TW201629234A - A desulfurizer and method for decreasing the sulfur content in steel fluid - Google Patents
A desulfurizer and method for decreasing the sulfur content in steel fluid Download PDFInfo
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- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
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本發明是有關於一種脫硫劑，特別是指一種用於降低鋼液中硫含量的脫硫劑。 The present invention relates to a desulfurizing agent, and more particularly to a desulfurizing agent for reducing the sulfur content in molten steel.
鋼廠在煉鋼脫硫的過程中，需使用具有較低熔點及黏度的脫硫劑，且需控制溫度為1600℃左右，氧分壓於20ppm以下才能順利對鋼液進行脫硫。 In the process of steelmaking desulfurization, the steel mill needs to use a desulfurizing agent with a lower melting point and viscosity, and the temperature needs to be controlled at about 1600 °C, and the oxygen partial pressure is below 20 ppm in order to smoothly desulfurize the molten steel.
傳統鋼廠會藉由添加生石灰(氧化鈣，CaO)提升脫硫劑的脫硫效果(即提升脫硫率)，以改善鋼的品質。不過當生石灰添加越多，會使脫硫劑的黏度上升，不利於脫硫反應，所以鋼廠還會再加入氟化鈣(CaF2)來降低脫硫劑的黏度。然而，添加氟化鈣除了會有爐襯被侵蝕的缺點外，其於脫硫過程中所揮發出的氟氣體對人體及環境都有很大的危害。 Traditional steel mills will improve the quality of steel by adding quicklime (calcium oxide, CaO) to enhance the desulfurization effect of the desulfurizer (ie, increase the desulfurization rate). However, the more the quicklime is added, the higher the viscosity of the desulfurizing agent is, which is not conducive to the desulfurization reaction. Therefore, the steel plant will further add calcium fluoride (CaF 2 ) to reduce the viscosity of the desulfurizing agent. However, in addition to the disadvantage that the addition of calcium fluoride will cause the lining to be eroded, the fluorine gas volatilized during the desulfurization process is very harmful to the human body and the environment.
CN 103882183A揭示一種不含氟化鈣的脫硫劑，是由50~60wt%的氧化鈣、7~12wt%的二氧化矽(SiO2)、28~33wt%的氧化鋁(Al2O3)及4~8wt%的氧化鎂(MgO)所組成(氧化鈣與氧化鋁的重量比值約為1.52~2.14)，且主要組成相為12CaO‧7Al2O3。然而，前述專利所揭示的脫硫劑之 脫硫率仍舊偏低。 CN 103882183A discloses a calcium fluoride-free desulfurizing agent which is composed of 50 to 60% by weight of calcium oxide, 7 to 12% by weight of cerium oxide (SiO 2 ), and 28 to 33% by weight of aluminum oxide (Al 2 O 3 ). And 4~8wt% magnesium oxide (MgO) composition (the weight ratio of calcium oxide to alumina is about 1.52~2.14), and the main composition phase is 12CaO‧7Al 2 O 3 . However, the desulfurization rate of the desulfurizing agent disclosed in the aforementioned patent is still low.
因此，如何改良前述的脫硫劑，找出一種不含氟化鈣且具有高脫硫率的脫硫劑，成為目前致力研究的目標。 Therefore, how to improve the aforementioned desulfurizing agent and find a desulfurizing agent which does not contain calcium fluoride and has a high desulfurization rate has become a goal of current research.
因此，本發明之第一目的，即在提供一種不含氟化鈣且具有高脫硫率的脫硫劑。 Accordingly, a first object of the present invention is to provide a desulfurizing agent which does not contain calcium fluoride and which has a high desulfurization rate.
於是本發明脫硫劑包含氧化鈣、二氧化矽及氧化鋁，其中，以該脫硫劑的總重為100wt%計，該氧化鋁的含量範圍為20~26wt%，該氧化鈣與該氧化鋁的重量比值範圍為2.19~3。 Therefore, the desulfurizing agent of the present invention comprises calcium oxide, ceria and alumina, wherein the content of the alumina ranges from 20 to 26% by weight based on the total weight of the desulfurizing agent: the calcium oxide and the oxidation The weight ratio of aluminum ranges from 2.19 to 3.
因此，本發明之第二目的，即在提供一種能有效降低鋼液中硫含量的方法，包含一使該鋼液與如前述的脫硫劑混合的步驟。 Accordingly, a second object of the present invention is to provide a method for effectively reducing the sulfur content in molten steel, comprising the step of mixing the molten steel with a desulfurizing agent as described above.
本發明之功效是由於本發明脫硫劑中的該氧化鋁含量範圍為20~26wt%，以及該氧化鈣與該氧化鋁的重量比值範圍為2.19~3，使得本發明脫硫劑中的主要組成相改變，因此使本發明的脫硫劑具有高脫硫率。 The efficacy of the present invention is that the alumina content in the desulfurizing agent of the present invention ranges from 20 to 26 wt%, and the weight ratio of the calcium oxide to the alumina ranges from 2.19 to 3, so that the main desulfurizing agent of the present invention The composition phase is changed, so that the desulfurizing agent of the present invention has a high desulfurization rate.
以下將就本發明內容進行詳細說明： The contents of the present invention will be described in detail below:
較佳地，以該脫硫劑的總重為100wt%計，該氧化鋁的含量範圍24~26wt%。 Preferably, the content of the alumina ranges from 24 to 26% by weight based on 100% by weight of the total weight of the desulfurizing agent.
較佳地，以該脫硫劑的總重為100wt%計，該氧化鈣的含量範圍為57~60wt%。更佳地，該氧化鈣的含量範圍為57~59wt%。 Preferably, the content of the calcium oxide ranges from 57 to 60% by weight based on 100% by weight of the total weight of the desulfurizing agent. More preferably, the calcium oxide is present in an amount ranging from 57 to 59% by weight.
較佳地，以該脫硫劑的總重為100wt%計，該二氧化矽的含量範圍為7~17wt%。更佳地，該二氧化矽的含量範圍為10~14wt%。 Preferably, the content of the cerium oxide ranges from 7 to 17% by weight based on 100% by weight of the total weight of the desulfurizing agent. More preferably, the content of the cerium oxide ranges from 10 to 14% by weight.
較佳地，本發明的脫硫劑還包含氧化鎂。更佳地，以該脫硫劑的總重為100wt%計，該氧化鎂的含量範圍為1~10wt%。又更佳地，該氧化鎂的含量範圍為3~7wt%。 Preferably, the desulfurizing agent of the present invention further comprises magnesium oxide. More preferably, the content of the magnesium oxide ranges from 1 to 10% by weight based on 100% by weight of the total weight of the desulfurizing agent. Still more preferably, the magnesium oxide is present in an amount ranging from 3 to 7 wt%.
本發明脫硫劑的該氧化鈣與該氧化鋁的重量比值範圍為2.19~3。更佳地，該氧化鈣與該氧化鋁的重量比值範圍為2.2~2.5。 The weight ratio of the calcium oxide to the alumina of the desulfurizing agent of the present invention ranges from 2.19 to 3. More preferably, the weight ratio of the calcium oxide to the alumina ranges from 2.2 to 2.5.
較佳地，本發明脫硫劑的主要組成相為Ca3SiO5和3CaO‧Al2O3。上述兩相具有相當低的熔點，更具有與CaF2相近的黏度，而能展現較佳的脫硫效果。 Preferably, the main constituent phases of the desulfurizing agent of the present invention are Ca 3 SiO 5 and 3CaO‧Al 2 O 3 . The above two phases have a relatively low melting point and a viscosity close to that of CaF 2 , and exhibit a better desulfurization effect.
較佳地，本發明的脫硫劑還可以再包含其他成分，例如但不限於白雲石[CaMg(CO3)2]或鋁礬土(aluminous soil)。 Preferably, the desulfurizing agent of the present invention may further comprise other components such as, but not limited to, dolomite [CaMg(CO 3 ) 2 ] or aluminous soil.
本發明的脫硫劑是先將氧化鈣、氧化鋁、二氧化矽，及/或氧化鎂與其他成分混合形成混合物後，升溫使該混合物熔化，再經降溫冷卻而製得。 The desulfurizing agent of the present invention is obtained by first mixing calcium oxide, aluminum oxide, cerium oxide, and/or magnesium oxide with other components to form a mixture, heating the mixture to melt, and cooling by cooling.
本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中：圖1是實施例1之脫硫劑的X-光繞射圖；圖2是實施例1之脫硫劑的熔點分析圖；圖3是比較例1之脫硫劑的熔點分析圖； 圖4是實施例1之脫硫劑於不同溫度下與黏度的關係圖；及圖5是比較例1之脫硫劑於不同溫度下與黏度的關係圖。 Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is an X-ray diffraction diagram of the desulfurizing agent of Example 1, and FIG. 2 is a departure of Example 1. The melting point analysis chart of the sulfur agent; FIG. 3 is the melting point analysis chart of the desulfurizing agent of Comparative Example 1; 4 is a graph showing the relationship between the desulfurizing agent of Example 1 and viscosity at different temperatures; and FIG. 5 is a graph showing the relationship between the desulfurizing agent of Comparative Example 1 and viscosity at different temperatures.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
製備脫硫劑Preparation of desulfurizer
步驟(1)：將純度皆為98%的碳酸鈣(氧化鈣來源)、氧化鋁、二氧化矽及氧化鎂粉末，依照下表1的含量比例(以脫硫劑的總重為100wt%計)混合後，製得混合物。需說明的是，前述碳酸鈣於加熱後即會變成氧化鈣，因此，前述98%的碳酸鈣亦可直接替換為95%的氧化鈣。 Step (1): calcium carbonate (calcium oxide source), alumina, cerium oxide and magnesium oxide powder each having a purity of 98%, according to the content ratio of the following Table 1 (based on the total weight of the desulfurizing agent: 100% by weight) After mixing, the mixture is prepared. It should be noted that the calcium carbonate may become calcium oxide after heating, and therefore, the 98% calcium carbonate may be directly replaced with 95% calcium oxide.
步驟(2)：將步驟(1)所得混合物放入石墨坩堝內，於一大氣壓下，利用感應週波熔煉爐使混合物升溫至1600℃且均勻熔化後，倒出並冷卻至30℃以下，即製得該脫硫劑。 Step (2): The mixture obtained in the step (1) is placed in a graphite crucible, and the mixture is heated to 1600 ° C by an induction cycle melting furnace under atmospheric pressure, and then uniformly melted, poured out and cooled to below 30 ° C. The desulfurizing agent is obtained.
製備脫硫劑(含氟化鈣)Preparation of desulfurizer (calcium fluoride)
比較例1的製備方法與實施例1類似，其差別在於，比較例1於步驟(1)還添加有氟化鈣粉末，且步驟(1)是依照下表2的含量比例(以脫硫劑的總重為100wt%計)添加各成分。 The preparation method of Comparative Example 1 was similar to that of Example 1, except that Comparative Example 1 was further added with calcium fluoride powder in the step (1), and the step (1) was in accordance with the content ratio of the following Table 2 (with a desulfurizing agent) The total weight is 100% by weight) and the ingredients are added.
製備脫硫劑Preparation of desulfurizer
比較例2~3的製備方法與實施例1類似，其差別在於，比較例2~3的步驟(1)是依照下表3的含量比例(以脫硫劑的總重為100wt%計)添加各成分。 The preparation methods of Comparative Examples 2 to 3 were similar to those of Example 1, except that the step (1) of Comparative Examples 2 to 3 was added in accordance with the content ratio of Table 3 below (total weight of the desulfurizing agent was 100% by weight). Each component.
利用X-光繞射觀察實施例1的脫硫劑，所得結果如圖1所示。由圖1可以發現，實施例1的主要組成相為Ca3SiO5和3CaO‧Al2O3。 The desulfurizing agent of Example 1 was observed by X-ray diffraction, and the results obtained are shown in Fig. 1. It can be seen from Fig. 1 that the main constituent phases of Example 1 are Ca 3 SiO 5 and 3CaO‧Al 2 O 3 .
利用DTA分析儀【Linseis STA PT 1600】(升溫 及降溫速率為2℃/min)分別對實施例1與比較例1的脫硫劑進行分析，所得結果如圖2(實施例1)與圖3(比較例1)所示。 The desulfurizing agents of Example 1 and Comparative Example 1 were analyzed by DTA analyzer [Linseis STA PT 1600] (temperature rising and cooling rate was 2 ° C / min), and the results are shown in Fig. 2 (Example 1) and Fig. 3 (Comparative Example 1).
由圖2與圖3可知，不含氟化鈣的實施例1之熔點約為1493℃，低於含有氟化鈣的比較例1(熔點約為1535℃)，說明本發明脫硫劑所揭示的成分含量比例，能使脫硫劑在不含氟化鈣的條件下也會具有低熔點特性，甚至低於含有氟化鈣的脫硫劑。 2 and FIG. 3, the melting point of Example 1 containing no calcium fluoride is about 1493 ° C, which is lower than that of Comparative Example 1 containing calcium fluoride (melting point is about 1535 ° C), which shows that the desulfurizing agent of the present invention is disclosed. The proportion of the component content enables the desulfurizing agent to have a low melting point characteristic even in the absence of calcium fluoride, even lower than a desulfurizing agent containing calcium fluoride.
利用黏度計(Brookfield-DV Ⅲ RV)分別於不同溫度下，量測實施例1與比較例1之脫硫劑的黏度，所得結果如圖4(實施例1)與圖5(比較例1)所示。 The viscosity of the desulfurizing agent of Example 1 and Comparative Example 1 was measured using a viscometer (Brookfield-DV III RV) at different temperatures, and the results are shown in Fig. 4 (Example 1) and Fig. 5 (Comparative Example 1). Shown.
由圖4與圖5的比較可知，於1600℃及1550℃時，不含氟化鈣的實施例1的黏度(1600℃：116cP、1550℃：122cP)皆低於比較例1(1600℃：122cP、1550℃：129cP)，說明本發明脫硫劑所揭示的成分含量比例，能使脫硫劑在不含氟化鈣的條件下也會具有低黏度特性，甚至低於含有氟化鈣的脫硫劑。 4 and FIG. 5, the viscosity (1600 ° C: 116 cP, 1550 ° C: 122 cP) of Example 1 containing no calcium fluoride at 1600 ° C and 1550 ° C was lower than that of Comparative Example 1 (1600 ° C: 122cP, 1550 ° C: 129 cP), indicating that the proportion of the components disclosed in the desulfurizing agent of the present invention enables the desulfurizing agent to have low viscosity characteristics even in the absence of calcium fluoride, even lower than that containing calcium fluoride. Desulfurizer.
(1)：分別於熱力學模擬軟體的指令碼內輸入TCS Steels/Fe-Alloys Database v7.0及TCS Fe-containing Slag Database v3.2兩種資料庫(database)。 (1): Two databases of TCS Steels/Fe-Alloys Database v7.0 and TCS Fe-containing Slag Database v3.2 are input into the instruction code of the thermodynamic simulation software.
(2)：依照下表4分別輸入參數，其中，以鋼液 和脫硫劑的總重為100wt%計，脫硫劑的含量為2wt%。 (2): Enter the parameters according to Table 4 below, in which steel liquid The total weight of the desulfurizing agent is 100% by weight, and the content of the desulfurizing agent is 2% by weight.
(3)：經熱力學模擬軟體運算平衡後所顯示的圖會出現鋼液經脫硫後各個元素的含量，從圖中找出於1600℃時的硫元素含量(wt%)，即為鋼液脫硫後硫元素含量(wt%)；此外，於1600℃時的氧元素含量(wt%)經單位換算後即為氧分壓(ppm)。 (3): The graph shown by the thermodynamic simulation software balance shows the content of each element after the desulfurization of the molten steel. The sulfur content (wt%) at 1600 °C is found in the figure, which is the molten steel. The sulfur element content (wt%) after desulfurization; in addition, the oxygen element content (wt%) at 1600 ° C is converted into oxygen partial pressure (ppm).
(4)：將鋼液初始硫元素含量(0.025wt%)與步驟(3)於1600℃時的鋼液脫硫後硫元素含量，經下式(I)計算後，即可得到脫硫劑的脫硫率。 (4): The initial sulfur element content (0.025wt%) of the molten steel and the sulfur element content after the desulfurization of the molten steel at the step (3) at 1600 °C are calculated by the following formula (I), and then the desulfurizing agent can be obtained. Desulfurization rate.
需先說明的是，「氧分壓」為影響脫硫率的重要因素之一，在脫硫過程中，當氧分壓越低時，脫硫劑的脫硫率就會越高(即脫硫效果越好)。 It should be noted that "oxygen partial pressure" is one of the important factors affecting the desulfurization rate. In the desulfurization process, when the partial pressure of oxygen is lower, the desulfurization rate of the desulfurizer is higher (ie, off The better the sulfur effect).
(a)實施例1與比較例1的比較：(a) Comparison of Example 1 and Comparative Example 1:
實施例1與比較例1透過前述【0042】~【0047】段方法，分別於不同氧分壓時，所得到的鋼液脫硫後硫元素含量及所計算出的脫硫率如下表5所示。 In Example 1 and Comparative Example 1, the content of sulfur element and the calculated desulfurization rate after desulfurization of the obtained molten steel were obtained by the above methods [0042] to [0047], respectively, as shown in Table 5 below. Show.
由表5可以發現，於1600℃且氧分壓接近的條件下，實施例1的脫硫率與比較例1並無太大差異，說明實施例1與比較例1的脫硫效果相近，證實本發明脫硫劑所揭示的成分含量比例，能使脫硫劑在不含氟化鈣的條件下，也具有高脫硫率，因此可以有效提升脫硫劑的脫硫效果。 It can be found from Table 5 that the desulfurization rate of Example 1 is not much different from that of Comparative Example 1 at 1600 ° C and the oxygen partial pressure is close, indicating that the desulfurization effect of Example 1 and Comparative Example 1 are similar, confirming The content ratio of the components disclosed by the desulfurizing agent of the invention can enable the desulfurizing agent to have a high desulfurization rate under the condition of not containing calcium fluoride, thereby effectively improving the desulfurization effect of the desulfurizing agent.
(b)實施例1與比較例2~3的比較：(b) Comparison of Example 1 and Comparative Examples 2 to 3:
實施例1與比較例2~3透過前述【0042】~【0047】段方法，分別於不同氧分壓時，所得到的鋼液脫硫後硫元素含量及所計算出的脫硫率如下表6所示。 Example 1 and Comparative Examples 2 to 3, through the above-mentioned methods [0042] to [0047], respectively, the sulfur content after desulfurization of the molten steel obtained at different oxygen partial pressures and the calculated desulfurization rate are as follows: 6 is shown.
由表6可以發現，氧化鋁的含量小於20wt%且氧化鈣與氧化鋁的重量比值大於3的比較例2，其氧分壓降至2ppm時的脫硫率為58.4wt%，低於實施例1在氧分壓高於2ppm(3.77ppm)時的脫硫率(83.7wt%)；又，氧化鋁的含量大於26wt%且氧化鈣與氧化鋁的重量比值小於2.19的比較例3，其氧分壓降至2.6ppm時的脫硫率為81.2wt%，仍舊低於實施例1在氧分壓高於2ppm(3.77ppm)時的脫硫率(83.7wr%)，說明相較於比較例2與比較例3，於氧分壓相同的條件下，實施例1會具有更高的脫硫率(即脫硫效果更好)，再次證實本發明脫硫劑所揭示的成分含量比 例，能使脫硫劑具有高脫硫率，因此可以有效提升脫硫劑的脫硫效果。 It can be found from Table 6 that in Comparative Example 2 in which the content of alumina is less than 20% by weight and the weight ratio of calcium oxide to alumina is more than 3, the desulfurization ratio when the oxygen partial pressure is lowered to 2 ppm is 58.4% by weight, which is lower than that of the examples. 1 Desulfurization rate (83.7 wt%) at an oxygen partial pressure higher than 2 ppm (3.77 ppm); further, Comparative Example 3 in which the alumina content is more than 26 wt% and the weight ratio of calcium oxide to alumina is less than 2.19, the oxygen thereof The desulfurization rate when the partial pressure fell to 2.6 ppm was 81.2 wt%, which was still lower than the desulfurization rate (83.7 wr%) when the partial pressure of oxygen was higher than 2 ppm (3.77 ppm) in Example 1, indicating that compared with the comparative example 2 and Comparative Example 3, under the same conditions of oxygen partial pressure, Example 1 will have a higher desulfurization rate (i.e., better desulfurization effect), and again confirm the content ratio of the components disclosed by the desulfurizing agent of the present invention. For example, the desulfurizing agent can have a high desulfurization rate, so that the desulfurization effect of the desulfurizing agent can be effectively improved.
綜上所述，由於本發明脫硫劑中的該氧化鋁含量範圍為20~26wt%，該氧化鈣與該氧化鋁的重量比值範圍為2.19~3，因此使本發明脫硫劑具有高脫硫率，故確實能達成本發明之目的。 In summary, since the alumina content in the desulfurizing agent of the present invention ranges from 20 to 26 wt%, the weight ratio of the calcium oxide to the alumina ranges from 2.19 to 3, thereby making the desulfurizing agent of the present invention high. The sulfur ratio is indeed sufficient for the purpose of the present invention.
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 However, the above is only the embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and the patent specification of the present invention are still It is within the scope of the patent of the present invention.
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| US15/010,472 US20160222479A1 (en) | 2015-02-02 | 2016-01-29 | Desulfurization composition |
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