Properties and hydration of blended cements with steelmaking slag

The present research study investigates the properties and hydration of blended cements with steelmaking slag, a by-product of the conversion process of iron to steel. For this purpose, a reference sample and three cements containing up to 45% w/w steel slag were tested. The steel slag fraction used was the “0-5 mm”, due to its high content in calcium silicate phases. Initial and final setting time, standard consistency, flow of normal mortar, autoclave expansion and compressive strength at 2, 7, 28 and 90 days were measured. The hydrated products were identified by X-ray diffraction while the non-evaporable water was determined by TGA. The microstructure of the hardened cement pastes and their morphological characteristics were examined by scanning electron microscopy. It is concluded that slag can be used in the production of composite cements of the strength classes 42.5 and 32.5 of EN 197-1. In addition, the slag cements present satisfactory physical properties. The steel slag slows down the hydration of the blended cements, due to the morphology of contained C₂S and its low content in calcium silicates.     

炼铜炉渣选铜尾矿制备矿微粉

以炼铜炉渣选铜尾矿资源化利用为目的,选用某有色金属公司炼铜炉渣的选铜尾矿为原料,采用条件实验、正交实验等研究方法和化学分析、原子吸收、XRD、SEM等检测手段,通过多因素优化实验考察砂浆的流动度,试块不同龄期的抗压强度以此确定微粉的活性指标,研究炼铜炉渣选铜尾矿制备矿微粉的可行性。结果表明：铜渣再选尾矿微粉的比表面积、激发剂、助磨剂和减水剂对制备矿微粉均具有一定的影响,其影响次序为：矿微粉的比表面积＞激发剂（Na₂SO₄）＞减水剂＞助磨剂（三乙醇胺）。当铜渣再选尾矿微粉掺量为10%时,可满足活性指数大于95%（S95级别）的标准要求,此时7天和28天的活性指数分别为97.56%和95.91%;而在尾矿微粉掺量为20%～30%时,可满足活性指数大于75%（S75级别）的标准要求。相关助剂的添加提高了铜渣再选尾矿的粉磨效率,细小颗粒有益于碱激发过程的发生,使得砂浆更加致密。重金属浸出表明,Cr、Cd的浸出量与水泥相比增加较小,Cu有少量增加,对环境影响较小,为工业固废资源化协同利用提供了新的发展途径。     

铜渣复合硅锰水淬渣后的改质提铁研究

铜材等金属材料在生产过程中产生的大量水渣、干渣等冶金渣,其综合利用水平较低,成为冶金业高质量绿色发展亟须解决的难点。为有效回收铜渣中的铁元素,将工业铜渣与硅锰水淬渣混合后按一定比例添加氧化钙及氧化锰进行成分改质,利用FactSage对混合渣料中矿物相随温度的变化趋势进行了预测,借助XRD对改质前后渣料中的矿物相变化进行了对比,通过SEM和EDS对改质后混合渣料中主要矿物相的形态、分布和特征进行了表征。实验结果表明：改质后混合渣料中的矿物相以尖晶石相和硅酸盐相为主;碱度提高后,改质样品中的硅酸盐相增多但尖晶石相减少;混合渣料的碱度为1.5时改质效果最好,其铁品位为44%（质量分数）、铁回收率为95%。     

硼酸钙对铜渣中夹杂铜沉降效果的影响

考察了添加剂CaB2O3对转炉铜渣中夹杂铜沉降效果的影响,并结合铜渣的粘度测试及红外光谱表征,研究其影响机理,采用FactSage软件计算了添加剂对铜渣液相线温度的影响。结果表明,随添加剂含量增大,铜渣中夹杂铜的沉降效果逐渐增强,添加剂含量由0增至6wt%时,底部渣含铜量由4.10wt%增至6.85wt%,这是由于添加剂可有效降低铜渣粘度。随添加剂含量增大,渣粘度降低,但降低效果随温度增大而趋于平缓。随添加剂含量增大,铜渣的硅酸盐结构趋于简化,添加剂通过破坏铜渣复杂的硅酸盐结构降低铜渣粘度。铜渣的液相线温度随添加剂含量增大而减小,添加剂通过减少渣中固体颗粒的方式降低铜渣粘度。     

Importance of mineralogy and reaction kinetics for selecting leaching methods of copper from copper smelter slag

Ammoniacal leaching and sulfuric acid leaching were explored separately to recover copper from smelter slag. The overall 75% copper recovery was achieved from the smelter slag under optimum condition using ammoniacal leaching. The low copper recovery in this process is directly related to the complex slag mineralogy and dissolution kinetics. To overcome such problems, sulfuric acid leaching was applied separately. This method provided an overall 89% copper recovery under atmospheric condition. The use of sulfuric acid as the leaching agent was found to be more advantageous than ammonia due to the complex interlocking nature of copper bearing particles and different reaction kinetics of the slag.     

响应曲面法优化氧化铜渣浮选提铜工艺

江西某炼铜炉渣含铜量高,具有较高的经济价值。由于该铜渣中铜矿物以氧化矿为主,且硫化矿表面被氧化,直接浮选铜回收率低、经济效益差。通过添加活化剂,活化氧化铜矿物,并利用响应曲面中心复合设计原理对浮选工艺条件进行优化,研究氧化钙、硫化钠、Z-200对浮选效果的响应。结果表明,Z-200用量是影响精矿品位和回收率的主要因素,且各响应因素间存在交互效应,在CaO用量为25 g/t,Na₂S用量为500 g/t,Z-200用量为100 g/t的最优条件下,闭路试验获得精矿平均品位12%,精矿铜回收率为86.57%,采用该浮选优化工艺能获得较好的回收效果。     

铜冶炼废渣脱硅工艺研究

以铜冶炼废渣[简称铜渣,主要成分为铁橄榄石（Fe₂SiO₄）]为原料,采用钠化焙烧的方法脱除废渣中的硅,研究了以氢氧化钠为钠化剂对铜渣脱硅的影响。首先采用正交实验探究了焙烧温度、矿碱质量比、焙烧时间等因素对铜渣脱硅的影响顺序,在此基础上采用单因素实验研究了铜渣脱硅的适宜工艺条件。结果表明：铜渣脱硅影响因素由大到小的顺序为焙烧温度、矿碱质量比、焙烧时间。铜渣脱硅的适宜工艺条件：焙烧温度为650 ℃,矿碱质量比为1∶1.75（氢氧化钠理论量的4.17倍）,焙烧时间为180 min。在此条件下铜渣钠化焙烧所得产物的水浸渣中二氧化硅的质量分数降至1.74%,脱硅率达到94.5%。焙烧产物及其水浸渣的X射线衍射分析表明,铜渣钠化焙烧脱硅的机理是铁橄榄石转化为铁酸钠和硅酸钠,铜渣中的铁最终以四氧化三铁的形式存在,硅以硅酸钠的形式脱除。     

Autoclave properties of kirschsteinite-based steel slag

The kirschsteinite-based steel slag is one kind of low-alkalinity steel slag. This steel slag hardly behaves as any hydraulicity. In this paper, the hydrothermal products and binding properties of this slag, after being subjected to autoclave treatments, were evaluated. The results show that a hydrothermal autoclave reaction could modify the binding behaviours of kirschsteinite-based steel slag. The main hydrothermal product of pure kirschsteinite-based steel slag was Fe-hydrogarnet, which exhibited poor binding strength. However, the system of quartz-kirschsteinite steel slag appeared to have excellent binding properties due to autoclave treatment, in which the kirschsteinite phase was hydrothermally changed into Fe-substituted tobermorite. Meanwhile, Fe-substituted tobermorite phase was still stable relative to xonotlite over 345 °C.     

铜渣综合回收利用研究进展

铜渣是火法炼铜的副产物,中国90%以上的铜是通过火法冶炼生产的,随着科学技术进步和人们生活需要,我国铜产量呈逐年上升的趋势。铜渣中含有大量可回收的有价金属,且铜渣本身也是一种优异的无机材料。综合回收铜渣中有价金属可以减少资源不足带来的压力,对余渣进行资源化利用既能减少环境污染,又能生产出有经济价值的产品。本文分析和讨论了火法贫化、湿法浸出、选矿富集和联合工艺等手段回收铜渣中有价金属的原理、现状和优缺点,总结了铜渣作为硅酸盐无机材料的在建筑材料和功能材料中的应用,并对铜渣未来的金属回收与资源化利用发展方向进行了展望。     

橡胶籽油还原作用下铜渣的贫化

针对铜渣贫化过程碳排放问题,以橡胶籽油取代柴油作为铜渣贫化的还原剂,研究铜渣贫化过程中的热力学,分析橡胶籽油贫化铜渣机理。在不同温度和时间条件下进行喷吹橡胶籽油贫化实验,分析铜渣磁性铁含量和粘度的变化,用XRD和SEM对贫化后炉渣进行分析。结果表明,喷吹还原过程中主要还原剂是裂解产生的碳单质、H2和CO。贫化过程中磁性铁被橡胶籽油在高温下的裂解产物(H2, CO, C)还原成FeO,与渣中的SiO2结合生成铁橄榄石(Fe2SiO4);随贫化温度升高,相同喷吹时间内铜渣的磁性铁含量和粘度逐渐降低,使渣中的Cu相互碰撞聚集,最终沉降到坩埚底部。随贫化进行铜渣中的铁橄榄石相增多,磁性铁相减少。在坩埚底部聚集的铜颗粒粒度由1 cm增至3 cm,铜回收率达86%。     

铜阳极泥脱铜渣中金、银、钯含量测定

建立了连续测定铜阳极泥脱铜渣中金、银、钯含量的分析方法,并与火试金法进行比较。首先,利用硝酸+乙二胺四乙酸（EDTA）+酒石酸消解铜阳极泥脱铜渣,得到含有银、钯和少量金的消解液,考察了硝酸、EDTA和酒石酸用量对消解效果的影响。结果表明,硝酸、EDTA和酒石酸用量分别为30mL、3mL、1.5g时,消解效果最好。然后,利用王水对残渣进行二次消解,得到含有金和少量银、钯的消解液,考察了王水用量对消解效果的影响。结果表明,王水用量为15mL时即可完成消解。最后采用火焰原子吸收光谱仪测定消解液中的金、银、钯含量。采用本方法测定铜阳极泥脱铜渣,Au、Ag、Pd各元素相对标准偏差均小于1%（n=10）,加标回收率在95.57%～98.70%之间,实验结果准确可靠、重现性好,与火试金法测定结果相一致。     

Alkali release characteristics of blended cements

This paper presents results of an experimental program conducted to investigate the capacity of hydration products of different cementing materials to retain “bound” alkalis when the alkalinity of the surrounding solution drops. The study covered paste samples containing high-alkali Portland cement and various levels of silica fume and/or fly ash. The results showed that the ability of the hydration products of cement-fly ash systems to bind alkalis is a function of the CaO content of the fly ash, the binding increasing as the calcium content decreases. High-alkali fly ashes (Na₂O_e > 5.0% and CaO in the range of 15% to 20%) showed considerable amounts of alkali contributed to the test solutions. Silica fume does not have a high capacity to retain alkalis in its hydration products; however, ternary blends containing silica fume and fly ash have excellent capacity to bind and retain alkalis.     

铜镍废渣生产工业硫酸铜工艺研究

采用湿法加压氧化一步浸取工艺处理铜镍废渣生产工业硫酸钠，并回收其中镍，试验结果表明，铜镍总回收率达到98．63％，硫酸铜产品达到国际优等品，终渣形成氧化铁铁红产品。     

Multi-phase hydration model for prediction of hydration-heat release of blended cements

Recently, the heat release during cement hydration and the so-caused temperature rise was exploited for (i) identification of material properties of early-age cement-based materials (stiffness, strength), and (ii) determination of the diameter and the cement content of jet-grouted structures. In this paper, the underlying hydration model for determination of the heat release and its rate is refined for Ordinary Portland Cements (OPC) and extended towards blended cements. Hereby, the overall degree of hydration with one kinetic law is replaced by a multi-phase hydration model, taking the hydration kinetics of the main clinker phases into account. As regards blended cements, which are commonly used in engineering practice, the effect of slag hydration is incorporated into the presented multi-phase model. The developed hydration model for both plain and blended cement is validated by means of differential-calorimetry (DC) experiments.     

Effect of TiO2 and 11 minor elements on the reactivity of ground-granulated blast-furnace slag in blended cements

Ground-granulated blast-furnace slags (GGBS) are glasses (>99%) of the CaO-Al₂O₃-SiO₂ compositional system and are widely used as supplementary cementitious materials. Differences in reactivity of GGBS were screened by modifying the content of 12 minor elements (namely Ba, Ce, Cs, Cr, K, Mn, P, Sn, Sr, Ti, V, and Zr). Scanning electron microscopy observations showed that most elements entered the silicate glass matrix, only Sn was reduced to its metallic form and P accumulated in minor minerals. Mortar strength tests showed that 2 day compressive strength was reduced by >50% for a TiO₂ content of 2.5 wt% in the slag. At 28 days the loss in compressive strength was still >40%. Calorimetric tests on other element additions showed that the content of network modifiers (Ba, Cs, K and Sr) and GGBS reactivity are positively correlated, whereas Ce, Cr, V, and Zr significantly decreased reactivity. Finally, it is shown that these effects can be estimated by the concentration and the weighted field strength of the added element.     

铜渣催化气化木屑的实验研究和热力学分析

以木屑为原料,在铜渣催化气化木屑的实验平台上研究了气化剂和载气对气体产物成分及热值的影响。根据实验结果,当水蒸气当量比为0.058时,焦油产率降低了约50%,氢气产率提高了63.04%,气化效率达75.03%。在优化的实验条件下基于能量平衡建立熔融铜渣催化气化木屑的热力学分析方法,得到铜渣、木屑及水蒸气之间的耦合关系,1250℃的熔融铜渣的余热高达1.773 MJ/kg,充分利用铜渣显热和潜热气化木屑产生的合成气热值可高达13319 kJ。在最优气化工况下,1 kg原料气化需要1.92 kg铜渣,热态铜渣催化气化木屑的能量利用率可达62.94%。     

铜熔渣喷吹地沟油还原贫化

以地沟油为生物质还原剂,高温裂解后对铜火法冶炼铜渣进行还原贫化。结果表明,地沟油裂解产物主要是C, H2, CO和CH4等还原性小分子物质,1373, 1473和1573 K下裂解积碳的转化率分别为78.36%, 79.83%和80.07%,因此地沟油高温裂解时碳元素主要以积碳形式存在。热力学计算发现,高温下裂解产物均有良好的还原Fe3O4的活性,用地沟油替代传统化石类还原剂还原铜渣中磁性铁在热力学上是可行的。以N2为载气不仅有利于高温下地沟油顺利喷入铜熔渣中,且通过动量传递起到搅拌熔渣的作用,增大了微小铜滴碰撞聚集长大的机会。在熔炼温度1573 K、载气流量3 L/min、地沟油喷吹量2.055 mL/min、喷吹时间4 min、沉降时间50 min的最优还原贫化条件下,铜渣中Fe3O4含量从33.40wt%降至1.60wt%,含铜量从4.49wt%降至0.49wt%,渣中Fe3O4相转变为2FeO?SiO2相。根据Einstein?Roscoe方程分析,渣中Fe3O4含量减少有利于降低熔渣粘度,改善铜滴的沉降条件。继续增加地沟油喷吹时间沉降金属中杂质含量增加;沉降时间过长时,由于铜渣对铜的机械夹带和化学溶解作用,沉降效果不会更好。实验的铜回收率达89.09%。     

少熟料高标号复合水泥的性能

工业废渣用于水泥混合材的研究一直是水泥研究领域的热点问题。从实际应用看 ,活性高的混合材 ,如矿渣已得到充分的利用。而活性低的混合材 ,如粉煤灰 ,利用率较低。针对矿渣、磷渣和粉煤灰的特点 ,通过强度和孔结构测试 ,研究了少熟料高标号复合水泥。强度和孔结构研究表明 ,利用混合材的优势互补原理 ,并引入外加剂可以得到性能优异的少熟料复合水泥     

Compressive strength and hydration of wastepaper sludge ash-ground granulated blastfurnace slag blended pastes

Compressive strength and hydration characteristics of wastepaper sludge ash-ground granulated blastfurnace slag (WSA-GGBS) blended pastes were investigated at a water to binder (w/b) ratio of 0.5. The strength results are compared to those of normal Portland cement (PC) paste and relative strengths are reported. Early relative strengths (1 day) of WSA-GGBS pastes were very low but a marked gain in relative strength occurred between 1 and 7 days and this increased further after 28 and 90 days. For the 50% WSA-50% GGBS blended paste, the strength achieved at 90 days was nearly 50% of that of the PC control paste. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric (TG) analysis were carried out to identify the mineral components in the WSA and the hydration products of WSA and WSA-GGBS pastes. The principal crystalline components in the WSA are gehlenite, calcium oxide, bredigite and α′-C₂S (stabilised with Al and Mg) together with small amounts of anorthite and calcium carbonate and traces of calcium hydroxide and quartz. The α′-C₂S and bredigite, which phase separate from liquid phase that forms a glass on cooling, are difficult to distinguish by XRD. The hydration products identified in WSA paste are CH, C₄AH₁₃, C₃A.0.5CC?.0.5CH.H_11.5 and C-S-H gel plus possible evidence of small amounts of C₂ASH₈ and C₃A.3CS?.H₃₂. Based upon the findings, a hydration mechanism is presented, and a model is proposed to explain the observed strength development.     

利用锰渣、矿渣、石灰石制备复合水泥

针对目前矿渣等高活性混合材资源的紧张,实验进行了锰渣、石灰石部分取代矿渣制备复合水泥的试验研究。研究表明,当石灰石粉掺量固定为10%时,相同水泥比例下,随着锰渣和矿渣比例的增加,胶砂试块3d强度增加,28d强度有所下降;当加入复合激发剂后复合混合材总掺量为60%,锰渣和矿渣质量比为4:1时,仍能配制合格的P.C32.5标号水泥。