TWI820222B - 在鉻鐵熔煉製程中利用含金屬氧化物之側流之方法 - Google Patents
在鉻鐵熔煉製程中利用含金屬氧化物之側流之方法 Download PDFInfo
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- 229910000604 Ferrochrome Inorganic materials 0.000 title claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 9
- 238000003723 Smelting Methods 0.000 title description 4
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- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims 1
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- 238000002474 experimental method Methods 0.000 description 7
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000005065 mining Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/54—Processes yielding slags of special composition
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
- C21B13/125—By using plasma
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/527—Charging of the electric furnace
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C21B3/06—Treatment of liquid slag
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
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Abstract
本發明係關於用基於水泥之黏合劑將金屬氧化物粉塵及細料壓成團塊。之後，可通過已存在的進口系統將團塊饋入至用於製造鉻鐵之電弧爐中。
Description
本發明係關於藉由在用於製造鉻鐵之潛弧電爐中使用基於水泥之團塊回收金屬而再利用金屬氧化物。在該方法中，來自鉻鐵及精細鋼製造之側流與水泥形成團塊，可通過標准進口系統及預熱爐將該團塊饋入至潛弧電爐中。在潛弧電爐中，主要用碳將金屬氧化物還原為金屬，並且在鉻鐵產物中回收該金屬。
在鉻鐵爐中，由於具有小粒徑之材料不會到達反應區域，而是由於在進料層上存在氣流而被停止，因此不能使用具有小粒徑之材料。在鉻鐵及不銹鋼製造中所產生之金屬氧化物粉塵典型地非常細小，因此無法將其饋入至潛弧電爐中。此外，細金屬氧化物增加爐內進料層之導電率，此降低了製造能力。由於上述此等原因，所有細料在饋入至用於製造鉻鐵之潛弧電爐之前都必須聚結。
典型地在混凝土攪拌機中將欲形成團塊之材料與水泥及水混合。該混合物用於在壓塊機中形成所需尺寸之團塊，並且使其乾燥一個所需時間段以達到所需強度。於此之製造方法與製造基於水泥之石板之方法相同。
可在選定條件下在潛弧電爐中還原之來自鉻鐵製造之金屬氧化物可用於形成團塊。在精細鋼製造中，合適的餾分為例如來自過濾設備之粉塵、來自鑄造機及輥軋機之薄片、來自水處理之漿料、來自冷軋機之珠粒噴擊粉塵、及在退火-酸洗製程中藉由酸處理所形成之金屬沉積物。在鉻鐵製造中，合適的餾分為例如在造粒及爐內饋料中所形成之細料。為了改良金屬產量，可將合適的還原材料（諸如碳）添加至團塊中，以加快反應動力學。
本發明在鉻鐵製造中之潛力在於改良鉻產量、減少廢料、更好地利用原料並且避免廢棄物填埋。藉由改變團塊之組成，可改變鉻鐵之組成以適合客戶。在精細鋼製造中，優點為可改良目前側流之再循環，並且使再循環更便宜。
先前關於與再循環側流有關之問題之解決方案係基於獨立的粉塵冶煉設備、與有機黏合劑形成團塊、及直接還原製程。由於所需之大量投資及可能的高運行成本，粉塵冶煉設備及直接還原製程具有挑戰性。使用有機黏合劑（諸如糖蜜）會致使團塊在到達用於製造鉻鐵之潛弧電爐中之反應區域之前散開。在精細鋼製造中，在電弧爐中使用此等團塊降低能量效率，從而降低產量。
美國專利US8409320 B2揭示將含氧化物之鋼製造側流與糖蜜團塊化，並且將其饋入至熔煉設備之電弧爐中，在其中還原金屬並且煮沸爐渣。該專利並無涉及用水泥將氧化物材料團塊化，並且將團塊饋入至用於製造鉻鐵之潛弧電爐中或用於製造鋼之電弧爐中。
美國專利公開案US2014/0352496及US 2013192422揭示基於水泥及糖蜜之團塊在用於製造精細鋼之電弧爐中之製備及用途。該專利專注於在電弧爐中與團塊一起煮沸之爐渣。該專利並無涉及在用於製造鉻鐵之潛弧電爐中使用團塊。
先前技術刊物中並無任何地方提出使用用於製造鉻鐵之潛弧電爐。潛弧電爐不能創造爐渣沸騰之條件，且除此之外，由於在還原區處之反應及受干擾的氣流，其不適合用於自沸騰的爐渣中還原材料。
根據本發明之解決方案係基於將來自鉻鐵及精細鋼製造之側流之材料饋入至鉻鐵爐中，此將很難與其他任何技術一起使用。此外，可能且合理地將來自金屬工業及採礦業之其他側流饋入至鉻鐵電弧爐中，該等側流含有可用碳還原之金屬氧化物。
表1列出原料之主要成分之化學組成。
表1. 團塊之典型組成。
| Cr2 O3 | Fe2 O3 | NiO | MoO3 | SiO2 | CaO | C (煤焦) |
| 0 – 30 % | 20 – 70 % | 0 –10% | 0 – 5 % | 0 – 20 % | 0 – 15% | 0 – 20% |
使用表根據1之材料，與水泥及水形成混合物。除水泥作為增強劑外，可根據需要例如使用鼓風爐渣。將該混合物澆鑄成團塊，例如鑄成6角之60 x 60 x 60 mm尺寸之團塊。典型地，成品團塊含有2-30%之水泥，其中一部分（10-70%）可用例如鼓風爐渣代替。團塊之尺寸取決於所使用之潛弧電爐中之饋料或進口系統或受其影響。在室外條件下，將團塊乾燥約4週，以達到最終強度，然後將其饋入至爐中。亦可能使用促進劑及加熱來調節硬度。若需要，可將0-25%之還原劑（煤焦、矽鐵、鋁、碳化矽）添加至團塊中，由於還原劑本身在物理上更接近金屬氧化物，因此還原效果更好。
較佳將團塊經由預熱爐饋入至潛弧電爐中，在該預熱爐中，在CO2
氛圍中將團塊乾燥並且加熱至約500℃。此破壞了矽酸鹽鍵，並且用碳酸鹽鍵代替該等矽酸鹽鍵，而團塊則保持其強度。團塊作為塞流通過入口管流動進入潛弧電爐之罐中，並且由於爐中氣體而同時開始加熱。當團塊到達熔融區時，內部之金屬氧化物開始還原，首先，藉由罐中之氣體部分還原氧化鐵，最後還原氧化鉻。在用於製造鉻鐵之潛弧電爐中，團塊中所含之水泥會增加爐渣之pH值，從而使爐渣中之鉻含量降低約0.5-5%。還原的金屬在爐中熔融並且溶解成金屬，並且熔體以可鑄造合金之形式在爐外熔融，可鑄造合金之組成取決於饋料中之金屬含量。實際上，例如，饋料中之所有Ni、Mo及Fe餾分皆被還原成金屬。表2列出金屬及爐渣之組成。
表2. 自潛弧電爐中所獲得之金屬及爐渣組成
| 金屬典型分析 | |||||
| Cr | Si | Ni | Mo | C | |
| 40 – 55 % | 3 – 10 % | 0 – 5 % | 0 – 2 % | 5 – 8 % | |
| 爐渣典型分析 | |||||
| Cr | Fe | SiO2 | Al2 O3 | MgO | CaO |
| 0.5 – 10 % | 0 - 4 % | 25 – 30 % | 22 - 28% | 20 – 25 % | 2-5 % |
在一個具體實例中，各種二次原料（諸如催化劑）係用作團塊原料，使金屬氧化物中之金屬被回收至鉻鐵中。此等原材料可為含有鎳、鉬、鈦、銅、錳或鈷之金屬氧化物。
接下來參考所附圖式更詳細地解釋本發明。
圖1之Ellingham圖定義了金屬氧化物之還原順序。可看到在選定條件下在電弧爐中可被碳還原之不同金屬。碳能夠還原出現碳反應之線以上之金屬。該還原反應本身取決於溫度及壓力。實際上，首先還原貴金屬，因此還原順序為Ni、Mo、Fe、Cr。該圖亦顯示根據氧化階段而變化之還原反應方程式，例如，鐵之不同氧化階段之各個方程式。
根據本發明，水泥為能夠在400-600度之預熱爐溫度下將團塊保持在一起之唯一黏合材料。此外，其使團塊具有足夠的機械強度，以便可通過進口系統將團塊饋入至爐中。在預熱烘箱之熱下，水泥之化學鍵變為碳酸鹽鍵，從而幾乎完全保持團塊之原始強度。使用基於水泥之團塊亦可為潛弧電爐提供石灰，該石灰可增加爐渣之pH值，從而致使更高的還原度及更高的鉻產量。
團塊之粒徑分佈取決於團塊形成過程中所使用之原料。粒徑分佈應盡可能接近富勒曲線，因為此可最大程度地減少水泥用量並且節省原料。根據當前獲得之爐渣材料分析，團塊之添加量可高達總饋料之20 w-%，較佳3-10 w-%。
本發明不限於以上提出之原料。藉助於該方法，亦可經濟地使用含有金屬氧化物之其他側流。例如，來自鎳工業之氧化物會將鎳摻合至鉻鐵中，由此形成之鉻鐵將更適合於製造奧氏體鋼等級。
圖2-4顯示實驗結果，其中將含有來自精細鋼製造之薄片之基於水泥之團塊饋入至用於製造鉻鐵之潛弧電爐中。
圖2顯示在饋料實驗期間，即金屬氧化物還原為最終產物，鉻鐵產物中鎳及錳含量之變化。
圖3顯示在實驗期間，最終產物中鉻鐵產物中鉻濃度之變化。鉻濃度隨其他金屬比例之增加而下降。
圖4顯示在團塊實驗期間，最終產物中之碳及矽濃度保持在正常程度。
無
圖1顯示Ellingham圖，該圖說明金屬氧化物之還原順序。
圖2顯示在饋料實驗期間，鉻鐵產物中鎳及錳之程度如何變化。
圖3顯示在實驗期間，鉻鐵產物中鉻含量之變化。
圖4顯示在實驗期間，鉻鐵產物之碳及矽含量。
Claims (4)
- 一種利用含有工業用金屬氧化物之側流之方法，其特徵在於將含有金屬氧化物之材料與水泥一起壓成團塊，並且將團塊通過預熱爐饋入至用於製造鉻鐵之潛弧電爐中，並且該預熱爐係在400℃至600℃之間及在CO2氛圍中。
- 如請求項1所述之方法，其特徵在於該含有金屬氧化物之材料為來自鑄造機之薄片、來自輥軋機之薄片、來自過濾作業之粉塵、來自水處理之側流、或來自退火-酸洗線上之金屬漿料。
- 如請求項1或2所述之方法，其特徵在於添加之團塊佔總饋料之最大20%。
- 如請求項1或2所述之方法，其特徵在於該含有金屬氧化物之材料含有選自由以下組成之群之金屬之氧化物：鉻、鐵、鎳、鈦、鈷、錳及銅。
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