Research status and prospects of titanium component enrichment in titanium-bearing blast furnace slag
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摘要: 钢铁行业作为高能耗、高污染行业，其节能减排路径对实现“可持续发展”目标至关重要。钒钛磁铁矿冶炼产生的高炉渣中含有大量钛组分，因其处理困难而大量堆存，造成了严重的环境污染和资源浪费。因此，高效清洁地利用含钛高炉渣，提高有价组元利用率，对钢铁行业意义重大。围绕含钛高炉渣中钛组分富集技术进行综述，包括选择性、湿法和火法等富集处理工艺，并对电炉熔分-光催化法预处理-微生物酸浸法进行了展望。目前，含钛高炉渣的处理和资源化利用仍面临诸多问题，重点需突破氯化法废渣脱氯、降低酸碱工艺污染和成本、推动绿色清洁技术发展和应用，以实现钛资源的高值化利用。Abstract: As a relatively high-energy-consumption and high-pollution industry, the steel industry's energy-saving and emission-reduction pathways are crucial for achieving the goal of sustainable development. The blast furnace slag generated from smelting vanadium-titanium magnetite contains a large amount of titanium components, which are difficult to treat and thus stockpiled in large quantities, causing serious environmental pollution and resource waste. Therefore, the efficient and clean utilization of titanium-containing blast furnace slag and the improvement of valuable component utilization are of great significance to the steel industry. This paper provides a comprehensive review of the enrichment technologies for titanium components in titanium-bearing blast furnace slag, including selective, hydrometallurgical, and pyrometallurgical enrichment processes. It also provides prospects for the electric furnace melting separation–photocatalytic pretreatment–microbial acid leaching method. Currently, the treatment and resource utilization of titanium-bearing blast furnace slag still face numerous challenges, with key priorities including breakthroughs in chlorine removal from chlorination process waste residues, reducing pollution and costs in acid–alkali processes, and promoting the development and application of green and clean technologies to achieve high-value utilization of titanium resources.
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图 1 含钛高炉渣中主要物相的结构
（a）钙钛矿（ABO3）结构；（b）钙钛矿晶体结构；（c）金红石结构；（d）假板钛矿结构
Figure 1. Structure of main phases in titanium-bearing blast furnace slag
图 3 反应（1）～（3）各温度下的吉布斯自由能
Figure 3. Gibbs free energy of reactions (1) ～ (3) at different temperatures
图 5 钛渣活化焙烧两段硫酸沸腾浸出钛渣流程
Figure 5. Process flow of two-stage sulfuric acid fluidized bed leaching for activated roasted titanium slag
图 12 高温碳化-低温氯化法流程示意
Figure 12. High-temperature carbonization and low-temperature chlorination process
图 13 碳化过程和氯化过程发生反应的吉布斯自由能变化
（a）碳化过程；（b）氯化过程
Figure 13. Gibbs free energy changes of reactions during the carbonization and chlorination processes
Table 1. Main chemical compositions of titanium-bearing blast furnace slag from different regions[9-18]
Region TiO2 MgO Al2O3 SiO2 CaO Panzhihua 19.23～
23.356.17～
9.2511.09～
14.6924.52～
25.4424.91～
29.08Hongge 13.6 4.24 3.36 3.12 1.10 Chengde 8.50 10.31 13.76 30.85 37.20 Russia 10.5 12.4 16.2 25.2 32.5 South
Africa35.6 14.1 18.0 16.2 14.1 New
Zealand34.3 13.6 17.6 12.1 14.5 
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表 2 含钛高炉渣的主要含钛物相及其特性[22]
Table 2. Main titanium-containing phases and their characteristics in titanium-bearing blast furnace slag[22]
Mineral name Chemical formula Crystal habit Crystal structure Density/% Anosovite Ti3O5 Prismatic or tabular Monoclinic 4.2～4.8 Pseudobrookite Fe2TiO5/MgTi2O5 Short prismatic Orthorhombic 4.5～5 Rutile TiO2 Elongated prismatic Tetragonal 4.2～4.3 Perovskite CaTiO3 Spindle-shaped Cubic 3.98～4.04 Titanium carbonitride Ti(C,N) Dotted Face-centered cubic 5.0～5.4 Panzhihua titanian diopside CaTiAl2O6 Prismatic Monoclinic 3.2～3.6
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Ca Mg Ti3+ Al Ti4+ Si B 2.02 3.7 6.1 9.0 9.44 18.56 22.67 其中，XP*Z/Rk参数被用于指明渣中阴离子的酸碱性，其中XP是元素电负性，Z和Rk分别是阴离子价和半径。
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表 4 含钛高炉渣钛富集工艺对比
Table 4. Comparison of titanium enrichment processes for titanium-bearing blast furnace slag
Extraction method Strengths Limitations Recovery efficiency/% Hydrometallurgical leaching Straightforward process Costly and highly polluting 85~98 Alkali fusion process Well-established process Complex procedures ~91 Electrolysis in molten salt Eco-friendly and highly efficient Technologically complex 80~95 Alumino-thermic reduction High recovery yield Sophisticated process ~91 Carbonization-chlorination method Well-developed technology Substantial pollution ~76
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