The influence of CaCl2 on the crystallization of calcium silicates in autoclave hydration of C3S

The influence of CaCl₂ on the autoclave hydration C₃S (5 hours at 190°C) after different precuring times (0–16 hours) at room temperature has been studied. The addition of calcium chloride retards the autoclave hydration of C₃S and prevents completely the formation of the crystalline hydrated silicates (-C₂SH and C₃SH_1.5). This result has been compared with that observed in the ball-mill hydration of C₃S in the presence of CaCl₂, i.e., the complete absence of crystalline afwillite.

Abstract

On a étudié l'influence du CaCl₂ sur l'hydratation en autoclave du C₃S (5 heures à 190°C) après différents temps de conservation (0–16 heures à température ambiante. L'addition de chlorure de calcium retarde l'hydratation en autoclave du C₃S et empêche complétement la formation des silicates cristallins hydratés -C₂SH et C₃SH_1.5. Ce résultat a été comparé avec le phenomene observé en étudiant l'hydration du C₃S dans un moulin à boulets en presence de CaCl₂, c'est à dire la disparition complète du composé crystallin afwillite.     

Preparation and hydration study of rich C2S cements

Three laboratory clinkers were made with variable C₂S content (28–57%), using industrial raw materials. These clinkers were cooled by air and studied by X-Ray Diffraction (XRD). It is concluded that by fast cooling, the active crystal forms of - and ′-C₂S were stabilized in the rich C₂S clinker.

The hydration phenomena were also studied in cements prepared from these clinkers by DTA-TG and XRD, at 2, 7, 28 and 90 days. The combined water and the liberated Ca(OH)₂ were quantitatively determined by means of thermogravimetry and the hydration rate was studied.

It is concluded that the hydration rate differs at the early ages, but it progresses with the same rate after 28 days. No significant differences in the formed hydration products of these cements were observed by XRD.     

CP/MAS NMR studies of the initial hydration processes of activated and ordinary beta-dicalcium silicates

The initial hydration processes of activated and ordinary dicalcium silicates (β-C₂S) have been followed by using high resolution ²⁹Si nuclear magnetic resonance (NMR) associated with cross-polarization and magic-angle spinning (CP/MAS) without enrichment of ²⁹Si. The preliminary results show that the initial hydration products contain monomeric silicate hydrates and the amount of these monomeric silicate hydrates determines the hydration rate in the initial hydration period. As the hydration process goes on, the end-group of tetrahedra anions (Q₁ units) appears and then gradually dominates the spectrum.     

镁渣晶体结构对脱硫活性影响实验

研究了激冷水合过程中镁渣晶体结构的变化,结合钙转化率研究了晶体结构对镁渣脱硫活性的影响。借助X射线衍射和透射电镜分析了镁渣的晶体结构和形貌特征。结果表明：β-C₂S中的Ca²⁺配位不规则是其水合活性高于γ-C₂S的原因。随着镁渣激冷温度升高,β-C₂S增加,促进了具有发达孔隙结构的C－S－H生成,提高了物理吸附能力;晶粒细化程度增大,晶胞参数变化引起的晶格缺陷增多,增强了化学吸附能力。950℃激冷温度下镁渣脱硫活性最高,钙转化率达到24.6%。     

Crystal lattice defects in di-calcium silicate

It is well documented that the impurity content of C₂S has a marked effect on its hydration properties. It is also a fact that pure C₂S at room temperature exists in a crystal configuration, γ, which is completely different from the clinker C₂S. Incorporation of impurity ions into pure C₂S inhibits the β → γ transition on cooling, even at impurity levels as low as 0.1%. Currently, there is no fully accepted model for the mechanism of the stabilization of the β phase over the γ phase by impurities. The presence of these trace impurities naturally raises the question of the location and role of the impurities in producing this marked stabilizing effect. A quantitative solution to this problem requires that the lattice defect disorder of C₂S be defined and related to the phase stabilization properties of the impurities. Definition of crystal defect disorder can be achieved through detailed measurements of the electrical conductance of the solid with the data being interpreted in terms of solid state physics. Data for the electrical conductance of pure and “intentionally” impure (doped) C₂S over the temperature range 300 to 1100°C is presented. These data are interpreted in terms of crystal defects, their formation, location and kinetics. Models are presented to account for the stabilizing action of impurity ions within the crystal lattice of C₂S.     

Hydration of Beta Dicalcium Silicate Alone and in the Presence of CaCl2 or C2H5OH

Beta C₂S was hydrated at room temperature with and without added CaCl₂ or C₂H₅OH by methods previously studied for the hydration of C₃S, i.e. paste, bottle, and ball-mill hydration. The amount of reacted β-C₂S, the Ca(OH)₂ concentration in the liquid phase, the CaO/SiO₂ molar ratio, and the specific surface area of the hydrate were investigated. A topochemical reaction occurs between water and β-C₂S, resulting in the appearance of solid Ca(OH)₂ and a hydrated silicate with a CaO/SiO₂ molar ratio of ≃1. As the liquid phase becomes richer in Ca(OH)₂, the first hydrate transforms to one with a higher CaO/SiO₂ ratio. Addition of CaCl₂ increases the reaction rate and the surface area of the hydrate but to a much lesser extent than in the hydration of C₃S, whereas C₂H₆OH strongly depresses the hydration rate of β-C₂S, as observed for C₃S hydration.     

Al2O3掺杂对γ-C2S碳化性能的影响

本文研究了Al₂O₃掺杂对γ-C₂S熟料粒径、微观结构和力学性能的影响。试验结果表明:Al₂O₃掺杂不会改变γ-C₂S的晶型,但显著改变了其形貌;纯相γ-C₂S颗粒表面褶皱较多,颗粒尺寸较大,掺杂Al₂O₃后γ-C₂S颗粒表面褶皱消失而变得光滑;γ-C₂S碳化体的抗压强度与碳化程度随着Al₂O₃掺量的提高逐渐增加。通过碳化反应温升并结合碳酸钙衍射峰的半峰宽和X射线衍射仪(XRD)定量分析表明,Al₂O₃掺杂延缓了碳化放热,有利于碳化反应的持久进行,同时促进了碳酸钙晶粒的生长和数量的增加,从而使碳化程度更高,基体结构更加密实,因而抗压强度更高。     

Calcium and silicon concentrations in solution during the early hydration of portland cement and tricalcium silicate

The solution chemistry of Portland cement and C₃S pastes has been studied with particular attention to the concentrations of calcium and silicon in the aqueous phase during early stages of hydration. Results are discussed in relation to solubility data available from studies of OPC and C₃S pastes and from the CaO---SiO₂---H₂O system. It is shown that under normal conditions the concentration of silicon in solution is extremely low (<2ppm) and this remains unchanged even when hydration is accelerated in the presence of CaCl₂. However, retarding admixtures such as oxalic acid and EDTA, which are strong calcium binding agents, release a flush of silicon into solution within the first few minutes of hydration. The results lend support to the osmotic membrane model of cement hydration and also provide insight into the mechanisms by which accelerating and retarding admixtures function.     

煅烧工艺对天然水硬性石灰中硅酸二钙晶相转变的影响

天然水硬性石灰(natural hydraulic lime, NHL)是由钙硅质原料煅烧消化所得,主要成分是硅酸二钙(Ca₂SiO₄, C₂S)和氢氧化钙(Ca(OH)₂, CH),与我国古代岩土类建筑物的兼容性较高,是一种优秀的古建筑修复材料。为探究NHL的煅烧工艺,本文使用方解石粉和石英粉作为NHL煅烧原料,设置不同冷却方式(急冷≈500 ℃/min、随炉冷却≈60 ℃/min)、恒温时间(0~180 min)和煅烧温度(1 000~1 200 ℃),通过X射线衍射和游离氧化钙(f-CaO)测试方法评价NHL烧成制度。结果表明:在低于1 150 ℃煅烧C₂S时,改变降温速率不会使C₂S在降温过程中发生晶相转变;同一温度下,随恒温时间的增加NHL煅烧产物中C₂S含量增多,在30~45 min时其含量达到该温度下的最大值,且温度升高能增加该最大值,在恒温过程中C₂S先以β-C₂S存在,随时间延长,逐渐转变为γ-C₂S;煅烧温度1 150 ℃,恒温时间45 min,急速冷却的煅烧制度可用于制备NHL。     

Investigation of CoNiMo/Al2O3 catalysts: Relationship between H2S adsorption and HDS activity

Sulfidation of trimetallic CoNiMo/Al₂O₃ catalysts was studied by thermogravimetry at 400 °C under flow and pressure conditions. Results were compared with those obtained on prepared and industrial CoMo/Al₂O₃ and NiMo/Al₂O₃ catalysts. The amount of sorbed H₂S on the sulfided solids was measured at 300 °C in the H₂S pressure range 0–3.5 MPa at constant H₂ pressure (3.8 MPa). The adsorption isotherms were simulated using a model featuring dissociated adsorption of H₂S on supported metal sulfides and bare alumina. The amount of sulfur-vacancy sites could thus be determined under conditions close to industrial practice. A relationship with activity results for thiophene HDS and benzene hydrogenation was sought for.     

Early Hydration of Tricalcium Silicate

The hydration of tricalcium silicate (C₃S) in the preacceleration stages was studied. The C₃S particles carry a positive charge during the early stages of hydration. Following a rapid hydrolysis of C₃S, calcium ions adsorbed on the Si-rich surface of C₃S particles, greatly reducing their further dissolution, thus initiating the induction period. The [Ca²⁺] and [OH^-] continue to increase at lower rates and, because Ca(OH)₂ crystal growth is inhibited by silicate ions, become supersaturated with respect to Ca(OH)₂. When the supersaturation reaches a value of ∼1.5 to 2.0 times the saturation concentration, nuclei are formed, and rapid growth of Ca(OH)₂ and C-S-H is initiated. These products act as sinks for the ions in solution, thus enhancing the further dissolution of C₃S.     

FeS与TiO2共存对水泥熟料中Ti的固化与迁移及矿物组成的影响

为研究FeS与TiO₂共存对水泥熟料中Ti的固化与迁移及矿物组成的影响,采用电感耦合等离子体发射光谱(ICP-OES)、能量色散光谱(EDS)、X射线衍射(XRD)与Rietveld全谱拟合法分别测量水泥熟料中Ti 的含量与分布以及熟料的矿物组成,根据X射线光电子能谱(XPS)、结构性差异因子D与Hume-Rothery经验公式探究S与Ti在水泥熟料中的存在形式。结果表明,FeS的掺入对水泥熟料固化Ti的能力影响较小,但使得Ti由中间相向硅酸盐相迁移。随着FeS含量增加,Ti在C₂S中的含量增加46.9%,促进α-C₂S的形成,增强了硅酸盐相对Ti的固化能力;熟料中Fe²⁺/Fe³⁺摩尔比增大和CaSO₄的生成是使C₃S和C₄AF含量降低,C₂S和C₃A含量增加的主要原因。     

Influence of Minor Ions on the Stability and Hydration Rates of β-Dicalcium Silicate

The effects of Al³⁺, B³⁺, P⁵⁺, Fe³⁺, S⁶⁺, and K⁺ ions on the stability of the β-phase and its hydration rate were studied in reactive dicalcium silicate (C₂S, Ca₂SiO₄) synthesized using the Pechini process. In particular, the dependences of the phase stability and degree of hydration on the calcination temperature (i.e., particle size) and the concentration of the stabilizing ions were investigated. The phase evolution in doped C₂S was determined using XRD, and the degree of hydration was estimated by the peak intensity ratio of the hydrates to the nonhydrates in ²⁹Si MAS NMR spectra. The stabilizing ability of the ions varied significantly, and the B³⁺ ions were quite effective in stabilizing the β-phase over a wide range of doping concentrations. The hydration results indicated that differently stabilized β-C₂S hydrated at different rates, and Al³⁺- and B³⁺-doped C₂S exhibited increased degree of hydration for all doping concentration ranges investigated. The effect of the doping concentration on degree of hydration was strongly dependent on the stabilizing ions.     

冷却方式对熟料矿物及C3S晶型的影响

C₃S矿物是熟料的主要成分,是水泥熟料强度的主要提供者,熟料的强度不仅受C₃S含量影响,与C₃S晶型也直接相关。为研究冷却方式式对熟料矿物成分和晶型结构的影响,将不同水泥厂工业生料经制样烘干后在1 450 ℃下煅烧保温30 min,采用液氮淬冷、空气快冷和随炉慢冷的方式制备熟料。通过TG-DSC、XRD、Rietveld全谱拟合、岩相分析等对熟料矿物组成、含量、晶型、形貌以及固溶情况进行分析。结果表明:冷却速度加快,熟料中C₃S含量提高,β-C₂S、C₃A及C₄AF含量降低,铝率较大生料的冷却速度对C₃S、C₃A含量影响更显著;冷却方式不同,C₃S晶型不同,液氮冷却和空气冷却时C₃S多为M1或M3型,随炉冷却时C₃S多为T型,冷却速度减慢使C₃S晶型从M型向T型转变。     

Catalytic reduction of SO2 over supported transition-metal oxide catalysts with C2H4 as a reducing agent

This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO₂ with C₂H₄ as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C₂H₄/SO₂, and pretreatment are all important factors affecting catalyst activity. Fe₂O₃/γ-Al₂O₃ was found to be the most active catalyst among six γ-Al₂O₃-supported metal oxide catalysts tested. With Fe₂O₃ as the active species, of the supports tested, CeO₂ is the most suitable one. Using this Fe₂O₃/CeO₂ catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C₂H₄/SO₂ is 1:1, and the catalyst presulfidized by H₂+H₂S exhibits a higher performance than those pretreated with H₂ or He. Although the feed concentrations of C₂H₄:SO₂ being 3000:3000 ppm provide a higher conversion of SO₂, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C₂H₄ temperature-programmed desorption (C₂H₄-TPD) and SO₂-TPD desorption patterns illustrate that Fe₂O₃/CeO₂ can adsorb and desorb C₂H₄ and SO₂ more easily than can Fe₂O₃/γ-Al₂O₃. Moreover, the SO₂-TPD patterns further show that Fe₂O₃/γ-Al₂O₃ is more seriously inhibited by SO₂. These findings may properly explain why Fe₂O₃/CeO₂ has a higher activity for the reduction of SO₂.     

不锈钢渣碳化影响因素及其机理研究

为开发γ-C₂S不锈钢渣碳储存的潜力,最大限度地提高不锈钢渣的综合利用率。通过研究主要碳化参数(如液固比、成型压力、CO₂分压)对不锈钢渣碳化性能的影响规律来评估不锈钢渣的CO₂储存能力,以期能够提供更佳的不锈钢渣碳化过程。利用XRD、SEM/EDS、DSC/TG分析对不锈钢渣碳化产物组成及微观形貌进行表征,并探索其碳化机理。结果表明,较佳碳化参数为成型压力为2.50 MPa,液固比为10%,CO₂分压为0.3 MPa。较佳碳化条件下每千克不锈钢渣可固化储存CO₂气体约123.6 g。不锈钢渣碳化过程以γ-C₂S碳化反应为主,碳化产物中出现了片状、颗粒状的CaCO₃,随碳化时间延长,晶体逐渐长大为团簇状。因此,利用不锈钢渣储备碳及制备碳化制品是可行的。     

Characterization of C-S-H from Highly Reactive β-Dicalcium Silicate Prepared from Hillebrandite

β-dicalcium silicate synthesized by thermal dissociation of hydrothermally prepared hillebrandite (Ca₂(SiO₃)(OH)₂) exhibits extremely high hydration activity. Characterization of the hydrates obtained and investigation of the hydration mechanism was carried out with the aid of trimethylsilylation analysis, ²⁹Si magic angle spinning nuclear magnetic resonance, transmission electron microscopy selected area electron diffraction, and XRD. The silicate anion structure of C-S-H consisted mainly of a dimer and a single-chain polymer. Polymerization advances with increasing curing temperature and curing time. The C-S-H has an oriented fibrous structure and exhibits a 0.73-nm dreierketten in the longitudinal direction. On heating, the C-S-H dissociates to form β-C₂S. The temperature at which βC₂S begins to form decreases with increasing chain length of the C-S-H or as the Ca/Si ratio becomes higher. The high activity of β-C₂S is due to its large specific surface area and the fact that the hydration is chemical-reaction-rate-controlled until its completion. As a result, the hydration progresses in situ and C-S-H with a high Ca/Si ratio is formed.     

Hydrodeoxygenation of aliphatic esters on sulphided NiMo/γ-Al2O3 and CoMo/γ-Al2O3 catalyst: The effect of water

Water formed during hydrotreating of oxygen-containing feeds has been found to affect the performance of sulphided catalysts in different ways. The effect of water on the activity of sulphided NiMo/γ-Al₂O₃ and CoMo/γ-Al₂O₃ catalysts in hydrodeoxygenation (HDO) of aliphatic esters was investigated in a tubular reactor by varying the amount of water in the feed. In additional experiments, H₂S was added to the feed, alone and simultaneously with water.

Under the same conditions, the NiMo catalyst exhibited a higher activity than the CoMo catalyst. The ester conversions decreased with increase in the amount of added water. When H₂S and water were added simultaneously, the conversion increased to the same level as without water addition on the NiMo catalyst and reached a higher value on the CoMo catalyst. The conversions were highest, however, when only H₂S was added. Unfortunately, the conversions decreased with time under all conditions. On both catalysts, the total yield of the C₇ and C₆ hydrocarbons decreased with the amount of added water, while the concentrations of the oxygen-containing intermediates increased. The presence of H₂S improved the total hydrocarbon yield and shifted the main products towards the C₆ hydrocarbons. Thus, the addition of H₂S effectively compensated the inhibition by water.     

A New Approach to Modeling the Nucleation and Growth Kinetics of Tricalcium Silicate Hydration

The hydration kinetics of tricalcium silicate (C₃S), the main constituent of portland cement, were analyzed with a mathematical "boundary nucleation" model in which nucleation of the hydration product occurs only on internal boundaries corresponding to the C₃S particle surfaces. This model more closely approximates the C₃S hydration process than does the widely used Avrami nucleation and growth model. In particular, the boundary model accounts for the important effect of the C₃S powder surface area on the hydration kinetics. Both models were applied to isothermal calorimetry data from hydrating C₃S pastes in the temperature range of 10°–40°C. The boundary nucleation model provides a better fit to the early hydration rate peak than does the Avrami model, despite having one less varying parameter. The nucleation rate (per unit area) and the linear growth rate of the hydration product were calculated from the fitted values of the rate constants and the independently measured powder surface area. The growth rate follows a simple Arrhenius temperature dependence with a constant activation energy of 31.2 kJ/mol, while the activation energy associated with the nucleation rate increases with increasing temperature. The start of the nucleation and growth process coincides with the time of initial mixing, indicating that the initial slow reaction period known as the "induction period" is not a separate chemical process as has often been hypothesized.     

CCUS环境下水泥单矿C3S的CO2腐蚀动力学研究

在碳捕集、利用和封存(CCUS)井下,油井水泥因长期受井下高温、高压和高酸性流体的作用会遭受碳化腐蚀导致水泥环失效。为了模拟CO₂地质封存井下碳化腐蚀环境,本文将油井水泥的主要单相矿物硅酸三钙(C₃S)置于不同温度(30 ℃、60 ℃、90 ℃),并密封在8.0 MPa的气相或液相的CO₂碳化环境下,采用XRD和TGA相结合的分析方法,分析水泥单矿C₃S受CO₂腐蚀环境的影响规律。根据非稳态Fick扩散的渗透理论模型,建立腐蚀产物定量分析结果与腐蚀龄期的数学模型,拟合得到C₃S受CO₂腐蚀后的产物生成系数,以此评价不同CO₂腐蚀因素对C₃S的影响程度。结果表明:在CO₂气相环境中,温度升高将显著加剧对C₃S的腐蚀且产生溶蚀现象;而在CO₂液相环境下,高温(90 ℃)使C₃S水化反应加剧并形成阻滞层,降低CO₂对C₃S的腐蚀速率。