Analysis of precipitates from reactions of hyperalkaline solutions with soluble silica

Cancrinite, sodalite, and zeolite A have been found to form upon contacting hyperalkaline simulated tank waste (STW) with vadose zone sediments from the Hanford Reservation. Here, soluble silica and STW are used to study mineral formation and transformation. Two Hanford sediment fractions (diameters <50 and >50 μm instead of soluble silica) are also used as silica sources for comparison. A series of batch experiments at 50 °C and 25 days duration were conducted by reacting 0.026 mol/kg soluble Si with 6 different STW solutions. The STW solutions differed in NaOH and Al concentrations. Cancrinite, sodalite, and zeolite A formed when soluble Si was used as the Si source. The minerals were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and ²⁷Al and ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS-NMR). Larger NaOH and Al concentrations favored formation of the more compact structures of cancrinite and sodalite. At larger NaOH concentration more Al for Si substitution occurred in the tetrahedral sites. A greater Al(4)/Al(6) ratio in the solids was found for the higher Si/Al ratio solutions based on NMR results. Mixtures of cancrinite and sodalite were characterized by particles with lepispheric morphology. At low Al concentration, increasing NaOH resulted in distinct hexagonal, prismatic particles common to crystalline cancrinite. At low Al/Si ratio, the characteristic cubic morphology of zeolite was observed in addition to cancrinite and sodalite.     

An experimental study on the process of zeolite formation

Results are reported of an experimental study which examined the effect of solution composition on the composition, structure, and crystallization path of phillipsite and merlinoite in the system Na₂OK₂O-Al₂O₃-SiO₂H₂O at 80°C and $\text{pH = 13.34–13.71}$.At a fixed 3.5 M total dissolved silica concentration, zeolite Si/Al ratio was found to be a linear function of pH within the pH range of the experiments.²⁹Si NMR spectra of the initial solutions show that pH determines the distribution of aqueous aluminosilicate species and, as a result, the precipitated zeolite Si/Al ratio. SEM observations reveal that zeolites may precipitate with or without the presence of an intermediary gel phase, depending on solution composition. The growth rate of the zeolites was found to be dependent upon solution pH and total dissolved aluminum concentration. These observations are discussed in terms of their possible applications to natural zeolite paragenesis and serve to delineate the framework of a comprehensive theory for the mechanism of zeolite crystallization from highly alkaline solutions.     

Effect of some additives on synthesis of zeolite from coal fly ash

Hydrothermal conversion of fly ash into zeolites was conducted and the effects of the addition of sodium halide and waste solutions produced after zeolitization of fly ash, as well as the adjustment of the Si/Al ratio prior to synthesis process on the formation and cation exchange capacity (CEC) of zeolite product were evaluated. Both the addition of NaCl and NaF ameliorated the crystallinity and CEC of synthesized zeolite, but NaF had a better improvement effect. Na⁺ was considered to enhance the crystallization of zeolite, while F⁻ favored the dissolution of fly ash. The type of zeolite formed depended on the Si/Al ratio of the starting material prior to the nucleation and crystallization of zeolite. The adjustment of the Si/Al ratio of fly ash by addition of Na₂SiO₄ and Al(OH)₃ changed the type and CEC of zeolite. Waste solutions contained large amount of Si and little Al due to the formation of a zeolite named NaP1 in zeolite terminology with the Joint Committee of Powder Diffraction Standard (JCPDS) code of 39-0219. The alkalinity decreased largely. As a result, the CEC value of zeolite products synthesized with waste solution as alkali source decreased. The supplementation of new alkali to adjust the alkalinity of waste solution could enhance the CEC of synthesized product. It was concluded that: (1) addition of sodium halide and adjustment of the Si/Al ratio prior to synthesis can improve the quality of zeolite; (2) waste solutions produced following the zeolitization of fly ash can be reused as an alkali source in the activation of fly ash; zero-emission of waste solution in the synthesis of zeolite from fly ash is possible.     

Hydrothermal and thermal treatment of natural clinoptilolite zeolite from Bigadiç, Turkey: An experimental study

The clinoptilolite rich zeolite from Bigadiç which was formed from alteration of volcanic glass were treated with acidic (HCl, H₃BO₃, H₃PO₄), alkaline (KOH, NaOH) solutions. Hydrothermally treated and untreated samples were heat treated at 400, 550 and 700°C. XRD, ICP-MS and N₂ gas adsorption were used for physicochemical characterization of zeolites. Considering the Si/Al > 4 and Na+K/Ca+Mg < 1 ratios, zeolite sample is included to earth alkali clinoptilolite class (Heu II) which is also revealed by thermal treatments. Since zeolite structure contains low alkalies it was at collapsed 550°C. The removal of oxide elements efficiency of acids and alkalies were in the order of HCl > H₃PO₄ > HBO₃ > KOH > NaOH. XRD analysis indicated that the structure of zeolite was not altered with acids and alkali treatments. The structure of zeolite treated with HCl and other acids started to deform at 400 and 550°C respectively. In treatment with HCl, Si/Al ratio increases with significant a decrease in K content which resulted in a decrease in the heat stability of zeolite. No change was observed in the structure and thermal stability of clinoptilolite after alkali treatments. The fact that although significant amount of Na is removed with H₃BO₃ acid and Na is increased with NaOH but the thermal stability remains the same indicates that Na cation is not an important parameter as much as K. HCl and H₃PO₄ acid treatments increased the surface area depending on the dissolution of amorphous material and H₃PO₄ was found to be more effective. However, the total pore size decreased due to formation of new micropores.     

Mechanisms and geochemical significance of Si–Al substitution in zeolite solid solutions

Rock-forming zeolites often exhibit complex solid solutions reflecting isomorphous substitutions between Si and Al in tetrahedral framework sites, between charge-balancing extraframework cations, and between water molecules and vacancies. Although the number of moles of charge on extraframework cations in a zeolite must equal the moles of Al in order to maintain charge balance, the relationships between Si–Al and extraframework substitutions vary considerably across this mineral group. Review of available compositional data suggests that there are three main modes of Si–Al substitution in zeolites: 1) coupled CaAl–NaSi substitution; 2) coupled substitution of a single extraframework cation plus Al for Si; and 3) completely uncoupled substitution among extraframework cations and Si and Al on tetrahedral sites. Among zeolites that exhibit the latter two modes of solid solution, Si–Al substitution can be described by an SiO₂ (± H₂O) compositional exchange vector from a hypothetical, pure-silica endmember composition. Recent calorimetric, structural, and theoretical investigations suggest that Si–Al substitution follows a non-ideal, athermal solution model characterized by no excess enthalpies of mixing and negative excess entropies of mixing. Because Si–Al exchange in these minerals can be explicitly or implicitly described by exchange of an SiO₂ component, the Si/Al ratio in their framework can be predicted solely as a function of temperature, pressure, and the chemical potential of SiO₂. Application of this model leads to calculated Si/Al ratios in stilbite (coexisting with albite), analcime, and chabazite consistent with observed mineral compositions and parageneses in very low-grade metamorphic environments. Coexistence of silica polymorphs with zeolites containing SiO₂·nH₂O exchange vectors potentially provides a means of performing thermobarometric calculations in very low-grade metamorphic and diagenetic environments.     

Spectroscopic investigation on the chemical forms of Cu during the synthesis of zeolite X at low temperature

The direct synthesis of zeolites in polluted soils has proved to be a promising process for the stabilization of metals inside these minerals. Nevertheless, more detailed information about this process is still needed in order to better foresee the fate of metals in treated soils. In this work, zeolite X has been synthesized under alkaline conditions in an aqueous solution containing 2500 mg kg⁻¹ of Cu, starting from Na silicate and Al hydroxide at 60 °C. Aluminium, Si and Cu concentrations in the aqueous phase, during zeolite synthesis, were measured over a period of 160 h. The solid products have been characterized over time by XRD, SEM-EDX, ESR, FT-IR, and synchrotron radiation X-ray microbeam absorption near edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. It appears that the marked reduction of Cu concentration in solution is not only due to a simple precipitation effect, but also to processes connected with the formation of zeolite X which could entrap, inside its porous structure, nano- or micro-occlusions of precipitated Cu hydroxides and/or oxides. In addition, EXAFS observations strengthen the hypothesis of the presence of different Cu phases even at a short-range molecular level and suggest that some of these occlusions could be even bound to the zeolite framework. The results suggest that zeolite formation could be used to reduce the availability of metals in polluted soils.     

Synthesis and characterization of zeolite X obtained from kaolin for adsorption of Zn（Ⅱ）

This study deals with the synthesis and characterization of low-silica zeolite X, from calcined Kalabsha kaolin, for adsorption of Zn(Ⅱ) ions from aqueous solution. The synthesis processes is performed under hydrothermal treatment in alkaline solutions. The obtained zeolite samples are characterized using X-ray diffraction, grain size distribution, surface area, and SEM. The critical molar ratios of both SiO2/Al2O3 and K2O/Na2O are about 2.9 and 0.16, respectively. Those ratios are needed to give individual low silica zeolite X in a minimum reaction time. The adsorption capacity of the synthesized products is determined by adsorption of Zn(Ⅱ) ions from solution. The results suggest that the zeolite obtained could be converted to a beneficial product, which will be used in future as an ion exchanger in removing heavy metals from wastewaters.     

Synthesis of sodium zeolites from a natural halloysite

 The kinetics of hydrothermal crystallisation of sodium zeolites from a natural mixture of halloysite and amorphous silica with Si/Al ≈ 4 was investigated. The sample collected at Scarpara (Tuscania, Italy) is the final product of an intense hydrothermal alteration process on the pre-existing leucitic tufites. In order to enhance its reactivity in the NaOH solution, the sample was thermally activated at 600 °C for 1 h. The hydrothermal crystallisation sequence of zeolites formed in the range 90–150 °C has been followed using real-time synchrotron powder diffraction. The reaction kinetics of Na-X, Na-P and analcime were analysed using a model developed for the study of the kinetic data from X-ray diffraction experiments. Na-X and Na-P cocrystallize with an autocatalytic nucleation at lower isothermal temperatures and with a heterogeneous nucleation at higher isothermal temperatures. Na-X tends to dissolve before Na-P, which in turn transforms into analcime. This work is part of a general project on the kinetics of formation of zeolites from clay precursors which is important for either engineering and production of valuable industrial materials and for the interpretation of poorly understood processes of formation of zeolites in natural hydrothermal environments. Received: 7 November 2000 / Accepted: 19 March 2001     

Biotite dissolution and Cr(VI) reduction at elevated pH and ionic strength

The effects of elevated pH, ionic strength, and temperature on sediments in the vadose zone are of primary importance in modeling contaminant transport and understanding the environmental impact of tank leakage at nuclear waste storage facilities like those of the Hanford site. This study was designed to investigate biotite dissolution under simulated high level waste (HLW) conditions and its impact on Cr(VI) reduction and immobilization. Biotite dissolution increased with NaOH concentrations in the range of 0.1 to 2 mol L^-1. There was a corresponding release of K, Fe, Si, and Al to solution, with Si and Al showing a complex pattern due to the formation of secondary zeolite minerals. Dissolved Fe concentrations were an order of magnitude lower than the other elements, possibly due to the formation of green rust and Fe(OH)₂. The reduction of Cr(VI) to Cr(III) also increased with increased NaOH concentration. A homogeneous reduction of chromate by Fe(II)_aq released through biotite dissolution was probably the primary pathway responsible for this reaction. Greater ionic strengths increased biotite dissolution and consequently increased Fe(II)_aq release and Cr(VI) removal. The results indicated that HLW would cause phyllosilicate dissolution and the formation of secondary precipitates that would have a major impact on radionuclide and contaminant transport in the vadose zone at the Hanford site.     

利用高铁钾长石粉合成13X沸石分子筛的实验研究

对江苏丰县的富钾页岩进行预处理，得到钾长石含量达76．4％的钾长石粉，其Fe2O3含量高达7．52％。以此钾长石粉为原料经过焙烧处理、水热合成实验，在铁含量较高情况下成功合成了13X沸石分子筛，并采用正交实验法确定了优化工艺参数。对实验产物的主要性能测试表明，合成的富铁沸石产品与13X沸石分子筛工业产品相似，吸附量达到国家化学工业产品标准，可用于对含重金属离子废水的吸附处理。     

Experimente zur Zeolithbildung durch hydrothermale Umwandlung

The formation of zeolites by hydrothermal alteration has been investigated by taking trass from the Laach volcanic area as a sample. Zeolites to be found are chabazite, phillipsite and analcime, all of which originated from the same phonolitic glass. This paper aims at explaining the formation of zeolites by means of experimental alteration of the pumice with various solutions. NaOH and KOH solutions were used in the experiments, these limited the formation conditions of chabazite, phillipsite, analcime in alkaline environments. Moreover, experiments were carried out with H₂O dist and with solutions that formed during the alteration of pumice by reacting with H₂O. These experiments were conducted to supply clues concerning the formation of zeolites in the Laach volcanic area. With NaOH solutions zeolites were formed from pumice within a temperature range of 70 to 250° C and a concentration range of 0.001 to 1.0 n; with KOH solutions they were formed in the same concentration range within a temperature range of 100 to 250° C. The formation of zeolites proved to depend much on temperature and concentration: At low temperatures high concentrations are necessary, higher temperatures need lower concentrations. With NaOH solutions the zeolites are formed in the succession, chabazite, phillipsite, analcime at increasing temperatures and increasing concentrations. With KOH solutions the same succession is to be found with rising temperature. With rising concentration, however, this succession is changed at higher temperatures: Phillipsite appears in place of analcime at high temperatures and concentrations. By the alteration of pumice with H₂O, zeolites are formed from 200° C onward. With solutions that had been formed during the alteration of pumice by reacting with H₂O, the minimum temperature for the formation of zeolites was 180° C. Concerning the genesis of zeolites in the Laach volcanic area, the experiments showed that the temperature for the formation of analcime was about 250° C; for the formation of chabazite and phillipsite it was between 150 and 190° C. The pH of the reacting solutions may have been between 7 and 8. Thus the experiments proved that from the same material different zeolites, chabazite, phillipsite, analcime may be formed by temperature change of the reacting solutions (H₂O to slightly alkaline solutions).     

Experimente zum Einfluß des Gesteinsglas-Chemismus auf die Zeolithbildung durch hydrothermale Umwandlung

In the formation of zeolites by hydrothermal alteration volcanic glasses are the starting material in most cases. The experiments aimed at demonstrating in what way the chemistry of the volcanic glass influences:

1. the alteration rate of the volcanic glass to zeolites,
2. the kind of zeolites being formed and their formation conditions.

Three volcanic glasses were used, a basaltic, a phonolitic, and a rhyolitic one. The experimental conditions were as similar as possible to the natural alteration conditions. Solutions being used: H₂O dist (pH ～5.5), 0.01 n NaOH (pH ～10.5), and solutions of similar chemistry to the natural ones. The temperatures were 180 °, 200 °, 250 ° C. The experiments were carried out both in closed and in open systems. The experimental results show a difference in the alteration rate and in the zeolites being formed between the basaltic and the phonolitic glasses on the one hand and the rhyolitic one on the other. In case of the closed system the SiO₂-poor volcanic glasses react more rapidly than the SiO₂-rich one. The zeolites being formed are chabazite, phillipsite, analcime respectively mordenite, analcime. In case of the open system the influence of the chemistry of the volcanic glass on the alteration rate and the zeolite being formed is less significant. Which zeolite is formed at a given temperature depends on: the chemistry of the starting material, the chemistry of the reacting solution and wether there is a closed or an open system.     

Fe2O3对13X沸石分子筛合成条件及性能的影响研究

对江苏丰县的富钾页岩进行预处理,得到不同Fe2O3 质量分数的钾长石粉体原料FXY1、FXY2,经中温焙烧得到偏铝硅酸盐前体化合物,水热晶化合成了13X沸石分子筛。采用正交实验法,确定了水热晶化反应的优化工艺条件,原料中Fe2O3 质量分数的不同导致水热晶化反应的工艺参数有所不同。合成的两种沸石的性能与13X沸石分子筛的工业产品相似,吸附量均达到国家化学工业产品标准HG/T 2690 95的要求。对比实验表明,原料中Fe2O3 质量分数的降低可使其在更宽的碱度范围内合成性能更优的13X沸石产品。由低Fe2O3 质量分数的FXY2为原料合成的沸石,其物相纯度、热稳定性、白度、比表面积、吸附性等性质更优。合成沸石均可用于对含重金属离子废水的深度净化处理,由FXY2为原料合成的13X沸石还可用作洗涤助剂。     

Lead Removal from Aqueous Solution by Natural and Pretreated Zeolites

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Pb(II) ions are removed from water by accumulating it on the surface of natural zeolite in three different forms; one untreated and two treated samples, one sample treated with 2 M HCI solution and other is treated with 3 M NaOH solution. Natural zeolite is mainly composed of clinoptilolite, and mordenite, with amount of non-zeolite phase (smectite and illite) and C and CT opal. The adsorption experiments are carried out using a batch process in environments of different pH, initial Pb(II) concentration, interaction time and amount of zeolites. Treated zeolite samples show high exchange capacity for Pb(II) compared to untreated sample, however, acid-treated sample shows an exceedingly good exchange capacity. Equilibrium data fitted well with the Langmuir isotherm model with maximum adsorption capacity of 115, 126, and 132 mg g⁻¹ of untreated natural zeolites, alkali-treated zeolites and acid-treated zeolites respectively. The rates of adsorption were found to confirm to pseudo-first order kinetic with good correlation and the overall rate of lead ions uptake.     

碱处理对河北围场天然沸石结构和性能的影响及其机理研究

采用NaOH对围场地区天然沸石进行处理,采用X射线衍射仪、红外光谱仪、N_2吸附-脱附技术、扫描电子显微镜等对材料进行表征分析,采用水蒸气吸附法评价材料的亲水性,采用Cr~(3+)和Mn~(2+)评价材料的离子交换性能,探讨了碱处理对天然沸石的结构、亲水性和离子交换性能的影响及其机理。实验结果表明,围场地区天然沸石中主要含有斜发沸石、石英和伊利石;碱处理可降低天然沸石的硅铝比,且沸石的硅铝比随着碱处理浓度的提高而不断降低;碱处理对斜发沸石结构的影响较石英和伊利石更大;高浓度碱处理导致天然沸石的结构发生破坏,比表面积降低,孔体积提高;伴随着天然沸石硅铝比的降低,其亲水性和离子交换性能不断提高。     

Extent of diagenetic transformations in severely altered biogenic silica deposits from Tunisia: new insights from mineralogy and geochemistry

Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The ²⁹Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). ²⁷Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.     

Mineral Surface after Reaction with Aqueous Solution at High Temperatures and Pressures

This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci     

Adsorption of H<Subscript>2</Subscript>O,NH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>6</Subscript> on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

Adsorption of H₂O, NH₃ and C₆H₆ on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH₃) > E(H₂O) > E(C₆H₆). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li⁺ cation, and (3) steric hindrances of the flat C₆H₆ molecule adsorbed on the cation in the cage of zeolite.     

准噶尔盆地西北缘沸石发育特征及成储机理初探：以玛南地区二叠系乌尔禾组为例

沸石类胶结物是准噶尔盆地西北缘玛南地区二叠系乌尔禾组发育的一种特殊胶结物类型。通过岩心观察、薄片鉴定、扫描电镜分析与岩石组分统计,明确了玛南地区乌尔禾组沸石胶结物的矿物特征、空间分布、成因机理与成储机制。研究区乌尔禾组主要发育浊沸石与片沸石,其中片沸石分为两期,早期富铁,晚期贫铁。研究区沸石胶结物的空间分布规律并不明显,仅在垂向上,从乌尔禾组到百口泉组,浊沸石与片沸石含量具有逐渐降低的趋势。沸石类胶结物的形成主要受控于母岩中凝灰岩砾石组分,中酸性火山岩砾石不利于浊沸石的形成,其他火山岩砾石与沸石的形成无明显关系,浊沸石大量发育的次生溶蚀孔隙是研究区油气赋存的主要储集空间类型。沸石类胶结物的沉淀与溶蚀可以简化为两阶段成岩作用过程,早期正常成岩胶结形成各类沸石胶结物,晚期深部成岩流体上涌,对储层进行溶蚀与改造,深部流体改造是成储的关键阶段。     

Effect of Microbial Siderophore DFOB on Pb, Zn, and Cd Sorption Onto Zeolite

Recent studies suggest that siderophores form stable complexes with divalent metals and affect their mobility. In this work, effects of trihydroxamate microbial siderophores and desferrioxamine-B (DFOB) on Pb(II), Zn(II), and Cd(II) sorption by two kinds of synthesized zeolites (13X and Na?CY) as a function of pH were investigated. Results showed that 13X zeolite has a higher sorption affinity for studied metals than Na?CY. DFOB strongly affected metal sorption on both zeolites. Under slightly acidic to neutral condition, DFOB increased the metal sorption on zeolites due to the sorption of positively charged heavy metal?CDFOB complexes. Whereas by increasing pH (>7), the mobilizing effect of DFOB was observed for Pb, Zn, and Cd. DFOB drastically decreased (80?%) Zn sorption in alkaline condition. As a result, siderophores can weaken the treatment efficiency of zeolites and increase the bioavailability of metals in soils. Surface complexation modeling revealed that the effects of DFOB on metal sorption by 13X and Na?CY zeolites can be explained by the differences in their surface charge. In general, the result shows the influence of DFOB on metal sorption by zeolites over the pH range 4?C9 and decreasing in the sequence Zn?>?Pb?>?Cd.