煤矸石质硅铝基材料胶凝机理的研究

系统地开展了利用低温煅烧煤矸石为主要原料制备早期强度高、水化热低且具有良好固土特性的硅铝基胶凝材料的基础研究.采用结构分析的方法,运用高分辨固体核磁共振、液体核磁共振和红外光谱等分析手段研究了煤矸石和高岭石在煅烧、碱介质中溶出和胶凝过程中硅、铝配位的变化,结合其胶凝产物的物相、形貌和水化热,从结构、配位和物相转变的角度来研究煤矸石质硅铝基胶凝材料胶凝机理.揭示了煤矸石的煅烧过程就是铝氧八面体中铝的四配位转化以及铝氧四面体和硅氧四面体解聚过程的重要规律,其中铝氧八面体中铝的四配位转化是煤矸石产生胶凝活性的本源.证明了煤矸石和高岭石在煅烧过程中铝配位的变化与地质界Thompson定律相吻合.比较研究了煤矸石和高岭石的活性与其结构之间的关系,发现低于900℃煅烧煤矸石的红外光谱中,560cm-1附近吸收峰的强度与Si、Al离子的溶出量具有正相关性;五配位铝是偏高岭石具有高活性的主要原因.证明了由于一价和二价阳离子的存在,以高岭石为主要矿物的煤矸石在煅烧过程中没有出现五配位铝.通过对硅铝质物料Si2p、Al2p和Ols结合能与其胶凝材料力学性能之间关系的研究,提出用硅、铝电子结合能评价硅铝物料胶凝活性的新方法.深入研究了不同介质条件下煅烧煤矸石的溶出特性及其胶凝机理.研究表明:煅烧煤矸石在碱性溶液中是以单聚体硅酸根离子和单聚体铝酸根离子的形式溶出;(HO)3SiO-和Al(OH)4-的溶出证明硅铝基胶凝材料反应初期是硅氧四面体和铝氧四面体的再解聚过程,体现在反应后,27Al和29Si NMR谱的共振峰向低场偏移;以硅酸钾为溶出介质,煅烧煤矸石溶出渣29Si MAS NMR谱中-97.36×10-6共振峰的出现揭示了硅铝基胶凝材料胶凝过程中原位键合的作用;随着反应的进行,27Al和29Si NMR共振峰都向高场偏移,表明胶凝过程中与中心铝原子在次级配位圈上直接连接[SiO4]四面体数量增多以及反应产物中硅氧四面体聚合度的增加.根据胶凝过程中硅、铝配位的变化,提出了硅铝基胶凝材料原位键合的反应机理,并将胶凝过程概括为解聚过程、胶结过程、原位键合过程和缩聚过程.     

粉煤灰的活化研究

本文用碳酸钠焙烧活化粉煤灰中的硅和铝，利用溶出活化粉煤灰中的硅和铝制备纯沸石分子筛。粉煤灰与碳酸钠以质量比为1：1．4，在850℃下焙烧活化1小时，研究活化粉煤灰在碱溶液中的溶出行为，发现在溶出过程中硅铝存在过饱和现象。利用这一现象，有效地解决了较低碱浓度条件下，粉煤灰中硅铝的共同溶出问题。用水溶液浸取活化粉煤灰和铝土矿，使其中的硅酸钠优先溶出，进而碱溶使其中的偏铝酸钠溶出。结果表明：在液固比为50ml／g，碱浓度达到2mol/L时，在过饱和期内过滤反应物得到硅铝的过饱和溶出液可用于制备各种纯沸石分子筛．结果表明，沸石的晶型完整，纯度较高。阳离子交换容量可达3．1meq／g以上。     

矿渣/偏高岭土复合前驱体原位转化沸石的影响因素研究

沸石具有良好的吸附、过滤、催化等性能，被广泛应用于建筑、农业、化工等领域。以碱激发胶凝材料为前驱体制备沸石是近年来开发的新技术，但纯偏高岭土基前驱体转化所得沸石往往存在机械强度偏低和界面分层的问题。鉴于此，本工作在前驱体中引入矿渣，发挥其高活性等效应，改善前驱体水热转化为NaA和NaP型沸石后试样的物理性能，研究了水热温度、水热时间及矿渣掺量等因素对沸石晶体种类、沸石转化率、抗压强度的影响。结果表明：在掺用矿渣条件下，提高水热温度，沸石晶体种类减少，沸石转化率先升高后降低；适当延长水热时间，沸石种类无明显变化，但沸石转化率升高；反应时间过长会导致沸石溶解，进而使得沸石转化率降低。矿渣可降低前驱体生成沸石所需的水热温度，缩短水热时间，提高样品强度，减弱分层现象。矿渣/偏高岭土前驱体转化沸石的适宜条件为矿渣掺量10%、水热温度110℃、水热时间20 h,此条件下水热后样品抗压强度达到62.2 MPa,沸石转化率达到70%。     

合成条件对粉煤灰合成沸石过程中沸石生成和品质的影响

系统研究了由粉煤灰合成沸石过程中温度、反应时间、液固比和NaOH浓度等合成条件对沸石生成及其阳离子交换容量(CEC,CationExchangeCapacity)的影响.结果表明,温度主要影响沸石矿物的结晶度;液固比主要影响沸石种类;NaOH浓度和反应时间对两者均产生明显影响.合成产物的CEC随温度、液固比、反应时间呈快速增加,并在分别达到110℃、2.5和16h时趋于一最大值.NaOH浓度越高,合成产物CEC也越高,至2mol·L^-1时达到最大,之后显著下降.考虑到合成成本,最佳合成条件初步归纳为:温度110-120℃,反应时间8-16h,液固比2.5,NaOH浓度2mol·L^-1.     

在泡沫碳化硅载体上原位生长silicalite-1型沸石晶体

以多晶硅颗粒为硅源, 在泡沫碳化硅载体上原位水热合成silicalite--1型沸石晶体。研究了硅颗粒加入量、NaOH浓度以及合成时间等因素对沸石晶体的负载量、晶体尺寸和沸石晶体/泡沫碳化硅复合材料比表面积的影响。结果表明,
以多晶硅颗粒为硅源控制硅酸根的释放速度, 使沸石晶体在碳化硅载体表面异质界面形核, 从而实现沸石晶体在泡沫碳化硅载体表面的连续生长; 当多晶硅量过少时, 溶液中的硅酸根浓度过低, 不能在载体表面形成连续生长的沸石层;
而当多晶硅量过大时, 溶液中硅的浓度过高, 部分沸石晶体在溶液当中形核, 使沸石晶体在载体表面的负载量下降; 提高溶液中NaOH的浓度, 加快硅的溶解, 使溶液中硅的饱和浓度升高, 沸石晶体的形核率也随之升高, 使沸石晶体的负载量增加。在最优条件下制备的silicalite--1/泡沫碳化硅复合材料其沸石晶体的比表面积为81.28 m²g^-1。     

纳米沸石的合成及其影响因素

纳米沸石的合成通常以水热法为主，此外尚有模板法、气固相法和微波加热法等不同方法合成的范例。低聚合度硅源、较高的碱度、较低的固液比和硅铝比、较低的晶化温度、合适的添加剂类型以及较高的添加剂用量有助于纳米沸石的形成；无钠碱源形成分立的纳米沸石胶体，有钠碱源形成聚集态纳米沸石。     

碱激发烧煤矸石胶凝材料的硬化机理研究

利用XRD,IR,SEM等方法,研究了NaOH、KOH和钠水玻璃激发烧煤矸石的反应进程和水化产物,对其力学性能、微观结构和硬化机理进行了探讨.结果表明:水化产物是类似于沸石类结构的无定形碱-硅铝凝胶,碱溶液、液固比、养护温度和养护时间等因素影响着水化产物及其强度的形成.采用模数为1.23钠水玻璃与烧煤矸石混合(液固比0.3),在90℃养护条件下反应生成无定型的碱-硅铝酸盐凝胶,而在65℃养护时,硬化浆体中还存在有一定量未反应的硅酸钠晶体.     

转化方式对粉煤灰地聚物原位转化沸石及其Pb2+吸附性能的影响

本工作以高铝粉煤灰为前驱体，通过碱激发及化学发泡的方式制备了富含类沸石相的多孔粉煤灰地聚物，并以此地聚物为骨架，通过原位转化将类沸石相转化为沸石，得到自支撑类沸石吸附材料。另外，研究了碱热、水热、微波三种原位转化方式下多孔粉煤灰地聚物的矿物组成变化规律、不同原位转化条件下制备的沸石类吸附材料对Pb²⁺的静态吸附行为。研究结果表明：碱热转化有利于多孔粉煤灰地聚物中的类沸石相原位转化生成沸石相，明显提高了其对Pb²⁺的吸附容量。碱热转化多孔粉煤灰地聚物对Pb²⁺的吸附属于単分子层吸附。吸附动力学拟合表明，碱热转化多孔粉煤灰地聚物对Pb²⁺的吸附方式分为物理吸附和化学吸附。当Pb²⁺初始浓度为100 mg/L和300 mg/L时，吸附过程以物理吸附为主；当Pb²⁺初始浓度为500 mg/L时，吸附过程伴随大量化学键形成，化学吸附作用更强。     

高炉矿渣的组成和结构对其在碱性环境中早期水化特性的影响

以不同组成和结构的高炉矿渣作为研究对象,借助XRD、ICP-MS以及²⁹Si MAS NMR等微观测试手段,探究了高炉矿渣在碱性环境中的离子溶出特性、硅氧四面体聚合状态随水化龄期变化的影响规律。研究表明:高炉矿渣中玻璃体的活性受其化学组成和结晶相含量影响,结晶相及铝氧结构单元的存在和增多降低了玻璃体结构的聚合度;网络改性剂在玻璃体结构中表现为不均匀分布,不同网络形成体结构单元的水解会伴随不同的水化特性;在碱性环境下,高炉矿渣玻璃体结构中硅氧四面体含量较大时,其硅氧结构更易被破坏,溶液中硅离子的浓度较高,溶液pH值维持在较低水平,生成的水化产物中高聚态硅氧四面体较多;高炉矿渣玻璃体结构中铝氧四面体含量较大时,其铝氧结构更易被破坏,溶液中铝离子及钙离子的浓度较高,液相pH值维持在较高水平,生成的水化产物中高聚态硅氧四面体较少。     

油页岩制油残渣制备氧化铝及其铝浸出率的研究

以抚顺东露天油页岩制油残渣为原料,用酸提法制备氧化铝,采用单因素考察法确定了抚顺东露天油页岩残渣提取氧化铝的酸溶反应最佳工艺条件为:煅烧温度850℃,煅烧时间1h,所需原料粒度0.074mm,盐酸浓度为12%,液固比为5∶1,酸溶反应温度100℃,反应时间1.5h,各项工艺指标在最佳工艺条件下,Al2O3浸出率为81.75%;采用均相化学沉淀法由酸溶反应得到的氯化铝滤液制备氧化铝的最佳工艺条件为:反应温度55℃,偏铝酸钠浓度0.4mol/L,乙酸乙酯与铝离子物质的量之比为1.7∶1,反应时间1.5h,表面活性剂的用量为总体系质量的0.3%。采用激光粒度分布仪、X射线衍射仪、X射线荧光光谱仪对所制得的产物氧化铝进行了表征和分析研究。     

Synthesis of type A zeolite from mechanoactivated metakaolin mixtures

The zeolite A was synthesized from the mechanically activated solid mixtures of metakaolin, sodium hydroxide and aluminum oxide. The stages of both thermal treatment and hydrothermal crystallization were investigated and optimized. The size of zeolite A particle was directly measured by scanning electron microscopy as well as calculated using the X-ray diffraction spectroscopy data. The thermal stability of the zeolite A was studied by the differential thermal analysis. It was shown that the optimum thermal treatment temperature providing the zeolite A yield of about 65 wt% and the particle size in the range of 0.2–0.3 μm is 600 °C. The furthermore increase in the thermal treatment temperature results in decreasing amount of zeolite A crystalline phase as well as in the formation of nepheline. It was also found that the optimum NaOH concentration providing the zeolite A yield of about 90 wt % and the particle size more than 0.7 μm after the hydrothermal crystallization stage is 2–4 mol/l. The higher alkali concentrations result decreasing amount of the zeolite A phase and cause the recrystallization into the sodalite. The use of KOH in the hydrothermal crystallization stage allows one to obtain the potassium-containing zeolite A by direct synthesis.     

Synthesis of pure NaA zeolites from coal fly ashes for ammonium removal from aqueous solutions

The pure NaA zeolites used as adsorbents for ammonium removal were successfully synthesized from coal fly ash by means of alkaline fusion followed by hydrothermal treatment. The experiment samples were characterized in terms of X-ray diffraction, X-ray fluorescence, Scanning electron microscopy, Fourier transform infrared spectroscopy, and Automated specific surface area and pore size analyzer. The results showed that the NaOH solution’s concentration, reaction temperature, and reaction time had significant effects on the species of the zeolite phases. Well-ordered cubic NaA zeolite with Brunauer–Emmett–Teller specific surface areas of 41.6 m²/g was prepared in 3 M NaOH solution at 353 K for 3 h. The adsorption behavior of NH₄ ⁺ from aqueous solution onto NaA zeolites was investigated at different initial concentrations, pH values, and contact times. The adsorbent equilibrium could be reached within 60 min, and the maximum removal efficiency of NH₄ ⁺ was achieved at pH 7.0. The Langmuir and Freundlich adsorption models were also applied to describe the equilibrium isotherms. The obtained results show that the experimental data have a better (R ² = 0.99) fit to Freundlich model and the adsorption of NH₄ ⁺ ions using synthesized NaA zeolite is favorable.     

Adsorption of carbon dioxide and methane on nanosized sodalite octahydrate zeolite

Nanosized sodalite octahydrate zeolite has been developed using a crystallization room temperature in the absence of organic templates. The best aging time found was 120?h and in this time the nanosized sodalite octahydrate zeolite is formed. The samples were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-Transform Infrared (FTIR) spectroscopy, x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and N₂ adsorption–desorption isotherm. The equilibrium adsorption capacities of pure gases CO₂ and CH₄ were measured at 298 and 308?K up to 20?bar on both powder and granules of sodalite octahydrate zeolite. With increasing temperature, the adsorption capacity decreases for both sodalite octahydrate zeolite powder and granules. The selectivity of CO₂ at 308?K over CH₄ was 6.53.     

Coal ash conversion into effective adsorbents for removal of heavy metals and dyes from wastewater

Fly ash was modified by hydrothermal treatment using NaOH solutions under various conditions for zeolite synthesis. The XRD patterns are presented. The results indicated that the samples obtained after treatment are much different. The XRD profiles revealed a number of new reflexes, suggesting a phase transformation probably occurred. Both heat treatment and chemical treatment increased the surface area and pore volume. It was found that zeolite P would be formed at the conditions of higher NaOH concentration and temperature. The treated fly ash was tested for adsorption of heavy metal ions and dyes in aqueous solution. It was shown that fly ash and the modified forms could effectively absorb heavy metals and methylene blue but not effectively adsorb rhodamine B. Modifying fly ash with NaOH solution would significantly enhance the adsorption capacity depending on the treatment temperature, time, and base concentration. The adsorption capacity of methylene blue would increases with pH of the dye solution and the sorption capacity of FA-NaOH could reach 5 x 10(-5) mol/g. The adsorption isotherm could be described by the Langmuir and Freundlich isotherm equations. Removal of copper and nickel ions could also be achieved on those treated fly ash. The removal efficiency for copper and nickel ions could be from 30% to 90% depending on the initial concentrations. The increase in adsorption temperature will enhance the adsorption efficiency for both heavy metals. The pseudo second-order kinetics would be better for fitting the dynamic adsorption of Cu and Ni ions.     

Preparation and characterization of zeolite from waste Linz-Donawitz (LD) process slag of steel industry for removal of Fe3+ from drinking water

Cubical-shaped zeolite A was synthesized from the Linz-Donawitz (LD) process slag of the Steel Industry, utilizing conventional fusion-assisted hydrothermal treatment. Morphological and Physico-chemical characterizations were performed by various characterization techniques. A weight ratio of 1:1.2 (LD-slag: NaOH) was maintained during fusion, which provides a better binding effect with better mechanical stability to the zeolite framework. Fe³⁺ adsorption studies were performed at 273, 298, 303, and 308 K, respectively, within the range of 10–40 mg L⁻¹ Fe³⁺ ion concentration for kinetic and isotherm studies. A maximum adsorption capacity of 27.55 mg g⁻¹ was obtained at a 1.4 g L⁻¹ adsorbent dosage, with 99.99% Fe³⁺ ion removal. Moreover, the Fe³⁺ adsorption study obeyed the pseudo-second-order kinetic model, whereas multistage diffusion controlled the adsorption process. Langmuir isotherm model best fitted the equilibrium data suggesting the highly negative charge over the adsorbent surface played a vital role in the electrostatic attraction of Fe³⁺ ions. Isomorphic replacement of silicon by aluminum ion imparted a highly negative charge over the zeolite surface in the primary structure unit. For real-life sample drinking water, the Fe³⁺ ion removal efficiency increases to 97.7%.     

Synthesis and characterization of mesoporous silicon directly from pure silica sodalite single crystal

Mesoporous silicon granules with high surface area were synthesized directly from pure silica sodalite single crystals, with the starting shape retained. The sodalite single crystals were reduced by a magnesiothermal process in vacuum at 630 °C. The X-ray diffraction patterns indicate the presence of crystal silicon. Transmission electron microscopy studies reveal that the obtained silicon granules are composed of a monocrystalline surface with an island-like mesoporous internal structure. The results of N₂ adsorption and desorption analysis indicate that the surface area is around 308 m² g⁻¹ and the single point pore volume is 0.37 cm³ g⁻¹. The photoluminescence emission centered at 2.7 eV may be due to both an oxidized surface and quantum confinement effects. These results reveal that the silicon granules possess a different microstructure from those of etched silicon films. The present synthetic design correlates the microporous zeolite and mesoporous silicon together and gives a new way for enlarging the structural diversity of porous silicon crystal.     

Formation process of Na-X zeolites from coal fly ash

In order to synthesize Na-X zeolite from coal fly ash (Fa), Fa was pretreated under stirring condition at various temperatures of 20–50°C for 72 h and then aged at 85°C for a given period with NaOH solutions. The resulting materials were characterized by various means. When Fa was aged for 72 h without pretreatment, species P were formed. As the pretreating temperature raised from 20 to 50°C, the degree of crystallinity of faujasite increased, while that of species P decreased. The faujasite species formed was identified as Na-X zeolite with molar ratio SiO₂/Al₂O₃ = 2.4. When Fa was pretreated at 50°C and aged for 60 h, the only species formed was Na-X zeolite. Increasing the pretreating temperature up to 50°C results in the increase of Si⁴⁺ and Al³⁺ concentrations in the treating solution by dissolution of amorphous material in Fa. With the conditions used, the crystalline phase, such as -quartz and mullite, was poorly dissolved during the treatment. Hence, the higher pretreating temperature would give the uniform nucleation and crystal growth of Na-X zeolite during the aging.     

Synthesis and characterization of low-cost zeolite NaA from coal gangue by hydrothermal method

Through this investigation, we have demonstrated a low-cost preparation method of zeolite NaA from coal gangue. The well-developed zeolite NaA of 87.56% crystallinity was successfully prepared by hydrothermal alkali activation method, which required low alkali concentration (1.8 mol/L) compared to other researches (3–6 mol/L). The characterization results of product prepared at different conditions suggest that the purity and crystallinity of zeolite NaA are high at low alkali concentration and longer crystallization time. The Ca²⁺ exchange value of synthesized zeolite attained 265 mg CaCO₃/g compared to commercial zeolite, which is typically 340 mg CaCO₃/g. The basic structure parameters and thermal stability have also been studied. The results suggest that the obtained zeolite has a potential to be used as hard water softening agent. Moreover, the result of Rietveld quantitative phase analysis and Box-Behnken's response surface methodology showed that the weight fraction of zeolite NaA in product can reach 71.9%, and the crystallinity can attain 88.14% at the optimal condition of n(SiO2)/n(Al2O3) of 2.60, NaOH(aq) concentration of 1.86 mol/L at 95 °C for 10.08 h.     

Synthesis and characterization of 13X zeolite from low-grade natural kaolin

In this study, 13X zeolite was successfully synthesized from low-grade natural kaolin via alkali fusion followed by hydrothermal treatment, without extra Si source or dealumination. Fusion with NaOH, followed by hydrothermal reaction, kaolinite, illite and trace of quartz in kaolin sample were converted into zeolite. The effects of various factors during the synthesis process such as NaOH addition amount, crystallization time and temperature on the crystalline products were studied. The optimum synthesis conditions to get purity 13X zeolite were found to be alkali fusion of kaolin with the weight ration of NaOH/kaolin = 2.0 at 200 °C for 4 h, and crystallized at 90 °C for 8 h after homogenization by agitated at 50 °C for 2 h. The product was characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and N₂ adsorption–desorption. The BET surface area of the product was found to be 326 m² g⁻¹. It can be concluded that the study provides the basic data and the process for extensive and efficient utilization of low-grade natural kaolin.