铬铁矿无钙焙烧渣的酸浸解毒及浸出行为

在对铬铁矿无钙焙烧渣的组成进行系统分析表征的基础上，提出了在酸性条件下，利用铬渣中未反应的铬铁矿（Fe，Mg）（Cr，Fe）2O4中的二价铁与重铬酸根离子发生氧化还原反应，实现铬渣自身解毒的新方法。研究表明：机械球磨对于铬渣酸浸解毒过程是一个主要的影响因素，对应的铬渣粒度为6~16.5 μm，铬渣酸浸解毒的较好工艺条件为：硫酸质量分数为5%，液固比为4 mL/g，反应温度为80 ℃，反应时间为60 min。解毒后铬渣中六价铬质量分数能降至2.5×10-5以下。     

铬渣中六价铬浸出方法对比实验研究

铬渣是一种环境污染极大的工业废渣,其中的六价铬是国际公认的致癌物,但如何科学评价铬渣中六价铬的含量及其危害性却很困难。通过实验对比了4种标准方法（USEPA 3060A、HJ/T 299-2007《固体废物 浸出毒性浸出方法 硫酸硝酸法》、HJ/T 300-2007《固体废物 浸出毒性浸出方法 醋酸缓冲溶液法》和GB 5086.2-1997《固体废物 浸出毒性浸出方法 水平振荡法》）对铬渣中六价铬的浸出效果,还比较了恒定pH条件下不同酸液及组合两步浸取的浸出效果。实验结果表明,标准的酸液浸出法难以有效浸出铬渣中的六价铬,除非破坏铬渣中的物相结构,否则任何浸出方法都无法完全浸出铬渣中的六价铬。     

铬渣矿物学性质及其湿法解毒意义

铬渣是铬盐生产中产生的一种危险工业固体废物,对环境造成了严重危害。湿法解毒是铬渣处理和处置的一种有效方法,但大规模应用依然存在困难。近年来,铬渣的矿物相研究取得了较大进展。总结了铬元素性质和铬渣产生过程,介绍了铬渣矿物相研究成果,总结了铬渣的性质,并探讨了其在湿法解毒中的潜在意义,分析了湿法解毒所存在的困难,提出了相应对策。     

The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 °C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na.     

高钙铬渣及其解毒后可溶六价铬含量分析方法研究

分析了铬渣中六价铬含量的测定方法、六价铬的浸取方法、解毒铬渣的评价方法等几个方面的问题。通过对比国内外大量的研究结果,指出了铬渣中六价铬浸取评价方法存在的问题。由于铬渣的强碱性及其强大的酸中和能力,所谓的酸液浸取大多名不符实,用硫酸、硝酸、盐酸稀溶液浸取铬渣中六价铬要比USEPA Method 3060A碱消解方法效果差很多;用HJ/T 299-2007和HJ/T 300-2007评价解毒后的铬渣存在很多问题;用GB 5085.3-2007 评价铬渣的浸出毒性也有不严密的地方。测定铬渣中六价铬最好用物理方法,例如XANES方法;浸取铬渣中的六价铬宜采用USEPA Method 3060A的碱消解方法。     

Preparation of glass-ceramics with low density and high strength using blast furnace slag,glass fiber and water glass

To reduce the production costs of glass-ceramics and broaden the application field of solid waste in steel industry, low-density and high-strength glass-ceramics were produced by using blast furnace slag as the basic material, choosing glass fiber and water glass as the strengthening agents. The effects of glass fiber and water glass on the phase composition, microstructure, apparent density, water absorption and compressive strength of glass–ceramics were investigated. The results show that the rod structure of glass fiber can be retained in the sintered samples and high content of diopside and augite significantly improve the compressive strength of glass-ceramics. Tiny spherical crystalline phases can be obtained for the glass-ceramics soaked in the moderate concentration of water glass. The BGW-2 samples fabricated with 70% blast furnace slag, 30% glass fiber and 4% water glass, exhibit excellent comprehensive properties. The bulk density, water absorption and compressive strength of BGW-2 are 1.76 g/cm³, 2.26% and 68 MPa, respectively. Consequently, using blast furnace slag to prepare glass-ceramics can be another applicable way to utilize blast furnace slag efficiently.     

铬铁矿无钙焙烧铬渣的深度提铬与无害化处理

铬铁矿无钙焙烧工艺是目前世界上铬化工行业的主流生产工艺,该工艺产出的铬渣中铬含量较高且含有六价铬,直接堆存或填埋不仅造成铬资源的浪费,还会污染环境。基于无钙焙烧铬渣的组成特点,提出了“酸浸预处理-钠化氧化焙烧-湿法解毒”的处理方法,确定了较优的工艺参数,分析了方案的可行性。研究结果表明,无钙焙烧铬渣通过两级酸浸预处理除杂,提高了铬的品位;酸浸渣经过氧化焙烧,实现了铬的深度提取;全流程铬的提取率最高达到73%以上,尾渣中氧化铬质量分数降至5.60%;尾渣经湿法解毒处理,浸出毒性满足进入一般工业固体废物填埋场填埋的污染控制指标限值的要求。该研究结果可为无钙焙烧铬渣的深度提铬和无害化处理提供新的技术思路。     

Performance of geopolymer foams of blast furnace slag covered with poly(lactic acid) for wastewater treatment

This research investigated a new method to produce geopolymer foams from blast furnace slag (BFS) with poly(lactic acid) (PLA) covering the developed porosity into the materials. A porous alkali-activated material was developed, and a biodegradable polymer was used to cover the geopolymer in the bulk state. Geopolymer foams were synthesized with a sodium metasilicate solution, and the porosity was developed by adding hydrogen peroxide (H₂O₂). Foams of materials were produced with two stoichiometries of 1.4 and 1.6 g/L between solid/liquid with a hydrogen peroxide solution. The dimensional stability was achieved after coating geopolymer foams with PLA, improving the molding capacity on different geometries for the composite materials. Specimens of the geopolymer foam/PLA composites were characterized by X-ray fluorescence (XRF), Fourier transformed infrared (FTIR), thermogravimetry (TGA), and field emission gun scanning electron microscopy (FEG-SEM). The permeation analysis of metal oxide particles through the composites foam specimens was performed using water dispersions containing bismuth oxide or titanium oxide. The test resulted in high performance in the retention of particulate materials. The highlights of the results indicated the efficiency in the synthesis of geopolymer foam, a good formation of porosity, and an effective PLA coating on the internal interfaces of geopolymer foam through the development of a new bulk state coating method, improving the dimensional stability and the retention of bismuth and titanium oxides particles by the produced geopolymer foams for water depollution.     

Effect of components fineness on strength of blast furnace slag cement

The strength development of 1:1 mixes of clinker and blast furnace slag with varying fineness of components from 3000 to 6000 cm²/g has been studied. Overall results indicate that in manufacturing blast furnace slag cement (BFSC), it is not only the fineness of the clinker-slag mix but also of the individual components which govern the choice of the mix composition for a desired strength.     

Ceramics composites from iron ore tailings and blast furnace slag

The search for materials and methods capable of reducing human impacts on the environment is of utmost importance nowadays. This study's primary purpose was to analyze the technical feasibility of ceramic composites production utilizing Fundão Dam's Iron Ore Tailings (IOT), Blast Furnace Slag (BFS) from charcoal, and Foundry Sand (FS) as partial substitutes for the traditional raw materials – sand and clay – for application in building industry materials. The composites were molded in rectangular specimens and fired at temperatures of 900, 950, 1000, 1050, and 1200 °C. The developed materials were analyzed and characterized by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Thermogravimetry (TGA), and Differential Thermal Analysis (DTA). The obtained materials had flexural strength modulus of up to 12.19 MPa, water absorption ranging from 2 to 22%, linear shrinkage ranging from 0.02 to 6.50%, and apparent density ranging from 2.03 to 1.63 g/cm³. The study of the internal structure formation process revealed the formation of amorphous structures in the composites. The results demonstrated that these waste materials may be jointly used in construction materials, contributing to the reduction of natural resource extraction, besides enabling their correct disposal, minimizing environmental impacts, and improving the life quality of the surrounding communities.     

不同异位修复工艺对高浓度铬渣污染土壤中Cr的去除特性

以我国某铬盐厂的两种不同污染特性铬渣污染土壤（A土和B土）为研究对象,探讨了三种异位修复工艺（淋洗、稳定化、湿法解毒）去除铬渣污染土壤中总Cr和Cr（Ⅵ）的效果,并采用改进BCR顺序提取法分析了不同修复工艺对土壤中各形态Cr的去除效果。实验结果表明,三种异位修复工艺对铬污染土壤中Cr（Ⅵ）的去除效果为湿法解毒 > 稳定化 > 淋洗,湿法解毒工艺对A土、B土中Cr（Ⅵ）的去除率分别高达83.26%、92.94%;对铬污染土壤总铬去除效果最佳的是异位淋洗工艺,异位淋洗工艺对A土、B土总铬消减分别达54.87%、80.16%。异位淋洗工艺实现了对水溶态Cr（Ⅵ）、酸溶态Cr（Ⅵ）的泥水分离,是总铬消减的主要原因;稳定化工艺和湿法解毒工艺降低了土壤pH,促进了水溶态Cr、酸溶态Cr及可还原态Cr向可氧化态Cr的转化,因此土中总Cr并未发生显著消减。高浓度铬渣污染土壤经三种异位修复工艺处理后,A土Cr（Ⅵ）仍然残留736.6 mg·kg^-1,B土Cr（Ⅵ）仍然残留245.47 mg·kg^-1,酸溶态Cr的残留是导致三种工艺修复Cr（Ⅵ）效果受限的主要原因。     

采用热熔态高炉渣和转炉渣生产水泥熟料的探讨

通过对炼铁高炉渣、转炉渣和水泥熟料的组分进行对比分析,发现其组分比较接近。经初步探讨认为,优化高炉渣和转炉渣的成分,使两者在热熔状态下混合均匀,或同时配加部分矿物,可以生成和水泥熟料基本一致的组分。这样既充分利用了高炉渣和转炉渣及其余热,又减少了水泥熟料的资源消耗,达到了废渣综合利用、节能减排和低碳的目的。     

铬铁矿无钙焙烧渣的SO2还原解毒

系统地对铬铁矿无钙焙烧渣进行了表征,并研究了SO₂还原解毒铬渣,提出了机械活化与SO₂还原相结合的解毒工艺。结果表明,该铬渣主要物相组成是（Fe,Mg）（Cr,Fe）₂O₄和MgAlFeO₄,铬渣中Cr₂O₃含量为12.23%,铬渣粒径越小,含有的总Cr（Ⅵ）、水溶性Cr（Ⅵ）、难溶性Cr（Ⅵ）量越小。SO₂还原解毒铬渣工艺过程中搅拌能有效强化外扩散过程,液固比增大有利于铬渣中Cr（Ⅵ）的浸出,铬渣中Cr（Ⅵ）的浸出随温度升高先增加后急剧降低,反应体系中压力变化对铬渣还原解毒效果影响不大。优化的SO₂还原解毒铬渣条件为：压力0.1 MPa、温度60℃、搅拌速度500 r·min^-1、反应时间60 min,此时铬渣中Cr（Ⅵ）的去除率达90%;机械活化90 min的铬渣进行SO₂还原解毒60 min后,渣中的Cr（Ⅵ）去除率达到98.1%,含量降至25 mg·kg^-1以下,达到国家排放标准。     

Influence of modified multi-walled carbon nanotubes on the mechanical behavior and toughening mechanism of an environmentally friendly granulated blast furnace slag-based geopolymer matrix

This study aimed to investigate the mechanical behavior of an environmentally friendly granulated blast furnace slag-based geopolymer matrix reinforced with modified multi-walled carbon nanotubes (MWCNTs). The modified MWCNTs were obtained using a modification method combining nitric acid and sulfuric acid and were then dispersed using sodium dodecylsulfate (SDS) as a dispersant. Two types and three concentrations of MWCNTs were mixed directly into the aqueous solution, sonicated, and then mechanically mixed with waste granulated blast furnace slag to form the geopolymer matrix. Raman and Fourier transform infrared (FT-IR) spectroscopy were used to evaluate the ordered structure and crystallization degree of the modified MWCNTs. Then, the dispersity of the modified MWCNTs was characterized using transmission electron microscopy (TEM). The compressive and bending strengths were measured to evaluate the mechanical behavior of specimens. Moreover, the polycondensation products, polycondensation degree, pore structure, and microscopic morphology of the geopolymer matrix were analyzed using X-ray diffraction (XRD), FT-IR spectroscopy, nuclear magnetic resonance (NMR), mercury intrusion porosimetry (MIP), and field emission scanning electron microscopy with energy dispersive X-ray spectroscopy (FESEM-EDS). The experimental results showed that the incorporation of 0.1% functionalized MWCNTs had an optimal influence on the fluidity and mechanical behavior. The slump diameters of geopolymers with 0.1% functionalized MWCNTs with and without SDS were increased by 16.3% and 23.5%, respectively, compared with the reference geopolymer matrix. For geopolymer matrix samples at a curing age of 28 d, the compressive strength of geopolymers with 0.1% functionalized MWCNTs with and without SDS were increased by 16.3% and 17.6%, respectively. For the bending strength, the corresponding increases were 17.6% and 18.7%, respectively. It was found that functionalized MWCNTs could increase the degree of polycondensation, leading to a more traditional amorphous N-A-S-H phase, a finer C–S–H phase, more Q⁴ (2Al) and Q⁴ (3Al), and lower porosity. In addition, the propagation of micro-cracks in the geopolymers was inhibited by the incorporation of functionalized MWCNTs.     

微波辐射对高炉渣浸取影响的研究

比较了用传统法和微波法浸取高炉渣的效果。研究发现,微波辐射大大加快了高炉渣浸取的速度。测定了微波辐射对高炉渣表面能的影响。结果显示,微波辐射提高了高炉渣的表面能,降低了其与液相的接触角。     

高炉用耐火材料的发展

结合当前国内外高炉对耐火材料的要求，概述了高炉炉身、炉腰、炉腹、炉缸用耐火材料的发展状况。     

生物质解毒液相氧化法铬渣的工艺研究

铬渣（COPR） 是采用铬铁矿生产铬化合物过程中产生的固体废弃物,因其含有六价铬被列为危险固体废物。铬渣的堆放对环境具有较强的危害,寻求经济、高效、无二次污染的治理方法是治铬工作者们关注的焦点。采用生物质香蕉皮对液相氧化法铬渣开展了解毒工艺研究。在反应温度为90 ℃、香蕉皮添加量为10%（以渣质量计）、反应时间为1.5 h、加酸量为4 mol/kg（以1 kg铬渣加入的氢离子物质的量计）、液固体积质量比为3 mL/g的最佳工艺条件下,解毒后铬渣的浸出毒性远小于一般工业固体废弃物的环保排放标准,可以作为一般固体废弃物进行填埋。通过对香蕉皮解毒铬渣过程中铬元素在各物流中的分布与价态变化分析,发现香蕉皮解毒铬渣的过程为吸附耦合还原机理。     

Resistance of alkali-activated slag concrete to acid attack

This paper presents an investigation into the durability of alkali-activated slag (AAS) concrete exposed to acid attack. To study resistance of AAS concrete in acid environments, AAS concrete was immersed in an acetic acid solution of pH=4. The main parameters studied were the evolution of compressive strength, products of degradation, and microstructural changes. It was found that AAS concrete of Grade 40 had a high resistance in acid environment, superior to the durability of OPC concrete of similar grade.     

Thermodynamic assessment and experimental validation of clinker formation from blast furnace slag through lime addition

In the present study thermodynamic simulation of chemistry modification of blast furnace slag by lime addition to obtain clinker composition has been carried out. The effects of lime addition on each mineralogical phase under the equilibrium are simulated using FactSage 6.4 thermodynamic software. The critical value of lime addition in slag for each mineralogical phases and its effect on liquidus temperature of the slag has been reported. The desired cementitious phase namely belite has been observed beyond 14.4% of lime addition. A decreasing trend is observed in the liquidus temperature of the mixture from 1530?°C to 1497?°C for the lime addition of 15–24%. The simulation results were further validated by experiments conducted on blast furnace slag in the laboratory. Energy-Dispersive X-ray Spectroscopy analysis were used to qualitatively estimate the mineralogical phases formed after melting of the slag mixtures in the laboratory followed by air cooling.     

Crystallisation behaviour of blast furnace slag modified by adding fly ash

Crystallisation of molten blast furnace (BF) slag can increase its viscosity, which can in turn affect the quality of slag fibres. Fly ash was added to BF slag to control its crystallisation and modify its chemical composition. FactSage simulation and analyses using X-ray diffraction (XRD), scanning electron microscope-backscattered electrons (SEM-BSE) coupled to an energy dispersive spectrometer (EDS), and single hot thermocouple technique (SHTT) were performed to explore the crystallisation behaviour of the modified BF slag. The relationship between temperature, mineral precipitation, and added fly ash content was investigated. The minerals contained in the modified BF were melilite, anorthite, clinopyroxene, and spinel. Variation in the fly ash content did not change the composition of the precipitate, but changed its content and the crystallisation temperature of the minerals, which affects the initial crystallisation temperature of the modified BF slag. It decreased as fly ash content increased, and was influenced by the crystallisation of melilite when the added fly ash content was between 5% and 20%. When the added fly ash content increased to 25%, the initial crystallisation temperature was influenced by the precipitation of anorthite. The initial crystallisation temperatures obtained by FactSage simulation, XRD analysis, and SHTT experiments differed due to kinetic effects. The modified BF slag with a fly ash content of 15% is considered suitable for manufacturing of slag fibres due to its low initial crystallisation temperature and cost.