201224155 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種高爐（Blast Furnace)之保護方 法，且特別是有關於一種高爐之爐床(Hearth)的保護方法。 【先前技術】 高爐大修的費用龐大，因此為了降低成本，各鋼鐵廠 莫不致力於延長高爐之爐代壽命。高爐之爐代壽命主要取 ^於高爐内耐火磚之殘留厚度。特別是爐床與爐底碳碑在 高爐運轉期間，長期受到液態鐵渣流動的沖刷、化學熔蝕 與熱的作用而逐漸損耗。爐床與爐底碳磚受損情況嚴重 時L其並無法在高爐運轉期間進行修補。因此，爐床與爐 底石反磚的殘厚往往成為爐代壽命的主要決定因素。 目前，為延長高爐之爐代壽命，最常見的做法就是藉 由含鈦物質的添加，並配合提升冷卻效果，來促進凝固層 的形成。所形叙凝固層具有阻絕侧，賴 較持久’且具衫必降產操作的優點。因此，此種方法^ 廣泛地應用在高爐之爐床的保護上。 然而，鈦的添加雖然可提供護爐的效果，但也產生了 負面的〜響。鈦的添加會造成渣與鐵水之黏度提高， 使鐵水的流動性變差，因此 鈦外加置比較尚時，會影響高 π a、。而且，鐵水中鈦含量的提升不僅會影響加 鐵的表面品質，也會影響產品之勒性、延展性與銲 此外’黏度高之難也容易_在爐蕊(Dead_)之焦 201224155 碳表面上，如此將導致焦碳間的間隙減少， ^ 之透氣性與透液性均變差，而影響出 而，致爐咖 物質價格較為昂貴，因此鈦的過量添加也;導== 太 的大幅增加。 冑導致用枓成本 【發明内容】 伴一態樣就是在提供一種高爐之爐床的 哲 添加物中力，物質，如此有利 矣=物質之還原’而可提升鈦的使用率’進而可在爐床 順利形成保護層。因此，可大大地強化護爐的效果。 另—態樣是在提供—種高爐之爐床的保護方 二鐵麵物質添加量時，添加含猛物質，藉以提 =查，動性，促進鈦的還原，擴大含㈣質的添加範 圍因此，可有效提高操作的穩定度。 二：明之又一態樣是在提供一種高爐之爐床的保護方 品曾ΐ助於精簡含欽物質的添加’不僅可有效維持產品 °古°擔墟—可使向爐之出鐵與出渣作業順利進行，避免污染 同爐爐焱，進而可使高爐維持正常產能。 =發明之再一態樣是在提供一種高爐之爐床的保護方 成本可大幅降低含鈦物質的使用量，因此可有效降低用料 根，本發明之上述目的’提出一種高爐之爐床的保護 壚侑U列步驟。將一含鈦添加物與煉鐵原料自高爐 =頂t料裝置投入高爐中或經由高爐之鼓風嘴送入高爐 、中，含鈦添加物包含—含鈦物f與—含弼物質，且 201224155 含鈣物質在含鈦添加物中之重量百分比介於1%至8%之 間。使前述之含鈦添加物於高爐内反應生成氮化鈦或碳化 鈦，而在爐床之表面上形成一含鈦保護層。 依據本發明之一實施例，上述之含鈣物質可包含氧化 鈣(CaO)、氫氧化鈣(Ca(OH)2)、碳酸氫鈣（Ca(HC03)2)或碳 酸鈣(CaC03)。 依據本發明之另一實施例，上述之含鈦物質可包含二 氧化鈦(Ti02)。 根據本發明之上述目的，另提出一種高爐之爐床的保 護方法，包含下列步驟。將一含鈦添加物與煉鐵原料自高 爐爐頂之加料裝置投入高爐中或經由高爐之鼓風嘴送入高 爐内。其中，含鈦添加物包含一含鈦物質、一含妈物質與 一含锰物質。含約物質在含鈦添加物中之重量百分比介於 1%至8%之間，且含猛物質在含鈦添加物中之重量百分比 介於5%至15%之間。使前述之含鈦添加物於高爐内反應生 成氮化鈦或碳化鈦’而在爐床之表面上形成一含鈦保護層。 依據本發明之一實施例’上述之含飼物質可包含氧化 約、氫氧化弼、碳酸氫約或碳酸I弓。 依據本發明之另一實施例，上述之含鈦物質可包含二 氧化鈦。 依據本發明之又一實施例，上述之含猛物質包含二氧 化猛(Mn〇2)、氧化錳(MnO)、四氧化三猛(Mn；5〇4)或草酸鑑 (MnOOH)。 應用本發明之方法，不僅可強化護爐的效果，更可使 高爐之出鐵與出渣作業順利進行，避免污染高爐爐蕊，而 201224155 可使高爐維持正常產能。此外，本發明之方法可大幅降低 含鈦物質的使用量，因此可有效降低用料成本。 【實施方式】 請參照第1圖，其係繪示依照一種高爐的剖面示意 圖。一般高爐100的主體架構為鐵殼内砌耐火材及冷卻系 統之中空反應器，含鐵原料、焦炭助熔劑等煉鐵原料自爐 頂之加料裝置102投入，在爐内下降的過程，與自位於爐 ^ 腰之鼓風嘴104所鼓入的熱風，進行熱交換與還原反應， 產出的鐵水與爐渣流入位於鼓風嘴104以下之空間即所謂 的爐床106，再由出鐵口 108流出爐外，其中爐床106及 爐底之耐火材主要是以碳磚為主。 請參照第2圖，其係繪示依照本發明一實施方式的一 種高爐之爐床的保護方法的流程圖。在一實施方式的方法 200中，如步驟202所述，可將含鈦添加物與煉鐵原料自 爐頂加料裝置102投入如第1圖所示之高爐100中或經由 鲁 鼓風嘴104送入高爐100内。 在一實施方式中，含鈦添加物包含有含鈦物質與含鈣 物質。其中，含J弓物質可例如包含氧化約、氫氧化辦、碳 酸氫鈣或碳酸鈣，而含鈦物質可例如包含二氧化鈦。在一 實施例中，含鈣物質在整個含鈦添加物中的重量百分比可 介於1%至8%之間。 在此實施方式中，如步驟204所述，在還原氣氛下， ' 含鈦添加物於高爐内進行反應生成氮化鈦或碳化鈦，而在 高爐100之爐床106之碳磚表面上形成含鈦保護層。含鈦 201224155 保護層的形成可提供阻絕作用，而可有效保護爐床ι〇6使 其不又鐵產相與知姓，進而完成高爐削之爐床⑽的 保護。 >含鈦保護層之形成機制為含鈦添加物中之二氧化鈦在 同爐100内的還原氣氛下，有—部分的二氧化鈦會還原成 金屬鈦或五氧化三鈦(灿5)、三氧化二鈦(Ti2⑹與氧化欽 (ΤιΟ)等低價氧化物。所生成之鈦金屬—部分進人鐵水中， 另-部㈣留在爐渣中，其中留在㈣中的鈦化合物大部 分係呈二氧化二鈦的型態。金屬鈦在碳與氮的鐵水環境 下，會分別生成碳化鈦(TiC)與氮化鈦(TiN)結晶，而在爐床 106之碳碑表面上形成含鈦保護層。 形成含鈦保護層的機制又可分長晶與形成凝固層兩種 型式。長晶機㈣鐵水巾的鈦與爐床1()6之碳磚接觸時， :能形成碳化鈦之日日日核，或者於鐵水巾已生成之碳化鈦與 氮化鈦也有可能附著於碳碑表面…旦有形成，繼之， =中的鈦或鈦化合物即可在碳磚表面上的晶核上慢慢的 成長，而形成含鈦保護層。 形成凝固層的機制係當高爐_之爐床106碳磚表面 ==到鐵與碳的共晶點溫度時，在靠近碳磚表面形成 融而成的黏稠膏狀層。此黏稠膏狀層的流動性不 融鐵水與碳磚之間形紐衝效果，因此可保護 稠纽層受爐床外部冷心舰溫 =;=時，即有固態共融物析一更 以下為二氧化鈦在高爐還原氣氛下可能進行的幾個反 201224155 應。 ⑴ (2) (3) (4)201224155 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a protection method for a blast furnace (Blast Furnace), and more particularly to a method for protecting a hearth of a blast furnace. [Prior Art] The cost of blast furnace overhaul is huge, so in order to reduce costs, the steel mills are not committed to extending the furnace life of the blast furnace. The furnace life of the blast furnace is mainly determined by the residual thickness of the refractory bricks in the blast furnace. In particular, the hearth and the bottom carbon sheet are gradually lost during the operation of the blast furnace due to the scouring, chemical ablation and heat of the liquid iron slag. When the hearth and the bottom carbon bricks are seriously damaged, they cannot be repaired during the operation of the blast furnace. Therefore, the residual thickness of the hearth and the bottom stone often becomes the main determinant of the life of the furnace. At present, in order to extend the furnace life of the blast furnace, the most common practice is to promote the formation of the solidified layer by adding titanium-containing substances and improving the cooling effect. The solidified layer is characterized by a barrier side, which is more durable and has the advantage of a production operation. Therefore, this method is widely used in the protection of the hearth of a blast furnace. However, although the addition of titanium can provide the effect of protecting the furnace, it also produces a negative ~ ring. The addition of titanium causes the viscosity of the slag to be increased with molten iron, which deteriorates the fluidity of the molten iron. Therefore, when titanium is added, it will affect the high π a. Moreover, the increase in the titanium content in the molten iron will not only affect the surface quality of the added iron, but also affect the product's attractiveness, ductility and welding. In addition, the 'high viscosity is also easy _ on the carbon of the 201210155 carbon surface of the core (Dead_) This will result in a decrease in the gap between the cokes, and the gas permeability and liquid permeability will be worse, and the effect will be more expensive. Therefore, the excessive addition of titanium is also a significant increase in the amount of titanium; .胄 枓 枓 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 The bed smoothly forms a protective layer. Therefore, the effect of the furnace can be greatly enhanced. In addition, when the amount of the iron-containing substance added to the hearth of the blast furnace is added, the substance containing the sturdy substance is added, so as to increase the check, the kinetic property, promote the reduction of the titanium, and expand the range of addition of the (four) substance. Can effectively improve the stability of operation. II: Another aspect of the Ming Dynasty is that the protection of the hearth of a blast furnace has helped to streamline the addition of the substance containing the chin, which not only effectively maintains the product, but also allows for the export of iron to the furnace. The slag operation is carried out smoothly, avoiding pollution of the same furnace, and thus maintaining the normal capacity of the blast furnace. A further aspect of the invention is that the cost of providing a hearth of a blast furnace can greatly reduce the amount of titanium-containing material used, thereby effectively reducing the amount of material used, and the above object of the present invention proposes a hearth of a blast furnace. Protect the 垆侑U column steps. The titanium-containing additive and the iron-making raw material are put into the blast furnace from the blast furnace=top material device or sent to the blast furnace through the blast furnace mouth of the blast furnace, and the titanium-containing additive comprises the titanium-containing material f and the cerium-containing material, and 201224155 The weight percentage of calcium-containing substances in titanium-containing additives is between 1% and 8%. The titanium-containing additive is reacted in a blast furnace to form titanium nitride or titanium carbide, and a titanium-containing protective layer is formed on the surface of the hearth. According to an embodiment of the present invention, the calcium-containing substance may comprise calcium oxide (CaO), calcium hydroxide (Ca(OH)2), calcium hydrogencarbonate (Ca(HC03)2) or calcium carbonate (CaC03). According to another embodiment of the present invention, the above titanium-containing substance may comprise titanium oxide (Ti02). According to the above object of the present invention, there is further provided a method of protecting a hearth of a blast furnace comprising the following steps. A titanium-containing additive and iron-smelting material are fed into the blast furnace from the top of the blast furnace or into the blast furnace via the blast furnace. Wherein, the titanium-containing additive comprises a titanium-containing substance, a mother-containing substance and a manganese-containing substance. The weight percentage of the filler-containing material in the titanium-containing additive is between 1% and 8%, and the weight percentage of the explosive-containing material in the titanium-containing additive is between 5% and 15%. The titanium-containing additive described above is reacted in a blast furnace to produce titanium nitride or titanium carbide, and a titanium-containing protective layer is formed on the surface of the hearth. According to an embodiment of the present invention, the above-mentioned feed material may comprise oxidized about, cerium hydroxide, hydrogencarbonate or carbonate. According to another embodiment of the invention, the titanium-containing material may comprise titanium dioxide. According to still another embodiment of the present invention, the above-mentioned explosive substance comprises Mn〇2, manganese oxide (MnO), osmium tetraoxide (Mn; 5〇4) or oxalic acid (MnOOH). By applying the method of the invention, not only the effect of the furnace can be enhanced, but also the tapping and slagging operation of the blast furnace can be smoothly carried out to avoid polluting the blast furnace core, and 201224155 can maintain the normal capacity of the blast furnace. In addition, the method of the present invention can greatly reduce the amount of use of the titanium-containing substance, thereby effectively reducing the cost of the material. [Embodiment] Referring to Figure 1, there is shown a schematic cross-sectional view of a blast furnace. Generally, the main structure of the blast furnace 100 is a hollow reactor in which a refractory material and a cooling system are built in an iron shell, and ironmaking raw materials such as iron raw materials and coke fluxes are input from the top feeding device 102, and the process is lowered in the furnace. The hot air blown by the blast nozzle 104 located at the waist of the furnace performs heat exchange and reduction reaction, and the produced molten iron and slag flow into a space below the blast nozzle 104, that is, a so-called hearth 106, and then the tap hole 108 flows out of the furnace, wherein the refractory material of the hearth 106 and the bottom of the furnace is mainly carbon brick. Referring to Fig. 2, there is shown a flow chart of a method for protecting a hearth of a blast furnace according to an embodiment of the present invention. In the method 200 of an embodiment, as described in step 202, the titanium-containing additive and the iron-making raw material may be supplied from the top charging device 102 into the blast furnace 100 as shown in FIG. 1 or sent through the blast furnace 104. Into the blast furnace 100. In one embodiment, the titanium-containing additive comprises a titanium-containing material and a calcium-containing material. Wherein, the J-containing material may, for example, comprise an oxidizing agent, a hydrazine hydroxide, a calcium hydrogencarbonate or a calcium carbonate, and the titanium-containing material may, for example, comprise titanium dioxide. In one embodiment, the calcium-containing material may be between 1% and 8% by weight of the total titanium-containing additive. In this embodiment, as described in step 204, the titanium-containing additive is reacted in a blast furnace to form titanium nitride or titanium carbide under a reducing atmosphere, and is formed on the surface of the carbon brick of the hearth 106 of the blast furnace 100. Titanium protective layer. Titanium-containing 201224155 The formation of the protective layer can provide a barrier effect, and can effectively protect the hearth 〇6 so that it does not have the iron phase and the surname, thereby completing the protection of the blast furnace bed (10). > The formation mechanism of the titanium-containing protective layer is that the titanium dioxide in the titanium-containing additive is reduced to titanium metal or pentoxide pentoxide (can 5) under the reducing atmosphere in the same furnace 100. Titanium (Ti2 (6) and oxidized chin (ΤιΟ) and other low-cost oxides. The titanium metal produced is partially entered into molten iron, and the other part (4) remains in the slag, and most of the titanium compounds remaining in (4) are dioxide. The form of dititanium. In the molten iron environment of carbon and nitrogen, titanium metal will respectively form titanium carbide (TiC) and titanium nitride (TiN) crystals, and form a titanium-containing protective layer on the surface of the carbonaceous monument of the hearth 106. The mechanism for forming the titanium-containing protective layer can be divided into two types: long crystal and solidified layer. When the titanium of the crystal water machine is contacted with the carbon brick of the hearth 1 () 6 , the date of formation of titanium carbide can be formed. The core of the day, or the titanium carbide and titanium nitride that have been formed in the iron towel, may also adhere to the surface of the carbon monument... Once formed, the titanium or titanium compound in the = can be on the surface of the carbon brick. Slowly grow up to form a titanium-containing protective layer. The mechanism for forming a solidified layer is the blast furnace. 106 carbon brick surface == to the eutectic point temperature of iron and carbon, forming a thick paste layer formed on the surface of the carbon brick. The fluidity of the thick paste layer is not melted between molten iron and carbon brick. New rush effect, so it can protect the thick layer from the outside of the hearth of the hearth of the hearth ===, that is, there is solid state eutectic precipitation. The following are some of the counter-201224155 that titanium dioxide may perform under the blast furnace reducing atmosphere. (1) (2) (3) (4)
Ti02+2C+ 1/2N2—TiN+2CO Ti02+CaO—CaO · Ti02Ti02+2C+ 1/2N2—TiN+2CO Ti02+CaO—CaO · Ti02
CaO · Ti02 + 2C+1/2N2—TiN+CaO + 2C〇 CaO · Ti〇2 + 2Si〇2 + AI2O3 + 2C + 1 /2N~2 —TiN+CaO · AI2O3 · 2Si〇2+2CO 發明人發現’含鈦添加物中之二氧化鈦還原成氮化鈦 之反應溫度至少需向於1200 C。但有氧化飼存在下，溫度 只要高於l〇〇〇°C，Ti〇2即可與CaO結合而形成Ca〇.Ti〇2。 然，一旦形成CaO · Ti〇2後，欲進行還原反應，則反應溫 度需高達1532°C。但是，在有爐渣（即28丨〇2與A丨2〇3)存在 下，則CaO· Ti〇2的可還原溫度降為1〇73艺。因此，發明 人認為在高爐反應中，氧化鈣的添加對氧化鈦的還原有正 面的作用。含鈣物質添加率的影響，請參照第3圖，其係 繪示氧化鈣和二氧化錳的添加率與鐵中總鈦含量的關係曲 線圖。從第3圖之曲線圖可知，氧化鈣所添加之量為重量 百分比低於8%的情況下，鐵中的總鈦含量相較於未添加氧 倾的情況，有顯著的提升。由此可知，含㈣f的添加 可促進鈦之氧化物的還原反應，提升鈦之利用率。 請參照第4圖，其係繪示氧化舞之添加率與殘留於鐵 水中之鈦含量之間的關係曲線圖。發明人由第4圖之關係 圖中^添加氧化躬的情況下，反應後殘留於鐵水中 it二=為提高。由此可知’添加氧化鈣所增加之 鈦的還原以有大部分可在爐床之碳碑 外’發明人更發現未加氧化_，欽集中在鐵碳介面；而 201224155 有添加氧化鈣者，鈦的分布範圍較廣，且鈦的量比未添加 氧化辦者多。因此，氧化辦等含妈物質的添加，可有效提 升含鈦添加物之鈦的利用率，且可順利於爐床之碳磚表面 上形成含鈦保護層’進而可達到保護高爐之爐床的效果。 然，CaO · Ti〇2會導致高爐渣之黏度上升，而隨著高 爐渣之黏度會影響上述化學式（4)之反應。因此，當氧化鈣 的添加量達到會使黏度所造成之負面效應高於正面效應 時，鐵水中的鈦含量反而降低。CaO · Ti02 + 2C+1/2N2—TiN+CaO + 2C〇CaO · Ti〇2 + 2Si〇2 + AI2O3 + 2C + 1 /2N~2 —TiN+CaO · AI2O3 · 2Si〇2+2CO The inventors found The reaction temperature of the reduction of titanium dioxide to titanium nitride in the titanium-containing additive needs to be at least 1200 C. However, in the presence of oxidative feed, Ti〇2 can combine with CaO to form Ca〇.Ti〇2 as long as the temperature is higher than l〇〇〇°C. However, once CaO·Ti〇2 is formed and the reduction reaction is to be carried out, the reaction temperature needs to be as high as 1532 °C. However, in the presence of slag (i.e., 28丨〇2 and A丨2〇3), the reducible temperature of CaO·Ti〇2 is reduced to 1〇73 art. Therefore, the inventors believe that the addition of calcium oxide has a positive effect on the reduction of titanium oxide in the blast furnace reaction. For the influence of the addition rate of calcium-containing substances, please refer to Fig. 3, which is a graph showing the relationship between the addition rate of calcium oxide and manganese dioxide and the total titanium content in iron. As can be seen from the graph of Fig. 3, when the amount of calcium oxide added is less than 8% by weight, the total titanium content in the iron is remarkably improved as compared with the case where no oxygen is added. From this, it is understood that the addition of (d)f can promote the reduction reaction of titanium oxide and improve the utilization of titanium. Please refer to Fig. 4, which is a graph showing the relationship between the addition rate of the oxidative dance and the titanium content remaining in the molten iron. In the case of the inventor's relationship of Fig. 4, when cerium oxide is added, the reaction remains in the molten iron after the reaction. It can be seen that 'the reduction of titanium added by the addition of calcium oxide is mostly outside the carbon footprint of the hearth'. The inventors have found that no oxidation is added, and the Qin is concentrated in the iron-carbon interface; while 201224155 has added calcium oxide. Titanium has a wide distribution range, and the amount of titanium is more than that of non-added oxidation. Therefore, the addition of the mother substance such as the oxidation office can effectively improve the utilization rate of the titanium containing titanium additive, and can smoothly form a titanium-containing protective layer on the surface of the carbon brick of the hearth to further protect the hearth of the blast furnace. effect. However, CaO · Ti〇2 causes the viscosity of the blast furnace slag to rise, and the viscosity of the blast furnace slag affects the reaction of the above chemical formula (4). Therefore, when the amount of calcium oxide added is such that the negative effect caused by the viscosity is higher than the positive effect, the titanium content in the molten iron is lowered.
因此’在另一實施方式中，為了降低高爐渣的影響， 投入高爐100之含鈦添加物除了包含有含鈦物質與含鈣物 質外，更包含了含猛物質。其中’含妈物質可例如包含氧 化鈣或碳酸鈣，含鈦物質可例如包含二氧化鈦，含錳物質 可例如包含二氧化錳、氧化錳、四氧化三錳或草酸錳。在 一實施例中’含鈣物質在整個含鈦添加物中的重量百分比 可介於1%至8%之間，且含錳物質在整個含鈦添加物1重 量百分比可介於5%至15%之間。 含錳物質的添加可針對高含鈣物質添加率者。請參照 第3圖，其係繪示氧化鈣和二氧化錳的添加率與鐵中總鈦 含量的關係曲線圖。從第3圖之曲線圖可知，在二氧化結 所添加之量為重量百分比10%的情況下，鐵中的總鍊含量 相較於未添加二氧化錳情況，有顯著的提升。由此可知， 含錳物質的添加可提升高爐渣的流動性，並可促進鈦的還 原反應。如此一來，可擴大含鈣物質的添加範圍，提升操 作的穩定度。 由上述本發明之實施方式可知，本發明之一優點就是 10 201224155 入含鈣物;之::::二1保護方法係於含欽添加物中加 大大地強化表面上順利形成保護層。因此，可 πΐίΐ本發明之實施方式可知，本發明之另-優點就 ===:_的保護方法可在高含_添 ,定r含輪添加範圍，，可有二 *因可:’本發明之又-優點就 =的添加，因此不僅可有效二 由上述本發明之實施方式可知，本發 是因為本發明之高爐之爐床的保護方法可大 ^點就 質的使用量，因此可有效降低用料成本。w -3鈦物 雖然本發明已以實施例揭露如 ::明’任何在此技術領域中具有通常::識;非= 圍圍Λ:Γ作各種之更動_，因= 準發月之保護圍备視後附之中請專利範圍所界定者為 圖式簡單說明】 特徵、優點與實施例 為讓本發明之上述和其他目的 201224155 能更明顯易懂，所附圖式之說明如下： 第1圖係纟會不依照一種南爐的剖面示意圖。 第2圖係繪示依照本發明一實施方式的一種高爐之爐 床的保護方法的流程圖。 第3圖係繪不氧化約和二氧化猛的添加率與鐵中總欽 含量的關係曲線圖。 第4圖係繪示氧化鈣之添加率與殘留於鐵 量之間的關係曲線圖。 、7中之鈦含 鬌 【主要元件符號說明】 100 兩爐 102 加料敦置 104 鼓風嘴 106 爐床 108 出鐵口 200 方法 202 步驟 204 步驟Therefore, in another embodiment, in order to reduce the influence of the blast furnace slag, the titanium-containing additive introduced into the blast furnace 100 contains a sturdy substance in addition to the titanium-containing substance and the calcium-containing substance. The 'mother-containing substance may, for example, comprise calcium oxide or calcium carbonate, and the titanium-containing substance may, for example, comprise titanium dioxide, and the manganese-containing substance may, for example, comprise manganese dioxide, manganese oxide, trimanganese tetraoxide or manganese oxalate. In one embodiment, the weight percentage of the calcium-containing material in the entire titanium-containing additive may be between 1% and 8%, and the manganese-containing material may be between 5% and 15% by weight of the entire titanium-containing additive. %between. The addition of the manganese-containing substance can be directed to the rate of addition of high calcium-containing substances. Please refer to Figure 3, which is a graph showing the relationship between the addition rate of calcium oxide and manganese dioxide and the total titanium content in iron. As can be seen from the graph of Fig. 3, in the case where the amount of the addition of the dioxide is 10% by weight, the total chain content in the iron is remarkably improved as compared with the case where manganese dioxide is not added. It can be seen that the addition of the manganese-containing substance enhances the fluidity of the blast furnace slag and promotes the reduction reaction of titanium. In this way, the addition range of the calcium-containing substance can be expanded to improve the stability of the operation. It can be seen from the above embodiments of the present invention that one of the advantages of the present invention is that 10 201224155 contains calcium; the ::: two-protection method is applied to the inclusion-containing additive to greatly enhance the surface of the protective layer. Therefore, it can be seen that the embodiment of the present invention has the advantage that the protection method of the ===:_ can be added in the high-added, fixed-r-added range, and there are two possible factors: According to the embodiment of the present invention, the present invention is because the method for protecting the hearth of the blast furnace of the present invention can be used in a large amount, so that it can be used. Effectively reduce the cost of materials. W -3 Titanium Although the present invention has been disclosed by way of example:: 'anything in this technical field has the usual:: knowledge; non = enclosure: Γ 各种 各种 各种 各种 , , , , , , , BRIEF DESCRIPTION OF THE DRAWINGS The features, advantages and embodiments of the present invention are made more obvious and easy to understand. The description of the drawings is as follows: 1 Figure will not follow the schematic diagram of a south furnace. Fig. 2 is a flow chart showing a method of protecting a hearth of a blast furnace according to an embodiment of the present invention. Figure 3 is a graph showing the relationship between the addition rate of non-oxidation and oxidization and the total content of iron in iron. Fig. 4 is a graph showing the relationship between the addition rate of calcium oxide and the amount of iron remaining. Titanium content in 7 and 鬌 [Description of main components] 100 Two furnaces 102 Feeding station 104 Blowing nozzle 106 Hearth 108 Outlet 200 Method 202 Step 204 Step