comprises the following steps of: smelting quartzite, silicon steel plate and petroleum coke serving as raw materials in an ore smelting furnace to obtain liquid silicon iron with low content of impurities and harmful substances; performing bottom blowing chlorination refining on the liquid silicon iron in the absence of air; and finally performing special slag blocking during a casting process. The product which has low content of nitrogen and does not contain harm substances can be produced by the method and is currently an important raw material for smelting high-efficiency and high-grade silicon steel, and meets the environment protection directives of the European Union and the environment protection requirements of the appliance industry.
Description
Technical field
The present invention relates to field of metallurgy, low nitrogen ferrosilicon is mainly used in produces senior electrical steel, because this product does not contain objectionable impuritiess such as arsenic, antimony, mercury, cadmium, poly-bromine two stupid ethers and poly-bromo biphenyl, only contains lead, the chromium of denier, is a kind of environmentfriendly products therefore.
Background technology
The nitrogen in steel too high levels will cause age hardening, hardness increases and the ductility variation, reduce the nitrogen content in the steel, can improve the maximum permeability (magnetic induction density) of siliconized plate, reduce coercive force (iron loss), will add ferrosilicon during the smelting silicon steel final alloy, content of elements such as the nitrogen in the ferrosilicon, lead, cadmium, arsenic, antimony directly influence the quality and the environmental requirement of silicon steel.Chinese patent 96120093.6,97109344.X, the ferrosilicon that ZL01112586.1 etc. produce only considers to reduce carbon, titanium, aluminium, impurity such as calcium are to satisfy the requirement of silicon steel in the past, but do not recognize nitrogen, plumbous, chromium, arsenic, antimony etc. are to efficient now, the requirement of the production of high grade silicon steel and environmental protection aspect, cause starting material in the process of producing these products in the past, slag former and oxygen, a large amount of nitrogen in the air, plumbous, chromium, arsenic, antimony etc. enter into product, N in the general high purity ferrosilicon is 100-200ppm, pb is 20-30ppm, Cr is 300-500ppm, As is 10-20ppm, Sb is 10-20ppm, can not satisfy efficient now, the production of high grade silicon steel and environmental requirement (European Union environmental protection instruction and household electric appliances environmental requirement), so far also there is not the ferrosilicon of N≤50ppm to occur, the objective of the invention is to provide a kind of and can overcome existing shortcoming of producing the ferrosilicon technology, can stably produce and contain N≤0.003%, Pb≤0.001%, Cr≤0.015%, Ti≤0.010%, C≤0.012%, Mn≤0.070%, do not contain arsenic, the silicon iron product with low content of nitrogen of antimony etc. (it is low more good more to require in the silicon steel) objectionable impurities, efficient now to satisfy, the demand that high grade silicon steel is produced.
Summary of the invention
The invention provides a kind of silicon iron product with low content of nitrogen, it consists of (wt%): Si 74-80%, and Fe 20-26%, N≤0.003%, Pb≤0.001%, Ti≤0.010%, C≤0.012%, Cr≤0.015%, Mn≤0.070%, surplus is a unavoidable impurities.
In a kind of preferred implementation, the invention provides a kind of silicon iron product with low content of nitrogen, it consists of (wt%): Si 74-80%, Fe 20-26%, N≤0.002%, Pb≤0.001%, Ti≤0.008%, C≤0.010%, Cr≤0.010%, Mn≤0.050%, surplus is a unavoidable impurities.
In the another kind of preferred implementation, the invention provides a kind of silicon iron product with low content of nitrogen, it consists of (wt%): Si 76-78%, Fe 22-24%, N≤0.002%, Pb≤0.001%, Ti≤0.007%, C≤0.008%, Cr≤0.010%, Mn≤0.035%, surplus is a unavoidable impurities.
Do not contain hazardous substance arsenic, antimony, bismuth, tin, mercury, cadmium, poly-bromine two stupid ethers and poly-bromine connection of preferred silicon iron product with low content of nitrogen of the present invention is stupid.
The method production of silicon iron product with low content of nitrogen of the present invention by may further comprise the steps:
(1) raw material is smelted: the electrode paste that adopts Graphite Electrodes or ash content to be not more than 4wt% is made self baking electrode, smelt adding the hot stove in ore deposit behind siliconized plate, quartzite and the reductive agent mixing, wherein reductive agent selects ash content to be not more than the refinery coke of 0.3wt%, and the dioxide-containing silica of quartzite is greater than 99wt%;
(2) refining: add dry rice straw 50-100 kilogram when tapping a blast furnace in the bag, after the perfect combustion rice-straw ash is made real, make it form the thick thermal insulation layer of one deck 20-40cm and isolated on the molten iron surface, open chlorine cylinder then chlorine is imported liquid ferrosilicon from molten iron refining bag bottom by gas permeable brick with air;
(3) the secondary debris retaining is handled: during casting with a wet straw blocking in the refining bag slips mouth, straw is by the clad compacting, ingot mould is interior to be blocked in the pour point back with carbon rod, carbon rod is 40-60mm apart from the height of ingot mould.
In a kind of preferred implementation, used refinery coke is not leaded, and the ash content of electrode paste is less than 3%, and titanium content is less than 0.003% and do not contain arsenic, antimony, bismuth, tin in the quartzite, and siliconized plate uses pure oriented silicon steel sheet waste material.
In the another kind of preferred implementation, the used refining encrust of step (2) is made thermal insulation layer with asbestos, and middle one deck refractory brick of building is coated with one deck Graphite Powder 99 as internal layer on the refractory brick, and a kind of integral air brick of resist chemical is equipped with at the bag end.
In the another kind of preferred implementation, the flow of chlorine is 2-5m in the step (2)
3/ h, the time of logical chlorine is 0.5-3 hour.
In the another kind of preferred implementation, siliconized plate use granularity is the pure oriented silicon steel sheet less than 50mm.
In the another kind of preferred implementation, the diameter of carbon rod is 8-15cm in the step (3), and length is 0.5-1.5m.
Smelting operation of the present invention is similar to common ore deposit hot stove production ferro-silicon, and different is: 1. all very strict to each starting material requirement, to guarantee nitrogen, lead, chromium, arsenic, objectionable impuritiess such as antimony do not enter in the product; 2. chlorine feeds from molten iron refining bag bottom, the refining encrust is made thermal insulation layer with the thick asbestos of 3mm, and middle one deck refractory brick of building is coated with one deck Graphite Powder 99 as internal layer on the refractory brick, to prevent that nitrogen higher in the refractory brick from dissolving in the molten iron, a kind of integral air brick of resist chemical is equipped with at the bag end; 3. guarantee the separation of slag iron and carry out secondary debris retaining processing.
By N≤0.003% in the ferrosilicon of production method production of the present invention, Pb≤0.001%, Cr≤0.015%, Mn≤0.05%.Utilize this ferrosilicon to produce siliconized plate same level trade mark iron loss and reduce by 15%～25%, magnetic strength improves 0.02～0.04T.Because raw material has passed through selected in the production process, do not contain lead in the refinery coke, do not contain arsenic, antimony, bismuth, tin in the quartzite, and the straw that has used cleaning is as lagging material, cause and do not contain arsenic, antimony, bismuth, tin, mercury, cadmium, poly-bromine two stupid ethers and poly-bromo biphenyl objectionable impurities, therefore a kind of especially environmentally friendly machine in this ferrosilicon.
Embodiment:
Embodiment 1:
In the hot stove in 6300KVA ore deposit, adopt ash content be 3.6% and fixed carbon be that 85% electrode paste is made self baking electrode, with dioxide-containing silica be 99.2%, titanium content is 200 kilograms of 0.002% quartzites, 28 kilograms in pure silicon steel disc waste material, ash content is 0.25%, fugitive constituent is 12%, fixed carbon is 95 kilograms of 87% refinery cokes, the mixing fed to boiler is smelted, secondary voltage 125V, primary current 400A, the molten iron of will coming out of the stove is then put into the refining bag, adds 70 kilograms of dry rice straw burnings, with spade plant ash is made real, form the thick thermal insulation layer of the about 30cm of one deck, then with 3m
3The flow of/h imported the ferrosilicon melt 1.5 hours by gas permeable brick with chlorine, block in the refining bag slips mouth with a big and wet straw handle during casting, the straw handle is by a clad compacting that 3mm is thick, and ingot mould is interior with a diameter 0.1m, the carbon rod of long 1m blocks in the pour point back, carbon rod is from the high 50mm of ingot mould, and gauge control is cooled off the back sampling analysis in the 50-70mm scope during casting, adopt potassium fluoride volumetry to analyze silicon, oxygen-nitrogen analyzer is analyzed nitrogen, and high frequency infrared ray carbon sulphur analyser is analyzed carbon, sulphur, atomic emission spectrometry (ICP) is analyzed aluminium, titanium, plumbous, manganese, metallic impurity elements such as chromium, detected result is Si 76.80%, Fe 22.98%, and N 0.0025%, Pb0.001%, Cr 0.011%, Ti 0.0085%, and C 0.010%, and Mn 0.068%, P 0.018%, S0.003%, Al 0.0088%, and Ca 0.0085%.
Embodiment 2:
In the hot stove in 6300KVA ore deposit, adopt ash content be 2.5% and fixed carbon be that 85% electrode paste is made self baking electrode, with dioxide-containing silica is 99.2%, titanium content is 200 kilograms of 0.002% quartzites, 27 kilograms of pure oriented silicon steel sheet waste materials, ash content is 0.25%, fugitive constituent is 12%, fixed carbon is 95 kilograms of 87% refinery cokes, the mixing fed to boiler is smelted, secondary voltage 125V, primary current 400A, the molten iron of will coming out of the stove is then put into the refining bag, add 80 kilograms of dry rice straw burnings, with spade plant ash are made real, form the thick thermal insulation layer of the about 35cm of one deck, flow with 3m3/h imported the ferrosilicon melt 1.5 hours by gas permeable brick with chlorine then, block in the refining bag slips mouth with a big and wet straw handle during casting, the straw handle is by a clad compacting that 3mm is thick, ingot mould is interior with a diameter 0.1m, the carbon rod of long 1m blocks in the pour point back, carbon rod is from the high 50mm of ingot mould, and gauge control is cooled off the back sampling analysis in the 50-70mm scope during casting, adopt potassium fluoride volumetry to analyze silicon, oxygen-nitrogen analyzer is analyzed nitrogen, and high frequency infrared ray carbon sulphur analyser is analyzed carbon, sulphur, atomic emission spectrometry (ICP) is analyzed aluminium, titanium, plumbous, manganese, metallic impurity elements such as chromium, detected result is Si 77.45%, Fe 22.28%, N0.0015%, and Pb 0.001%, Cr 0.0095%, Ti 0.007%, and C 0.008%, and Mn 0.035%, P0.013%, S 0.002%, and Al 0.0085%, and Ca 0.0085%.
Comparative Examples
Explained hereafter according to Chinese patent ZL01112586.1 embodiment.Smelt in the hot stove in 6300KVA ore deposit, the ore main component is a dioxide-containing silica 98.8%; Steel cuttings is selected silicon steel bits waste material for use; The refinery coke main component: ash content is 0.2%, and fugitive constituent is 13%, and fixed carbon is 86%; The electrode paste main component is: ash content is 3.2%, and fugitive constituent is 13%, and fixed carbon is 84%; After going into the stove smelting, obtain the lower liquid ferrosilicon of foreign matter content, strengthen refining further with Impurity removal by two-way pair of gas then, be blown into liquid ferrosilicon by gas permeable brick from platform bag bottom by air compressor compressed and supplied air, air pressure is regulated by control valve, initiation pressure transfers to 0.1～0.2Mpa, transfers to 0.2～0.3Mpa after 5 minutes, transfers to 0.3～0.4Mpa after 15 minutes; Service life is 60～120 minutes/ton ferrosilicon.Chlorine (or oxygen) is imported the liquid ferrosilicon from the Tai Bao top by carbon tube, and its pressure is adjusted to 0.2～0.4Mpa by control valve, and aeration time is 45～100 minutes/ton ferrosilicon.After refining is finished, liquid ferrosilicon is injected ingot mould ingot casting, cooling, sampling analysis, the finishing fragmentation, the packing warehouse-in, chemical ingredients sees Table 1.
The chemical ingredients of ferrosilicon (%) after table 1 refining treatment
| Element | ??Si | ??Ti | ??C | ??Al | ??N | ??S | ??Pb | ??Cr | ??Mn | ??P |
| Comparative Examples | ??≥??76 | ??＜??0.008 | ??＜??0.008 | ??＜??0.002 | ??0.017 | ??＜??0.002 | ??＜??0.001 | ??＜??0.05 | ??0.10 | ??＜??0.02 |
| Embodiment 2 | ??77.45 | ??0.007 | ??0.008 | ??0.0085 | ??0.0015 | ??0.002 | ??0.001 | ??0.0095 | ??0.035 | ??0.013 |
The production method of Comparative Examples is to raw-material requirement and basically identicals of the present invention such as quartzite, refinery coke, electrode paste, silicon steel bits, different just these methods are used pressurized air, cause nitrogen a large amount of in the pressurized air to enter in the ferrosilicon, because this method is not handled through debris retaining, the product qualified rate of its C≤0.008% is less than 20% simultaneously.It is 170ppm that product is delivered to research institute of Wuhan Iron ﹠ Steel (Group) Corp. check nitrogen content; And nitrogen of the present invention only is below the 25ppm.Use this ferrosilicon can only produce IF steel, car and can not produce efficient, high grade silicon steel with steel and common silicon steel.
The silicon iron product of producing with above-mentioned two kinds of methods makes the siliconized plate of the same level trade mark, and its performance sees Table 2.
The silicon iron product that two kinds of methods of table 2 are produced is to the siliconized plate Effect on Performance
As can be seen, production same level grade silicon steel uses the low nitrogen ferrosilicon of the present invention can make silicon steel magnetic induction density improve 0.04T, and iron loss reduces by 20%.And this product only contain the trace lead, chromium, do not contain objectionable impuritiess such as arsenic, antimony, tin, bismuth, mercury, cadmium, a kind of especially environmentally friendly machine.
Claims (10)
1. silicon iron product with low content of nitrogen, it consists of (wt%): Si 74-80%, Fe 20-26%, N≤0.003%, Pb≤0.001%, Ti≤0.010%, C≤0.012%, Cr≤0.015%, Mn≤0.070%, surplus is a unavoidable impurities.
2. silicon iron product with low content of nitrogen as claimed in claim 1, it consists of (wt%): Si 74-80%, Fe 20-26%, N≤0.002%, Pb≤0.001%, Ti≤0.008%, C≤0.010%, Cr≤0.010%, Mn≤0.050%, surplus is a unavoidable impurities.
3. silicon iron product with low content of nitrogen as claimed in claim 2, it consists of (wt%): Si 76-78%, Fe 22-24%, N≤0.002%, Pb≤0.001%, Ti≤0.007%, C≤0.008%, Cr≤0.010%, Mn≤0.035%, surplus is a unavoidable impurities.
4. one kind as claim 1-3 silicon iron product with low content of nitrogen as described in each, the arsenic that it is characterized in that not containing hazardous substance, antimony, bismuth, tin, mercury, cadmium, poly-bromine two stupid ethers and poly-bromo biphenyl.
5. a production may further comprise the steps as the method for claim 1-4 silicon iron product with low content of nitrogen as described in each:
(1) raw material is smelted: the electrode paste that adopts Graphite Electrodes or ash content to be not more than 4wt% is made self baking electrode, smelt adding the hot stove in ore deposit behind siliconized plate, quartzite and the reductive agent mixing, wherein reductive agent selects ash content to be not more than the refinery coke of 0.3wt%, and the dioxide-containing silica of quartzite is greater than 99wt%;
(2) refining: add dry rice straw 50-100 kilogram when tapping a blast furnace in the bag, after the perfect combustion rice-straw ash is made real, make it form the thick thermal insulation layer of one deck 20-40cm and isolated on the molten iron surface, open chlorine cylinder then chlorine is imported liquid ferrosilicon from molten iron refining bag bottom by gas permeable brick with air;
(3) the secondary debris retaining is handled: during casting with a wet straw blocking in the refining bag slips mouth, straw is by the clad compacting, ingot mould is interior to be blocked in the pour point back with carbon rod, carbon rod is 40-60mm apart from the height of ingot mould.
6. method as claimed in claim 5, wherein refinery coke is not leaded, and the ash content of electrode paste is less than 3%, and titanium content is less than 0.003% and do not contain arsenic, antimony, bismuth, tin in the quartzite, and siliconized plate uses pure oriented silicon steel sheet waste material.
7. method as claimed in claim 5, wherein the used refining encrust of step (2) is made thermal insulation layer with asbestos, and middle one deck refractory brick of building is coated with one deck Graphite Powder 99 as internal layer on the refractory brick, and a kind of integral air brick of resist chemical is equipped with at the bag end.
8. method as claimed in claim 5, wherein the flow of chlorine is 2-5m in the step (2)
3/ h, the time of logical chlorine is 0.5-3 hour.
9. method as claimed in claim 5, wherein to use granularity be pure oriented silicon steel sheet less than 50mm to siliconized plate.
10. method as claimed in claim 5, wherein the diameter of carbon rod is 8-15cm in the step (3), length is 0.5-1.5m.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047393A (en) * | 2015-07-03 | 2015-11-11 | 安徽广正电气科技有限公司 | Fabrication method for transformer silicon steel sheet |
| CN107012384A (en) * | 2016-01-27 | 2017-08-04 | 鞍钢股份有限公司 | A kind of silicon steel high-purity low-carbon ferrosilicon and its smelting process |
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| SU407955A1 (en) * | 1971-02-23 | 1973-12-10 | изобретени И. И. Барашкин, В. А. Арбузов, П. С. Солошенко, В. В. Земл ков, А. Г. Лихачев, Ю. Ф. Лотц, Э. И. Линкер, А. М. Швец, Э. В. Николаев | |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105047393A (en) * | 2015-07-03 | 2015-11-11 | 安徽广正电气科技有限公司 | Fabrication method for transformer silicon steel sheet |
| CN107012384A (en) * | 2016-01-27 | 2017-08-04 | 鞍钢股份有限公司 | A kind of silicon steel high-purity low-carbon ferrosilicon and its smelting process |
| CN107012384B (en) * | 2016-01-27 | 2018-05-29 | 鞍钢股份有限公司 | A kind of silicon steel high-purity low-carbon ferrosilicon and its smelting process |
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| CN101886203B (en) | 2012-01-25 |
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Application publication date: 20101117 Assignee: Hubei Wall Technology Co., Ltd. Assignor: Hubei Seruty Industrial Group Co., Ltd. Contract record no.: 2012420000124 Denomination of invention: Silicon iron product with low content of nitrogen Granted publication date: 20120125 License type: Exclusive License Record date: 20120906 |
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