CN106929631A - The dross method that high-titanium blast furnace slag carbonization is smelted - Google Patents
The dross method that high-titanium blast furnace slag carbonization is smelted Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 90
- 239000010936 titanium Substances 0.000 title claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000003763 carbonization Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000005540 biological transmission Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000000571 coke Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 241001062472 Stokellia anisodon Species 0.000 claims description 3
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012768 molten material Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 18
- 239000012467 final product Substances 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/54—Processes yielding slags of special composition
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Abstract
本发明公开的是金属冶炼领域的一种高钛型高炉渣碳化冶炼的挂渣方法，其过程为，首先将含钛矿、焦碳磨制成粉料后加入电炉中，通电熔炼，使电极中心至炉衬内壁之间形成流动性的熔池，然后加大送电功率，完成TiO2的碳化反应，最后，待反应结束后，减小送电功率，逐步降低熔池温度，在降温过程中，接近炉壁处的挂渣产物慢慢凝固并与炉衬致密结合，待挂渣层厚度达到理想厚度时，迅速提高送电功率，使剩余挂渣产物保持流动性从出渣口排出。采用本方法制得的挂渣层与炉衬紧密结合，挂渣层中起护壁作用的TiC与最终产品的主要成分一致，不会因挂渣层脱落而污染产品，从而在保证产品质量的同时大大延长了炉衬的使用寿命，节约了生成维护成本。The invention discloses a slag-hanging method for carbonization and smelting of high-titanium blast furnace slag in the field of metal smelting. A fluid molten pool is formed between the center and the inner wall of the furnace lining, and then the power transmission power is increased to complete the carbonization reaction of TiO2 . Finally, after the reaction is completed, the power transmission power is reduced to gradually reduce the temperature of the molten pool. During the cooling process, it is close to The slag products on the furnace wall solidify slowly and are closely combined with the furnace lining. When the thickness of the slag layer reaches the ideal thickness, the power transmission power is rapidly increased, so that the remaining slag products maintain fluidity and are discharged from the slag outlet. The slag layer prepared by this method is closely combined with the furnace lining, and the TiC in the slag layer, which acts as a wall protection, is consistent with the main components of the final product, and will not pollute the product due to the falling off of the slag layer, thereby greatly improving product quality while ensuring product quality. The service life of the furnace lining is extended, and the generation and maintenance costs are saved.
Description
技术领域technical field
本发明涉及金属冶炼领域，尤其涉及一种高钛型高炉渣碳化冶炼的挂渣方法。The invention relates to the field of metal smelting, in particular to a slag-hanging method for carbonization and smelting of high-titanium blast furnace slag.
背景技术Background technique
目前，攀钢掌握了一种从高炉渣中制备TiCl4的工艺新技术，其中一项关键技术就是攀钢高炉渣高温碳化工艺，该工艺简单来说就是用电炉配碳冶炼熔融态高炉渣。从现在中试规模的生产情况来看，电炉炉衬损耗严重，使用寿命较低，原因在于冶炼过程中，熔融态高炉渣所富含的TiO2化学活性极强，几乎能与所有的耐火材料发生反应，从而侵蚀耐火材料。为了避免熔渣侵蚀炉衬而影响电炉寿命，需要在炉衬上保留一定厚度的挂渣层，使熔渣与炉衬隔离。At present, Panzhihua Iron and Steel has mastered a new technology for preparing TiCl 4 from blast furnace slag. One of the key technologies is the high-temperature carbonization process of Panzhihua Iron and Steel's blast furnace slag. This process is simply smelting molten blast furnace slag with carbon in an electric furnace. Judging from the current pilot-scale production situation, the lining loss of the electric furnace is serious and the service life is low. The reason is that during the smelting process, the TiO 2 rich in molten blast furnace slag has a strong chemical activity and can react with almost all refractory materials. reaction, thereby eroding the refractory material. In order to prevent the slag from corroding the furnace lining and affecting the life of the electric furnace, it is necessary to reserve a certain thickness of hanging slag layer on the furnace lining to isolate the slag from the furnace lining.
发明内容Contents of the invention
为了解决高炉渣高温碳化工艺炉衬使用寿命较低等不足，本发明所要解决的技术问题是：提供一种能够在炉衬上设置挂渣层的高钛型高炉渣碳化冶炼的挂渣方法。In order to solve the disadvantages of low service life of the furnace lining in the high-temperature carbonization process of blast furnace slag, the technical problem to be solved by the present invention is to provide a slag-hanging method for carbonization and smelting of high-titanium blast furnace slag that can provide a slag-hanging layer on the furnace lining.
本发明解决其技术问题所采用的技术方案是：高钛型高炉渣碳化冶炼的挂渣方法，包括以下步骤：The technical solution adopted by the present invention to solve the technical problem is: the slag hanging method of high-titanium type blast furnace slag carbonization smelting, comprising the following steps:
a、对含钛矿、焦碳做预处理，将其磨制成粉料后预混，其中含钛矿与焦碳的配比以反应生成TiC的含量不低于30％为准；a. Pre-treat titanium-containing ore and coke, grind it into powder and pre-mix, wherein the ratio of titanium-containing ore and coke is based on the content of TiC produced by the reaction not less than 30%;
b、将预混料加入电炉中，通电熔炼，使电极中心至炉衬内壁之间形成流动性的熔池；b. Add the premixed material into the electric furnace and smelt with electricity to form a fluid molten pool between the center of the electrode and the inner wall of the furnace lining;
c、待熔池完全形成后，进一步加大送电功率，完成TiO2的碳化反应；c. After the molten pool is completely formed, further increase the power transmission to complete the carbonization reaction of TiO2 ;
d、碳化反应到达临界点后，减小送电功率，逐步降低熔池温度，在降温过程中，接近炉壁处的挂渣产物慢慢凝固并与炉衬致密结合，待挂渣层厚度达到理想厚度时，迅速提高送电功率，使剩余挂渣产物保持流动性从出渣口排出。d. After the carbonization reaction reaches the critical point, reduce the power transmission and gradually reduce the temperature of the molten pool. During the cooling process, the slag products close to the furnace wall will slowly solidify and be closely combined with the furnace lining. When the thickness of the slag layer reaches the ideal thickness , rapidly increase the power transmission power, so that the remaining slag products maintain fluidity and are discharged from the slag outlet.
进一步的是，步骤a中选择的含钛矿中TiO2百分含量为35～50％，Fe2O3百分含量≤3％，焦碳中固定碳含量≥80％，灰分≤5％，含钛矿与焦碳的质量比为1:1～1:1.5。Further, the percentage content of TiO2 in the titanium-containing ore selected in step a is 35-50%, the percentage content of Fe2O3 is ≤3%, the fixed carbon content in coke is ≥80%, and the ash content is ≤5%, The mass ratio of titanium-containing ore to coke is 1:1-1:1.5.
进一步的是，步骤a中对原料进行预处理时，将含钛矿和焦碳研磨成粒度≤2mm的粉料。Further, when the raw material is pretreated in step a, the titanium-containing ore and coke are ground into a powder with a particle size of ≤2 mm.
进一步的是，在步骤b中进行通电熔炼时以熔化物料为主，熔池温度控制在1500℃～1600℃之间。Further, in the step b, the electrified smelting is mainly based on the molten material, and the temperature of the melting pool is controlled between 1500°C and 1600°C.
进一步的是，步骤c中进行碳化反应时，熔池温度控制在1700℃～1750℃，以熔池剧烈翻腾，熔渣液面急剧上升，熔池中暴露出明弧作为充分反应的依据。Furthermore, when the carbonization reaction is carried out in step c, the temperature of the molten pool is controlled at 1700°C to 1750°C, and the molten pool is violently churned, the molten slag level rises sharply, and the bright arc is exposed in the molten pool as the basis for sufficient reaction.
进一步的是，步骤d中以熔渣液面开始下降，熔渣明显粘稠作为临界点，熔池温度逐渐下降到1450℃～1480℃。Further, in step d, the liquid level of the molten slag begins to drop, and the molten slag is obviously viscous as the critical point, and the temperature of the molten pool gradually drops to 1450°C-1480°C.
进一步的是，最终形成的挂渣层厚度为炉衬厚度的1/4～1/3。Further, the thickness of the finally formed slag layer is 1/4-1/3 of the thickness of the furnace lining.
本发明的有益效果是：采用本方法在炉衬上设置挂渣层，挂渣过程中温度区间变化明显，使得挂渣层与电炉炉衬结合更紧密，降低了挂渣层脱落的风险，并且由于实际挂渣温度远大于熔融态高炉渣碳化还原生成过程的温度，可减少熔渣侵蚀挂渣层的可能性，挂渣层中起护壁作用的TiC与最终产品的主要成分一致，不会因挂渣层脱落而污染产品，从而在保证产品质量的同时大大延长了炉衬的使用寿命，节约了生成维护成本。The beneficial effects of the present invention are: adopting this method to set a slag layer on the furnace lining, the temperature range changes significantly during the slag hanging process, which makes the slag layer and the electric furnace lining more closely combined, reduces the risk of the slag layer falling off, and due to the actual The slag temperature is much higher than the temperature of the molten blast furnace slag during the carbonization reduction process, which can reduce the possibility of slag erosion by the slag layer. The layer falls off and pollutes the product, thus greatly prolonging the service life of the furnace lining while ensuring the product quality, and saving the cost of production and maintenance.
具体实施方式detailed description
以下通过具体实施方式对本发明作进一步描述。The present invention will be further described below through specific embodiments.
高钛型高炉渣碳化冶炼的挂渣方法，包括以下步骤：A slag-hanging method for high-titanium type blast furnace slag carbonization smelting, comprising the following steps:
a、对含钛矿、焦碳做预处理，将其磨制成粉料后预混，其中含钛矿与焦碳的配比以反应生成TiC的含量不低于30％为准；a. Pre-treat titanium-containing ore and coke, grind it into powder and pre-mix, wherein the ratio of titanium-containing ore and coke is based on the content of TiC produced by the reaction not less than 30%;
b、将预混料加入电炉中，通电熔炼，使电极中心至炉衬内壁之间形成流动性的熔池；b. Add the premixed material into the electric furnace and smelt with electricity to form a fluid molten pool between the center of the electrode and the inner wall of the furnace lining;
c、待熔池完全形成后，进一步加大送电功率，完成TiO2的碳化反应；c. After the molten pool is completely formed, further increase the power transmission to complete the carbonization reaction of TiO2 ;
d、碳化反应到达临界点后，减小送电功率，逐步降低熔池温度，在降温过程中，接近炉壁处的挂渣产物慢慢凝固并与炉衬致密结合，待挂渣层厚度达到理想厚度时，迅速提高送电功率，使剩余挂渣产物保持流动性从出渣口排出。d. After the carbonization reaction reaches the critical point, reduce the power transmission and gradually reduce the temperature of the molten pool. During the cooling process, the slag products close to the furnace wall will slowly solidify and be closely combined with the furnace lining. When the thickness of the slag layer reaches the ideal thickness , rapidly increase the power transmission power, so that the remaining slag products maintain fluidity and are discharged from the slag outlet.
由于攀钢高炉渣高温碳化工艺所得的最终产物为TiC(百分含量13～15％)，为避免挂渣层在冶炼中熔化而引入其他含钛杂质，需保证挂渣层中TiC百分含量≥30％。在进行原料的配比时，含钛矿与焦碳的质量比依TiO2品位不同而有所调整，根据攀枝花当地矿石成分，结合反应效率和质量等因素综合考虑，原料最佳选择方案为：含钛矿中TiO2百分含量为35～50％，Fe2O3百分含量≤3％，焦碳中固定碳含量≥80％，灰分≤5％，含钛矿与焦碳的质量比为1:1～1:1.5。为了保证含钛矿与焦炭充分反应，最好将含钛矿和焦碳研磨成粒度≤2mm的粉料后再进行熔炼。Since the final product obtained from the high-temperature carbonization process of Panzhihua Iron and Steel’s blast furnace slag is TiC (13-15%), in order to prevent the slag layer from being melted during smelting and introducing other titanium-containing impurities, it is necessary to ensure the percentage content of TiC in the slag layer ≥30%. In the proportioning of raw materials, the mass ratio of titanium-containing ore and coke is adjusted according to the grade of TiO2 . According to the local ore composition in Panzhihua, combined with factors such as reaction efficiency and quality, the best choice of raw materials is: The percentage content of TiO 2 in titanium-containing ore is 35-50%, the percentage content of Fe 2 O 3 is ≤3%, the fixed carbon content in coke is ≥80%, the ash content is ≤5%, the mass ratio of titanium-containing ore to coke It is 1:1～1:1.5. In order to ensure the full reaction of titanium-containing ore and coke, it is best to grind titanium-containing ore and coke into a powder with a particle size of ≤2mm before smelting.
熔炼分为三个阶段，第一阶段为物料熔化，第二阶段为碳化反应，第三阶段为凝固形成挂渣层。物料熔化阶段以使电极中心至炉衬内壁之间形成流动性较好的熔池为准，熔炼温度控制在1500℃～1600℃之间最佳。待粉状物料完全形成熔池时，便进行碳化反应阶段，该阶段主要是使TiO2与还原碳反应生成TiC，反应过程需极高的温度，需使熔池保持在1700℃～1750℃。判断物料是否充分反应，以熔池剧烈翻腾，熔渣液面急剧上升，熔池中暴露出明弧作为充分反应的依据；判断反应是否结束，则以熔渣液面开始下降，熔渣明显粘稠为临界点，此时含钛矿中TiO2至TiC的转化率≥85％，挂渣产物基本形成。反应结束后进入熔炼的第三阶段，逐渐减小输电功率，使熔池温度逐渐降低到1450℃～1480℃，在降温过程中，接近炉壁处的挂渣产物会慢慢凝固并与炉衬致密结合，待挂渣层厚度达到理想厚度时，迅速提高送电功率，使剩余挂渣产物保持流动性从电炉出渣口排出。最终附着在炉衬上的挂渣形成一层保护炉衬的挂渣层，采用该方法形成的挂渣层厚度可为炉衬厚度的1/4～1/3。Melting is divided into three stages, the first stage is material melting, the second stage is carbonization reaction, and the third stage is solidification to form slag layer. In the material melting stage, a molten pool with good fluidity is formed between the center of the electrode and the inner wall of the furnace lining, and the melting temperature is best controlled between 1500°C and 1600°C. When the powdery material completely forms a molten pool, the carbonization reaction stage is carried out. This stage is mainly to make TiO 2 react with reduced carbon to form TiC. The reaction process requires extremely high temperatures, and the molten pool needs to be kept at 1700 ° C to 1750 ° C. Judging whether the material is fully reacted, the molten pool is violently tumbling, the slag liquid level rises sharply, and the bright arc is exposed in the molten pool as the basis for sufficient reaction; to judge whether the reaction is over, the slag liquid level begins to drop, and the slag is obviously viscous. Thickness is the critical point, at this time the conversion rate of TiO2 to TiC in titanium-bearing ore is ≥85%, and the hanging slag product is basically formed. After the reaction is finished, enter the third stage of smelting, gradually reduce the power transmission, so that the temperature of the molten pool is gradually reduced to 1450 ° C ~ 1480 ° C, during the cooling process, the hanging slag products near the furnace wall will slowly solidify and become dense with the furnace lining In combination, when the thickness of the slag layer reaches the ideal thickness, the power transmission power is rapidly increased, so that the remaining slag products maintain fluidity and are discharged from the slag outlet of the electric furnace. The slag attached to the furnace lining finally forms a slag layer to protect the furnace lining, and the thickness of the slag layer formed by this method can be 1/4 to 1/3 of the thickness of the furnace lining.
实施例一：Embodiment one:
在50KVA直流电弧炉中用某种含钛熔分渣和焦粉制得挂渣层。采用50KVA直流电弧炉，原料配比为：某种含钛熔分渣50％，石油焦60％。其中某种含钛熔分渣中TiO2含量为45％，石油焦中固定碳含量为82％，灰分为5％。首先将某种含钛熔分渣和焦粉磨制成粒度≤2mm的粉料，混合均匀后加到直流电弧炉中开始送电冶炼。初始熔化温度为1250℃，待温度达到1550℃时，炉内粉料基本全部熔化并形成流动性较好的熔池。加大送电功率，熔池温度保持在1730±20℃，此时熔池剧烈翻腾，熔渣液面急剧上升。当熔渣液面开始下降，熔渣明显变粘稠后可判断为碳化反应基本结束，取样检测某种含钛熔分渣中TiO2至TiC的转化率≥85％，由此挂渣产物形成。随后逐步减小送电功率，使熔池温度缓慢下降，当熔池中心温度为1460℃时，接近炉壁处的挂渣产物慢慢凝固并与炉衬致密结合，测得挂渣层厚度为炉衬厚度的1/3，最后通过检测分析得到挂渣层中TiC百分含量为34.5％。In a 50KVA DC electric arc furnace, a certain titanium-containing slag and coke powder are used to make a hanging slag layer. A 50KVA DC electric arc furnace is used, and the ratio of raw materials is: 50% of a certain titanium-containing molten slag, and 60% of petroleum coke. Among them, the TiO2 content in a certain titanium-containing molten slag is 45%, the fixed carbon content in petroleum coke is 82%, and the ash content is 5%. First, a certain titanium-containing fused slag and coke powder are ground into a powder with a particle size of ≤2mm, mixed evenly, and then added to a DC electric arc furnace to start smelting with electricity. The initial melting temperature is 1250°C. When the temperature reaches 1550°C, the powder in the furnace is basically completely melted and a molten pool with good fluidity is formed. Increase the power transmission, and the temperature of the molten pool is kept at 1730±20°C. At this time, the molten pool is violently churned, and the molten slag level rises sharply. When the liquid level of slag begins to drop and the slag becomes viscous obviously, it can be judged that the carbonization reaction is basically over. Sampling and testing the conversion rate of TiO2 to TiC in a certain titanium-containing slag is ≥85%, and the slag product is formed. . Then gradually reduce the power transmission to make the temperature of the molten pool drop slowly. When the central temperature of the molten pool is 1460°C, the hanging slag products near the furnace wall will slowly solidify and be closely combined with the furnace lining. The measured thickness of the hanging slag layer is the thickness of the furnace lining. 1/3 of the TiC percentage in the slag layer was found to be 34.5% through detection and analysis.
由此可见，采用本方法来为炉衬增设挂渣层，挂渣过程中温度区间变化明显，使得挂渣层与电炉炉衬结合紧密，降低了挂渣层脱落的风险，并且由于实际挂渣温度远大于熔融态高炉渣碳化还原生成过程的温度，可减少熔渣侵蚀挂渣层的可能性，挂渣层中起护壁作用的TiC与最终产品的主要成分一致，不会因挂渣层脱落而污染产品，从而在保证产品质量的同时大大延长了炉衬的使用寿命，节约了生成维护成本，具有很好的实用性和社会经济价值。It can be seen that when this method is used to add a dross layer to the furnace lining, the temperature range changes significantly during the drossing process, so that the dross layer is closely combined with the electric furnace lining, reducing the risk of the dross layer falling off, and because the actual dross temperature is too high The temperature in the process of carbonization and reduction of molten blast furnace slag can reduce the possibility of molten slag corroding the slag layer. The TiC in the slag layer, which acts as a wall protection, is consistent with the main component of the final product, and will not be polluted by the slag layer falling off Products, thus greatly prolonging the service life of the furnace lining while ensuring product quality, saving maintenance costs, and having good practicality and social and economic value.
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