TW202409300A - Methods for melting direct reduced iron, solid iron and methods for manufacturing solid iron, and materials for civil engineering and construction and methods for manufacturing materials for civil engineering and construction - Google Patents
Methods for melting direct reduced iron, solid iron and methods for manufacturing solid iron, and materials for civil engineering and construction and methods for manufacturing materials for civil engineering and construction Download PDFInfo
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Abstract
本發明係提供：從直接還原鐵很有效率地除去脈石成分之直接還原鐵的熔解技術。其係具備：將直接還原鐵利用感應加熱熔解爐進行熔解而製得熔融鐵之熔解步驟；將前述熔解步驟中所生成的爐渣排出到前述感應加熱熔解爐的爐外之排渣步驟；還有可依照需求而實施的將前述熔解步驟所製得的熔融鐵進行精煉之精煉步驟；其中，前述熔解步驟是包含：在熔解步驟的其中部分期間或整個期間，將氣體吹入前述熔融鐵中之第1工序，並且可依照需求而又包含從下列(1)至(3)的工序之中選出的一種以上的工序，(1)是添加爐渣成分調整劑之第2工序、(2)是從設置在前述感應加熱熔解爐的爐上之熱源對於爐渣進行熱供給之第3工序、以及(3)是進行供給一種以上之還原性的固體或氣體之第4工序。The present invention provides a direct reduced iron melting technology that efficiently removes gangue components from direct reduced iron. It has: a melting step of melting direct reduced iron in an induction heating melting furnace to produce molten iron; a slag discharge step of discharging the slag generated in the aforementioned melting step to the outside of the aforementioned induction heating melting furnace; and a slag discharge step. The refining step of refining the molten iron produced in the foregoing melting step can be implemented according to requirements; wherein the foregoing melting step includes: blowing gas into the foregoing molten iron during part or the entire period of the melting step. The first step, and may include one or more steps selected from the following steps (1) to (3) as needed, (1) is the second step of adding a slag component regulator, (2) is the second step of adding a slag component regulator, A third step of supplying heat to the slag from a heat source installed on the furnace of the induction heating melting furnace, and (3) a fourth step of supplying one or more reducing solids or gases.
Description
本發明係關於：用以除去含在直接還原鐵中的脈石成分之直接還原鐵的熔解方法、使用了這種方法之固體鐵及固體鐵的製造方法、以及土木建築用資材及土木建築用資材的製造方法。The present invention relates to a method for melting direct-reduced iron for removing a ore component contained in the direct-reduced iron, solid iron using the method, a method for producing the solid iron, and a civil engineering and construction material and a method for producing the civil engineering and construction material.
近年來，製鐵業界擴大使用冷鐵源(回收廢料)的需求正在提高。為了建構循環型社會，鐵資源的回收再利用是不可或缺。此外，基於防止地球暖化的考量，就削減CO 2排出量的需求而言，增加回收廢料的使用量也是不可或缺。回收廢料係與氧化鐵(Fe 2O 3)也就是鐵礦石不同，在熔製過程中並無需進行還原工序，因而可以減少CO 2排出量。因此，乃走向增加冷鐵源使用量的途徑。 In recent years, there has been an increasing demand in the iron and steel industry to expand the use of cold iron sources (recycled scrap). In order to build a circular society, the recycling and reuse of iron resources is indispensable. In addition, in order to prevent global warming and reduce CO2 emissions, increasing the use of recycled waste is also indispensable. Recycling waste materials is different from iron oxide (Fe 2 O 3 ), that is, iron ore, in that there is no need for a reduction process during the melting process, thus reducing CO 2 emissions. Therefore, the approach is to increase the usage of cold iron sources.
高爐-轉爐法，係將原料也就是鐵礦石(Fe 2O 3)與還原材也就是焦炭(碳源)一起載入高爐內，以熔製成C濃度為4.5至5質量%程度的鐵水，然後，將該鐵水載入轉爐內來將雜質成分也就是C和Si、P予以氧化除去的製鋼程序。利用高爐來製造鐵水時，為了將鐵礦石予以還原等的理由，每一公噸的鐵水需要使用500kg程度的碳源。並且還會產生約兩公噸程度的CO 2氣體。相對於此，如果是以鐵回收廢料作為原料來製造熔鋼的話，就不必使用到還原鐵礦石時所需的碳源。因此，即使單就將鐵回收廢料熔解所需的熱能來考慮，藉由將每一公噸的鐵水置換成每一公噸的鐵回收廢料，即可降低約1.5公噸的CO 2排出量。從上述的情事可知，為了要兼顧削減溫室效應氣體的排出量以及維持生產活動的雙重考量，必須增加回收廢料的使用量。 In the blast furnace-converter method, the raw material, which is iron ore (Fe 2 O 3 ), and the reducing material, which is coke (carbon source), are loaded into the blast furnace to melt it into iron with a C concentration of about 4.5 to 5 mass%. water, and then loading the molten iron into a converter to oxidize and remove the impurity components, namely C, Si, and P. When a blast furnace is used to produce molten iron, approximately 500kg of carbon source is required per metric ton of molten iron for reasons such as reducing iron ore. And about two metric tons of CO 2 gas will also be produced. In contrast, if iron recycling scrap is used as a raw material to produce molten steel, there is no need to use the carbon source required to reduce iron ore. Therefore, even considering the heat energy required to melt the iron recycling scrap alone, by replacing each metric ton of molten iron with each metric ton of iron recycling scrap, approximately 1.5 metric tons of CO 2 emissions can be reduced. From the above, it can be seen that in order to balance the dual considerations of reducing greenhouse gas emissions and maintaining production activities, it is necessary to increase the use of recycled waste.
然而，鐵回收廢料，尤其是用來製造高級鋼不可或缺之高品位的鐵回收廢料的供需不足，因此，改以還原鐵來取代回收廢料的需求正在上昇中。還原鐵是將鐵礦石予以還原而製造出來的。但是，還原鐵並無需如同高爐-轉爐法所生成的鐵水這般地必須將鐵中的C濃度設定在高濃度，所以只需使用較少的碳源，因而每一公噸的鐵可以減少約0.2公噸的CO 2排出量。再者，還原材並不是採用碳源，而是採用氫氣或天然氣等的碳化氫系氣體，因此可更為減少CO 2的排出量。 However, the supply and demand of recycled iron waste, especially high-grade recycled iron waste that is indispensable for making high-grade steel, is insufficient, so the demand for reducing iron to replace recycled waste is increasing. Reduced iron is produced by reducing iron ore. However, reduced iron does not need to have a high C concentration in iron like molten iron produced by the blast furnace-converter process, so only a small amount of carbon source is needed, and CO2 emissions can be reduced by about 0.2 tons per ton of iron. Furthermore, the reducing material does not use a carbon source, but a carbonized hydrogen-based gas such as hydrogen or natural gas, so CO2 emissions can be further reduced.
然而，作為還原鐵的原料之鐵礦石，其成分是依照其挖掘地的不同而有所差異。鐵礦石的成分，主要是根據Fe的含量和脈石的含量來作評量。表1係顯示鐵礦石的成分組成的例子。However, the composition of iron ore, which is the raw material for reduced iron, varies depending on where it is excavated. The composition of iron ore is mainly evaluated based on the Fe content and gangue content. Table 1 shows an example of the chemical composition of iron ore.
Fe含量是以鐵礦石中的總含鐵量T.Fe(質量%)來表示，這個數値愈大Fe含量愈多，因此作為原料的價值愈高。脈石含量則是以鐵礦石中之Fe以外的氧化物合計含量來表示，其大部分是SiO 2和Al 2O 3，其他則是含有0.1質量%程度的CaO和MgO等。在將鐵礦石煉製成鐵的過程中，脈石成分是被視為雜質而被除去，因此，脈石量愈多Fe含量愈低，每單位Fe量的運輸成本和煉製成本都會增大。 The Fe content is expressed as the total iron content T.Fe (mass %) in the iron ore. The larger this value is, the more Fe content there is, and therefore the higher the value as a raw material. The ore content is expressed as the total content of oxides other than Fe in the iron ore, most of which are SiO 2 and Al 2 O 3 , and the rest are CaO and MgO, etc., which contain about 0.1 mass %. In the process of refining iron ore into iron, the ore components are considered impurities and are removed. Therefore, the more ore there is, the lower the Fe content is, and the transportation cost and refining cost per unit of Fe will increase.
又，以鐵礦石作為原料而製造出來的還原鐵，其金屬化率和組成分等的性狀，係依據：其所使用之鐵礦石的廠牌、混合進來之原料成分調整劑的種類及原單位、還原材的種類及原單位、還原溫度以及還原鐵製造設備的方式而有所不同。表2係顯示還原鐵的組成分的例子。In addition, the properties of reduced iron produced from iron ore as raw material, such as metallization rate and composition, are based on: the brand of the iron ore used, the type of raw material component regulator mixed in, and It differs depending on the original unit, type and original unit of reducing material, reduction temperature, and method of reducing iron manufacturing equipment. Table 2 shows examples of compositions of reduced iron.
一般而言，在製造還原鐵的過程中，係添加一些CaO來當作原料成分調整劑，以使其與鐵礦石中含有的脈石成分一起形成爐渣，藉此來確保作為還原鐵的強度。如果是爐渣量被抑制在最小限度且金屬化率愈高之還原鐵的話，對於後續之輸送、熔解、精煉工序的負荷愈小。另一方面，這種還原鐵必須使用到高品位的鐵礦石，因此，不僅原料成本會增加，而且用來提昇金屬化率之還原處理的成本也會增大，這些都是尚待解決的技術課題。因此，業界還在期待能夠早日開發出：從以廉價之低品位的鐵礦石為原料而製造出來之爐渣量較多的還原鐵，很有效率地將爐渣予以分離來提高金屬鐵含量的製程。Generally speaking, in the process of producing reduced iron, some CaO is added as a raw material component adjuster so that it forms slag together with the gangue component contained in the iron ore, thereby ensuring the strength of the reduced iron. . If the slag amount is kept to a minimum and the metallization rate is high, the load on the subsequent transportation, melting, and refining processes will be smaller. On the other hand, this reduced iron must use high-grade iron ore. Therefore, not only the cost of raw materials will increase, but also the cost of reduction treatment to increase the metallization rate will increase. These are yet to be solved. Technical topics. Therefore, the industry is still looking forward to the early development of a process that efficiently separates the slag from reduced iron with a large amount of slag produced from cheap, low-grade iron ore to increase the metallic iron content. .
以往已經有人提出：將含在這種礦石中的脈石作為爐渣予以除去之還原金屬的製造方法之技術方案。例如：專利文獻1和2的技術方案，係將內含金屬含有物的原料載入已經堆積在移動型爐床爐之爐床上的固體還原材層上，進行加熱還原處理，並且至少有一度形成熔融狀態，以將金屬與爐渣分離來製造還原金屬的方法。 [先前技術文獻] [專利文獻] In the past, a method for producing a reduced metal by removing gangue contained in such an ore as slag has been proposed. For example, the technical solutions of Patent Documents 1 and 2 are to load the raw material containing metal content onto the solid reducing material layer that has been deposited on the hearth of the mobile hearth furnace, perform heating and reduction treatment, and form at least once A method of producing reduced metal by separating metal from slag in the molten state. [Prior technical literature] [Patent Document]
[專利文獻1]日本特開2000-292069號公報 [專利文獻2]日本特開2004-204293號公報 [非專利文獻] [Patent Document 1] Japanese Patent Publication No. 2000-292069 [Patent Document 2] Japanese Patent Publication No. 2004-204293 [Non-patent Document]
[非專利文獻1]Slag Atlas, 2nd ed., Verlag Stahleisen GmbH, Duesseldorf, (1995), 105, 126.[Non-patent document 1] Slag Atlas, 2nd ed., Verlag Stahleisen GmbH, Duesseldorf, (1995), 105, 126.
[發明所欲解決的問題][The problem the invention is trying to solve]
然而，在習知的技術中，還存在著下列之尚待解決的技術課題。 專利文獻1和2所開示的技術，其前提條件是：在將金屬與爐渣分離時，使用碳系的固體原料來作為還原材。因此，如果採用基於削減CO 2排出量的觀點而被認為是今後的主流之利用氫系的還原材來實施還原處理之製程的話，會被認為：金屬與爐渣的分離效率很低。具體而言，旋轉爐床爐等之移動型爐床爐的爐內氛圍氣體的溫度通常是1300℃程度。在這種溫度下，被還原後的金屬處於熔融狀態的原因被認為：是因為碳系的固體原料滲碳進入金屬內，而導致金屬的融點降低的緣故。因此，利用氫系的還原材來實施還原處理的製程，不會發生因為滲碳所導致之金屬融點降低的現象，因此，係被預測為：載入物的液相率較低，且金屬與爐渣不容易分離的製程。 However, the following technical issues remain to be solved in the known technology. The technology disclosed in Patent Documents 1 and 2 is based on the premise that a carbon-based solid raw material is used as a reducing material when separating metal from slag. Therefore, if a process using a hydrogen-based reducing material for reduction treatment is adopted, which is considered to be the mainstream in the future from the perspective of reducing CO2 emissions, it is considered that the separation efficiency of metal and slag is very low. Specifically, the temperature of the atmosphere gas in a movable furnace such as a rotary furnace is generally about 1300°C. At this temperature, the reason why the reduced metal is in a molten state is believed to be that the carbon-based solid raw material carburizes into the metal, causing the metal's melting point to drop. Therefore, the process using hydrogen-based reducing materials for reduction treatment will not cause the metal's melting point to drop due to carburization. Therefore, it is predicted that the liquid phase ratio of the load is low and the metal and slag are not easily separated.
換言之，只是利用還原工序還是會有難以除去脈石的時候，還是必須從所製造出來的還原鐵將脈石予以分離出去。具體而言，在利用感應加熱熔解爐來將還原鐵予以熔解時，必須要防止從脈石所產生的爐渣硬化。In other words, there may be times when it is difficult to remove the gangue just by using the reduction process, and the gangue must still be separated from the produced reduced iron. Specifically, when reducing iron is melted using an induction heating melting furnace, it is necessary to prevent slag generated from gangue from hardening.
本發明係有鑑於上述的情事而開發完成的，其目的是要提供：可以很有效率地從直接還原鐵除去脈石成分之直接還原鐵的熔解方法。另一個目的是要提供：使用了該熔解方法之高純度的固體鐵及固體鐵的製造方法、以及活用了其副產品之土木建築用資材及土木建築用資材的製造方法。 [解決問題之技術手段] The present invention was developed in view of the above circumstances, and its purpose is to provide a method for melting direct-reduced iron that can efficiently remove the ore component from the direct-reduced iron. Another purpose is to provide high-purity solid iron and a method for producing solid iron using the melting method, as well as civil engineering and construction materials and a method for producing civil engineering and construction materials that utilize the by-products. [Technical means for solving the problem]
本發明人等發現了一個創見就是：在利用感應加熱熔解爐來將直接還原鐵予以熔解時，藉由促進熔融鐵與爐渣之間的熱傳導及/或藉由控制爐渣的組成分來抑制爐渣的硬化，就可以讓爐渣更容易排出到爐外，進而完成了本發明。The inventors of the present invention have discovered an innovative idea: when using an induction heating melting furnace to melt direct reduced iron, the heat conduction between the molten iron and the slag is promoted and/or the composition of the slag is controlled to suppress the deformation of the slag. By hardening, the slag can be discharged out of the furnace more easily, thus completing the present invention.
可有效地解決上述課題之本發明所提供之直接還原鐵的熔解方法，其特徵為，係具備：將直接還原鐵利用感應加熱熔解爐進行熔解而製得熔融鐵之熔解步驟；將前述熔解步驟中所生成的爐渣排出到前述感應加熱熔解爐的爐外之排渣步驟；還有可依照需求而實施的將前述熔解步驟所製得的熔融鐵進行精煉之精煉步驟；其中，前述熔解步驟是包含：在該熔解步驟的其中部分期間或整個期間，將氣體吹入前述熔融鐵中之第1工序，並且可依照需求而又包含從下列(1)至(3)的工序之中選出的一種以上的工序，(1)是添加爐渣成分調整劑之第2工序、(2)是從設置在前述感應加熱熔解爐的爐上之熱源對於爐渣進行熱供給之第3工序、以及(3)是進行供給一種以上之還原性的固體或氣體之第4工序。The method for melting direct reduced iron provided by the present invention, which can effectively solve the above problems, is characterized in that it includes: a melting step of melting direct reduced iron in an induction heating melting furnace to produce molten iron; and the above melting step A slag discharge step of discharging the slag generated in the induction heating melting furnace to the outside of the furnace; and a refining step of refining the molten iron produced in the aforementioned melting step, which can be implemented according to needs; wherein the aforementioned melting step is It includes: the first step of blowing gas into the aforementioned molten iron during part or all of the melting step, and may also include one selected from the following steps (1) to (3) as needed. Among the above steps, (1) is the second step of adding a slag component adjusting agent, (2) is the third step of supplying heat to the slag from a heat source installed on the furnace of the induction heating melting furnace, and (3) is The fourth step of supplying one or more reducing solids or gases is performed.
此外，本發明所提供之直接還原鐵的熔解方法之更好的解決手段，係如下列(a)(b)(c)所示： (a)在前述第1工序中，從用來將前述氣體吹入前述熔融鐵中之氣體供給噴嘴的位置至前述熔融鐵浴面的高度H(m)係以下列數式(1)來表示，並且是以符合下列數式(2)的條件來將前述氣體吹入前述熔融鐵中， 其中，ρ g：供給氣體的密度(kg/m 3)、ρ 1：熔融鐵的密度(kg/m 3)、Q：氣體供給速度(Nm 3/分鐘)、N：氣體供給噴嘴的個數(-)、d：氣體供給噴嘴的直徑(m)、D：感應加熱爐的爐內徑(m)、W DRI：供給到感應加熱爐內的還原鐵重量(kg)、(%T.Fe) DRI：含在還原鐵內的總含鐵濃度(質量%)、h：從感應加熱爐的爐底至氣體供給噴嘴位置的高度(m)。 (b)在前述第2工序中進行調整前述爐渣成分調整劑的種類及添加量，以使得前述熔解步驟所生成之爐渣的組成分，以質量%計，CaO濃度(%CaO)對於SiO 2濃度(%SiO 2)的比值也就是鹼度是落在0.5～2.0的範圍，Al 2O 3濃度(%Al 2O 3)是落在10～25質量%的範圍。 (c)在前述第4工序中進行調整前述還原性之固體或氣體的種類及供給量，以使得前述熔解步驟所生成之爐渣的組成分的總含鐵濃度(%T.Fe)是落在20質量%以下。 In addition, a better solution to the direct reduced iron melting method provided by the present invention is as shown in the following (a) (b) (c): (a) In the aforementioned first step, from The height H (m) from the position of the gas supply nozzle for blowing gas into the molten iron to the surface of the molten iron bath is expressed by the following equation (1), and is determined by satisfying the conditions of the following equation (2) The aforementioned gas is blown into the aforementioned molten iron, Among them, ρ g : density of supply gas (kg/m 3 ), ρ 1 : density of molten iron (kg/m 3 ), Q: gas supply speed (Nm 3 /min), N: number of gas supply nozzles (-), d: diameter of the gas supply nozzle (m), D: furnace inner diameter of the induction heating furnace (m), W DRI : weight of reduced iron supplied to the induction heating furnace (kg), (%T.Fe ) DRI : total iron concentration (mass %) contained in reduced iron, h: height from the bottom of the induction heating furnace to the gas supply nozzle position (m). (b) In the second step, the type and amount of the slag component adjusting agent are adjusted so that the composition of the slag produced in the melting step is, in mass %, CaO concentration (%CaO) relative to SiO 2 concentration The ratio of (%SiO 2 ), that is, the alkalinity, falls in the range of 0.5 to 2.0, and the Al 2 O 3 concentration (%Al 2 O 3 ) falls in the range of 10 to 25 mass%. (c) In the aforementioned fourth step, the type and supply amount of the reducing solid or gas are adjusted so that the total iron concentration (%T.Fe) of the composition of the slag generated in the aforementioned melting step falls within 20% by mass or less.
可有效地解決上述課題之本發明所提供之固體鐵的製造方法，其特徵為：將利用上述之任一種直接還原鐵的熔解方法所製得的熔融鐵進行凝固而成為固體鐵。又，本發明所提供之固體鐵，係利用該製造方法所製造的固體鐵，其特徵為：總含鐵濃度T.Fe為93質量%以上，且氧化物成分的合計為3質量%以下。The method for producing solid iron provided by the present invention, which can effectively solve the above problems, is characterized in that the molten iron produced by any of the above-mentioned direct reduction iron melting methods is solidified to form solid iron. Furthermore, the solid iron provided by the present invention is produced by this production method and is characterized in that the total iron concentration T.Fe is 93% by mass or more and the total amount of oxide components is 3% by mass or less.
可有效地解決上述課題之本發明所提供之土木建築用資材的製造方法，其特徵為，係具備：將直接還原鐵利用感應加熱熔解爐進行熔解而製得熔融鐵之熔解步驟；將前述熔解步驟中所生成的爐渣排出到前述熔解爐的爐外之排渣步驟；以及將前述排渣步驟中所排出的爐渣進行冷卻硬化以做成土木建築用資材原料之冷卻硬化步驟；其中，前述熔解步驟是包含：在該熔解步驟的其中部分期間或整個期間，將氣體吹入前述熔融鐵中之第1工序，並且可依照需求而又包含從下列(1)至(2)的工序之中選出的一種以上的工序，(1)是添加爐渣成分調整劑之第2工序、以及(2)是從設置在前述感應加熱熔解爐的爐上之熱源對於爐渣進行熱供給之第3工序。又，本發明所提供之土木建築用資材，係利用該製造方法所製造的土木建築用資材，其特徵為：以質量%計，CaO濃度(%CaO)對於SiO 2濃度(%SiO 2)的比值也就是鹼度是落在0.5～2.0的範圍，Al 2O 3濃度(%Al 2O 3)是落在10～25質量%的範圍。 [發明之效果] The present invention can effectively solve the above-mentioned problems and provides a method for producing civil engineering and construction materials. The method is characterized by comprising: a melting step of melting direct reduced iron in an induction heating melting furnace to obtain molten iron; a slag discharge step of discharging slag generated in the aforementioned melting step to the outside of the aforementioned melting furnace; and a cooling and hardening step of cooling and hardening the slag discharged in the aforementioned slag discharge step to produce a raw material for civil engineering and construction materials; The melting step comprises a first step of blowing gas into the molten iron during part of or the entire period of the melting step, and may further comprise one or more steps selected from the following steps (1) to (2) as required, wherein (1) is a second step of adding a slag composition regulator, and (2) is a third step of supplying heat to the slag from a heat source installed on the induction heating melting furnace. Furthermore, the civil engineering and construction material provided by the present invention is a civil engineering and construction material manufactured by the manufacturing method, and is characterized in that, in terms of mass %, the ratio of CaO concentration (%CaO) to SiO 2 concentration (%SiO 2 ), that is, the alkalinity, is in the range of 0.5 to 2.0, and the Al 2 O 3 concentration (%Al 2 O 3 ) is in the range of 10 to 25 mass %. [Effects of the Invention]
根據本發明所提供之直接還原鐵的熔解方法，在利用感應加熱熔解爐將直接還原鐵予以熔解時，係將氣體吹入熔融鐵中，並且還可以依照需求來實施：以適當的流量將氣體供給到熔融鐵內、控制所生成的爐渣之組成分、以及從設置在爐上的熱源對於爐渣進行熱供給，之至少其中一種以上，如此一來，可將爐渣保持在流動狀態，因而既可一邊將直接還原鐵中的金屬鐵進行熔解，又可一邊將爐渣進行分離。According to the direct reduced iron melting method provided by the present invention, when the direct reduced iron is melted using an induction heating melting furnace, gas is blown into the molten iron, and it can also be implemented according to needs: the gas is blown into the molten iron at an appropriate flow rate. By supplying at least one of molten iron, controlling the composition of the generated slag, and supplying heat to the slag from a heat source installed on the furnace, the slag can be kept in a flowing state. While the metallic iron in the direct reduced iron is melted, the slag can be separated at the same time.
根據本發明所提供之固體鐵的製造方法及固體鐵，因為是先將熔融鐵與爐渣分離之後，才讓熔融鐵凝固，因此能夠製造出高純度的固體鐵，所以很可取。又，根據本發明所提供之土木建築用資材的製造方法及土木建築用資材，係將副產品予以回收，尤其是先調整組成分之後才進行回收，藉此可達成有效地活用副產品。The solid iron manufacturing method and solid iron provided by the present invention are very desirable because the molten iron is first separated from the slag and then solidified, so that high-purity solid iron can be manufactured. In addition, the civil engineering and construction material manufacturing method and civil engineering and construction material provided by the present invention recycles by-products, especially recycles after adjusting the composition, thereby achieving effective utilization of by-products.
以下將具體地說明本發明的實施方式。以下的實施方式只是舉例表示將本發明的技術思想具體化的系統及/或方法，並不是用來將本發明的構成要件限定於下列的構成要件。亦即，本發明的技術思想，係可以在申請專利範圍所記載之技術性的範圍內加入各種的變更。The embodiments of the present invention will be specifically described below. The following embodiments merely exemplify systems and/or methods that embody the technical idea of the present invention, and are not intended to limit the constituent elements of the present invention to the following constituent elements. That is, the technical idea of the present invention can be modified in various ways within the technical scope described in the patent application.
本發明人等，針對於如何將脈石從還原鐵除去的作法，係以利用感應加熱熔解爐先將還原鐵熔解的作法為前提條件，來進行了檢討。利用感應加熱熔解爐來將還原鐵進行加熱和熔解的作法之特徵，係在於：可利用感應電流直接對於還原鐵中的金屬鐵成分很有效率地進行加熱。但是，就另一方面而言，因為無法對於爐渣成分進行直接加熱，因此會有所謂的「因為比重上的差異而漂浮在熔融鐵上面的爐渣硬化而難以再追加載入還原鐵」之問題。The inventors of the present invention have examined how to remove veinstone from reduced iron, based on the premise that the reduced iron is first melted in an induction heating melting furnace. The characteristic of heating and melting reduced iron in an induction heating melting furnace is that the metallic iron component in the reduced iron can be directly heated by the induction current very efficiently. However, on the other hand, since the slag component cannot be directly heated, there is a problem that "the slag floating on the molten iron hardens due to the difference in specific gravity, making it difficult to load additional reduced iron."
＜第一實施方式＞ 因此，本發明人等，乃針對於：哪一種條件才是將利用感應加熱熔解爐來將還原鐵熔解後的脈石成分當成爐渣予以分離出來的適合條件?進行了探索。其結果，得知了：利用感應加熱熔解爐來將還原鐵進行熔解時，如果將氣體吹入鐵水內的話，可以抑制爐渣的凝固，能夠很有效率地進行還原鐵的熔解以及爐渣的分離工作。此外，也發現了一種創見，就是藉由至少執行：將適當的流量之氣體供給到熔融鐵內、控制所生成的爐渣之組成分、從設置在爐上的熱源對於爐渣進行熱供給，之三種作法中的至少一種以上的話，就能夠將爐渣保持在流動狀態，而能夠更合適地既可將還原鐵中的金屬鐵予以熔解，又可將爐渣予以分離出來。此處所稱的「爐渣保持在流動狀態」係指：爐渣整體上呈現赤熱且高溫的爐渣一直都在進行循環的狀態。 <First Embodiment> Therefore, the present inventors searched for which conditions are suitable for separating the gangue components after melting reduced iron as slag using an induction heating melting furnace. As a result, it was found that when reduced iron is melted in an induction heating melting furnace, if gas is blown into the molten iron, the solidification of the slag can be suppressed, and the melting of the reduced iron and the separation of the slag can be performed very efficiently. Work. In addition, an innovative idea was also found, which is to perform at least three steps: supplying an appropriate flow rate of gas into the molten iron, controlling the composition of the generated slag, and supplying heat to the slag from a heat source installed on the furnace. By using at least one of these methods, the slag can be kept in a flowing state, and the metallic iron in the reduced iron can be more appropriately melted and the slag can be separated. "The slag remains in a flowing state" here refers to a state in which the entire slag is red-hot and high-temperature slag is constantly circulating.
以這種方式來將爐渣保持在流動狀態的話，再追加載入還原鐵的時候，就不會受到已經凝固的爐渣所阻礙，而能夠有效地活用感應加熱熔解爐的容積。再者，因為爐渣處於流動狀態，可以使用讓爐渣從爐上部溢流出來之爐渣刮扒機構來進行排渣，而使得熔融鐵與爐渣的分離也變容易。基於高溫爐渣的後續處理及/或耗損處所的修補等的觀點考量，較好的作法是在將爐渣進行分離的時候，限定出藉由將爐體傾倒而使爐渣排出的場所(地點)。By keeping the slag in a flowing state in this way, when additional reduced iron is added, it will not be hindered by the solidified slag, and the capacity of the induction heating melting furnace can be effectively utilized. Furthermore, because the slag is in a flowing state, a slag scraping mechanism that allows the slag to overflow from the upper part of the furnace can be used to discharge the slag, making it easier to separate the molten iron and the slag. From the viewpoint of subsequent processing of high-temperature slag and/or repair of damaged areas, a better approach is to limit the place (location) where the slag can be discharged by dumping the furnace body when separating the slag.
本發明的第一實施方式，係根據上述的檢討而獲得的，係具備：將直接還原鐵利用感應加熱熔解爐進行熔解而製得熔融鐵之熔解步驟；將熔解步驟中所生成的爐渣排出到感應加熱熔解爐的爐外之排渣步驟；其中，熔解步驟是包含：在熔解步驟的其中部分期間或整個期間，將氣體吹入熔融鐵中之第1工序，並且可依照需求而又包含從下列(1)至(2)的工序之中選出的一種以上的工序，(1)是添加爐渣成分調整劑之第2工序、以及(2)是從設置在前述感應加熱熔解爐的爐上之熱源對於爐渣進行熱供給之第3工序。The first embodiment of the present invention was obtained based on the above review, and includes a melting step of melting direct reduced iron in an induction heating melting furnace to produce molten iron; and discharging the slag generated in the melting step to The slag discharge step outside the induction heating melting furnace; wherein the melting step is the first step of blowing gas into the molten iron during part or all of the melting step, and may include additional steps as required. One or more steps selected from the following steps (1) to (2), (1) is the second step of adding a slag component adjusting agent, and (2) is the step from the furnace installed on the aforementioned induction heating melting furnace. The third step in which the heat source supplies heat to the slag.
＜第二實施方式＞ 其次，針對於氣體的吹入條件的最佳化進行了檢討。將氣體供給到熔融鐵內的話，將會因為氣體的上浮而使得熔融鐵受到攪拌，所生成且上浮後的爐渣會受到來自熔融鐵的熱傳導，其結果，爐渣的溫度會上昇，藉此，將可改善爐渣的流動性。所供給的氣體，只要是在利用配管來進行供給的時候不會液化之氣體即可，其種類不拘。例如：氧氣及/或二氧化碳之類的氧化性氣體會將熔融鐵予以氧化而導致鐵的良率降低，因此，係採用Ar、N 2之類的惰性氣體為宜。 <Second embodiment> Next, the optimization of the gas injection conditions was examined. If the gas is supplied to the molten iron, the molten iron will be stirred due to the floating of the gas, and the generated and floating slag will be subjected to heat conduction from the molten iron. As a result, the temperature of the slag will rise, thereby improving the fluidity of the slag. The gas supplied can be of any type as long as it does not liquefy when supplied using a pipe. For example, oxidizing gases such as oxygen and/or carbon dioxide will oxidize the molten iron and reduce the yield of iron. Therefore, it is appropriate to use an inert gas such as Ar or N2 .
然而，供給氣體量過多的話，氣體將會以保持連續的狀態上昇通過熔融鐵的浴面(鐵水上表面)而發生所謂的「空廊現象」。發生「空廊現象」的話，熔融鐵的飛濺(spitting)將會明顯地增加，並且會降低所供給之氣體的攪拌效率及反應效率，因而熔融鐵對於爐渣的熱傳導效果也會變小。本發明人等，乃進行改變了條件的各種實驗。其結果，發現了一種創見，就是：在將氣體吹入熔融鐵中的時候，如果將從氣體供給噴嘴的位置至熔融鐵浴面的高度H(m)設定成符合下列數式(1)的關係，並且以符合下列數式(2)的條件來將氣體吹入熔融鐵中的話，就可以避免發生「空廊現象」。 其中，ρ g：供給氣體的密度(kg/m 3)、 ρ 1：熔融鐵的密度(kg/m 3)、 Q：氣體供給速度(Nm 3/分鐘)、 N：氣體供給噴嘴的個數(-)、 d：氣體供給噴嘴的直徑(m)、 D：感應加熱爐的爐內徑(m)、 W DRI：供給到感應加熱爐內的還原鐵重量(kg)、 (%T.Fe) DRI：含在還原鐵內的總含鐵濃度(質量%)、 h：從感應加熱爐的爐底至氣體供給噴嘴位置的高度(m)。 However, if the amount of supplied gas is too large, the gas will continue to rise through the bath surface of the molten iron (the surface of the molten iron), resulting in a so-called "empty gallery phenomenon". If the "empty gallery phenomenon" occurs, the spattering of the molten iron will significantly increase, and the stirring efficiency and reaction efficiency of the supplied gas will be reduced, so the heat conduction effect of the molten iron to the slag will also be reduced. The present inventors conducted various experiments in which conditions were changed. As a result, an innovative idea was found: when blowing gas into molten iron, the height H (m) from the position of the gas supply nozzle to the molten iron bath surface is set to satisfy the following equation (1) relationship, and by blowing gas into the molten iron under the conditions of the following equation (2), the "empty gallery phenomenon" can be avoided. Among them, ρ g : density of supply gas (kg/m 3 ), ρ 1 : density of molten iron (kg/m 3 ), Q: gas supply speed (Nm 3 /min), N: number of gas supply nozzles (-), d: diameter of the gas supply nozzle (m), D: furnace inner diameter of the induction heating furnace (m), W DRI : weight of reduced iron supplied to the induction heating furnace (kg), (%T.Fe ) DRI : total iron concentration (mass %) contained in reduced iron, h: height from the furnace bottom of the induction heating furnace to the gas supply nozzle position (m).
另一方面，氣體的吹入量太少的話，氣體的上浮對於熔融鐵的攪拌效果會變小，熔融鐵對於爐渣的熱傳導也會變小，因此，針對於每一單位的熔融鐵，係以至少0.01Nm 3/(每分鐘暨每公噸熔融鐵)的合計氣體供給量來供給氣體為宜。 On the other hand, if the gas injection amount is too small, the stirring effect of the gas floating on the molten iron will be reduced, and the heat conduction of the molten iron to the slag will also be reduced. Therefore, for each unit of molten iron, it is advisable to supply gas with a total gas supply of at least 0.01Nm3 /(per minute and per ton of molten iron).
本發明的第二實施方式，係根據上述的檢討而獲得的，係就第一實施方式，在第1工序中，將從用來將氣體吹入前述熔融鐵中之氣體供給噴嘴的位置至熔融鐵浴面的高度H(m)設定成符合上述數式(1)的關係，並且以符合上述數式(2)的條件來將氣體吹入熔融鐵中。The second embodiment of the present invention is obtained based on the above review. In the first step, in the first embodiment, from the position of the gas supply nozzle for blowing gas into the molten iron to the molten iron The height H (m) of the iron bath surface is set so as to satisfy the relationship of the above-mentioned mathematical expression (1), and the gas is blown into the molten iron under the conditions satisfying the above-mentioned mathematical expression (2).
＜第三至第五實施方式＞ 其次，針對於爐渣的組成分的最佳化進行了檢討。爐渣的流動性係隨著爐渣組成分而有很大的差異。針對於表2所示之還原鐵組成分的例子，將其所含之爐渣成分以Al 2O 3-CaO-SiO 2、或CaO-SiO 2-FeO的三種成分的合計為100%的方式來換算之後的組成分，分別予以標定在三元系相圖上的話，就會如圖1及圖2的圖表所示。各個三元系相圖是參考了非專利文獻1。此處之還原鐵中的FeO濃度，是將總含鐵濃度T.Fe與金屬鐵濃度M.Fe的差值乘以71.85(FeO的分子量)/55.85(Fe原子量)而計算出來的。 <Third to Fifth Embodiments> Next, the optimization of the composition of slag was examined. The fluidity of slag varies greatly depending on the composition of slag. For the example of the reduced iron composition shown in Table 2, the slag components contained therein are converted to the composition after the total of the three components of Al2O3 - CaO - SiO2 or CaO- SiO2 -FeO is converted to 100%, and the components are respectively marked on the ternary phase diagram, as shown in Figures 1 and 2. Each ternary phase diagram is referenced to Non-Patent Document 1. The FeO concentration in the reduced iron here is calculated by multiplying the difference between the total iron concentration T.Fe and the metallic iron concentration M.Fe by 71.85 (molecular weight of FeO)/55.85 (atomic weight of Fe).
從圖1可以看出，係存在著較諸還原鐵所含之爐渣成分更低融點的組成分。然而，如果是高濃度的SiO 2之爐渣組成分的話，雖然是低融點，但卻是高黏度而導致流動性降低。因此，以質量%計，將CaO濃度(%CaO)對於SiO 2濃度(%SiO 2)的比值也就是鹼度(以下，稱為：爐渣鹼度)設定在0.5以上為宜。又，基於將爐渣予以低融點化之觀點考量，爐渣鹼度是設定在2.0以下，Al 2O 3濃度是設定在10～25質量%的範圍為宜。作為用來調整這種爐渣組成分的手段，係可添加含有CaO、SiO 2及Al 2O 3的其中一種以上的物質來作為在製造還原鐵時的原料成分調整劑或者在將還原鐵熔解時的爐渣成分調整劑為宜。含有CaO的物質，係可以採用：石灰石、消石灰、生石灰、製鋼爐渣等。此外，如果採用石灰石及/或消石灰的話，會因為分解時的吸熱反應而導致溫度降低，製鋼爐渣的CaO濃度只有40～50質量%的程度，必須增大添加量而會衍生出還原鐵熔解時所生成的爐渣量增大之問題，因此是使用生石灰為佳。含有SiO 2的物質，可以採用：矽石、煤炭灰、製鋼爐渣等。此外，也可以活用：藉由添加金屬Si及/或矽泥來與殘留在還原鐵中的氧化鐵成分發生反應而生成的SiO 2。含有Al 2O 3的物質，除了剛玉及/或鋁礬土等的天然石材之外，也可以活用：藉由添加金屬Al及/或鋁渣與殘留在還原鐵中的氧化鐵成分發生反應而生成的Al 2O 3。 As can be seen from Figure 1, there are components with lower melting points than the slag components contained in the reducing iron. However, if the slag component is a high concentration of SiO2 , although it has a low melting point, it has a high viscosity and reduces fluidity. Therefore, in terms of mass%, it is advisable to set the ratio of CaO concentration (%CaO) to SiO2 concentration (% SiO2 ), that is, the alkalinity (hereinafter referred to as slag alkalinity) to 0.5 or more. In addition, from the perspective of lowering the melting point of the slag, the slag alkalinity is set to less than 2.0, and the Al2O3 concentration is set to a range of 10-25 mass%. As a means for adjusting the composition of this slag group, it is preferable to add one or more substances containing CaO, SiO2 and Al2O3 as a raw material composition adjuster when manufacturing reduced iron or a slag composition adjuster when melting reduced iron. The substances containing CaO can be: limestone, slaked lime, quicklime, steelmaking slag, etc. In addition, if limestone and/or slaked lime are used, the temperature will decrease due to the endothermic reaction during decomposition. The CaO concentration of steelmaking slag is only 40-50% by mass. The amount of addition must be increased, which will lead to the problem of increasing the amount of slag generated when reducing iron is melted. Therefore, it is better to use quicklime. The substances containing SiO2 can be: silica, coal ash, steelmaking slag, etc. In addition, SiO2 generated by reacting the iron oxide components remaining in the reduced iron with the addition of metal Si and/or silica mud can also be used. Materials containing Al2O3 include natural stones such as corundum and/or alumina, and Al2O3 generated by reacting the iron oxide components remaining in the reduced iron with the addition of metal Al and / or aluminum slag.
本發明的第三實施方式，係根據上述的檢討而獲得的，係就第一或第二實施方式，在第2工序中，針對於在熔解步驟中所生成之爐渣的組成分，進行調整前述爐渣成分調整劑的種類及添加量，以使得爐渣的鹼度是落在0.5～2.0的範圍，Al 2O 3濃度是落在10～25質量%的範圍。 The third embodiment of the present invention is obtained based on the above review. In the second step of the first or second embodiment, the composition of the slag generated in the melting step is adjusted as described above. The type and amount of the slag component adjuster should be such that the alkalinity of the slag falls in the range of 0.5 to 2.0, and the Al 2 O 3 concentration falls in the range of 10 to 25 mass %.
又，從圖2可以看出，還原鐵所含的爐渣成分是含有高濃度的FeO，就降低爐渣的融點來確保流動性的觀點而言是有效的。但是，這種狀態下的話，Fe的良率較低，再對於爐渣進行還原處理，以使得因熔解而分離後之爐渣中的總含鐵濃度(%T.Fe)落在20質量%以下、更好是落在10質量%以下、更優是落在5質量%以下為佳。還原手段則可以採用下列(a)(b)(c)的其中一種或其組合，(a)是將至少含有C、Al、Si等的還原材的其中一種以上之固體供給到所生成且浮上來的爐渣；(b)是使用至少含有CO、H 2、碳化氫等的還原性氣體的其中一種以上之氣體來作為供給到熔融鐵內的氣體；(c)是在製造還原鐵的時點增加還原材的原單位。 As can be seen from FIG. 2, the slag component contained in the reduced iron contains a high concentration of FeO, which is effective from the viewpoint of lowering the melting point of the slag to ensure fluidity. However, in this state, the yield of Fe is low, and the slag is further reduced so that the total iron content (%T.Fe) in the slag after separation by melting is less than 20 mass%, more preferably less than 10 mass%, and more preferably less than 5 mass%. The reduction means may be one of the following (a), (b), or (c), or a combination thereof: (a) supplying at least one solid of reducing materials such as C, Al, Si, etc. to the generated and floating slag; (b) using at least one reducing gas such as CO, H2 , hydrogen carbide, etc. as the gas supplied to the molten iron; (c) increasing the raw unit of reducing materials at the time of producing reduced iron.
本發明的第四實施方式，係根據上述的檢討而獲得的，係就第一至第三實施方式的任何一種實施方式，在熔解步驟中包含了供給一種以上之還原性的固體或氣體之第4工序。此外，本發明的第五實施方式，係就第四實施方式，進行調整還原性之固體或氣體的種類及供給量，以使得在熔解步驟中所生成之爐渣的組成分的總含鐵濃度(%T.Fe)落在20質量%以下。The fourth embodiment of the present invention is obtained based on the above-mentioned examination, and is a fourth step of supplying one or more reducing solids or gases in the melting step, in any one of the first to third embodiments. In addition, the fifth embodiment of the present invention is a fourth embodiment in which the type and supply amount of the reducing solid or gas are adjusted so that the total iron content (%T.Fe) of the components of the slag generated in the melting step falls below 20 mass %.
＜第3工序＞ 為了抑制利用感應加熱熔解爐中之還原鐵熔解所生成之爐渣的溫度降低，還具有：在爐上設置加熱源來對於爐渣進行熱供給的第3工序為佳。作為加熱源，例如：噴火加熱、使用電極的通電加熱、將導電體浸泡在爐渣中進行感應加熱之類的可將爐渣直接進行加熱的手段即可，並不限於此，併用複數種手段也可以。噴火加熱可以採用燃料油等的液體燃料、CO、H 2、碳化氫等的氣體燃料，或者這些燃料的組合。浸泡在爐渣中的導電體，只要是可以利用感應電流來發熱的物體即可，但是基於成本考量，可以將鐵棒、碳棒等予以保持成浸泡在爐渣中的狀態，或者從上方來添加入被製作成：與所生成的爐渣的密度具有同等的表觀密度之還原鐵的粒子來使其滯留在爐渣中。 <Third step> In order to suppress a decrease in the temperature of the slag generated by melting reduced iron in the induction heating melting furnace, it is preferable to have a third step of providing a heating source on the furnace to supply heat to the slag. The heating source may be any means that can directly heat the slag, such as flame heating, electric heating using electrodes, induction heating by immersing a conductor in the slag, etc., but it is not limited to these, and a plurality of means may be used in combination. . Spitfire heating can use liquid fuel such as fuel oil, gaseous fuel such as CO, H 2 , hydrocarbon, or a combination of these fuels. The conductor immersed in the slag can be anything that can be heated by induced current. However, based on cost considerations, iron rods, carbon rods, etc. can be kept in a state of being immersed in the slag, or added from above. It is made so that particles of reduced iron with an apparent density equal to the density of the generated slag are retained in the slag.
＜第六實施方式＞ 原料也就是直接還原鐵的雜質當中含有磷的話，係從熔融鐵將磷予以除去為佳。此外，也會有在熔融鐵中添加所期望的成分之情況。本發明的第六實施方式，就是針對於這種期望而開發完成的。 <Sixth embodiment> If the raw material, i.e., the impurities of the direct-reduced iron, contains phosphorus, it is better to remove the phosphorus from the molten iron. In addition, there is also a case where a desired component is added to the molten iron. The sixth embodiment of the present invention is developed and completed in response to this expectation.
如下列數式(A)所示般地，脫磷反應必須具有氧氣源以及CaO源。 其中，[P]是表示熔融鐵中的磷。例如：作為將雜質中的磷從熔融鐵予以除去的方法，可以對於在熔解步驟中所製得的熔融鐵、或者在排渣步驟中排出爐渣之後的熔融鐵供給氧氣源和CaO源。 As shown in the following mathematical formula (A), the dephosphorization reaction requires an oxygen source and a CaO source. Where [P] represents phosphorus in molten iron. For example, as a method of removing phosphorus among impurities from molten iron, an oxygen source and a CaO source may be supplied to the molten iron produced in the melting step or the molten iron after the slag is discharged in the slag discharge step.
脫磷處理的氧氣源，一般是採用純氧氣體。但是，考慮到脫磷反應是發熱反應所以是在低溫下進行脫磷處理較為有利，因而獲得了：只要是在處理上不會造成問題的範圍內，將熔融鐵溫度降低的作法較為有利之結論。The oxygen source for dephosphorization treatment is generally pure oxygen gas. However, considering that dephosphorization reaction is an exothermic reaction, it is more advantageous to perform dephosphorization treatment at a low temperature. Therefore, it is concluded that it is more advantageous to lower the temperature of the molten iron as long as it does not cause problems in the treatment.
經過檢討後的結果，發現了一種創見，就是：藉由供給空氣或者鐵礦石及/或鐵鏽皮膜等的氧化鐵源來作為氧氣源的話，既可將熔融鐵予以冷卻又可充分地脫磷。如果是利用空氣的話，則是藉由被視為空氣中含有之氮氣的顯熱所進行的散熱，而可獲得對於純氧氣體的冷卻效果。又，如果是利用氧化鐵源的話，當氧化鐵源受到還原而變成金屬Fe或者以氧化鐵的形態來形成熔融爐渣時將會吸熱，藉此，可獲得對於純氧氣體的冷卻效果。As a result of the review, we found a new idea: by supplying air or iron oxide sources such as iron ore and/or iron rust film as an oxygen source, it is possible to cool the molten iron and dephosphorize it sufficiently. If air is used, the sensible heat of nitrogen contained in the air is dissipated, and a cooling effect on pure oxygen gas can be obtained. In addition, if an iron oxide source is used, when the iron oxide source is reduced to metallic Fe or forms molten slag in the form of iron oxide, it absorbs heat, thereby obtaining a cooling effect on pure oxygen gas.
其次，因為石灰石所含的碳酸鈣在分解成CaO與CO 2時將會吸熱，因此，如果使用石灰石作為CaO源的話，也可將熔融鐵予以冷卻。同樣的冷卻效果，雖然也可以藉由供給原白雲石之類的碳酸鹽而獲得，但是，如果副原料中之CaO的比率降低的話，將會衍生出：需要添加之副原料的量會變多，爐渣生成量會增大，添加時所需花費的時間會變長等等，在實際作業上的課題，因此，先考慮想要謀求的冷卻效果與穩定的作業性之後，再來調整想要添加之副原料的種類和量為宜。 Secondly, because the calcium carbonate contained in limestone will absorb heat when it decomposes into CaO and CO2 , if limestone is used as the CaO source, the molten iron can also be cooled. The same cooling effect can also be obtained by supplying carbonates such as raw dolomite. However, if the ratio of CaO in the auxiliary raw material is reduced, it will derive: the amount of the auxiliary raw material that needs to be added will increase. , the amount of slag generated will increase, the time required for addition will become longer, etc., which are issues in actual operations. Therefore, first consider the desired cooling effect and stable workability, and then adjust the desired The type and amount of auxiliary raw materials added are appropriate.
依據用來實施脫磷處理之容器的自由空間(從熔融鐵的上表面位置至容器上端位置的高度)及/或上位氣體噴槍之噴嘴的形狀的不同，所發生的噴濺行為也不同，因此，係配合脫磷處理的實際作業狀況來調整純氧或空氣的供給速度及/或噴槍的高度為宜。此外，為了使熔融鐵獲得攪拌作用，也可以吹入惰性氣體。可以設置多氣孔塞及/或噴槍來吹入惰性氣體。爐渣鹼度是落在1.5～4.0的範圍為宜，係可藉由調整：排渣步驟所殘留下來之含有較多SiO 2之爐渣的量、所添加之CaO源的種類及量來調整爐渣鹼度。也可以配合需要而添加矽石及/或矽鐵之類的SiO 2源及/或生石灰之類的CaO源。 Depending on the free space of the container used for dephosphorization (the height from the upper surface of the molten iron to the upper end of the container) and/or the shape of the nozzle of the upper gas lance, the splashing behavior will be different. Therefore, it is appropriate to adjust the supply rate of pure oxygen or air and/or the height of the lance in accordance with the actual working conditions of the dephosphorization. In addition, in order to stir the molten iron, inert gas may be blown in. A multi-hole plug and/or a lance may be provided to blow inert gas. The alkalinity of the slag is preferably in the range of 1.5 to 4.0, which can be adjusted by adjusting: the amount of slag containing more SiO2 left after the deslagging step, the type and amount of the added CaO source. SiO2 sources such as silica and/or ferrosilicon and/or CaO sources such as quicklime can also be added as needed.
此外，爐渣鹼度太低的話，實施脫磷處理所達成之除磷量也會變小。爐渣鹼度太高的話，當熔融鐵溫度降低時，將會有部分的爐渣凝固而附著到耐火物上，因而導致在脫磷處理之後難以除去爐渣，進而可能會發生：在下一次的脫磷處理時，載入熔融鐵的時候產生異常反應，或者殘留爐渣混入新生成爐渣之中而成為脫離爐渣成分範圍的原因之類的問題。又，這種使用空氣的脫磷處理，將會產生大量之高溫的排放氣體，因此，也可使用鍋爐等來將排熱予以回收。In addition, if the alkalinity of the slag is too low, the amount of phosphorus removal achieved by the dephosphorization treatment will also become smaller. If the basicity of the slag is too high, when the temperature of the molten iron decreases, part of the slag will solidify and adhere to the refractory, making it difficult to remove the slag after the dephosphorization treatment. This may lead to: Problems such as an abnormal reaction occurring when molten iron is loaded, or residual slag being mixed into newly generated slag causing the slag composition to deviate from the range. In addition, this kind of dephosphorization treatment using air will generate a large amount of high-temperature exhaust gas, so a boiler or the like can also be used to recover the exhaust heat.
此外，以上述的實施方式製得的熔融鐵，也可以直接就進入下一個工序進行精煉變成具有必要的成分之熔鋼。也可以先注入型模內進行凝固來製造成固體鐵，運送到需求地點之後，再熔解之後進行精煉而成為熔鋼。前者的情況下，無需實施凝固和再熔解的工序，因此雖然在節能上有優勢，但是，必須連續地配置：還原鐵製造廠、感應加熱熔解爐、精煉設備，如果想要將其設置在既有的製鐵廠的話，會發生場地受到制約的情事。或者，如果全部都全新設置的話，不僅需要龐大的費用，也無法活用既有的設備。後者的情況下，係可將：還原鐵製造廠、感應加熱熔解爐及凝固設備、再熔解設備及精煉設備予以分離，例如：從製造還原鐵起迄凝固的工序，係可以在出產鐵礦石的國家實施，再將凝固鐵運送到需求地點，進行再熔解和精煉。這種情況，不僅可活用既有的精煉設備，還能夠以減掉鐵礦石中所含的脈石成分重量後的狀態之凝固鐵來進行運送，因而對於降低運輸成本也有助益。至於要選擇採用哪一種構成方式的製程，只要考慮事業單位的位置及/或其所具有的設備等之因素來做合宜的選擇即可。In addition, the molten iron produced in the above-described embodiment may be directly refined into the next step to become molten steel having necessary components. It can also be injected into a mold and solidified to produce solid iron. After being transported to the required location, it can be melted and refined to become molten steel. In the former case, there is no need to perform solidification and remelting processes, so although it is advantageous in terms of energy saving, it must be continuously arranged: reduced iron manufacturing plant, induction heating melting furnace, and refining equipment. If you want to install them in an existing location. In some ironworks, the space may be restricted. Or, if everything is newly installed, it will not only require huge expenses, but also make it impossible to utilize the existing equipment. In the latter case, the reduced iron manufacturing plant, induction heating melting furnace and solidification equipment, remelting equipment and refining equipment can be separated. For example, the process from manufacturing reduced iron to solidification can be carried out in the production of iron ore. Implemented by the country, the solidified iron is then transported to the demand location for re-melting and refining. In this case, existing refining equipment can be utilized, and solidified iron can be transported in a state minus the weight of the gangue component contained in the iron ore, which is also helpful in reducing transportation costs. As for which type of manufacturing process to use, you only need to consider factors such as the location of the business unit and/or the equipment it has to make an appropriate choice.
本發明的第六實施方式，係根據上述的檢討而獲得的，係就第一至第五實施方式的任何一種實施方式，還具備了將熔解步驟所製得的熔融鐵進行精煉的精煉步驟。該精煉步驟是在排渣步驟之後才實施為宜。The sixth embodiment of the present invention is obtained based on the above review, and is any one of the first to fifth embodiments, further including a refining step of refining the molten iron produced in the melting step. This refining step is preferably implemented after the slag removal step.
＜第七實施方式＞ 本發明的第七實施方式，係將利用上述第一至第六實施方式的任一種實施方式所提供的直接還原鐵的熔解方法所製得的熔融鐵予以凝固而做成固體鐵。該固體鐵的總含鐵濃度T.Fe是在93質量%以上，且氧化物成分的合計是在3質量%以下為佳。又，用來讓固體鐵凝固之鑄模的形狀及/或大小雖然沒有限制，但是，考量到後續的貨物裝卸、包裝、搬運、供給到使用設備時的方便性等的各種因素，將固體鐵凝固成粒徑為10～100mm之範圍內的粒狀固體鐵為佳。 <Seventh embodiment> The seventh embodiment of the present invention is to solidify the molten iron obtained by the melting method of direct reduction iron provided by any one of the first to sixth embodiments to make solid iron. The total iron concentration T.Fe of the solid iron is preferably above 93 mass %, and the total oxide component is preferably below 3 mass %. In addition, although the shape and/or size of the casting mold used to solidify the solid iron is not limited, it is preferred to solidify the solid iron into granular solid iron with a particle size range of 10 to 100 mm in consideration of various factors such as the convenience of subsequent cargo loading and unloading, packaging, transportation, and supply to the equipment used.
＜第八實施方式＞ 本發明的第八實施方式，係活用作為副產品的爐渣當作土木建築用資材。亦即，還具備：將上述第一實施方式的排渣步驟所排出的爐渣冷卻硬化而做成土木建築用資材原料之冷卻硬化步驟。冷卻硬化後的爐渣，係落在上述鹼度範圍內，並且依照冷卻方法的不同而具有各種的粒度分布，可配合需求來進行追加的破碎和分級處理等之粒度調整處理，而可作為利用其特性的資材來使用。例如：將所排出的爐渣進行水碎處理的話，將變成細微的玻璃狀，比表面積落在0.35m 2/g以上且低於0.50m 2/g，因此，可以作為水泥原料(結合材)來使用。此外，如果是在大氣中進行緩慢冷卻，且配合其使用用途來調整其粒度的話，可作為路基材及/或混凝土骨材來使用。是以，冷卻硬化的方法係配合所排出之爐渣之使用目的，由事業單位做合宜的選定即可。 [實施例] <Eighth Embodiment> The eighth embodiment of the present invention is to utilize the slag produced as a by-product as a civil engineering material. That is, it further comprises a cooling and hardening step of cooling and hardening the slag discharged in the slag discharge step of the first embodiment to make it a raw material for civil engineering materials. The slag after cooling and hardening falls within the above alkalinity range and has various particle size distributions depending on the cooling method. It can be subjected to additional particle size adjustment treatment such as crushing and classification treatment according to needs, and can be used as a material utilizing its characteristics. For example, if the discharged slag is subjected to water crushing treatment, it becomes fine glass, and the specific surface area falls between 0.35m2 /g and less than 0.50m2 /g, so it can be used as a cement raw material (binder). In addition, if it is slowly cooled in the atmosphere and its particle size is adjusted according to its use, it can be used as a road base material and/or concrete aggregate. Therefore, the cooling and hardening method is to be selected appropriately by the business unit in accordance with the use purpose of the discharged slag. [Example]
(實施例1) 使用內徑為0.9m且從爐底至出湯槽道的下端為止的高度為1.8m的感應加熱熔解爐，預先進行熔解0.5公噸的種湯(預熔鐵水)，再將表2所示的還原鐵C添加到爐內，並且不要讓鐵水從爐體溢流出來，確認了正在進行熔解且爐內的原料堆積高度已經下降之後，反覆地從設在上部的料斗進行添加還原鐵，直到還原鐵的合計添加量達到5.0公噸為止。該感應加熱熔解爐是建構成：在爐底之間距圓直徑(PCD)為0.3m及0.6m的位置處，分別等間隔地設置有六個底吹噴嘴，並且可透過氣體供給頭，對於依照需求來組合的噴嘴分別供給相同流量的氣體。在爐上方設置了可供給副原料的料斗，可以在處理過程中之所需的時間點，以10kg為單位進行副原料的供給。以適當的次數測定爐內之熔融鐵的溫度，並以溫度保持在1600±20℃的方式來控制感應加熱熔解爐的輸入電力以及調整還原鐵、副原料的供給速度。 (Example 1) An induction heating melting furnace with an inner diameter of 0.9m and a height of 1.8m from the furnace bottom to the lower end of the soup outlet was used to melt 0.5 metric tons of seed soup (pre-melted molten iron) in advance, and then add the liquid as shown in Table 2 Add the reduced iron C into the furnace without letting the molten iron overflow from the furnace body. After confirming that melting is in progress and the raw material accumulation height in the furnace has dropped, repeatedly add the reduced iron from the hopper at the top until The total amount of reduced iron added reaches 5.0 metric tons. The induction heating melting furnace is constructed in such a way that six bottom blowing nozzles are provided at equal intervals between the furnace bottoms at positions where the distance circle diameter (PCD) is 0.3m and 0.6m, and the gas supply head is permeable. The combined nozzles are required to supply the same flow rate of gas respectively. A hopper for supplying auxiliary raw materials is installed above the furnace. The auxiliary raw materials can be supplied in units of 10kg at the required time point during the treatment process. The temperature of the molten iron in the furnace is measured an appropriate number of times, and the input power of the induction heating melting furnace is controlled and the supply speed of reduced iron and auxiliary raw materials is adjusted to maintain the temperature at 1600±20°C.
並且實施了：變更了來自噴嘴所供給的氣體流量以及所添加之副原料的種類和數量之熔解處理。作為副原料使用的生石灰，係採用：將石灰石進行高溫烘焙而除去CO 2之後的生石灰，CaO的濃度近乎100質量%。矽石係採用：將碎石場所採取的矽石經過粉碎處理後的細矽石，SiO 2的濃度約98質量%，只含有少量的Al 2O 3及MgO。鋁礬土係採用：將作為提煉Al用的原料而輸入的礦石經過粉碎處理後的鋁礬土，Al 2O 3的濃度約50質量%，剩餘部分是含有被視為雜質的結晶水、SiO 2、TiO 2等。熔解處理之後，將爐體傾倒而完全地排出爐內的熔融鐵，對於排出之鐵水的重量進行秤重。此外，採取了爐渣將其進行粉碎至53μm以下，供實施化學分析使用。將所獲得的數値與處理條件一起標示於表3-1及表3-2。此外，為了進行比較，也以未從爐底供給氣體的條件來實施了熔解處理。 In addition, the melting process was implemented by changing the gas flow rate supplied from the nozzle and the type and amount of the auxiliary materials added. The quicklime used as the auxiliary material is the quicklime obtained by high-temperature baking of limestone to remove CO2 , and the CaO concentration is nearly 100% by mass. The silica is fine silica obtained by crushing silica taken from the crushing site, and the SiO2 concentration is about 98% by mass, containing only a small amount of Al2O3 and MgO. The alumina is the alumina obtained by crushing the ore imported as the raw material for refining Al, and the Al2O3 concentration is about 50% by mass, and the rest contains crystal water, SiO2 , TiO2 , etc., which are considered impurities. After the melting process, the furnace body was tilted to completely discharge the molten iron in the furnace, and the weight of the discharged molten iron was weighed. In addition, the slag was taken and crushed to less than 53μm for chemical analysis. The obtained values are shown in Table 3-1 and Table 3-2 together with the treatment conditions. In addition, for comparison, the melting process was also carried out under the condition that the gas was not supplied from the bottom of the furnace.
表3-2中所標示之關於爐渣流動性的判定基準如下：從設在爐上的視窗觀察爐內的爐渣表面，如果是整體上呈現赤熱且高溫的爐渣一直保持循環狀態的話，就予以標示為○；如果是其中有一部分呈現焦黑的固體狀態，但是固體狀態的爐渣一直都保持在鐵水表面移動狀態的話，就予以標示為△；如果是全體上呈現焦黑只有龜裂的部分呈現赤熱的程度且爐渣處於停滯狀態的話，就予以標示為×。此處，在爐渣流動性標示為○的條件下，從開始添加5.0公噸的還原鐵到完全熔解且為了倒出鐵水而開始將爐體傾倒為止的時間是在90分鐘以內，相對於此，在爐渣流動性標示為△的條件下，所耗費的時間是較諸90分鐘更長。這個差異是因為有一部分爐渣變成了固體，在排渣步驟中爐渣往出湯口移動需要較長的時間的緣故。在爐渣流動性標示為×的條件下，即使追加載入還原鐵及副原料，也都是只是堆積在已經凝固後的爐渣表面上，沒有進入到熔融鐵的內部，只有最初被載入到爐內的還原鐵熔解而已。The criteria for judging the fluidity of slag indicated in Table 3-2 are as follows: Observe the surface of the slag in the furnace through the window on the furnace. If the slag is red-hot as a whole and the high-temperature slag is always in a circulating state, it is marked as ○; if a part of the slag is in a charred solid state, but the solid slag is always in a moving state on the surface of the molten iron, it is marked as △; if the slag is charred as a whole and only the cracked part is red-hot and is in a stagnant state, it is marked as ×. Here, under the condition of slag fluidity marked as ○, the time from the start of adding 5.0 tons of reduced iron to complete melting and the start of tipping the furnace body to pour out the molten iron is within 90 minutes. In contrast, under the condition of slag fluidity marked as △, the time consumed is longer than 90 minutes. This difference is because part of the slag has become solid, and it takes a longer time for the slag to move to the soup outlet in the slag discharge step. When the slag fluidity is marked as ×, even if additional reduced iron and auxiliary materials are added, they are only accumulated on the surface of the solidified slag and do not enter the interior of the molten iron. Only the reduced iron initially loaded into the furnace is melted.
就處理No.1～19而言，其爐渣流動性的評比都是標示為○或者△，相對地，處理No.20之爐渣流動性的評比是標示為×。處理No.20被認為是：因為並未從爐底供給氣體，由熔融鐵對於爐渣的熱供給不足而導致爐渣已經凝固。處理No.1～19都是有進行供給氣體，因此，無論爐渣是哪一種組成分，都保持爐渣流動性，因而可進行排渣。此外，從表3-1及表3-2可以看出，符合上述數式(1)及數式(2)的條件，爐渣的鹼度C/S落在0.5以上且2.0以下的範圍內，且換算成CaO-SiO 2-Al 2O 3之三元系之爐渣中的Al 2O 3濃度落在10質量%以上且25質量%以下的範圍時，具有特別良好的爐渣流動性。 For treatments No. 1 to 19, the slag fluidity ratings are all marked as ○ or Δ. In contrast, the slag fluidity ratings for treatment No. 20 are marked as ×. In Process No. 20, it is considered that the gas was not supplied from the furnace bottom and the heat supply to the slag from the molten iron was insufficient, causing the slag to solidify. Gas is supplied in Process Nos. 1 to 19. Therefore, regardless of the composition of the slag, the fluidity of the slag is maintained and slag discharge can be performed. In addition, it can be seen from Table 3-1 and Table 3-2 that the conditions of the above equations (1) and (2) are met, and the basicity C/S of the slag falls in the range of 0.5 or more and 2.0 or less. Furthermore, when the Al 2 O 3 concentration in the slag converted into the ternary system of CaO-SiO 2 -Al 2 O 3 falls within the range of 10 mass % or more and 25 mass % or less, the slag fluidity is particularly good.
處理No.13～15之從爐底供給的氣體量太多，因此發生了前述的「空廊現象」，熔融鐵的飛濺很顯著。其結果，倒出來的鐵水的金屬量與其他的發明例相較，較為低品位。處理No.16是添加了過多的生石灰，其結果是爐渣鹼度C/S超過2.0，爐渣的融點上昇而導致流動性變差，排渣時間變長。處理No.17是添加了過多的矽石，其結果，爐渣鹼度C/S低於0.5，爐渣的黏度上昇而導致流動性變差，排渣時間變長。處理No.18是添加了過多的鋁礬土，因此其結果，換算成CaO-SiO 2-Al 2O 3之三元系之Al 2O 3的濃度超過25質量%，爐渣的融點上昇而導致流動性變差，排渣時間變長。處理No.19是添加了過多的生石灰與矽石的結果，換算成CaO-SiO 2-Al 2O 3之三元系之Al 2O 3的濃度被稀釋成低於5質量%，爐渣的融點上昇而導致流動性變差，排渣時間變長。 In treatments No. 13 to 15, the amount of gas supplied from the bottom of the furnace was too much, so the aforementioned "empty corridor phenomenon" occurred, and the splashing of molten iron was very significant. As a result, the amount of metal in the poured molten iron was lower than that of other invention examples. In treatment No. 16, too much quicklime was added, and as a result, the alkalinity C/S of the slag exceeded 2.0, the melting point of the slag increased, resulting in poor fluidity and a longer slag discharge time. In treatment No. 17, too much silica was added, and as a result, the alkalinity C/S of the slag was less than 0.5, the viscosity of the slag increased, resulting in poor fluidity and a longer slag discharge time. Treatment No. 18 is the result of adding too much alumina, so the concentration of Al 2 O 3 in the ternary system of CaO-SiO 2 -Al 2 O 3 exceeds 25% by mass, the melting point of the slag rises, resulting in poor fluidity and a longer slag discharge time. Treatment No. 19 is the result of adding too much quicklime and silica, the concentration of Al 2 O 3 in the ternary system of CaO-SiO 2 -Al 2 O 3 is diluted to less than 5% by mass, the melting point of the slag rises, resulting in poor fluidity and a longer slag discharge time.
此外，確認了副原料並不侷限於生石灰、矽石、鋁礬土，利用上述以外的其他之物質來控制爐渣組成分也沒有問題。並且也得知副原料的添加時期，是在從開始熔解至結束熔解的期間內，分階段來進行添加更好。其原因被認為是因為：如果在開始熔解後隨即添加大量的副原料的話，將會妨礙還原鐵與還原鐵之間，或者還原鐵與種湯(預熔鐵水)之間的接觸，感應加熱的效率不佳而導致所需的熔解時間增大。此外，其他的問題點是：此時，熔解結束後就已經有爐渣生成，依據組成分的不同，有些爐渣已經凝固了，即使再添加副原料，也都成為只是置放在已經凝固之爐渣的上面的狀態而已，無助於使爐渣低融點化。In addition, it was confirmed that the auxiliary raw materials are not limited to quicklime, silica, and bauxite, and there is no problem in using other substances other than the above to control the slag composition. It was also found that the addition period of the auxiliary raw materials is from the beginning to the end of melting, and it is better to add them in stages. The reason is thought to be that if a large amount of auxiliary raw materials are added immediately after the start of melting, it will hinder the contact between reduced iron and reduced iron, or between reduced iron and seed soup (pre-melted molten iron), and induction heating will be inhibited. Poor efficiency results in increased melting time. In addition, other problems are: at this time, slag has already been generated after the melting is completed. Depending on the composition, some slag has solidified. Even if auxiliary raw materials are added, they will only be placed on the solidified slag. The above state is just the above, and it does not help to lower the melting point of the slag.
即使沒有種湯(預熔鐵水)，也可以進行還原鐵的熔解，但是，有種湯(預熔鐵水)的話，可以從已經被感應加熱的種湯(預熔鐵水)將熱供給到固體的還原鐵，其結果，可以縮短熔解還原鐵所需的時間，因此有種湯(預熔鐵水)比較好。相對於所投入的還原鐵，具有5質量%程度以上的種湯(預熔鐵水)特別有效，然而，種湯(預熔鐵水)太多的話，對於感應加熱熔解爐的容積所佔據的比率增加，而導致可進行熔解之還原鐵的量變少，因此將種湯(預熔鐵水)的比率設定在所投入之還原鐵的70質量%以下為宜。又，種湯(預熔鐵水)可以藉由將表觀密度較大的回收廢料及/或大鐵塊予以重新熔解來製作，除此之外，也可以將前一次的熔解處理時之已經熔解後的熔融鐵的一部分預先殘留在爐內。Reduced iron can be melted even if there is no seed soup (pre-melted iron). However, if there is a seed soup (pre-melted iron), heat can be supplied from the seed soup (pre-melted iron) that has been induction heated. As a result, the time required to melt the reduced iron can be shortened, so it is better to use a kind of soup (pre-melted molten iron). A seed soup (pre-melted iron) containing about 5 mass % or more of the input reduced iron is particularly effective. However, if there is too much seed soup (pre-melted iron), the capacity of the induction heating melting furnace will be occupied. As the ratio increases, the amount of reduced iron that can be melted decreases. Therefore, it is appropriate to set the ratio of the seed soup (premelted molten iron) to 70 mass % or less of the input reduced iron. In addition, seed soup (pre-melted molten iron) can be made by re-melting recycled scraps and/or large iron blocks with a relatively high apparent density. In addition, the molten iron that has been melted during the previous melting process can also be made. A part of the melted molten iron remains in the furnace.
此外，實施了將噴嘴的位置及/或組合變更後的處理，無論是哪一種位置及/或組合方式，只要對於每一個噴嘴所供給的氣體量是符合上述數式(2)之條件的話，即可確保爐渣的流動性，並且熔融鐵的飛濺很少，相對地，如果沒有符合數式(2)之條件的話，熔融鐵的飛濺增加，金屬的良率變差。In addition, the process of changing the position and/or combination of the nozzles is performed. Regardless of the position and/or combination, as long as the amount of gas supplied to each nozzle satisfies the condition of the above equation (2), This ensures the fluidity of the slag and reduces the splash of molten iron. On the other hand, if the conditions of equation (2) are not met, the splash of molten iron increases and the metal yield deteriorates.
此外，也確認出：噴嘴的位置不是設在爐底而是設在爐的側面也沒有問題。但是從設在爐的側面的噴嘴至爐底的距離h較大，亦即，如果H高度值太小的話，符合數式(2)之氣體供給速度將會降低，難以有效地將熔融鐵的熱傳遞到爐渣，因此，還是儘量地將噴嘴的位置選定在爐底或爐底附近為佳。In addition, it was also confirmed that there is no problem in locating the nozzle not at the bottom of the furnace but at the side of the furnace. However, the distance h from the nozzle on the side of the furnace to the bottom of the furnace is relatively large. That is, if the H height value is too small, the gas supply speed consistent with equation (2) will be reduced, making it difficult to effectively transfer the molten iron. Heat is transferred to the slag, so it is better to position the nozzle at or near the furnace bottom as much as possible.
(實施例2) 採用與實施例1相同的感應加熱爐，來實施對於含在生成爐渣中的FeO成分所進行的還原處理。從底吹噴嘴供給CO、H 2及CH 4的氣體當作還原材，氣體還原材的供給時間固定為90分鐘。並且分別實施了從上方來對於生成爐渣進行添加固體C、金屬Al及金屬Si來作為固體還原材的還原處理。此處，以金屬Al及金屬Si來進行還原處理的話，生成爐渣的鹼度及Al 2O 3的濃度會產生變化，因此，乃添加了生石灰或矽石來當作副原料，以調整爐渣鹼度及Al 2O 3的濃度。還原處理之後，將爐體傾倒而完全地排出爐內的熔融鐵，對於排出之鐵水的重量進行秤重。此外，採取了爐渣將其進行粉碎至53μm以下，供實施化學分析使用。將所獲得的數値與處理條件一起標示於表4-1及表4-2。 (Example 2) The same induction heating furnace as in Example 1 was used to perform a reduction treatment on the FeO component contained in the generated slag. The gases of CO, H2 and CH4 supplied from the bottom blow nozzle are used as reducing materials, and the supply time of the gas reducing materials is fixed at 90 minutes. Furthermore, a reduction process was performed from above by adding solid C, metal Al, and metal Si as solid reducing materials to the generated slag. Here, if metal Al and metal Si are used for reduction treatment, the alkalinity of the generated slag and the concentration of Al 2 O 3 will change. Therefore, quicklime or silica is added as an auxiliary raw material to adjust the slag alkali. degree and the concentration of Al 2 O 3 . After the reduction treatment, the furnace body is tilted to completely discharge the molten iron in the furnace, and the weight of the discharged molten iron is weighed. In addition, slag was collected and ground to less than 53 μm for chemical analysis. The obtained numerical values are shown in Table 4-1 and Table 4-2 together with the processing conditions.
可以得知：在處理No.21～27之供給還原性氣體的條件中，與實施例1的處理No.4相較，金屬出湯量(鐵水量)有增加，爐渣中的T.Fe濃度有降低。亦即，可以證明：氣體還原材對於生成爐渣中FeO的還原很有助益。此外，將處理No.23～27進行比較的話，可以得知：因為所供給之還原性氣體(CH 4)的供給量增加，所以爐渣中的T.Fe降低，金屬出湯量(鐵水量)有增加。 It can be seen that under the reducing gas supply conditions of Process Nos. 21 to 27, compared with Process No. 4 of Example 1, the amount of metal soup (amount of molten iron) increased, and the T.Fe concentration in the slag increased. reduce. In other words, it was proved that the gas reducing material is very helpful for the reduction of FeO in the generated slag. In addition, when processing Nos. 23 to 27 are compared, it can be seen that since the supply amount of the reducing gas (CH 4 ) is increased, the T.Fe in the slag is reduced, and the amount of metal soup (the amount of molten iron) is reduced. Increase.
此外，也得知：即使在處理No.28～30之添加固體還原材的條件中，與實施例1的處理No.4相較，金屬出湯量(鐵水量)有增加，爐渣中的T.Fe濃度有降低。可以證明：與氣體還原氣體同樣地，固體還原材對於生成爐渣中FeO的還原很有助益。In addition, it was also found that even under the conditions of adding solid reducing materials in Treatment Nos. 28 to 30, compared with Treatment No. 4 of Example 1, the amount of metal soup (the amount of molten iron) increased, and the T in the slag. Fe concentration decreased. It was proven that, like the gas reducing gas, the solid reducing material contributes to the reduction of FeO in the generated slag.
此外，也針對改變了還原材的種類及組合、添加量、添加時機等的條件來進行各種的評比，與未添加還原材的條件相較，都是有增加金屬出湯量(鐵水量)，爐渣中的T.Fe濃度都有降低。相對於用來製造熔融鐵之本發明技術之目的，藉由供給還原材來改善鐵的良率，最好是以可使得爐渣中的T.Fe濃度降低到20質量%以下、更好是降低到10質量%以下、更優是降低到5質量%以下的方式，來對於爐渣進行還原處理為佳。然而，隨著還原的進行，所供給之還原材的利用效率將會降低，因此，預先考量還原鐵、副原料及還原材的組成分與價格之後，才決定選擇哪一種處理方法是很重要的作法。In addition, various evaluations were conducted based on the conditions where the type and combination of reducing materials, addition amount, addition timing, etc. were changed. Compared with the conditions without adding reducing materials, the amount of metal soup (the amount of molten iron) and the amount of slag increased. The T and Fe concentrations in the samples were reduced. For the purpose of the technology of the present invention for producing molten iron, the iron yield is improved by supplying reducing materials, preferably in such a way that the T.Fe concentration in the slag can be reduced to 20 mass % or less, more preferably, It is better to reduce the slag to less than 10% by mass, and more preferably to less than 5% by mass, to reduce the slag. However, as reduction proceeds, the utilization efficiency of the supplied reducing materials will decrease. Therefore, it is important to consider the composition and price of reduced iron, auxiliary raw materials, and reducing materials before deciding which treatment method to choose. practice.
(實施例3) 先將實施例1及2所製得的熔融鐵調整溫度之後，予以移載到鍋型的容器內。此時，將因為還原鐵所含的脈石而在感應加熱熔解爐進行熔解時所生成的爐渣之中，以約10kg/每公噸熔融鐵之比率的爐渣與熔融鐵一起移載到鍋型的容器，其餘的爐渣移載到其他的爐渣容器。然後，將鍋型的容器移動到脫磷處理設備，並且改變所供給之氧氣源與石灰源的種類及供給量來進行脫磷處理。脫磷處理設備係具有：上位氣體噴槍、副原料分開供給料斗、底吹型多氣孔塞。從上位氣體噴槍係可以約1Nm 3/(每分鐘暨每公噸熔融鐵)的速度來供給含有純氧或空氣的氣體。副原料分開供給料斗係有三座，分別充填著：鐵礦石、生石灰(CaO)、碳酸鈣(CaCO 3)，分別能夠以約10kg/分鐘的速度進行供給。從底吹型多氣孔塞係能夠供給氣體，本實施例以約0.1Nm 3/(每分鐘暨每公噸熔融鐵)的速度來供給純Ar氣體。 (Example 3) After adjusting the temperature of the molten iron produced in Examples 1 and 2, it was transferred to a pot-shaped container. At this time, among the slag generated when the gangue contained in the reduced iron is melted in the induction heating melting furnace, the slag at a ratio of approximately 10 kg/ton of molten iron is transferred to the pot-type pot together with the molten iron. container, and the remaining slag is transferred to other slag containers. Then, the pot-shaped container is moved to the dephosphorization treatment equipment, and the type and supply amount of the supplied oxygen source and lime source are changed to perform dephosphorization treatment. The dephosphorization treatment equipment system includes: an upper gas spray gun, a separate auxiliary raw material supply hopper, and a bottom-blowing multi-hole plug. Gas containing pure oxygen or air can be supplied from an upper gas lance system at a rate of approximately 1 Nm 3 /(per minute per metric ton of molten iron). There are three separate supply hoppers for auxiliary raw materials, which are respectively filled with: iron ore, quicklime (CaO), and calcium carbonate (CaCO 3 ), and can be supplied at a speed of about 10kg/minute. Gas can be supplied from a bottom-blown porous plug system. In this embodiment, pure Ar gas is supplied at a rate of approximately 0.1 Nm 3 /(per minute per metric ton of molten iron).
以將脫磷處理前的熔融鐵溫度保持在1590℃程度的方式，來調整了在感應加熱熔解爐內的熔解溫度。在即將使上位氣體噴槍下降之前的時間點、以及在完成處理後將上位氣體噴槍上昇完畢之後的時間點，分別視為：脫磷處理的前後，分別都使用熔斷型熱電偶測溫槍來實施測溫暨採樣。採樣出來的樣本經過切斷和研磨之後，利用發光分光分析法且根據預先製作好的基準測量線，針對於熔融鐵中的碳濃度[C]及磷濃度[P]進行了評比。此外，可測定在以熔斷型熱電偶測溫槍進行測溫暨採樣的時間點之鐵水的凝固溫度，並且也實際測定了脫磷處理後之熔融鐵的凝固溫度T m。 The melting temperature in the induction heating melting furnace was adjusted so that the temperature of the molten iron before dephosphorization was maintained at approximately 1590°C. The time points immediately before lowering the upper gas lance and the time point after the upper gas lance is raised after completion of the treatment are regarded as: before and after the dephosphorization treatment, and each is carried out using a fuse-type thermocouple temperature measuring gun. Thermometry and sampling. After the sample was cut and ground, the carbon concentration [C] and phosphorus concentration [P] in the molten iron were evaluated using luminescence spectrometry and based on a pre-made reference measurement line. In addition, the solidification temperature of the molten iron at the time point of temperature measurement and sampling with the fuse-type thermocouple temperature measuring gun can be measured, and the solidification temperature T m of the molten iron after the dephosphorization process can also be actually measured.
將上位氣體噴槍開始下降的時間點視為開始進行脫磷處理，在上位氣體噴槍到達預定的高度之後，就開始進行供給氧氣體源及添加副原料。結束了既定量之氧氣體源及副原料的供給之後，將上位氣體噴槍上昇到達待機位置的時間點視為脫磷處理結束。而這個期間被視為脫磷處理時間t f(分鐘)。 The time when the upper gas spray gun starts to descend is regarded as the start of the dephosphorization process. After the upper gas spray gun reaches a predetermined height, supply of the oxygen gas source and addition of auxiliary raw materials begin. After the supply of the predetermined amount of oxygen gas source and auxiliary raw materials is completed, the time when the upper gas lance is raised to the standby position is deemed to be the end of the dephosphorization process. And this period is regarded as the dephosphorization treatment time t f (minutes).
脫磷處理之後，將鍋型容器傾倒，利用爐渣刮扒機構將熔融鐵上面的爐渣予以除去。採集被除去之爐渣的其中一部分來進行化學分析。然後，利用吊車將鍋型容器往上吊起之後予以傾倒，來將熔融鐵移載到澆鑄用餵料桶，將熔融鐵從澆鑄用餵料桶流下與平台進行碰撞而成為粒滴狀的熔融鐵，使該種熔融鐵落入冷卻水槽內凝固，藉以製造出鐵粒。所製得之鐵粒的粒徑為0.1～30mm。粒度分布為：+0.1mm-1mm佔17.2質量%、+1mm-10mm佔31.3質量%、+10mm-20mm佔38.8質量%、+20mm-30mm佔12.7質量%。此處的「+N-M」係指：N號篩網的篩上且M號篩網的篩下之意。After the dephosphorization treatment, the pot-shaped container is dumped and the slag on the molten iron is removed using the slag scraper mechanism. A portion of the removed slag is collected for chemical analysis. Then, the pot-shaped container is lifted up by a crane and then dumped to transfer the molten iron to the casting feed bucket. The molten iron flows down from the casting feed bucket and collides with the platform to become drop-shaped molten iron. , causing the molten iron to fall into the cooling water tank and solidify, thereby producing iron particles. The particle size of the iron particles produced is 0.1 to 30 mm. The particle size distribution is: +0.1mm-1mm accounts for 17.2 mass%, +1mm-10mm accounts for 31.3 mass%, +10mm-20mm accounts for 38.8 mass%, and +20mm-30mm accounts for 12.7 mass%. "+N-M" here means: above the sieve of No. N sieve and below the sieve of No. M sieve.
脫磷處理後之熔融鐵溫度T f係調整成：較諸脫磷處理前的熔融鐵溫度T i更低，且將爐渣鹼度C/S調整在1.5～4.0的範圍，將脫磷處理後的熔融鐵溫度T f調整成：較諸該熔融鐵的凝固溫度T m更高20℃以上。其結果，脫磷處理前之熔融鐵的磷濃度[P] i為0.12質量%的程度，降低成脫磷處理後之熔融鐵的磷濃度[P] f為0.02～0.04質量%的程度。而且能夠對於鐵粒的生產性毫無阻礙地製造出固體鐵。 The molten iron temperature T f after the dephosphorization treatment is adjusted to be lower than the molten iron temperature T i before the dephosphorization treatment, and the slag basicity C/S is adjusted to the range of 1.5 to 4.0. The molten iron temperature T f is adjusted to be at least 20°C higher than the solidification temperature T m of the molten iron. As a result, the phosphorus concentration [P] i of the molten iron before the dephosphorization treatment was about 0.12 mass %, and the phosphorus concentration [P] f of the molten iron after the dephosphorization treatment was reduced to about 0.02 to 0.04 mass %. Furthermore, solid iron can be produced without hindering the productivity of iron particles.
此外，也確認出：包含以上述方式製造出來的粒鐵在內，只要將實施例1及實施例2之發明例所生成的熔融鐵予以凝固的話，無論鑄模的大小和形狀如何，都可以製得：總含鐵量T.Fe為93質量%以上，氧化物成分的合計為3質量%以下的固體鐵。鑄模的大小和形狀，只要配合該固體鐵之今後的使用用途來變更即可，但是，考量到後續的貨物裝卸、包裝、搬運、供給到使用設備時的方便性等的各種因素，將固體鐵凝固成10～100mm之範圍內的粒狀固體鐵為佳。Furthermore, it was confirmed that, as long as the molten iron produced by the invention examples of Examples 1 and 2, including the granular iron produced in the above manner, was solidified, solid iron having a total iron content T.Fe of 93 mass % or more and a total oxide content of 3 mass % or less could be produced regardless of the size and shape of the casting mold. The size and shape of the casting mold can be changed in accordance with the future use of the solid iron, but in consideration of various factors such as the convenience of subsequent cargo loading and unloading, packaging, transportation, and supply to the use equipment, it is preferred to solidify the solid iron into granular solid iron within the range of 10 to 100 mm.
實施例1及實施例2之發明例中所生成的爐渣，為了要進行排渣，必須具有所需的流動性。爐渣的鹼度C/S都同樣落在0.5～2.0的範圍，換算成CaO-SiO 2-Al 2O 3之三元系的Al 2O 3濃度則是落在10～25質量%的範圍。並且也確認了：藉由對於熔融爐渣進行水碎處理，使其變成細微的玻璃狀，比表面積是落在0.35m 2/g以上且低於0.50m 2/g的範圍，可作為水泥原料來利用。此外，也確認了：將熔融爐渣在大氣中緩慢冷卻的話，可以製得數百mm程度以下的爐渣塊，將其進行破碎和分級來進行調整到適當的粒度的話，可作為路基材及/或混凝土骨材來利用。 The slag produced in the inventive examples of Embodiment 1 and Embodiment 2 must have the required fluidity in order to discharge the slag. The basicity C/S of the slag also falls in the range of 0.5 to 2.0, and the Al 2 O 3 concentration converted into the ternary system of CaO-SiO 2 -Al 2 O 3 falls in the range of 10 to 25 mass %. It was also confirmed that by subjecting the molten slag to a fine glassy state through water crushing treatment, the specific surface area falls within the range of 0.35m 2 /g or more and less than 0.50m 2 /g, and it can be used as a cement raw material. use. In addition, it was also confirmed that by slowly cooling molten slag in the atmosphere, slag blocks of several hundred mm or less can be obtained. If they are crushed and classified to adjust to an appropriate particle size, they can be used as road base materials and/or Or use concrete aggregate.
在本說明書中，質量的單位「t」是以10 3kg(公噸)來表示。又，附加在體積的單位「Nm 3」中的N是表示氣體的標準狀態，在本說明書中，是以1atm(=101325Pa)、0℃來表示氣體的標準狀態。化學式中的[M]是表示元素M已經熔解在熔融鐵及/或還原鐵中之意。 [產業上的可利用性] In this specification, the unit of mass "t" is expressed in 10 3 kg (ton). In addition, the N in the unit of volume "Nm 3 " represents the standard state of the gas. In this specification, the standard state of the gas is expressed in 1atm (=101325Pa) and 0°C. [M] in the chemical formula means that the element M has been dissolved in molten iron and/or reduced iron. [Industrial Applicability]
根據本發明的直接還原鐵的熔解方法，係在利用感應加熱熔解爐將直接還原鐵進行熔解時，將氣體吹入熔融鐵中以提高爐渣的流動性，而將爐渣與熔融鐵予以分離，可以製造出高品質的固體鐵及副產品，因此，具有產業上的實用價值。According to the direct-reduction iron melting method of the present invention, when the direct-reduction iron is melted in an induction heating melting furnace, gas is blown into the molten iron to improve the fluidity of the slag, and the slag and the molten iron are separated, so that high-quality solid iron and by-products can be produced. Therefore, the method has practical value in industry.
[圖1]係將從表2所揭示的還原鐵組成分所獲得之爐渣的組成分標定在Al 2O 3-CaO-SiO 2的三元系相圖中的圖表。 [圖2]係將從表2所揭示的還原鐵組成分所獲得之爐渣的組成分標定在CaO-SiO 2-FeO的三元系相圖中的圖表。 [Fig. 1] is a graph showing the composition of the slag obtained from the reduced iron composition disclosed in Table 2, mapped onto the Al2O3 - CaO - SiO2 ternary phase diagram. [Fig. 2] is a graph showing the composition of the slag obtained from the reduced iron composition disclosed in Table 2, mapped onto the CaO- SiO2 -FeO ternary phase diagram.
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