铝酸钠和含硅铝酸钠溶液结构和性质的研究

本文通过对铝酸钠和硅铝酸钠溶液的红外光谱、拉曼光谱、粘度、表面张力、丁达尔现象和聚沉等光谱和物理化学性质的研究测定,分析了硅在铝酸钠溶液中的行为.认为硅主要是取代Al-O-Al结构中的Al,形成Al-O-Si结构和Al-O-Si-O-Al-O结构等多种形式硅氧铝键以及由氢键相连的大分子结构.这种结构直接影响其物理化学性质,表现为随硅含量增加表面张力增加,粘度上升,具有丁达尔现象等.说明含硅铝酸钠溶液中存在大分子的胶性基团,属于无机高分子溶液,这种网络状"大分子"结构是硅铝酸钠溶液稳定的原因.     

铝酸钠溶液脱硅的研究进展

对硅在铝酸钠溶液中的存在状态,深度脱硅机理和研究进展,碱法生产氧化铝过程中铝酸钠溶液脱硅的重要性以及铝酸钠溶液脱硅的研究方向进行了综述。     

过饱和铝酸钠溶液结构性质与分解机理研究现状*

过饱和铝酸钠溶液分解是氧化铝生产过机理的研究是氧化铝生产过程的重要基础问题.本文对过饱和铝酸钠溶液中铝酸根离子存在的基本形态,浓度、苛性比和阳离子对铝酸钠溶液结构性质的影响,溶液中多种铝酸根离子平衡与转化规律,以及铝酸钠溶液分解机理研究的现状进行了总结和评述;分析了现有铝酸钠溶液结构性质与分解机理研究的不足;围绕强化氧化铝生产中铝酸钠溶液分解过程的目的,提出了铝酸钠溶液结构性质与分解机理研究的重点.     

^29Si,^27AIMASNMR研究不同脱铝深度稀土 超稳Y沸石中Si、Al的分布

本文应用^29Si,^27AIMASNMR和XRD技术,测量了四种不同脱铝深度的稀土超稳Y沸石的骨架硅铝比,得到了一致的结果,并研究了稀土超稳Y沸石的脱铝过程和稀土离子和Y沸石骨架铝的机理.发现稀土离子存在时,Y沸石骨架中Si、Al的分布与相同硅铝比的ＨＹ不同,在浅、中度脱铝时,主要脱除的是Si(2Al)和Si(3Al)中的铝,深度脱铝时,主要是Si(1Al)和少量Si(2Al)中的铝,而Si(3Al)几乎不变,提出稀土离子最可能是位于方钠的Si(3Al)附近,平衡三个AlO 四面体上的负电荷,起到稳定Si(3Al)结构单元的作用.其次,稀土超稳Y沸石中总的非骨架铝(N~Al)~EF,随脱铝深度的增加而增加,仅只在REUSY-38的^27AIMAS NMR谱中观察到Al^3+非骨架铝的存在.^29Si,^27AIMASNMR     

Ca-Al水滑石的制备及其在铝酸钠溶液中的脱硅

控制铝酸钠溶液中硅的含量在氧化铝工业中是非常重要的.本文以制碱工业中的副产物氯化钙为原料合成了两种Ca-Al水滑石,Friedel盐和Kuzel盐,并以合成的两种盐为脱硅剂对铝酸钠溶液的脱硅进行了研究.考察了脱硅温度、脱硅时间、苛性比(铝酸钠溶液中Na2O与Al2O3的摩尔数比)、铝酸钠溶液浓度、初始硅量指数(铝酸钠溶液中Al2O3与SiO2的质量比)及Ca-Al水滑石的添加量对脱硅效果的影响,并对Ca-Al水滑石与CaO的脱硅效果进行了比较.实验结果表明用Ca-Al水滑石作为脱硅剂时,可使硅量指数由75提高到600以上.Ca-Al水滑石的脱硅效果优于CaO,而Kuzel盐优于Friedel盐.动力学结果表明Friedel盐脱硅反应对SiO2的浓度是一级反应,表观活化能为17.3kJ/mol.通过XRD对脱硅产物进行了分析,并探讨了Ca-Al水滑石的脱硅机理.     

水合碳铝酸钙的性质及脱硅反应研究

应用XRD、IR和TG-DTA分析等手段考察了脱硅剂水合碳铝酸钙的性质及其在铝酸钠溶液中的行为。发现水合碳铝酸钙在90℃不含硅的铝酸钠溶液中稳定,加热30min晶型未发生改变。提出了水合碳铝酸钙的合成机理和脱硅机理。认为水合碳铝酸钙是一种高水合、分散度高的含钙化合物,晶面间距大,脱硅反应在水合碳铝酸钙层间进行,因此脱硅反应速度快,脱硅活性高。硅对其晶型的转变起着关键作用。     

高硅Y沸石的研制及吸附热力学性质

Ｙ沸石用ＬｉＣｌ溶液交换得ＬｉＮａＹ沸石,再经ＳｉＣｌ４气相同晶取代进行脱铝补硅,获得高结晶度的高硅Ｙ沸石,硅铝比可大于１００［１］．在脱铝过程中,随着硅铝比的升高其孔结构和表面性质均发生变化,直接关联到Ｙ沸石在炼油中的催化裂化性能．通过对不同大小、结?..     

叠氮二乙基铝三聚体和单体的缔合-解离平衡的研究

尽管叠氮二乙基铝Et₂AlN₃(DEAA)是一个重要的化合物,但人们对它研究还是很少的。本文通过温度-蒸气压关系研究了纯态DEAA的三聚体和单量体之间的缔合-解离平衡;通过相对分子质量测定、核磁共振氢谱和核磁共振铝谱的测定,研究了在苯和甲苯溶液中DEAA的三聚体和单量体之间的缔合-解离平衡。借助温度-蒸气压曲线分别计算了DEAA三聚体和单量体的气化焓和解离焓;通过相对分子质量测定、核磁共振铝谱测定等方法计算得到了溶液中DEAA三聚体和单量体的解离平衡常数、解离焓和解离熵等热力学数据。     

溶胶-凝胶法制备纳米氢氧化铝溶胶

研究了利用铝酸钠溶液碳酸化产生的沉淀, 经胶溶作用制备出纳米氢氧化铝溶胶的过程. 分析了铝酸钠溶液滴加到大量碳酸氢钠溶液中时发生的反应. X射线衍射研究结果表明, 在纳米氢氧化铝溶胶制备过程中, 从无定形氢氧化铝沉淀到拟薄水铝石的晶型转变过程是氢氧化铝沉淀胶溶时溶解再析出的过程. 将碳酸氢钠加入到苛性比为1.7的铝酸钠溶液中, 中和至苛性比为1.3后, 溶液诱导期中的紫外光谱显示270 nm处的Al(OH)3-6吸收增强. 经与含铝原子六配位的晶体紫外光谱对比后表明, 在铝酸钠分解生成氢氧化铝的过程中, 其铝的配位结构从四配位转化为六配位. 拟薄水铝石溶胶粒子的形貌与胶溶所用的酸和分散剂有关.     

铝化β沸石的硅铝分布及表面酸性质

研究了铝酸钠溶液处理对β沸石硅铝分布及表面酸性质的影响。通过XRD，NH3－TPD，Pyridine-IR及NMR表征了经NaAlO2溶液处理后的Hβ沸石的表面酸性质。结果表明，Hβ沸石的总酸量增加，B酸量和L酸量亦增加。NaAlO2溶液处理对β沸石具有补铝功能，补铝机理为Al(OH4)^-阴离子在Si(0Al)A位发生同晶取代。甲苯歧化与C9芳烃烷基转移反应的催化性能考察结果表明，NaAlO2溶液处理可以提高β沸石催化剂的芳烃转化率和（B＋X）选择性。     

^29Si（^27Al）MAS NMR考察镧离子在LaDAlY型沸石中的作用

用~(29)Si(~(27)Al)MAS NMR和辅加乙酰丙酮(acac)处理样品的静态~(27)Al NMR研究了镧离子对脱铝Y型沸石(DAIY)骨架硅、铝和非骨架铝(EFAL)的影响.结果表明,~(29)Si MAS谱的化学位移及其形状不仅取决于连接[SiO_4]四面体的[AlO]-四面体数目,而且还与引入镧离子的量有关.镧离子的引入导致~(27)Al MAS谱的明显宽化和不对称形变.另外,还讨论了镧离子对非骨架铝的影响.     

Aluminum-27 NMR studies of alcoholic (2-hydroxyethyl)trimethylammonium aluminate solutions

²⁷Al NMR spectroscopy is a power tool for investigation of the aluminate species existing in both aqueous and non-aqueous solutions. Aluminum-27 nuclear magnetic resonance (NMR) spectroscopy also can be used to determine thermodynamic properties of complexes in the solution. In this report, ²⁷Al NMR spectroscopy was used to characterize species present in alkaline alcoholic aluminate solutions. (2-Hydroxyethyl)trimethylammonium (2-EHTMA) hydroxide was used as base. In solution of CH₃OH and H₂O in a mole ratio of 64:1 it was possible to detect five signals by aluminum-27 NMR, indicating formation of [Al(OH)_4−n(CH₃OH)_n]⁽ⁿ⁻¹⁾⁺ (n = 0,1, 2, 3 and 4) species. Aluminum-27 NMR spectroscopy has also used for investigation of the species present in the ethanolic 2-HETMA aluminate solutions. The equilibrium constants for the formation of aluminate complexes were also determined for both methanolic and ethanolic aluminate solutions. Aluminum-27 NMR spectra of propanolic and butanolic 2-HETMA aluminate solutions were also studied.     

Magic-Angle-Spinning NMR (MAS-NMR) Spectroscopy and the Structure of Zeolites

After outlining the chemical features and properties which make zeolites such an important group of catalysts and sorbents, the article explains how high-resolution solid-state NMR with magic-angle spinning reveals numerous new insights into their structure. ²⁹Si-MAS-NMR readily and quantitatively identifies five distinct Si(OAl)_n(OSi)_4-n structural groups in zeolitic frameworks (n = 0, 1,….4), corresponding to the first tetrahedral coordination shell of a silicon atom. Many catalytic and other chemical properties of zeolites are governed by the short-range Si, Al order, the nature of which is greatly clarified by ²⁹Si-MAS-NMR. It is shown that, as expected from Pauling's electroneutrality principle and Loewenstein's rule, both in zeolite X and in zeolite A (with Si/Al = 1.00) there are no ? Al? O? Al? linkages. In zeolite A and zeolite X with Si/Al = 1.00 there is strict alternation of Si and Al on the tetrahedral sites. Ordering models for Si/Al ratios up to 5.00 (in zeolite Y) may also be evaluated by a combination of MAS-NMR experiments and computational procedures. ²⁹Si-MAS-NMR spectra reveal the presence of numerous crystallographically distinct Si(OSi)₄ sites in silicalite/ZSM-5, suggesting that the correct space group for these related porosilicates is not Pnma. ²⁷Al-MAS-NMR clearly distinguishes tetrahedrally and octahedrally coordinated aluminum, proving that, contrary to earlier claims, Al in silicalite is tetrahedrally substituted within the framework. In combination, ²⁹Si- and ²⁷Al-MAS-NMR is a powerful tool for monitoring the course of solid-state processes (such as ultrastabilization of synthetic faujasites) and of gas-solid reactions (dealumination of zeolites with silicon tetrachloride vapor at elevated temperatures). They also permit the quantitative determination of framework Si/Al ratios in the region 1.00 < Si/Al < 10 000. Since most elements in the periodic table may be accommodated within zeolite structures, either as part of the exchangeable cations or as building units of the anionic framework, there is immense scope for investigation by MAS-NMR and its variants (cross-polarization, multiple pulse and variable-angle spinning) of bulk, surface and chemical properties. Some of the directions in which future research in zeolite science may proceed are adumbrated.     

Characterization of the malate-aluminum(III) complex using 1H and 27Al NMR spectroscopy

Structural elucidation of a malate-aluminum(III) complex has been carried out using 1H and 27Al NMR spectroscopy. The 1H chemical shift perturbation clearly indicated the interaction between malate and Al(III) ion. The measurements of 27Al NMR and 1H-13C HSQC spectra demonstrated that the major form of a complex comprised two equivalent malate ions and two unequivalent Al(III) ions. With this constraint, an equilibrium geometry of the complex was proposed by a semi-empirical molecular orbital calculation.     

Structural Development of Single Phase (Type I) Mullite Gels

Single phase (type I) mullite gels were prepared by sol-gel techniques starting from alkoxides (Al-butylate, tetraethylorthosilicate) and alkoxides plus nitrates (tetraethylorthosilicate, Al(NO₃)₃·9H₂O). After drying at 150°C the aluminosilicate gels are non-crystalline and remain so up to 900°C. Above 900°C the gels transform into Al₂O₃-rich mullite plus a coexisting SiO₂ phase. Structural studies on temperature-dependent dehydroxylation and condensation of the gels were carried out by large angle X-ray scattering, by infrared spectroscopy and by²⁹ Si NMR spectroscopy. Heat-treatment (<150°C) of dried gels first causes removal of the H₂O and organic residuals weakly bound at the open pore surfaces of the gels while the stronger, structurally bound OH groups are not affected. At temperatures <600°C OH groups are released and recombine to molecular H₂O. If the temperature does not exceed 800°C the newly formed H₂O is trapped in closed nanopores of the gel-network. Corresponding electron microscopical investigations reveal agglomerates of 10 nm sized primary particles virtually unaffected by the heat-treatment below 900°C. NMR investigation provided a new structural model on type and distribution of coordination polyhedra in aluminium silicate gel networks. Unlike Si, which according to ²⁹Si NMR is always 4-fold coordinated with O, ²⁷Al NMR spectroscopy revealed that Al cordination is more complex and is influenced by thermal treatment. Al occurs six-fold (octahedrally) and four-fold (tetrahedrally) coordinated. A third ²⁷Al NMR signal which has been attributed to five-fold-coordinated Al in the literature increased in intensity with the heat-treatment. A comparison of NMR data of the gels with those of mullite suggests that tetrahedra triclusters (3 tetrahedra having one oxygen atom in common) occur as major structural units in aluminium silicate gels rather than five-fold-coordinated Al. Triclusters of tetrahedra may compensate the excess negative charge in the network caused by Si⁴⁺ Al³⁺ substitution. The charge compensation model is supported by aluminosilicate gels doped with network modifiers (e.g., Na⁺). Since equimolar addition of Na⁺ compensates Si⁴⁺ Al³⁺ substitution the formation of triclusters is no longer required which actually can be deduced from²⁷ Al NMR studies.     

Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alane-phosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect ²⁷Al-³¹P spin-spin coupling constants, and ²⁷Al nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the ³¹P NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The ²⁷Al NMR central transition signals are spread out over a broad frequency range (>200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static ²⁷Al wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. ²⁷Al chemical shifts and quadrupole tensor components offer a facile and clear distinction between three- and four-coordinate aluminum environments. For measuring internuclear Al⋅⋅⋅P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al⋅⋅⋅P distances in these compounds can be measured within a precision of ±0.1 Å.     

Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics

Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework Al_FR Lewis acid sites are often found in their H‐forms. The formation of Al_FR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of Al_FR Lewis sites in dehydrated zeolites and their precursors—“perturbed” Al_FR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)₃AlOH groups and are characterized by a broad ²⁷Al NMR resonance (δ_i=59–62 ppm, C_Q=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the ²⁷Al MAS NMR spectrum. Dehydroxylation of (SiO)₃AlOH occurs at mild temperatures and leads to the formation of Al_FR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)₃Al Lewis sites exhibit an extremely broad ²⁷Al NMR resonance (δ_i≈67 ppm, C_Q≈20 MHz, and η≈0.1).     

Unravelling Local Atomic Order of the Anionic Sublattice in M(Al1−xGax)4 with M=Sr and Ba by Using NMR Spectroscopy and Quantum Mechanical Modelling

The quasibinary section of the intermetallic phases MAl₄ and MGa₄ with M=Sr and Ba have been characterised by means of X‐ray diffraction (XRD) studies and differential thermal analysis. The binary phases show complete miscibility and form solid solutions M(Al_1?xGa_x)₄ with M=Sr and Ba. These structures crystallise in the BaAl₄ structure type with four‐ and five‐bonded Al and/or Ga atoms (denoted as Al(4b), Al(5b), Ga(4b), and Ga(5b), respectively) that form a polyanionic Al/Ga sublattice. Solid state ²⁷Al NMR spectroscopic analysis and quantum mechanical (QM) calculations were applied to study the bonding of the Al centres and the influence of Al/Ga substitution, especially in the regimes with low degrees of substitution. M(Al_1?xGa_x)₄ with M=Sr and Ba and 0.925≤x≤0.975 can be described as a matrix of the binary majority compound in which a low amount of the Ga atoms has been substituted by Al atoms. In good agreement with the QM calculations, ²⁷Al NMR investigations and single crystal XRD studies prove a preferred occupancy of Al(4b) for these substitution regimes. Furthermore, two different local Al environments were found, namely isolated Al(4b1) atoms and Al(4b2), due to the formation of Al(4b)–Al(4b) pairs besides isolated Al(4b) atoms within the polyanionic sublattice. QM calculations of the electric field gradient (EFG) using superlattice structures under periodic boundary conditions are in good agreement with the NMR spectroscopic results.     

Aluminium‐27 NMR investigation of the influence of cation type on aluminosilicate solutions

The effects of tetraalkylammonium (TAA) and alkali metal cations on the equilibrium distribution of aluminosilicate oligomers in aqueous alkaline aluminosilicate solutions were investigated using ²⁷Al NMR spectra and their evolution with time. The results indicate that there are no differences in the initial equilibria involving solutions containing both TAA and alkali metal cations on the one hand and those containing alkali metal cations only. However, re‐equilibration of the aluminosilicate species for TAA/Na aluminosilicates is slow (usually not detectable on the time‐scale of the experiments), whereas when purely alkali metal cations are used, the spectra alter over a period of ～1 h, such that resolution is degraded substantially. In the latter case, it is suggested that the anions aggregate into larger systems, although the solutions are still clear. ²⁹Si NMR evidence for slow equilibration of silicate and aluminosilicate solutions at higher concentrations is also discussed. Copyright © 2002 John Wiley & Sons, Ltd.