TWI602925B - Steelmaking desulfurizer and desulfurization method - Google Patents
Steelmaking desulfurizer and desulfurization method Download PDFInfo
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Description
本發明是有關於一種煉鋼用脫硫劑及脫硫方法，特別是指一種含有精煉渣的煉鋼用脫硫劑及使用此煉鋼用脫硫劑的脫硫方法。The present invention relates to a desulfurizing agent for steel making and a desulfurizing method, and more particularly to a desulfurizing agent for steel making containing refining slag and a desulfurizing method using the desulfurizing agent for steel making.
傳統電弧爐煉鋼的過程主要分為兩部份：(1) 先使用電爐進行初煉氧化脫磷；(2)再以盛鋼桶進行精煉還原脫硫。常見的脫硫劑是以氧化鈣(CaO)為主要成份，但氧化鈣熔點高達2570°C，熔解速率緩慢，導致熔煉時間延長。為了解決上述問題，同時使脫硫劑同時具有理想的脫硫能力及較低的熔點，大多會於脫硫劑中添加助熔劑，以減少熔煉所需的時間。常用的助熔劑包括氟化鈣(CaF 2)，但氟化鈣可能會導致爐襯被侵蝕，於脫硫過程中所揮發出的氟氣體對人體及環境也有很大的危害，因此，目前脫硫劑中會避免再加入氟化鈣，並轉而運用其他助熔劑。 The traditional electric arc furnace steelmaking process is mainly divided into two parts: (1) first using an electric furnace for primary oxidative dephosphorization; (2) refining and reducing desulfurization with a steel drum. The common desulfurizer is calcium oxide (CaO) as the main component, but the melting point of calcium oxide is as high as 2570 ° C, and the melting rate is slow, resulting in prolonged melting time. In order to solve the above problems, and at the same time, the desulfurizing agent has the desired desulfurization ability and a low melting point at the same time, most of the flux is added to the desulfurizing agent to reduce the time required for the melting. Commonly used fluxes include calcium fluoride (CaF 2 ), but calcium fluoride may cause the lining to be eroded. The fluorine gas volatilized during the desulfurization process is also very harmful to the human body and the environment. Therefore, the current desulfurization Avoid adding calcium fluoride to the agent and switch to other fluxes.
TW 201329242A1專利公開案提出一種熔融鋼液之脫硫方法，包含於電弧爐內提供一硫含量為0.03~0.06wt%之熔融鋼液；加熱此熔融鋼液，使之成為溫度為1600~1700°C之加熱熔融鋼液；接著將脫硫劑加入加熱熔融鋼液中，使脫硫劑於加熱熔融鋼液之表面形成一覆蓋層，再加入碳粉使該覆蓋層增厚並進行脫硫反應。此專利公開案所使用的脫硫劑包含一次脫硫渣與氧化鈣，二者質量比為1：1。該一次脫硫渣係指以氧化鈣為脫硫劑，對加熱熔融鋼液進行一次脫硫反應所產出之脫硫渣，其成分包含氧化鈣、氧化矽、氧化鋁及氧化鐵。上述專利公開案的脫硫方法於40分鐘的脫硫反應後可達成45%~60%的脫硫率。The TW 201329242A1 patent publication proposes a method for desulfurizing molten steel, comprising providing a molten steel having a sulfur content of 0.03 to 0.06 wt% in an electric arc furnace; heating the molten steel to a temperature of 1600 to 1700° C is heated to melt the molten steel; then the desulfurizing agent is added to the heated molten steel liquid, so that the desulfurizing agent forms a coating layer on the surface of the heated molten steel liquid, and then the carbon powder is added to thicken the coating layer and perform desulfurization reaction. . The desulfurizing agent used in this patent publication contains primary desulfurization slag and calcium oxide in a mass ratio of 1:1. The primary desulfurization slag refers to a desulfurization slag produced by subjecting the molten molten steel to a desulfurization reaction by using calcium oxide as a desulfurizing agent, and the composition thereof comprises calcium oxide, cerium oxide, aluminum oxide and iron oxide. The desulfurization method of the above patent publication can achieve a desulfurization rate of 45% to 60% after 40 minutes of desulfurization reaction.
由上述說明可知，現有脫硫劑的脫硫率仍有待提升。It can be seen from the above description that the desulfurization rate of the existing desulfurizing agent still needs to be improved.
為了有效提升脫硫劑的脫硫率，本案發明人首先思及將鋼廠廢棄使用且無法掩埋處理的精煉渣回收使用，並進一步將其調製成脫硫劑。In order to effectively improve the desulfurization rate of the desulfurizing agent, the inventor of the present invention first considered the recycling of the refining slag which was abandoned by the steel plant and could not be buried, and further prepared into a desulfurizing agent.
因此，本發明的目的，即在提供一種減少煉鋼廢料、降低製造成本且能發揮較佳脫硫率的煉鋼用脫硫劑。Accordingly, an object of the present invention is to provide a desulfurizing agent for steel making which can reduce steelmaking waste, reduce manufacturing cost, and exhibit a preferable desulfurization rate.
於是，本發明煉鋼用脫硫劑包含精煉渣及補充材，以該精煉渣總重量為100 wt%，該精煉渣包括52~56 wt%的氧化鈣、6~30 wt%的氧化矽、6~28 wt%的氧化鋁、5~7 wt%的氧化鎂、2~8 wt%的氟化鈣及0.7~1.1 wt%的硫。該補充材包括氧化鈣、氧化鋁及氧化矽。以該煉鋼用脫硫劑的總重量為100重量份計算，該精煉渣的含量範圍為30~50重量份，以及該補充材的含量範圍為50~70重量份。以該精煉渣及補充材的總重為100 wt%，該氧化鈣的總含量範圍為55~60 wt%，該氧化鋁的總含量範圍為25~30 wt%及該氧化矽的總含量範圍為10~15 wt%。Therefore, the desulfurizing agent for steelmaking according to the present invention comprises refining slag and a supplementary material, and the total weight of the refining slag is 100 wt%, and the refining slag comprises 52 to 56 wt% of calcium oxide and 6 to 30 wt% of cerium oxide. 6~28 wt% alumina, 5-7 wt% magnesium oxide, 2-8 wt% calcium fluoride and 0.7~1.1 wt% sulfur. The supplement includes calcium oxide, aluminum oxide and cerium oxide. The refining slag is contained in an amount ranging from 30 to 50 parts by weight, based on the total weight of the steelmaking desulfurizing agent, and the content of the supplementary material is in the range of 50 to 70 parts by weight. The total weight of the refining slag and the supplementary material is 100 wt%, the total content of the calcium oxide ranges from 55 to 60 wt%, the total content of the alumina ranges from 25 to 30 wt%, and the total content of the cerium oxide It is 10~15 wt%.
本發明的另一目的是提供一種脫硫方法。Another object of the present invention is to provide a desulfurization method.
於是，本發明脫硫方法包含將上述煉鋼用脫硫劑加入熔融鋼液中進行脫硫反應。Therefore, the desulfurization method of the present invention comprises adding the above-mentioned desulfurization agent for steel making to a molten steel liquid for desulfurization reaction.
本發明的功效在於：本發明煉鋼用脫硫劑含有特定組成的精煉渣及補充材，同時調控精煉渣與補充材所含有的氧化鈣、氧化鋁及氧化矽的總含量範圍，除了能讓精煉渣回收再利用及降低製造成本外，更讓本發明煉鋼用脫硫劑於後續應用在熔融鋼液的脫硫反應時，能有效提升脫硫率並縮短脫硫反應時間。The effect of the invention is that the desulfurizing agent for steelmaking of the invention contains the refining slag and the supplementary material of a specific composition, and at the same time regulates the total content range of calcium oxide, aluminum oxide and cerium oxide contained in the refining slag and the supplementary material, in addition to allowing In addition to recycling and refining the refining slag and reducing the manufacturing cost, the desulfurizing agent for steelmaking of the present invention can effectively improve the desulfurization rate and shorten the desulfurization reaction time in the subsequent desulfurization reaction of the molten steel.
以下將就本發明作進一步的詳細說明：The invention will be further described in detail below:
本發明煉鋼用脫硫劑包含精煉渣及補充材。該精煉渣的來源主要是鋼廠盛鋼桶精煉爐脫硫後所生成的爐渣。以該精煉渣的總重量為100wt%，該精煉渣包括52~56 wt%的氧化鈣、6~30 wt%的氧化矽、6~28 wt%的氧化鋁、5~7 wt%的氧化鎂、2~8 wt%的氟化鈣及0.7~1.1 wt%的硫。於本發明的具體例中，該精煉渣包括52.5~55.3 wt%的氧化鈣、6.8~29.4 wt%的氧化矽、6.4~27.1 wt%的氧化鋁、5.5~6.7 wt%的氧化鎂、2~7.3 wt%的氟化鈣及0.7~1.1 wt%的硫。精煉渣除了必須包括特定含量範圍的上述成分外，該精煉渣還可選擇地包括其他成分，但這些成分不可以影響該煉鋼用脫硫劑的助熔及脫硫能力。The desulfurizing agent for steelmaking according to the present invention comprises refining slag and a supplementary material. The source of the refining slag is mainly the slag generated after the desulfurization of the refining furnace of the steel mill. The refining slag comprises 52 to 56 wt% of calcium oxide, 6 to 30 wt% of cerium oxide, 6 to 28 wt% of alumina, and 5 to 7 wt% of magnesium oxide, based on 100% by weight of the total weight of the refining slag. 2~8 wt% calcium fluoride and 0.7~1.1 wt% sulfur. In a specific example of the present invention, the refining slag comprises 52.5 to 55.3 wt% of calcium oxide, 6.8 to 29.4 wt% of cerium oxide, 6.4 to 27.1 wt% of alumina, 5.5 to 6.7 wt% of magnesium oxide, 2~ 7.3 wt% calcium fluoride and 0.7 to 1.1 wt% sulfur. The refining slag may optionally include other components in addition to the above-mentioned components in a specific content range, but these components may not affect the melting and desulfurizing ability of the steelmaking desulfurizing agent.
較佳地，該精煉渣中的氧化鋁與氧化矽的重量比值範圍為0.2~4。於本發明的具體例中，該精煉渣中的氧化鋁與氧化矽的重量比值範圍為0.22~3.99。Preferably, the weight ratio of alumina to cerium oxide in the refining slag ranges from 0.2 to 4. In a specific example of the present invention, the weight ratio of alumina to cerium oxide in the refining slag ranges from 0.22 to 3.99.
該補充材包括氧化鈣、氧化鋁及氧化矽。該氧化鈣、氧化鋁及氧化矽的用量是依據該精煉渣所含的氧化鈣、氧化鋁及氧化矽含量進行調整，最終須讓精煉渣及補充材中包含總含量範圍為55~60 wt%的氧化鈣，總含量範圍為25~30 wt%的氧化鋁，及總含量範圍為10~15 wt%的氧化矽。The supplement includes calcium oxide, aluminum oxide and cerium oxide. The amount of the calcium oxide, aluminum oxide and cerium oxide is adjusted according to the content of calcium oxide, aluminum oxide and cerium oxide contained in the refining slag, and finally the total content of the refining slag and the supplementary material is 55 to 60 wt%. The calcium oxide has a total content ranging from 25 to 30% by weight of alumina and a total content of 10 to 15% by weight of cerium oxide.
較佳地，該補充材還包括氧化鎂。Preferably, the supplement further comprises magnesium oxide.
較佳地，以該精煉渣及補充材的總重為100wt%，該氧化鎂的總含量範圍為0.1~5 wt%。Preferably, the total weight of the refining slag and the supplementary material is 100% by weight, and the total content of the magnesium oxide ranges from 0.1 to 5% by weight.
本發明脫硫方法包含將煉鋼用脫硫劑加入熔融鋼液中進行脫硫反應。該煉鋼用脫硫劑的成分、含量範圍及變化態樣如前面段落所述。The desulfurization method of the present invention comprises adding a desulfurizing agent for steel making to a molten steel liquid for desulfurization reaction. The composition, content range and variation of the desulfurizing agent for steel making are as described in the previous paragraph.
較佳地，該煉鋼用脫硫劑於20分鐘脫硫反應後具有55%以上的脫硫率。更佳地，該煉鋼用脫硫劑於20分鐘脫硫反應後具有57.6%以上的脫硫率。Preferably, the steelmaking desulfurizing agent has a desulfurization rate of 55% or more after a desulfurization reaction for 20 minutes. More preferably, the steelmaking desulfurizing agent has a desulfurization rate of 57.6% or more after the desulfurization reaction for 20 minutes.
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.
精煉渣分析Refining slag analysis
分別取用三種不同來源的精煉渣(表1中標註為A、B及C)並利用波長分散式X光光譜儀(wavelength-dispersive X-ray spectroscopy，WDS-XRF)進行成分及含量分析，其中，CaF2之含量是由100wt%扣除其他氧化物含量後獲得。分析結果整理於下表1中。 Three different sources of refining slag (labeled A, B and C in Table 1) were used and analyzed by composition and content using wavelength-dispersive X-ray spectroscopy (WDS-XRF). The content of CaF 2 is obtained by subtracting other oxide contents from 100% by weight. The results of the analysis are summarized in Table 1 below.
[實施例1~5]煉鋼用脫硫劑的製備[Examples 1 to 5] Preparation of Desulfurizer for Steelmaking
依據下表2的成分、含量、比例及精煉渣，分別將精煉渣與補充材進行混合，接著升溫至精煉渣與補充材完全熔融液化(約1500℃)，最後再倒出冷卻至室溫，以製得實施例1至5的煉鋼用脫硫劑。 According to the composition, content, proportion and refining slag in Table 2, the refining slag and the supplementary material are respectively mixed, and then the temperature is raised until the refining slag and the supplementary material are completely melted and liquefied (about 1500 ° C), and finally poured out to cool to room temperature. The desulfurizing agents for steel making of Examples 1 to 5 were obtained.
a.以煉鋼用脫硫劑的總重量為100重量份計算。 a. Calculated based on 100 parts by weight of the total weight of the desulfurizing agent for steel making.
c.以精煉渣及補充材中的CaO、Al2O3、SiO2與MgO的總重量為100wt%。 c. The total weight of CaO, Al 2 O 3 , SiO 2 and MgO in the refining slag and the supplementary material is 100% by weight.
[助熔能力測試][Fusing ability test]
將56克的實施例1的脫硫劑加入放置有700克鋼塊的週波爐中進行脫硫試驗(脫硫溫度為1600~1630℃，氧分壓小於20ppm)，並分別於0、2、4、10、15及20分鐘時觀察液化狀態並拍攝照片，結果如圖1所示。 56 g of the desulfurizing agent of Example 1 was added to a centrifugal furnace placed with 700 g of steel block for desulfurization test (desulfurization temperature was 1600 to 1630 ° C, oxygen partial pressure was less than 20 ppm), and was respectively at 0, 2, At 4, 10, 15 and 20 minutes, the liquefied state was observed and photographs were taken. The results are shown in Fig. 1.
由圖1的結果可發現，0分鐘的照片是在完全液化情況下的鋼液中投入塊狀的脫硫劑；於10分鐘後，幾乎已看不見塊狀的脫硫劑，顯示週波爐內的脫硫劑於10分鐘後就已變成液化狀態，證明脫硫劑確實具備良好的助熔能力。 From the results of Fig. 1, it can be found that the 0 minute photograph is to put a bulk desulfurizing agent into the molten steel in the case of complete liquefaction; after 10 minutes, almost no bulk desulfurizing agent is visible, indicating that the centrifugal furnace is in the furnace. The desulfurizing agent has become liquefied after 10 minutes, which proves that the desulfurizing agent does have a good fluxing ability.
[脫硫率測試][Desulfurization rate test]
分別將56克實施例1~5所製得脫硫劑加入放置有鋼塊的週波 爐中進行脫硫試驗(脫硫溫度為1600~1630℃，氧分壓小於20ppm)，並於0、10、15及20分鐘量測鋼液中的硫含量，其中實施例1~3的結果分別如圖2至4所示，實施例1~5的脫硫率結果如下表3所示。 56 grams of the desulfurizing agent prepared in Examples 1 to 5 were added to the cycle in which the steel block was placed. Desulfurization test was carried out in the furnace (desulfurization temperature was 1600~1630 °C, oxygen partial pressure was less than 20 ppm), and the sulfur content in the molten steel was measured at 0, 10, 15 and 20 minutes, and the results of Examples 1~3 were measured. The results of the desulfurization rates of Examples 1 to 5 are shown in Table 3 below, as shown in Figs. 2 to 4, respectively.
由圖2至4的結果，證明實施例1~3的脫硫劑隨時間增加，脫硫率也隨著提升，且於20分鐘後可達到57.6%~70.7%。 From the results of FIGS. 2 to 4, it was confirmed that the desulfurizing agents of Examples 1 to 3 increased with time, and the desulfurization rate also increased, and reached 57.6% to 70.7% after 20 minutes.
於表3中，將實施例1~3的結果進行比較，可以發現當Al2O3/SiO2為0.22時，脫硫劑於20分鐘試驗後的脫硫率可達70.7%。 In Table 3, comparing the results of Examples 1 to 3, it was found that when Al 2 O 3 /SiO 2 was 0.22, the desulfurization rate of the desulfurizing agent after the 20-minute test was 70.7%.
進一步將實施例1、4及5的結果進行比較，可以發現脫硫率是隨著補充材用量增加而增加，且當精煉渣與補充材的重量比例為30：70時，20分鐘試驗後的脫硫率可達77.5%。 Further comparing the results of Examples 1, 4 and 5, it can be found that the desulfurization rate increases as the amount of the supplementary material increases, and when the weight ratio of the refining slag to the supplementary material is 30:70, after 20 minutes of the test The desulfurization rate can reach 77.5%.
於TW 201329242A1專利公開案中，脫硫劑是使用重量比例為1：1的一次脫硫渣及氧化鈣，由此專利公開案的第4圖中可知，從0分鐘硫含量為0.045wt%下降至20分鐘硫含量0.021wt%，脫硫率為53%[(0.045-0.021)/0.045×100%]。同樣由第5 圖可知脫硫率為49%，顯示此專利公開案的脫硫劑於20分鐘的脫硫試驗後，可達到49%~53%的脫硫率。 In the TW 201329242A1 patent publication, the desulfurizing agent is a primary desulfurization slag and calcium oxide having a weight ratio of 1:1, and as shown in FIG. 4 of the patent publication, the sulfur content is decreased by 0.045 wt% from 0 minutes. The sulfur content was 0.021% by weight to 20 minutes, and the desulfurization rate was 53% [(0.045-0.021) / 0.045 × 100%]. Also by the 5th The figure shows that the desulfurization rate is 49%, indicating that the desulfurization agent of this patent publication can reach a desulfurization rate of 49% to 53% after a 20-minute desulfurization test.
然而，由表3的結果顯示：本發明煉鋼用脫硫劑於20分鐘的脫硫試驗後，可達到57.6%~77.5%的脫硫率，高於上述專利公開案於20分鐘試驗後的脫硫率(49%~53%)；此外，本發明脫硫劑於20分鐘即可達到57.6%~77.5%，也較此專利公開案於40分鐘試驗後的脫硫率(45%~60%)更為有效率。經由上述說明，證明本發明煉鋼用脫硫劑可有效縮短脫硫反應時間以及提升脫硫率。 However, the results from Table 3 show that the desulfurization agent for steelmaking of the present invention can reach a desulfurization rate of 57.6% to 77.5% after a desulfurization test for 20 minutes, which is higher than the test of the above patent publication after 20 minutes. The desulfurization rate (49%~53%); in addition, the desulfurizing agent of the present invention can reach 57.6%~77.5% in 20 minutes, and the desulfurization rate after the test in the 40 minutes of this patent publication (45%~60) %) is more efficient. Through the above description, it is proved that the desulfurizing agent for steelmaking of the present invention can effectively shorten the desulfurization reaction time and increase the desulfurization rate.
綜上所述，本發明煉鋼用脫硫劑含有特定組成的精煉渣及補充材，同時調控精煉渣與補充材所含有的氧化鈣、氧化鋁及氧化矽的總含量範圍，除了能讓精煉渣回收再利用及降低製造成本外，更讓本發明煉鋼用脫硫劑於後續應用在熔融鋼液的脫硫反應時，能有效提升脫硫率並縮短脫硫反應時間，故確實能達成本發明的目的。 In summary, the desulfurizing agent for steelmaking of the present invention contains a specific composition of refining slag and supplementary materials, and at the same time regulates the total content range of calcium oxide, aluminum oxide and cerium oxide contained in the refining slag and the supplementary material, in addition to allowing refining The slag is recycled and reused, and the manufacturing cost is reduced. Moreover, the desulfurizing agent for steelmaking of the present invention can effectively improve the desulfurization rate and shorten the desulfurization reaction time in the subsequent desulfurization reaction of the molten steel, so that it can be achieved. The object of the invention.
惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。 However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the simple equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still Within the scope of the invention patent.
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 無 </td><td> </td></tr></TBODY></TABLE><TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> None</td><td> </td></tr></TBODY>< /TABLE>
本發明的其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是一照片，說明本發明煉鋼用脫硫劑的實施例1隨時間增加的液化狀態變化； 圖2是一散佈圖，說明本發明煉鋼用脫硫劑的實施例1的脫硫試驗結果； 圖3是一散佈圖，說明本發明煉鋼用脫硫劑的實施例2的脫硫試驗結果； 及 圖4是一散佈圖，說明本發明煉鋼用脫硫劑的實施例3的脫硫試驗結果。Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: Figure 1 is a photograph illustrating the liquefaction state change of Example 1 of the desulfurizing agent for steelmaking of the present invention over time. 2 is a scatter diagram illustrating the results of the desulfurization test of Example 1 of the desulfurizing agent for steelmaking according to the present invention; and FIG. 3 is a scatter diagram illustrating the desulfurization of Example 2 of the desulfurizing agent for steelmaking of the present invention. The test results; and Fig. 4 is a scatter diagram showing the results of the desulfurization test of Example 3 of the desulfurizing agent for steelmaking of the present invention.
Claims (5)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025717A1 (en) * | 1996-12-11 | 1998-06-18 | Performix Technologies, Ltd. | Basic tundish flux composition for steelmaking processes |
| CN101649371A (en) * | 2009-08-26 | 2010-02-17 | 武汉科技大学 | Desulfurating agent for out-of-furnace treatment and preparation method thereof |
| CN102453785A (en) * | 2010-10-21 | 2012-05-16 | 金素玉 | Pre-molten desulfurizing agent and preparation method thereof |
| TW201329243A (en) * | 2012-01-12 | 2013-07-16 | Nat Univ Chung Hsing | Modifier for steel refinement |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025717A1 (en) * | 1996-12-11 | 1998-06-18 | Performix Technologies, Ltd. | Basic tundish flux composition for steelmaking processes |
| CN101649371A (en) * | 2009-08-26 | 2010-02-17 | 武汉科技大学 | Desulfurating agent for out-of-furnace treatment and preparation method thereof |
| CN102453785A (en) * | 2010-10-21 | 2012-05-16 | 金素玉 | Pre-molten desulfurizing agent and preparation method thereof |
| TW201329243A (en) * | 2012-01-12 | 2013-07-16 | Nat Univ Chung Hsing | Modifier for steel refinement |
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