锰尾矿基胶凝材料配方优化及水化机理分析

为研究低品位锰尾矿胶凝活性,将生石灰、氢氧化钠、水玻璃和石膏等激发剂添加到湖南永州低品位碳酸锰尾矿中,采用正交实验研究不同激发剂及掺量对锰尾矿基胶凝材料抗压强度和软化系数的影响,探究其潜在胶凝活性激发的最佳配方。实验结果表明,当生石灰、水玻璃、石膏掺量分别为10%、1.5%和4%时,胶凝材料净浆试体的各个龄期抗压强度最大,其中28 d抗压强度达到4.91 MPa,软化系数达到0.74。XRD、DTA和SEM微观实验发现:锰尾矿基胶凝材料主要水化产物为钙矾石和水化硅酸钙凝胶,随龄期持续增多并相互交织搭接,使试体内部结构逐渐致密,缝隙减少,提高了试体抗压强度和软化系数,因此,该激发剂可有效激发锰尾矿潜在胶凝活性。     

低品位锰尾矿基胶凝材料配方优化

为了探究尾矿胶凝活性,将生石灰、氢氧化钠、水玻璃和石膏等激发剂添加到湖南永州低品位氧化锰尾矿中,通过正交实验研究不同激发剂掺量对锰尾矿胶凝活性的激发效果。实验结果表明:当生石灰、氢氧化钠、水玻璃、石膏掺量分别为10%、2%、1.5%、6%时,锰尾矿基胶凝材料净浆试样的各个龄期抗压强度最大,28 d抗压强度可达到6.64 MPa,软化系数可达到0.81。SEM分析发现:低品位氧化锰尾矿基胶凝材料主要水化产物为钙矾石和水化硅酸钙凝胶,随着龄期延长,水化产物持续增加并相互交织搭接,内部缝隙减少,内部结构致密,提高了试样抗压强度和软化系数。     

磷石膏中杂质及预处理对α半水石膏性能的影响

磷石膏在建筑材料上的应用受到限制源于其中的杂质对产品质量和生产经济产生了不利影响。磷石膏中可溶性磷和氟化物的存在对α半水石膏的强度和凝结时间有负面影响。采用XRD、SEM和FTIR分析,结合宏观性能实验,对磷石膏中杂质及预处理对α半水石膏的性能的影响进行了研究。研究结果表明,由于杂质的存在,原状磷石膏制备出的α半水石膏强度很低,不易凝结,不能应用于实际生产。经过石灰中和后的磷石膏作为原料,强度较好。杂质可溶磷中的磷酸对α半水石膏的性能影响最大,强度显著降低,凝结时间延长,可溶氟含量大于1%时对其性能影响较大,有促凝作用。石灰处理磷石膏时,中性和弱碱性环境最利于α半水石膏形成和生长,性能最好。     

Plackett-Burman设计和响应曲面法优化除磷陶粒的制备

为制备得到除磷效果较强的功能型陶粒,采用Plackett-Burman和响应曲面法对陶粒原料配比进行优化研究。采用Plackett-Burman实验设计筛选出具有显著除磷效应的4种原料——粉煤灰、水泥、石膏和氢氧化钠。以Box-Behnken Design响应面法建立数学回归模型,确定了最佳原料配比为:粉煤灰60.0 g、水泥15.0 g、氨基材料2.0 g、生石灰15.0 g、石膏3.0 g、氢氧化钠15.0 g,制得的陶粒磷去除率可达93.04%,颗粒强度为118.3 N。通过显著性检验和响应曲面等高线图分析,粉煤灰和氢氧化钠是显著影响陶粒磷去除率的主要原料,且粉煤灰与石膏、粉煤灰与氢氧化钠对陶粒的磷去除率有显著的交互影响,显著性p值分别为0.010 8和0.029 5。     

提高硅钙渣胶凝活性的热活化实验

硅钙渣作为高铝粉煤灰碱-石灰烧结法提取氧化铝后产生的二次固废,为了使其能够大量地应用于建材领域,研究了热活化温度对硅钙渣水化胶凝性活性的影响,并采用TG-DSC和XRD对机理进行了分析。结果表明,硅钙渣中方解石的分解是硅钙渣活性得以提高的主要因素,在煅烧温度在600~700℃时,其胶凝活性最佳。     

超细粉煤灰-氟石膏在道路修补工程中的综合利用研究

针对我国现有水泥混凝土路面的破坏问题,研究开发了以工业废料--超细粉煤灰和氟石膏为主要组分的水泥基道路修补材料,利用氟石膏与超细粉煤灰在水泥水化过程中的相互激发作用,通过试验优选出超细粉煤灰-氟石膏高性能道路修补材料,并应用于道路修补混凝土的配制,同时测试了其力学性能及部分长期性能,试验表明其性能优良,在此基础上对其水化硬化机理作了初步的探讨.     

超细粉煤灰-氟石膏在道路修补工程中的综合利用研究

针对我国现有水泥混凝土路面的破坏问题,研究开发了以工业废料——超细粉煤灰和氟石膏为主要组分的水泥基道路修补材料,利用氟石膏与超细粉煤灰在水泥水化过程中的相互激发作用,通过试验优选出超细粉煤灰-氟石膏高性能道路修补材料,并应用于道路修补混凝土的配制,同时测试了其力学性能及部分长期性能,试验表明其性能优良,在此基础上对其水化硬化机理作了初步的探讨.     

碱激发胶凝材料及其固化Pb^2＋的试验研究

对碱激胶凝材料（碱-偏高岭土、碱-矿渣和碱-粉煤灰）与水-水泥体系固化Ph^2＋进行了试验研究,其中水-水泥体系为对比样。结果表明：对于相同稠度的碱激发胶凝材料,即使Pb^2＋含量达到2．4％,除了碱-粉煤灰的抗压强度略低外,其他都达到30MPa以上,满足填埋或做建筑基材的使用要求;与水泥相比,碱激发胶凝材料能显著降低重金属离子（Ph^2＋）浸出浓度,其规律性与其NH4交换容量大小的规律性一致,与其固化体的抗压强度的大小没有相关性。     

粉煤灰聚苯乙烯新型保温建筑材料的制备及其机理分析

以石灰、石膏作为粉煤灰活性激发剂,用废弃聚苯乙烯颗粒(EPS)作为保温成分,通过优化配比,研制新型节能环保墙体砌块材料,分析了砌块材料的水化机理。XRD（X射线衍射）、TGA-DTA（热重-差热分析）和SEM（扫描电子显微镜）分析证实：当粉煤灰掺量为20%~25%、EPS为2.5%时,保温砌块材料的施工及保温性良好,耐久与耐候性能优良。     

碱激发胶凝材料及其固化Pb2+的试验研究

对碱激胶凝材料（碱-偏高岭土、碱-矿渣和碱-粉煤灰）与水-水泥体系固化Pb²⁺进行了试验研究,其中水-水泥体系为对比样。结果表明：对于相同稠度的碱激发胶凝材料,即使Pb²⁺含量达到2.4%,除了碱-粉煤灰的抗压强度略低外,其他都达到30 MPa以上,满足填埋或做建筑基材的使用要求;与水泥相比,碱激发胶凝材料能显著降低重金属离子（Pb²⁺）浸出浓度,其规律性与其NH⁺₄交换容量大小的规律性一致,与其固化体的抗压强度的大小没有相关性。     

Preparation of Calcium Silicate Reagent from Fly Ash and Lime in a Flow Reactor

Abstract

The batch reaction between fly ash and hydrated lime in water to produce high surface area calcium silicates for flue gas desulfurization has been examined extensively. This paper examines the reaction in a flow reactor using two low-calcium fly ashes and introducing gypsum, calcium sulf ite hemihydrate, and calcium chloride as additives to the reaction. The flow system is compared to the batch reaction at similar operating conditions and a segregated flow model is used to approximate flow reactor behavior.

Experiments with calcium chloride and gypsum additives were modeled fairly well by the segregated flow approximation at residence times less than 12 hours. The flow reactor produced low surface area material at longer residence times when gypsum was present. Because the changing solution chemistry affected the batch reaction rate the fly ash and hydrated lime system without gypsum or calcium chloride could not be approximated using batch reaction data. In this case, the flow reactor produced higher surface area product than the batch reactor for a given residence time due to the increased calcium hydroxide availability.     

粉煤灰处理煤矿酸性废水的研究

采用石灰石中和沉淀，粉煤灰吸附处理煤矿酸性废水，取得了良好的效果。用石灰石调节pH至4.5，再用石灰中和至中性，并用粉煤灰吸附，粉煤灰用量为10g／L时处理效果较好。     

Surface Consolidation of Pentelic Marble: Criteria for the selection of methods and materials - The Acropolis case (6 pp)

Goal and Scope In order to realize surface consolidation of Pentelic marble on the Acropolis monuments, we have collected the criteria that have to be fulfilled by the methods and materials without side effects on the marbles (and other stones). When the existing methods and materials did not satisfy the requirements (criteria), we invented new ones.Methods The criteria were collected from the literature, by thermodynamic and kinetic viewpoints, by laboratory experiments and in situ observations on monuments, both in Greece and in several countries in which the various methods and materials were applied. Concerning our method of ‘Inversion of sulfation’, performed by spraying a K2CO3 solution, its concentration and its temperature were controlled in order to have a total inversion (certified by liquid crystals) of gypsum back to CaCO3. For the new material of ours, ‘Reinforced Lime’, in order to eliminate the disadvantages of plain lime (low carbonation rate, low mechanical properties of CaCO3 formed, lack of carbonation in the bulk of lime), measurements of the rate of carbonation were performed in plain lime and in lime with a different CaCO3 concentration beforehand as well as in a different CO2 environments, using DTG and XRD to measure the rate of carbonation. The detachment (kg/cm2) of marble specimens stuck by lime in each case was also measured. A microscope was also used to measure the dimensions of the grain in each case as well as ammonium citrate and thymolphthalein to certify the depth of carbonation in each case. Part of the work was communicated in an international congress.Results A table with the criteria of the selection of the methods and materials for the consolidation of Pentelic marble surfaces (and other stones) was established. None of the employed methods and materials fulfilled the criteria. Only the ‘Inversion of gypsum ‘ and the ‘Reinforced Lime’ were adopted and applied to the Acropolis monuments and to other monuments in Greece and in several other countries.Recommendation and Outlook All criteria must be used for the selection of methods and materials for the consolidation of the monument surfaces. This is why we have already studied with the same procedures, methods and materials for restoration, surface cleaning and protection.     

Preparation of calcium silicate absorbent from iron blast furnace slag

Calcium silicate hydrate (CSH) solids were prepared from hydrated lime and iron blast furnace slag in an aqueous agitated slurry at 92 degrees C. While it was hoped a minimal lime/slag ratio could be used to create near-amorphous CSH, the surface area of the product improved by increasing the lime/slag weight ratio to 2. The addition of gypsum to the lime/slag system dramatically improved the formation of surface area, creating solids with 139 m2/g after 30 hr of reaction when only a minimal amount of lime was present. The SO2 reactivity of solids prepared with gypsum greatly exceeded that of hydrated lime, achieving greater than 70-80% conversion of the alkalinity after 1 hr of reaction with SO2. The use of CaCl2 as an additive to the lime/slag system, in lieu of gypsum, also produced high-surface-area solids, 115 m2/g after 21 hr of reaction. However, the SO2 reactivity of these sorbents was relatively low given the high surface area. This emphasized that the correlation between surface area and SO2 reactivity was highly dependent on the solid phase, which was subsequently dependent on slurry composition.     

Black layers on historical architecture

Background, aim and scope

The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called ‘black crusts’. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider ‘black crusts’ all similar, whilst only a careful diagnostic investigation can distinguish ‘black crusts’ and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out.

Materials and methods

Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy.

Results

Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay.

Discussion

The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in ‘recent’ crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out.

Conclusions

In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past.

Recommendations and perspectives

New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.     

Preparation of Calcium Silicate Absorbent from Iron Blast Furnace Slag

ABSTRACT

Calcium silicate hydrate (CSH) solids were prepared from hydrated lime and iron blast furnace slag in an aqueous agitated slurry at 92 °C. While it was hoped a minimal lime/slag ratio could be used to create near-amorphous CSH, the surface area of the product improved by increasing the lime/slag weight ratio to 2. The addition of gypsum to the lime/slag system dramatically improved the formation of surface area, creating solids with 139 m²/g after 30 hr of reaction when only a minimal amount of lime was present. The SO₂ reactivity of solids prepared with gypsum greatly exceeded that of hydrated lime, achieving greater than 70-80% conversion of the alkalinity after 1 hr of reaction with SO₂. The use of CaCl₂ as an additive to the lime/slag system, in lieu of gypsum, also produced high-surface-area solids, 115 m²/g after 21 hr of reaction. However, the SO₂ reactivity of these sorbents was relatively low given the high surface area. This emphasized that the correlation between surface area and SO₂ reactivity was highly dependent on the solid phase, which was subsequently dependent on slurry composition.     

Use of Seawater in Flue Gas Desulfurization

For seasite power plants using seawater for condenser cooling, Bechtel developed a new process to remove better than 90 percent of flue gas SO₂ using seawater and lime. Tests demonstrate that marine life is not affected by the effluent from this unique scrubbing process; therefore, the aqueous effluent containing reacted products (gypsum) in solution at low concentration is suitable for discharge to the sea.     

Embryonic sulphated black crusts on carbonate rocks in atmospheric simulation chamber and in the field: role of carbonaceous fly-ash

Experimental conditions characteristic of the urban pollution in many European cities over the last decades were reproduced in a simulation chamber in which samples of limestone were exposed for a period of 12 months, both naked or sprinkled with carbonaceous fly-ash. In agreement with the findings reported in the literature the fly-ash emitted by heavy fuel combustion are highly reactive, undergoing chemical and morphological transformations which give rise to crystals growth, especially gypsum. The development of gypsum crystals was observed overall in close proximity of fly-ash anchoring them to the limestone surface. Samples of the same limestone exposed in the field in a polluted environment for the same period of time led to similar results. The preliminary mechanisms leading to the genesis of sulphated black crusts in polluted environments were thus highlighted. Because of their roughness the embryonic black crusts increase the development of the crust by trapping new particles. This trapping is also facilitated by the wetness of the stone surface leading to the development of hydrated mineral (gypsum) in the water meniscus between fly-ash and stone surface.     

Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

PCDD/F in waste water discharges from flue gas scrubbers of waste incinerators and coal operated power plants

Scrubber water samples from different combustion plants and gypsum samples as obtained in the flue gas washing with lime water were analyzed for PCDD/F. Three of the investigated nine scrubber water samples showed PCDD/F contents between 0,4 and 11,5 ng I-TEq/1 where as in the 17 gypsum samples examined only in a few cases very low levels of HpCDD and OCDD could be detected.