CN116023047A - Calcium aluminate cement raw material with ferro-titanium slag as main material and preparation method thereof - Google Patents
Calcium aluminate cement raw material with ferro-titanium slag as main material and preparation method thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 69
- 229910001200 Ferrotitanium Inorganic materials 0.000 title claims abstract description 62
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002994 raw material Substances 0.000 title claims abstract description 44
- 239000004568 cement Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 title abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 26
- 239000000292 calcium oxide Substances 0.000 claims abstract description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000002075 main ingredient Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000020169 heat generation Effects 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 abstract 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
技术领域technical field
本发明涉及工业废料回收利用技术领域，尤其涉及一种以钛铁渣为主料的铝酸钙水泥原料及其制备方法。The invention relates to the technical field of industrial waste recycling, in particular to a calcium aluminate cement raw material with ferro-titanium slag as the main material and a preparation method thereof.
背景技术Background technique
钛铁渣是铝热法冶炼钛铁合金时产生的废渣，目前主要作为次生矿从中回收钛和铝，或用于建筑材料的配料，或者加工后用以耐火材料行业中替代传统的矾土原料，利用价值不高。钛铁渣外观为黑色或深褐色固体，硬度大，断面光亮，类似黑SiC，在自然条件下稳定，不与空气及水反应。钛铁渣中还含有部分金属单质钛和氧化铁，钛铁渣可不经处理作为耐火材料原料直接使用，但实际使用中会在1400℃时体积膨胀较大，且会出现增重，降低材料的高温使用性能。因此，钛铝酸钙作为一种耐火原料，有必要在进行回收钛铁渣时对钛铝酸钙进行处理，降低杂质及低熔物含量。Ferro-titanium slag is the waste slag produced during the aluminothermic smelting of ferro-titanium alloys. At present, it is mainly used as secondary ore to recover titanium and aluminum from it, or used as ingredients for building materials, or processed to replace traditional bauxite raw materials in the refractory industry. , the use value is not high. The appearance of ferro-titanium slag is black or dark brown solid, with high hardness and bright cross-section, similar to black SiC, stable under natural conditions, and does not react with air and water. Ferro-titanium slag also contains some elemental titanium and iron oxide. Ferro-titanium slag can be directly used as refractory raw materials without treatment, but in actual use, the volume expansion will be large at 1400 ° C, and there will be weight gain, which will reduce the material High temperature performance. Therefore, calcium aluminate titanate is used as a refractory raw material, and it is necessary to treat the calcium aluminate titanate during the recovery of ferrotitanium slag to reduce the content of impurities and low melts.
中国专利文献CN1554778A公开了一种低钛铝酸钙及其制备方法，其采用工业氧化铝及其副产品、方解石或石灰石、萤石和长石为原料，经粉碎、混合熔融、冷却、粉碎筛分而制成一种低钛铝酸钙，该材料用以替代低档矾土原料使用，没有产生较好的利用价值。Chinese patent document CN1554778A discloses a low calcium aluminate titanate and its preparation method, which uses industrial alumina and its by-products, calcite or limestone, fluorite and feldspar as raw materials, and is crushed, mixed and melted, cooled, crushed and screened. A kind of low calcium aluminate titanate is made, and the material is used to replace the low-grade bauxite raw material, but does not produce better utilization value.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种以钛铁渣为主料的铝酸钙水泥原料及其制备方法，本铝酸钙水泥原料及其制备方法节能环保、成本低廉，成分稳定，具有结合强度高、发热低等优点，可以在耐火浇注料体系中替代部分纯铝酸钙水泥，适合于作为耐火原料使用，且制备工艺简单。The technical problem to be solved by the present invention is to provide a calcium aluminate cement raw material with ferro-titanium slag as the main material and its preparation method. With the advantages of high strength and low heat generation, it can replace part of pure calcium aluminate cement in the refractory castable system, and is suitable for use as a refractory raw material, and the preparation process is simple.
为解决上述技术问题，本发明以钛铁渣为主料的铝酸钙水泥原料包括50.0～58.0wt% Al2O3、7.0～9.5wt% TiO2、32.0～38.0wt%CaO、1～2wt%MgO、0～0.5wt% Fe2O3和0～1wt% SiO2。In order to solve the above-mentioned technical problems, the calcium aluminate cement raw material of the present invention with ferro-titanium slag as the main material includes 50.0-58.0wt% Al 2 O 3 , 7.0-9.5wt% TiO 2 , 32.0-38.0wt% CaO, 1-2wt% %MgO, 0~0.5wt% Fe 2 O 3 and 0~1wt% SiO 2 .
进一步，所述原料的物相组成为一铝酸钙、二铝酸钙和钛酸钙以及部分玻璃相。Further, the phase composition of the raw material is calcium monoaluminate, calcium dialuminate, calcium titanate and part of glass phase.
一种上述以钛铁渣为主料的铝酸钙水泥原料的制备方法包括如下步骤：A kind of preparation method of the above-mentioned calcium aluminate cement raw material taking ferro-titanium slag as main ingredient comprises the steps:
步骤一、在钛铁合金冶炼过程进行生产排渣时，将熔融状钛铁渣直接排放到设于邻近的电炉中；Step 1. When carrying out production slag discharge during the ferro-titanium alloy smelting process, the molten ferro-titanium slag is directly discharged into an adjacent electric furnace;
步骤二、根据钛铁渣渣量外加入渣量的25～40wt%生石灰，电炉加热至1350～1450℃，保温30～60分钟，生石灰与钛铁渣充分反应；Step 2: According to the amount of ferro-titanium slag, add 25-40wt% quicklime according to the amount of slag, heat it in an electric furnace to 1350-1450°C, keep it warm for 30-60 minutes, and fully react the quicklime and ferro-titanium slag;
步骤三、将处于熔融状态的钛铁渣吹出，冷却后破碎成200目以下的粉料，即得到以钛铁渣为主料的铝酸钙水泥原料。Step 3: Blow out the ferro-titanium slag in the molten state, and after cooling, crush it into a powder of less than 200 meshes to obtain calcium aluminate cement raw material with ferro-titanium slag as the main ingredient.
进一步，所述钛铁渣成分包括70.0～80.0wt% Al2O3、10.0～15.0 wt % TiO2、8.0～12.0 wt %CaO、1～2.5 wt %MgO、0～0.5 wt % Fe2O3和0～0.5 wt % SiO2。Further, the ferrotitanium slag composition includes 70.0-80.0 wt% Al 2 O 3 , 10.0-15.0 wt % TiO 2 , 8.0-12.0 wt % CaO, 1-2.5 wt % MgO, 0-0.5 wt % Fe 2 O 3 and 0~0.5 wt % SiO 2 .
进一步，所述步骤二中外加的生石灰中CaO含量的质量百分比为90.0～95.0%。Further, the mass percentage of CaO content in the quicklime added in the step 2 is 90.0-95.0%.
由于本发明以钛铁渣为主料的铝酸钙水泥原料及其制备方法采用了上述技术方案，即本铝酸钙水泥原料包括50.0～58.0wt% Al2O3、7.0～9.5wt% TiO2、32.0～38.0wt%CaO、1～2wt%MgO、0～0.5wt% Fe2O3和0～1wt% SiO2。本方法在钛铁合金冶炼过程进行生产排渣时，将熔融状钛铁渣直接排放到设于邻近的电炉中；根据钛铁渣渣量外加入渣量的25～40wt%生石灰，电炉加热至1350～1450℃，保温30～60分钟，生石灰与钛铁渣充分反应；将处于熔融状态的钛铁渣吹出，冷却后破碎成200目以下的粉料，即得到以钛铁渣为主料的铝酸钙水泥原料。本铝酸钙水泥原料及其制备方法节能环保、成本低廉，成分稳定，具有结合强度高、发热低等优点，可以在耐火浇注料体系中替代部分纯铝酸钙水泥，适合于作为耐火原料使用，且制备工艺简单。Since the calcium aluminate cement raw material and its preparation method based on ferro-titanium slag in the present invention adopt the above-mentioned technical scheme, that is, the calcium aluminate cement raw material includes 50.0-58.0wt% Al 2 O 3 , 7.0-9.5wt% TiO 2. 32.0-38.0 wt% CaO, 1-2 wt% MgO, 0-0.5 wt% Fe 2 O 3 and 0-1 wt% SiO 2 . In this method, during production and slag discharge in the ferro-titanium alloy smelting process, the molten ferrotitanium slag is directly discharged into an adjacent electric furnace; according to the amount of ferrotitanium slag, 25-40wt% quicklime is added to the amount of slag, and the electric furnace is heated to 1350 ~1450°C, keep warm for 30-60 minutes, the quicklime and ferro-titanium slag fully react; blow out the ferro-titanium slag in the molten state, break it into powder below 200 mesh after cooling, and obtain aluminum with ferro-titanium slag as the main material Calcium acid cement raw material. The calcium aluminate cement raw material and its preparation method are energy-saving, environmentally friendly, low in cost, stable in composition, have the advantages of high bonding strength and low heat generation, can replace part of pure calcium aluminate cement in refractory castable systems, and are suitable for use as refractory raw materials. , and the preparation process is simple.
具体实施方式Detailed ways
本发明以钛铁渣为主料的铝酸钙水泥原料包括50.0～58.0wt% Al2O3、7.0～9.5wt% TiO2、32.0～38.0wt%CaO、1～2wt%MgO、0～0.5wt% Fe2O3和0～1wt% SiO2。The calcium aluminate cement raw material of the present invention with ferro-titanium slag as the main ingredient includes 50.0-58.0wt% Al 2 O 3 , 7.0-9.5wt% TiO 2 , 32.0-38.0wt% CaO, 1-2wt% MgO, 0-0.5 wt% Fe 2 O 3 and 0~1wt% SiO 2 .
优选的，所述原料的物相组成为一铝酸钙、二铝酸钙和钛酸钙以及部分玻璃相。Preferably, the phase composition of the raw material is calcium monoaluminate, calcium dialuminate, calcium titanate and a part of glass phase.
一种上述以钛铁渣为主料的铝酸钙水泥原料的制备方法包括如下步骤：A kind of preparation method of the above-mentioned calcium aluminate cement raw material taking ferro-titanium slag as main ingredient comprises the steps:
步骤一、在钛铁合金冶炼过程进行生产排渣时，将熔融状钛铁渣直接排放到设于邻近的电炉中；Step 1. When carrying out production slag discharge during the ferro-titanium alloy smelting process, the molten ferro-titanium slag is directly discharged into an adjacent electric furnace;
步骤二、根据钛铁渣渣量外加入渣量的25～40wt%生石灰，电炉加热至1350～1450℃，保温30～60分钟，生石灰与钛铁渣充分反应；Step 2: According to the amount of ferro-titanium slag, add 25-40wt% quicklime according to the amount of slag, heat it in an electric furnace to 1350-1450°C, keep it warm for 30-60 minutes, and fully react the quicklime and ferro-titanium slag;
步骤三、将处于熔融状态的钛铁渣吹出，冷却后破碎成200目以下的粉料，即得到以钛铁渣为主料的铝酸钙水泥原料。Step 3: Blow out the ferro-titanium slag in the molten state, and after cooling, crush it into a powder of less than 200 meshes to obtain calcium aluminate cement raw material with ferro-titanium slag as the main ingredient.
优选的，所述钛铁渣成分包括70.0～80.0wt% Al2O3、10.0～15.0 wt % TiO2、8.0～12.0 wt %CaO、1～2.5 wt %MgO、0～0.5 wt % Fe2O3和0～0.5 wt % SiO2。Preferably, the ferrotitanium slag composition includes 70.0-80.0 wt% Al 2 O 3 , 10.0-15.0 wt % TiO 2 , 8.0-12.0 wt % CaO, 1-2.5 wt % MgO, 0-0.5 wt % Fe 2 O 3 and 0-0.5 wt % SiO 2 .
优选的，所述步骤二中外加的生石灰中CaO含量的质量百分比为90.0～95.0%。Preferably, the mass percentage of CaO content in the quicklime added in the step 2 is 90.0-95.0%.
实施例1，在冶炼钛铁合金进行生产排渣时，将熔融状钛铁渣直接排放到邻近的电炉中，根据渣量外加入渣量的30wt%生石灰，利用电炉加热，加热至1380℃保温30分钟，将处于熔融状态的钛铁渣吹出，冷却后破碎成200目以下的粉料，即得以钛铁渣为主料的铝酸钙水泥原料。经X射线衍射分析，该原料的物相组成主要为一铝酸钙、二铝酸钙、钛酸钙。原料物相组成中的一铝酸钙和二铝酸钙均为纯铝酸钙水泥的物相组成。Example 1, when smelting ferro-titanium alloy for production and slagging, the molten ferrotitanium slag is directly discharged into the adjacent electric furnace, 30wt% quicklime is added according to the amount of slag, and the electric furnace is heated to 1380°C and kept for 30 Minutes, the ferro-titanium slag in the molten state is blown out, and after cooling, it is broken into a powder below 200 meshes, that is, the calcium aluminate cement raw material with ferro-titanium slag as the main ingredient. According to X-ray diffraction analysis, the phase composition of the raw material is mainly calcium monoaluminate, calcium dialuminate and calcium titanate. The calcium monoaluminate and calcium dialuminate in the phase composition of the raw material are both the phase composition of pure calcium aluminate cement.
实施例2，在冶炼钛铁合金进行生产排渣时，将熔融状钛铁渣直接排放到邻近的电炉中，根据渣量外加入渣量的34wt%生石灰，利用电炉加热，加热至1400℃保温45分钟，将处于熔融状态的钛铁渣吹出，冷却后破碎成200目以下的粉料，即得以钛铁渣为主料的铝酸钙水泥原料。经X射线衍射分析该原料的物相组成主要为一铝酸钙、二铝酸钙、钛酸钙。原料物相组成中的一铝酸钙和二铝酸钙均为纯铝酸钙水泥的物相组成。Example 2, when smelting ferro-titanium alloy for production and slagging, the molten ferrotitanium slag is directly discharged into the adjacent electric furnace, 34wt% quicklime is added according to the amount of slag, and the electric furnace is used to heat it to 1400°C and keep it for 45 Minutes, the ferro-titanium slag in the molten state is blown out, and after cooling, it is broken into a powder below 200 meshes, that is, the calcium aluminate cement raw material with ferro-titanium slag as the main ingredient. According to X-ray diffraction analysis, the phase composition of the raw material is mainly calcium monoaluminate, calcium dialuminate and calcium titanate. The calcium monoaluminate and calcium dialuminate in the phase composition of the raw material are both the phase composition of pure calcium aluminate cement.
以钛铁渣为主料制备铝酸钙水泥原料，充分利用熔渣的潜热，制备成本低，且电熔制备的铝酸钙水泥原料成分稳定，具有结合强度高、发热低等优点，可以在耐火浇注料体系中替代部分昂贵的纯铝酸钙水泥，适合于作为耐火原料使用。The raw material of calcium aluminate cement is prepared by using ferro-titanium slag as the main material, making full use of the latent heat of slag, the preparation cost is low, and the raw material composition of calcium aluminate cement prepared by electrofusion is stable, it has the advantages of high bonding strength and low heat generation, and can be used in It can replace some expensive pure calcium aluminate cement in the refractory castable system and is suitable for use as a refractory raw material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB908073A (en) * | 1959-01-26 | 1962-10-17 | Steinwerke Feuerfest Karl Albe | Improvements in the manufacture of refractory alumina cements |
| CN1554778A (en) * | 2003-12-26 | 2004-12-15 | 张延大 | Low-titanium calcium aluminate and its preparing method |
| US20070266902A1 (en) * | 2006-05-16 | 2007-11-22 | Harsco Technologies Corporation | Regenerated calcium aluminate product and process of manufacture |
| CN102923976A (en) * | 2012-11-23 | 2013-02-13 | 攀枝花钢城集团有限公司 | Aluminate cement preparation method |
| CN106904982A (en) * | 2017-03-24 | 2017-06-30 | 武汉科技大学 | High alumina insulating refractory raw material with ferrotianium slag as major ingredient and preparation method thereof |
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2021
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB908073A (en) * | 1959-01-26 | 1962-10-17 | Steinwerke Feuerfest Karl Albe | Improvements in the manufacture of refractory alumina cements |
| CN1554778A (en) * | 2003-12-26 | 2004-12-15 | 张延大 | Low-titanium calcium aluminate and its preparing method |
| US20070266902A1 (en) * | 2006-05-16 | 2007-11-22 | Harsco Technologies Corporation | Regenerated calcium aluminate product and process of manufacture |
| CN102923976A (en) * | 2012-11-23 | 2013-02-13 | 攀枝花钢城集团有限公司 | Aluminate cement preparation method |
| CN106904982A (en) * | 2017-03-24 | 2017-06-30 | 武汉科技大学 | High alumina insulating refractory raw material with ferrotianium slag as major ingredient and preparation method thereof |
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| Title |
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| 李祖树，徐楚韶，李在妙，周友全: "用高炉钛渣冶炼钛硅合金的研究", 重庆大学学报(自然科学版), no. 04 * |
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