Preparation of Ti-rich material from titanium slag by activation roasting followed by acid leaching

A method of activation roasting followed by acid leaching using titanium slag was introduced to prepare Ti-rich material. The effects of H₃PO₄ dosage, roasting temperature, and roasting time on TiO₂ grade were investigated. A Ti-rich material containing 88.54% TiO₂, 0.42% (CaO+MgO) was obtained when finely ground titanium slag was roasted with 7.5% H₃PO₄ at 1000 °C for 2 h, followed by a two-stage leaching in boiling dilute sulfuric acid for 2 h. The XRD patterns show that the product is titanium dioxide with a rutile structure. Mechanism studies show that structures of anosovite solid solution and silicate minerals are destroyed in the roasting process. As a result, titanium components in titanium slag are transformed into TiO₂ (rutile) while impurities are transformed into acid-soluble phosphate and quartz.     

Upgrading ilmenite into a high-grade synthetic rutile

Titanium, the ninth most abundant element, occurs mainly in minable form as ilmenite (95%) and rutile (5%) minerals. The current world consumption of these minerals is used mainly to produce titanium dioxide pigments, with the balance in welding rod flux and titanium metal. Ilmenite is currently being mined in annual quantities eight times larger than rutile. In the past 35 years, an increasing percentage of the pigments have been produced via the chloride method, which requires rutile. This has caused the need to produce a synthetic rutile of more than 90% TiO₂ content and large amounts of an 85% TiO₂ slag from ilmenite. The direct chlorination of 61% TiO₂ ilmenite is being done on a large scale in the United States.     

Appropriate titanium slag composition during smelting of vanadium titanomagnetite metallized pellets

The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis. According to the thermodynamic results, low-melting-point regions and MgTi₂O₅ primary phase area in the phase diagrams, the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of 50% TiO₂, 8%–12% MgO and 13% Al₂O₃ (mass fraction) with a binary basicity of 0.8–1.2. Finally, the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained. The obtained vanadium-containing molten iron contains 0.681% V and 0.267% Ti, and the obtained titanium slag contains 52.21% TiO₂ (mass fraction), in which MgTi₂O₅ is the primary phase. The titanium resource in the final titanium slag production could be used to produce TiO₂ pigment by acid leaching methods.     

改性含钛高炉渣中铁、钒和钛的回收

提出两段氧化—碱浸—酸浸工艺来回收改性含钛高炉渣中的铁、钒和钛.较佳的提铁实验条件为一段氧化时间40 s和保温时间8 min,铁的回收率为89.93％.较佳的提钒实验条件为总氧化时间126 s、NaOH浓度4.0 mol/L、浸出温度95℃、浸出时间90 min和碱浸循环次数4,钒的浸出率为92.13％.较佳的提钛实验...     

Phase conversion and removal of impurities during oxygen-rich alkali conversion of high titanium slag

In order to achieve high-efficiency alkali conversion and impurity removal of high titanium slag under the condition of low alkali concentration, a new way of oxygen-rich alkali conversion in KOH solution was proposed. The conversion law of element occurrence state and the influence of the conversion conditions on the titanium conversion rate and removal rate of silicon and aluminum were studied. The results showed that the KOH solution converted the titanium oxide in high titanium slag into whisker-like potassium titanate. Silicon and aluminum elements were dissolved into the solution. Under the following conditions, KOH concentration of 6 mol/L, conversion temperature of 260 °C, initial oxygen partial pressure of 2 MPa, liquid?solid ratio of 35 mL/g, conversion time of 4 h, and high titanium slag particle size of 48?74 μm, the conversion rate of titanium was 97.0%, and the removal rates of silicon and aluminum were 90.2% and 76.2%, respectively. Oxygen-rich alkali conversion product was converted to rutile with a TiO₂ grade of 99.1% by acid hydrolysis conversion.     

Post-mortem analysis of high alumina brick attacked by vanadium and titanium bearing slag after service in torpedo ladle

Abstract

High alumina brick after service in a torpedo ladle was analysed by means of atomic emission spectroscopy, X-ray diffraction, electron probe microanalysis and themochemical analysis in order to determine the corrosion mechanism during industrial application in a steel works. The results showed that slag containing vanadium and titanium oxide is more corrosive than common silica slags, and that this facilitates corrosion and penetration into the high alumina brick. Mineralogical observation confirmed that V₂O₅, TiO₂, MnO and FeO and MgO in the slag reacted with native phases presented in high alumina brick to form complex spinel, corundum and anorthite solid solution, etc. The dissolved content of V₂O₅ in the spinel decreased from 6·08 to 2·78 wt-% from the working face to the inner area. However, the FeO and MnO content in the spinel varied little with a slight increase in the TiO₂ content. The expansion coefficient mismatch between the penetrated zone and cold face zones, which results in densification spalling and increased porosity, play a key role in the failure of the high alumina brick.     

电渣重熔中TiO2对低氟CaF2-CaO-Al2O3-MgO-Li2O渣黏度和结构的影响

本文研究了连续冷却条件下电渣重熔中TiO₂对低氟CaF₂-CaO-Al₂O₃-MgO-Li₂O渣黏度的影响,并利用傅里叶变换红外光谱和拉曼光谱分析水淬渣和对应结构的关系。结果表明,渣的黏度随着TiO₂的增加而降低,当TiO₂含量达到13.1%,随着温度从1743K, 1793K, 1843K 增加至1893K时, 对应黏度从0.067 Pa?s, 0.059 Pa?s, 0.056 Pa?s 降低到0.054 Pa?s;当温度达到1843K或之上时,TiO₂的加入对降低黏度有较小的影响。随着TiO₂含量从0,4.3%,8.7%增加至13.1%,黏流活化能从58.0 kJ/mol,47.7 kJ/mol,42.8 kJ/mol降低到38.6 kJ/mol。此外,红外光谱结果表明,随着TiO₂的加入,渣中[AlOnF_4-n]-四面体络合物和[AlO₄]-四面体网状结构被解聚,但[AlO₆]-八面体结构没有发现;同时,拉曼光谱分析表明,TiO₂加入可解聚[AlO₄]-四面体网状结构中Al-O-Al键, 并且Q^₄单元转化为Q^₂单元,同时形成O-Ti-O和Ti-O-Ti键。这些结果都表明TiO₂可降低渣的聚合度,并且有利于渣的结构简单化。最终,黏度变化与渣的对应结构有很好的一致性。     

TiO2对水下湿法焊接熔渣形貌及微观组织的影响

文中采用自制的金红石型碳钢焊条进行水下湿法焊接,重点分析了药皮中TiO₂的加入量对熔渣形貌及微观组织结构的影响.由熔渣的成分及物相分析得出,熔渣的主要组成相为Fe₂MnTi₃O₁₀,还含有少量的Ca₂SiO₄和自由氧化物.对熔渣的宏观形貌及微观组织结构分析发现,当药皮中TiO₂加入量较大时,熔渣致密松脆,熔渣的微观组织中灰白色条状相粗大,有利于熔渣脱渣;当减小TiO₂的加入量,增大CaCO₃的加入量时,熔渣变得松散,出现粘渣现象,此时微观组织中的灰白色条状相变得细小,不利于熔渣脱渣.     

Dissociation of Ti2O3 from titania slag under mechanical activation

In this present study, the effects of mechanical activation on the characterization of titania slag were systematically investigated. The crystal structures, surface chemical functional groups, and microstructure of the samples were characterized before and after mechanical activation using XRD, FT-IR, and Raman spectroscopy techniques, respectively. It was found that untreated titania slag under mechanical activation was mainly composed of Fe₃Ti₃O₁₀ and rutile TiO₂, but that of being treated by mechanical activation was mainly composed of Fe₃Ti₃O₁₀, Ti₂O₃ and rutile TiO₂. Ti₂O₃ is transformed partially from Fe₃Ti₃O₁₀ under moderate mechanical activation conditions for 12 h. The demonstration of mechanical activation techniques can be applied effectively and efficiently to the treatment processing of titania slag.     

Removal of magnesium and calcium from electric furnace titanium slag by H3PO4 oxidation roasting–leaching process

H₃PO₄ oxidation roasting followed by HCl acid leaching was proposed to remove magnesium and calcium from electric furnace titanium slag containing 3.12% MgO and 0.86% CaO. XRF, XRD and SEM techniques were used to characterize the composition, mineral phase component and microstructure of the titanium slag. The H₃PO₄ oxidation thermodynamic, mineral phase transformation, microstructure, element distribution in titanium slag during H₃PO₄ oxidation process and leaching process were investigated. The thermodynamic analysis indicated that H₃PO₄ could promote the decomposition of MgTi₂O₅ and CaSiO₃. The results indicated that H₃PO₄ could effectively promote the transformation of titanium-bearing mineral to rutile and enrich the impurities in M_xTi_3–xO₅ into phosphate which could be removed by acid leaching process. Under the studied conditions, the leaching rates of magnesium and calcium reached 94.68% and 87.19%, respectively. The acid leached slag containing 0.19% MgO and 0.13% CaO (mass fraction) was obtained.     

Extraction of valuable metals from Ti-bearing blast furnace slag using ammonium sulfate pressurized pyrolysis–acid leaching processes

A novel method of extracting valuable metals from Ti-bearing blast furnace slag (TBBF slag) via pressure pyrolysis of recyclable ammonium sulfate (AS)–acid leaching process was proposed. The results show that when pressurized roasting at an AS-to-slag mass ratio 3:1 and 370 °C for 90 min, the extraction rates of titanium, aluminum and magnesium reached 94.5%, 91.9% and 97.4%, respectively. The acid leaching solution was subjected to re-crystallization in a boiling state to obtain a titanium product having a TiO₂ content of 94.1%. The above crystallization mother liquor was adjusted to pH=6 and pH≥12.2, respectively, and then qualified Al₂O₃ and MgO products were obtained. The analysis through XRD and SEM–EDS proves that the main phases in roasted samples were NH₄AlSO₄, CaSO₄ and TiOSO₄. The thermodynamic analysis presents that the main minerals of perovskite, spinel and diopside in raw ore could spontaneously react with the intermediate produced by AS under optimal conditions.     

热喷涂法制备的La3+掺杂纳米TiO2粉末的表征

采用等离子热喷涂法以钛酸四丁酯为主要原料制备出稀土离子掺杂的纳米TiO2光催化剂.通过XRD,XPS,TEM,UV-Vis等检测手段对样品进行表征,同时检测了其光催化性能,并分析了掺杂对TiO2的影响机理.结果表明,所制备的La3 掺杂纳米TiO2是锐钛矿相和金红石相混晶结构,粒径分布在10～50nm之间;La3 掺杂能够促进锐钛矿向金红石的转变,同时抑制TiO2晶粒的长大;La3 掺杂使TiO2紫外-可见吸收光谱发生红移;适量La3 掺杂能显著提高TiO2的光催化活性,最佳掺杂浓度为0.5%(与Ti原子摩尔比),甲基橙降解率在90min内可达到82.4%.比纯TiO2高出13.2%.     

废弃SCR脱硝催化剂与废NaCl盐焙烧回收催化剂中的钛、钒、钨（英文）

通过废弃选择性催化还原(SCR)脱硝催化剂与废NaCl盐焙烧,可以将催化剂中的钨和钒与钛分离。在最佳浸出条件下(焙烧温度900℃,焙烧时间3 h,废盐与废催化剂的质量比为0.5,浸出温度80℃,反应时间60 min),钨和钒的浸出率分别达到84.63%和66.42%,同时钛的损失率仅为1.3%。废NaCl盐和焙烧温度可以促进锐钛矿型TiO₂转化为金红石型TiO₂,反应后得到了金红石型TiO₂。金红石型TiO₂中的钛的价态为四价,晶格氧和化学吸附氧分别占57.26%和42.74%。该方法可以同时解决2种废弃物的处置问题。     

Formation of a wear-resistant nanocrystalline layer strengthened by TiO2 (Rutile) particles on the surface of titanium

The effect of a thermomechanical treatment including severe plastic deformation under dry sliding friction conditions and subsequent heating in air to 350–650°C with further holding for 1 h on the structure and wear resistance of commercial titanium of grade VT1-0 has been studied. It has been shown that the deformation by friction leads to the formation of a nanocrystalline structure with α crystals 20–100 nm in size in a surface layer of titanium of about 10 μm thick. The heating of titanium deformed by friction at temperatures of 450–650°C for 1 h in air leads to the formation in the surface layer of this material ～10 μm thick of nanocrystalline particles of the titanium oxide TiO₂ (rutile), the volume fraction of which reaches tens of percents, while the dimensions are ～10 nm. The presence in the surface layer of titanium of a nanocrystalline two-phase (α-Ti + rutile) structure leads to a significant increase in the wear resistance of the VT1-0 titanium in pair with steel 40Kh13. This is explained by the enhanced strength of the arising nanocrystalline layer and its positive influence (as of a transition layer) on the reduction of the level of internal stresses that exist at the interface between the titanium oxide TiO₂ and the host metal.     

液料等离子热喷法制备Fe3+/TiO2纳米粉末

通过对液料等离子热喷前驱物添加掺杂成分实现了液料等离子热喷TiO2纳米粉末的掺杂改性,并利用TEM,XRD及XPS对其进行表征.结果表明,采用液料等离子热喷法可以制备Fe3 掺杂TiO2纳米粉末,所制备粉末形貌基本呈球形或近球形,粒径分布为10～35 nm,掺杂量小于2.0%时粉末为锐钛矿及金红石相混晶,Fd3 掺杂促进锐钛矿向金红石相的转变,掺杂量为10.0%时析出了Fe2Ti3O9相.Fe3 掺杂不会引起TiO2粒径的大范围波动.粉末中含有O,Ti,Fe和C等元素,Fe元素在TiO2中仍为 3价.     

TEM and X-ray diffraction investigation of the structural characteristics of the microporous oxide film formed on polycrystalline Ti

The microporous TiO₂ layer in the vicinity of the Ti–TiO₂ interface is formed by a great amount of tiny crystallites. Bigger anatase and rutile crystals stand in the outer region of the oxide. The orientation of a proportion of the TiO₂ crystals is influenced by the underlying textured Ti substrate.     

Passivation and oxygen ion implantation double surface treatment on porous NiTi shape memory alloys and its Ni suppression performance

The surfaces of porous NiTi shape memory alloys (SMAs) were modified by double treatment of passivation (PA) in HNO₃ solution and oxygen plasma immersion ion implantation (O-PIII) methods. SEM and XPS were used to characterize the modified surface. It has been found that a protective film consists of three layers formed on the surface after modification. From the outmost surface towards inside, they are a 10 nm thick layer consisting of rutile and anatase TiO₂ with pure rutile TiO₂ on the surface and their ratio varying in gradient, a 45 nm thick layer containing anatase TiO₂ and NiTi with constant ratios and a 40 nm thick layer of TiO₂, TiO and NiTi with their ratio varying in gradient. The immersion tests in simulated human body fluid demonstrated that the modified porous NiTi samples exhibit a good Ni suppression performance, approaching to that of the untreated dense NiTi samples. The Ni ion content released from the porous NiTi SMAs double treated by PA and O-PIII is one magnitude lower than that from the untreated porous samples. Moreover, the released Ni ion content after 8 weeks can be reduced into the safe range acceptable to the human body.     

Enhancement of the photocurrent generation in dye-sensitized solar cell based on electrospun TiO2 electrode by surface treatment

We investigated the dye-sensitized solar cell (DSSC) using TiO₂ electrode electrospun directly onto the substrate from a mixture of titanium propoxide and poly(vinyl acetate) in dimethyl formamide (DMF). The electrospun electrode could be penetrated efficiently by a viscous polymer gel electrolyte because of porous structure. The energy conversion efficiency obtained from the DSSC with poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) gel electrolyte was over 90% of that obtained from liquid electrolyte. In order to improve the short-circuit photocurrent, we treated the electrospun TiO₂ electrode with TiCl₄ aqueous solution. The rutile crystal was grown epitaxially on anatase TiO₂ fibers. An additional TiO₂ layer increased the volume fraction of active materials resulting in an increase of sensitizer adsorption. The incident photon-to-current conversion efficiency (IPCE) of TiCl₄-treated electrode was higher than the untreated. In particular, the contribution from TiO₂ increases after the surface treatment due to an increase in packing density. The photocurrent of the DSSC with electrospun TiO₂ electrode was enhanced more than 30% after TiCl₄ treatment.     

Leaching of Titanium and Silicon from Low-Grade Titanium Slag Using Hydrochloric Acid Leaching

Acid-leaching behaviors of the titanium slag obtained by selective reduction of vanadium-bearing titanomagnetite concentrates were investigated. It was found that the optimal leaching of titanium and silicon were 0.7% and 1.5%, respectively. The titanium and silicon in the titanium slag were firstly dissolved in the acidic solution to form TiO²⁺ and silica sol, and then rapidly reprecipitated, forming hydrochloric acid (HCl) leach residue. Most of the silicon presented in the HCl leach residue as floccules-like silica gel, while most of the titanium was distributed in the nano-sized rod-like clusters with crystallite refinement and intracrystalline defects, and, as such, 94.3% of the silicon was leached from the HCl leach residue by alkaline desilication, and 96.5% of the titanium in the titanium-rich material with some rutile structure was then digested by the concentrated sulfuric acid. This provides an alternative route for the comprehensive utilization of titanium and silicon in titanium slag.     

利用铅锌废渣制备银修饰纳米复合材料的研究

以含银的铅锌废渣为银源,联合采用氯盐法、Stober法、溶胶凝胶法以及光沉积法制备银修饰纳米复合材料Ag@TiO_2@SiO_2。XRD和TEM的分析表明:Ag@TiO_2@SiO_2具有核壳结构的纳米材料,Ag以10nm团簇的形式沉积在锐钛矿型TiO_2壳层上。XPS分析指出:TiO_2以Ti-O-Si键化学吸附在SiO_2上,而沉积在TiO_2上的银是银的单质。Uv-Vis的分析表明:材料Ag@TiO_2@SiO_2对光响应范围扩大到可见光区。罗丹明的光降解反应表明,Ag@TiO_2@SiO_2的光催化性能优良。