Preparation,characterization and photocatalytic activity of sulfuric acid-modified titanium-bearing blast furnace slag

The feasibility of reducing Cr(VI)from the aqueous solution by sulfuric acid-modified titanium-bearing blast furnace slag(SATBBFS)as a photocatalyst was investigated.The photocatalysts were examined by X-ray diffraction(XRD),UV-vis diffuse reflectance spectra,thermogravimetric analysis(TG)and Fourier transform infrared spectroscopy(FTIR).The photocatalytic activities of the different catalysts were evaluated by the photocatalytic reduction of Cr(VI)under UV-vis light irradiation.The results show that the photocatalytic activities of SATBBFS catalysts are strongly dependent on CaTiO3-to-TiO2 mass ratio,adsorption capacity and surface acidity,and SATBBFS calcined at 400°C shows a higher photocatalytic activity compared with other catalysts.

Simultaneous preparation of TiO2 and ammonium alum,and microporous SiO2 during the mineral carbonation of titanium-bearing blast furnace slag

In this study,a route for simultaneous mineralization of CO2 and production of titanium dioxide and ammonium alum,and microporous silicon dioxide from titanium-bearing blast furnace slag(TBBF slag)was proposed,which is comprised of(NH4)2 S04 roasting,acid leaching,ammonium alum crystallization,silicic acid flocculation and Ti hydrolysis.The effects of relevant process parameters were systematically investigated.The re sults showed that under the optimal roasting and leaching conditions about 85%of titanium and 84.6%of aluminum could be extracted while only 30%of silicon entered the leachate.84%of Al^3+was crystallized from the leachate in the form of ammonium aluminum sulfate dodecahydrate with a purity up to 99.5 wt%.About 85%of the soluble silicic acid was flocculated with the aid of secondary alcohol polyoxyethylene ether 9(AEO-9)to yield a microporous SiO2 material(97.4 wt%)from the crystallized mother liquor.The Al-and Si-depleted solution was then hydrolyzed to generate a titanium dioxide(99.1 wt%)with uniform particle size distribution.It was figured out that approximately 146 kg TiO2 could be produced from 1000 kg of TBBF slag.Therefore,the improved process is a promising method for industrial application.

Recent progress of efficient utilization of titanium-bearing blast furnace slag

Titanium-bearing blast furnace slag(BFS)has valuable compositions and potential environmental hazardousness.Thus,developing efficient and green approaches to utilize BFS is highly desired for resource economization and environmental protection.In the past decades,many attempts have been adopted to reuse BFS efficiently,and significant advances in understanding the fundamental features and the development of efficient approaches have been achieved.This review provides a comprehensive overview of the latest progress on the efficient utilization of BFS and discusses the mechanism and characteristics of various approaches,along with their application prospects.In particular,the extraction and enrichment of titanium-bearing phases from BFS are highlighted because of the high availability of titanium resources.This systemic and comprehensive review may benefit the design of new and green utilization routes with high efficiency and low cost.

Antibacterial Properties of V-doped Titanium-bearing Blast Furnace Slag Prepared at Different Calcination Temperatures

Perovskite-type V-doped titanium-bearing blast furnace slag (VTBBFS) photocatalyst was prepared by high-temperature solid phase method.The influence of calcination temperature on the photocatalytic and antibacterial properties of VTBBFS was studied in details.Its composition and microstructure were evaluated by X-ray diffractometer,ultraviolet-visible absorption spectrometer,Fourier transform infrared spectrometer and scanning electron microscope.The antibacterial properties of VTBBFS to Candida albicans were investigated by flask oscillation method.The results showed that the optical absorption and antibacterial properties of VTBBFS were the best with 10%(ω) doping of vanadium,prepared at 800℃ for 2 h,and its sterilization rate was close to 100% to Candida albicans (ATCC10231).The minimum inhibitory and minimum bactericidal concentrations were 25 and 50 mg/mL.When the concentration was 0.2 μg/mL,the catalyst had the least toxic toxicity.

Recovery of titanium,aluminum,magnesium and separating silicon from titanium-bearing blast furnace slag by sulfuric acid curing-leaching

An energy-efficient route was adopted to treat titanium-bearing blast furnace slag(TBBFS)in this study.Titanium,aluminum,and magnesium were simultaneously extracted and silicon was separated by low temperature sulfuric acid curing and low concentration sulfuric acid leaching.The process parameters of sulfuric acid curing TBBFS were systematically studied.Under the optimal conditions,the recovery of titanium,aluminum,and magnesium reached 85.96%,81.17%,and 93.82%,respectively.The rapid leaching model was used to limit the dissolution and polymerization of silicon,and the dissolution of silicon was only 3.18%.The mechanism of sulfuric acid curing-leaching was investigated.During the curing process,the reaction occurred rapidly and released heat massively.Under the attack of hydrogen ions,the structure of TBBFS was destroyed,silicate was depolymerized to form filterable silica,and titanium,magnesium,aluminum,and calcium ions were replaced to form sulfates and enriched on the surface of silica particles.Titanium,aluminum,and magnesium were recovered in the leaching solution,and calcium sulfate and silica were enriched in the residue after leaching.This method could effectively avoid the formation of silica sol during the leaching process and accelerate the solid-liquid separation.

Synthesis of Foliar Fertilizer and Ca-S-Si Compound Fertilizer from Titanium-bearing Blast Furnace Slag

With titanium-bearing blast furnace slag, ammonium sulfate, citric acid and potassium carbonate as raw materials to produce foliar fertilizer and Ca-S-Si compound fertilizer by means of heating process for the first time, which improved the solubility of the slag and converted the nutritional elements into such ones which are prone to be absorbed by plants. The effects of process conditions on dissolution rate of titanium were mainly analyzed through the orthogonal experiment. The results showed that the optimum synthesis process conditions of foliar fertilizer from the slag were 360 ℃ for 35 min, the mass ratio of ammonium sulfate and titanium-bearing blast furnace slag was 8：1. Under these conditions more than 80% of iron, titanium, magnesium and part of silicon in titanium-bearing blast furnace slag converted into water-soluble substances and existing in foliar fertilizer. Foliar fertilizer contained nitrogen, sulfur, potassium, iron, titanium, magnesium and silicon, and pH value of foliar fertilizer was 6. Ca-S-Si compound fertilizer mainly contained calcium silicate and calcium sulfate, which existed in the form of citric acid-soluble substance and slightly soluble substance, respectively.

Volume and Surface Nucleation of Crystals in Glass Based on Blast-Furnace Slag

Using differential thermal analysis, X-ray phase analysis, electron microscopy, and optical microscopy, the nucleation of crystals in glass obtained by blending metallurgical slag with silicon dioxide has been studied. The type of crystallization (homogeneous or heterogeneous, volume or surface) is revealed for each of nine compositions of synthesized glass. It is shown that the first crystalline phase in a volume crystallizing glass is perovskite (CaO·TiO2);in this phase a nucleation of the main phase occurs: melilite (solid solution of gehlenite 2CaO·Al2O3·SiO2 in akermanite 2CaO·MgO·2SiO2). The fundamental characteristics of homogeneous (for a catalizing phase, perovskite) and heterogeneous (for a catalyzed phase, melilite) of crystallization are determined: the steady state nucleation rate Ist, time of unsteady state nucleation τ, crystal growth rate U, and activation energy of frictional flow. The temperature dependences of Ist, τ, and U are obtained. The kinetics of the crystallization of glass is studied and the rates of the surface crystal growth are determined in the glass of nine compositions. The influence of grinding the particles of the original glass on the sequence of deposition of the crystalline phases was studied. Practical recommendations are presented for the use of blast-furnace slag as a raw material for the synthesis of glass and their further utilization.

Determination of dielectric properties of titanium carbide fabricated by microwave synthesis with Ti-bearing blast furnace slag

The preparation of functional material titanium carbide by the carbothermal reduction of Ti-bearing blast furnace slag with microwave heating is an effective method for valuable metals recovery;it can alleviate the environmental pressure caused by slag stocking.The dynamic dielectric parameters of Ti-bearing blast furnace slag/pulverized coal mixture under high-temperature heating are measured by the cylindrical resonant cavity perturbation method.Combining the transient dipole and large π bond delocalization polarization phenomena, the interaction mechanism of the microwave macroscopic non-thermal effect on the titanium carbide synthesis reaction was revealed.The material thickness range during microwave heating was optimized by the joint analysis of penetration depth and reflection loss, which is of great significance to the design of the microwave reactor for the carbothermal reduction of Ti-bearing blast furnace slag.

Preparation of high acidity coefficient slag wool fiber with blast furnace slag and modifying agents

Preparation of high acidity coefficient slag wool fiber with molten slag and modifying agents is considered to be a positive approach for value-added utilization of blast furnace slag. In order to achieve the multi-purposes of fiber-forming, energy saving, and waste heat recovery, the modifying agents that can improve the acidity coefficient of slag effectively, economically, and environmentally were investigated. Three agents with different acidity coefficients were adopted to modify slag and manufacture wool fibers. The effect of agent and slag proportion on the melting temperature and viscosity of molten slag was studied at a fixed acidity coefficient of 1.8 and 2.0. The results indicate that the sample modified with high acidity coefficient agent and high slag proportion has lower melting temperature and viscosity. The effect of agent and slag temperature on the fiber diameter was also investigated when the acidity coefficient of slag is 2.0. At a fixed slag proportion of 50 wt.%, the mean diameter decreases with increasing temperature and decreasing viscosity coefficient. Besides, the temperature drops caused by the addition of agents and energy consumption of samples for heating the slag were also analyzed.

石灰-高炉矿渣改良膨胀土强度特性试验研究

因膨胀土具有吸水膨胀、失水收缩等不稳定性特征,使用高炉矿渣作为新型固化剂,并与无机材料石灰组合对膨胀土进行改良。对改良膨胀土开展自由膨胀率、液塑限、无侧限抗压强度和抗剪强度等指标的研究,探讨并分析了石灰-高炉矿渣(L-BLS)改良膨胀土在不同养护龄期以及不同改良剂掺量下的无侧限抗压强度变化规律。结果表明:使用L-BLS改良膨胀土能够显著提高膨胀土的早期强度;改良膨胀土的强度随养护龄期及改良剂掺量的增加而增强;当掺入6%石灰及9%高炉矿渣时,对应龄期的无侧限抗压强度最大,材料的有效利用率最佳。

含钛高炉渣氯化铵活化焙烧工艺优化研究

针对钒钛磁铁矿高炉炼铁产出的含钛高炉渣,开展了氯化铵活化焙烧技术研究,使用响应曲面法对工艺条件进行优化,探究焙烧温度、保温时间、氯化铵配比等因素对TiO_(2)品位和杂质脱除的影响,并建立活化焙烧过程的二次回归方程模型。根据模型计算,焙烧温度、保温时间、氯化铵配比等因素对TiO_(2)品位和铝脱除率影响显著,根据模型预测,在焙烧温度为469℃、保温时间为0.97 h、氯化铵配比为41%时,TiO_(2)品位38.94%、铝脱除率91.43%;通过试验验证,在此条件下,浸出渣TiO_(2)品位38.39%、铝脱除率90.39%,试验值与模型预测值误差范围在1.5%以内,证明该优化模型具有可靠性。

高炉渣基沸石分子筛材料的制备及其响应面优化

以高炉渣(BFS)为原料制备高炉渣基沸石分子筛(BFSZ),为实现对BFSZ制备工艺条件的优化,基于单因素试验结果,采用Box-Behnken Design(BBD)响应面法考察晶化时间(A)、晶化温度(B)、初始硅铝物质的量比(C)等因素对BFSZ阳离子交换量(CEC)的影响。结果表明:响应面法建立的回归模型方程具有高度的显著性,可信度和精确度较高,得到制备BFSZ的优化工艺条件:碱熔温度为600℃、液固比为5∶1 mL/g、晶化时间为8.74 h、晶化温度为98.41℃、初始硅铝物质的量比1.18,此时BFSZ的CEC为3.21 meq/g。经验证,BFSZ的CEC实际值与预测值的相对误差约为1.9%,表明该模型能够很好地反映各因素对BFSZ的CEC影响。

工业废渣超细微粉在水泥及混凝土中的应用分析

高炉矿渣超细微粉、超细钢渣微粉、超细粉煤灰和工业硅灰等工业废渣超细微粉既可用作生产水泥的高活性混合材料,又可在混凝土配制过程中作为第六组分材料——矿物外加剂或矿物掺合料。配入水泥或混凝土,能够充分发挥其优良的“微集料填充效应”,“火山灰化学活性效应”以及“颗粒形态与轴承效应”,提高混凝土抗渗性、抗冻性、抗碳化能力以及抵抗SO_(4)^(2-)和Cl^(-)化学侵蚀的综合性能;能够使水泥石与混凝土体系的微观更加密实,获得更高的结构强度;降低水化热,减少混凝土的温度应力收缩与化学收缩,有效避免混凝土开裂;能够有效抑制碱-骨料反应(AAR),显著提高混凝土结构的耐久性能。

气淬作用下熔渣粒化机理及破碎效果分析

针对熔渣气淬粒化工艺,在实验的基础上开展了气淬作用下的熔渣粒化过程数值模拟.利用VOF模型追踪自由界面、Realizableκ-ε模型处理湍流流动.模拟得到了气淬熔渣粒化过程,并分析了熔渣破碎机理.进一步建立了无量纲数局部动量比,对熔渣的黏度及气渣局部动量比进行了影响因素分析.结果表明:熔渣存在两种破碎形式,一种为R-T不稳定性所产生的柱状破碎,主要由渣流迎风面和背风面存在的局部高压区所导致;另一种为K-H不稳定性主导的表面液膜破碎,其主要由气渣界面间的速度梯度所引起.熔渣黏度的增加会使熔渣的颗粒粒径增大,破碎效果降低;气渣局部动量比的增大增强了熔渣的表面液膜波动,使剥离的颗粒数量增多,破碎长度减小,熔渣破碎效果加强.

利用烧结脱硫灰制备胶凝材料的研究

研究了烧结烟气半干法脱硫灰复掺矿渣、钢渣，辅之外加剂，制备胶凝材料的可行性。结果表明，采用改性脱硫灰（GXTLH）、钢渣、矿渣及水泥熟料再混磨制备的复合胶凝材料，具有良好的安定性等水化性能和力学性能；当GXTLH掺入量为20％、CFII1．5％、减水剂0．5％及水泥熟料23％时，矿渣掺量在12％～44％、钢渣掺量11％～44％之间制备的胶凝材料初凝时间、终凝时间、力学性能满足GB13592．92《钢渣矿渣水泥标准》；矿渣与钢渣比、水泥熟料及外加剂等掺量一定，GXTLH掺量超过30％时，GXTLH胶凝材料的抗压抗折强度均有所下降。

粒化高炉矿渣成分和细度对活性的影响

为了研究矿渣成分和细度对其活性的影响,本文对六种不同种类的矿渣进行了化学成分分析和不同比表面积下活性指数的测定,并且对其水化产物进行微观结构分析。结果表明:细度和成分是影响矿渣活性的主要因素,矿渣细度变细,活性指数明显增大,并且矿渣的成分对活性的影响要低于细度对活性的影响;微观结构分析发现,矿渣颗粒表面被严重水化侵蚀,并且生成一些低C/S(Ca/Si)比的水硅酸钙凝胶和低C/A(Ca/Al)比的水化铝酸钙等物质。

助磨剂对高炉矿渣的粉磨及性能的影响

从比表面积、筛余、粒度分布等方面研究了5种助磨组分对粒化高炉矿渣粉磨的作用效果,并探讨了助磨组分对矿渣微粉活性、流动度等性能的影响。结果表明:助磨剂对矿粉的粉磨均有一定的助磨作用,使矿粉的颗粒分布呈宽化分布,<3μm和>60μm颗粒数量均增加;同时使凝结时间缩短,标准稠度需水量增加。掺入0.02%改性多元醇的1、7、28d活性指数较空白样增加了7.45%、8.25%和5.33%。

改性含钛高炉渣的盐酸加压浸出

经选择性富集的改性含钛高炉渣含TiO232%左右,是宝贵的钛资源。为此,采用盐酸加压浸出对改性含钛高炉渣提取其中的Ti进行了试验研究,并考察了盐酸浓度、反应时间、反应温度、矿酸比、物料粒度等因素对TiO2浸出率的影响。结果表明,在适宜的条件下,TiO2的浸出率可达到95%以上,所得钛液经水解获得的富钛料其TiO2含量大于95%,为改性含钛高炉渣加压浸出分离提供了技术依据。

硫酸盐修饰的含钛高炉渣光催化还原Cr(Ⅵ)

采用高能球磨法,在300℃煅烧2 h合成了具有钙钛矿型的硫酸盐修饰的含钛高炉渣(sulfate-modified titanium-bearing blast furnace slag,STBBFS)催化剂.用X射线衍射、扫描电子显微镜和紫外-可见漫反射分析对硫酸盐修饰的含钛高炉渣催化剂进行了表征,确定其具有钙钛矿型;粉体的颗粒形态均为不规则形状,平均粒径为1.5μm左右;在紫外区域具有很强的光吸收能力.由六价铬的还原率来评价STBBFS催化剂的光催化活性,结果表明:与市售TiO2相比,钙钛矿型的STBBFS催化剂具有较高的光催化活性,500 W中压汞灯照射4 h,可将质量浓度为20 mg/L的六价铬废水完全降解.

高温固相法制备钒掺杂含钛高炉渣光催化抗菌材料

采用高温固相法,掺杂不同质量分数的V2O5,在800℃煅烧2h合成了钒掺杂的含钛高炉渣催化剂(vanadium oxide modified titanium bearing blast furnace slag,VTBBFS)。用X射线衍射、扫描电子显微镜和紫外-可见漫反射光谱仪对钒掺杂的含钛高炉渣催化剂进行了表征,确定其具有钙钛矿结构;粉体的颗粒形态均为不规则块状,800℃煅烧后出现了团聚现象;在紫外区域具有强光吸收能力,并发生红移。以白色念珠菌为实验菌种考察钒掺杂的含钛高炉渣催化剂抗真菌能力。结果表明,V2O5掺杂量为10%时,催化剂具有较强的抗白色念珠菌能力,在普通光照下杀菌率可达到100%。