Study on the effect of sodium removal from citric acid pretreated red mud on the physical properties of red mud.

Red mud is a highly alkaline solid waste discharged from the alumina industry, and its high sodium content is the key factor limiting its wide utilization. Therefore, effective control of the "frosting" phenomenon during the application of red mud has received significant attention. In this study, the changes of particle size, phase, morphology, and pore size of red mud after sodium removal with different amounts of citric acid pretreatment were investigated. The single-factor experiment shows that the Na+ leaching rate is 86.33% under a citric acid dosage of 15%, liquid-to-solid ratio of 7 mL/g, leaching temperature of 80 °C, stirring speed of 300 rpm, and leaching time of 10 min. The leachate is characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. The results reveal that Na+ mainly exists in a combined state in the form of cancrinite. With the increase of citric acid dosage, red mud agglomerates, calcite, and cancrinite are dissolved, and new phases such as calcium oxalate and magnesium aluminum hydroxide are formed. The specific surface area, pore volume, and pore diameter show irregular changes with the increase in the citric acid dosage. Citric acid pretreatment can effectively reduce the sodium content in red mud, the treatment cost of leaching solution is low, and the leaching residue is neutral, which is helpful to promote the practical application of red mud.

Hydrothermal Synthesis of Cancrinite from Coal Gangue for the Immobilization of Sr.

The primary objective of this study is to investigate and develop a rapid and effective method for the immobilization of Sr in the event of a nuclear leakage incident. Coal gangue, an underutilized form of solid waste from the coal industry, can be used as a raw material for curing Sr due to its high content of silica-alumina oxides. In the present study, Sr was successfully solidified in cancrinite synthesized using a hydrothermal method with coal gangue as raw material. A stable cancrinite phase was formed at a relative alkali concentration of more than 6 M. When the Sr/Al(Si) ratio was <1/6, cancrinite was the only stable phase that varied with the hydrothermal temperature and time. When the Sr/Al(Si) ratio increased to 1/2, the cancrinite phase completely disappeared, and a new strontium feldspar phase (SrAl2Si2O8) appeared. PCT leaching experiments showed that when Sr/Al(Si) < 1/6, the Sr leaching rate of Sr-cancrinite samples obtained by hydrothermal synthesis at 180 °C for 24 h was very low.

Infrared spectroscopy as a tool for the analysis of framework topology and extra-framework components in microporous cancrinite- and sodalite-related aluminosilicates.

The identification of the framework type in multilayer cancrinite- and sodalite-group minerals and synthetic compounds is predominantly based on the unit-cell dimensions determined from powder or single-crystal X-ray diffraction data, by analogy with previously characterized samples with known crystal structures. However, topological type of the framework cannot be reliably determined in this way because of the different possible ABC staking sequences and different sets of cages with the same number of layers in the repeat unit. To solve this problem, additional criteria are required. The use of infrared (IR) spectroscopy makes it possible to distinguish topologically different types with the same unit-cell parameters. The most important diagnostic range in the IR spectrum (the "finger-print region", from 510 to 760 cm-1) corresponds to the O-T-O bending vibrations (T = Si, Al). The spectral bands at 705 ± 8, 528 ± 5, 547 ± 4, and 555 ± 3 cm-1 indicate the presence of the sodalite, Losod, liottite, and giuseppettite cages, respectively. The band at 528 ± 5 cm-1 shifts towards ∼518 cm-1 in the case when Losod cage hosts carbonate group. The IR spectrum in the "finger-print region" can be also used to identify a mineral species belonging to two-layer or three-layer minerals with different extra-framework compositions. The wavenumber of the antisymmetric stretching mode of the 12CO2 molecule, which is a common admixed extra-framework constituent in minerals belonging to the cancrinite and sodalite groups, depends on the kind of the host cage or channel: 2340-2343 cm-1 for the sodalite cage, 2338 cm-1 for the Losod cage, and 2351-2353 cm-1 for the liottite cage and wide channel in the cancrinite-type framework.

Mixed-Phase Ion-Exchangers from Waste Amber Container Glass.

This study investigated the one-pot hydrothermal synthesis of mixed-phase ion-exchangers from waste amber container glass and three different aluminium sources (Si/Al = 2) in 4.5 M NaOH(aq) at 100 °C. Reaction products were characterised by X-ray diffraction analysis, Fourier transform infrared spectroscopy, 27Al and 29Si magic angle spinning nuclear magnetic resonance spectroscopy and scanning electron microscopy at 24, 48 and 150 h. Nitrated forms of cancrinite and sodalite were the predominant products obtained with reagent grade aluminium nitrate (Al(NO3)3∙9H2O). Waste aluminium foil gave rise to sodalite, tobermorite and zeolite Na-P1 as major phases; and the principal products arising from amorphous aluminium hydroxide waste were sodalite, tobermorite and zeolite A. Minor proportions of the hydrogarnet, katoite, and calcite were also present in each sample. In each case, crystallisation was incomplete and products of 52, 65 and 49% crystallinity were obtained at 150 h for the samples prepared with aluminium nitrate (AN-150), aluminium foil (AF-150) and amorphous aluminium hydroxide waste (AH-150), respectively. Batch Pb2+-uptake (~100 mg g-1) was similar for all 150-h samples irrespective of the nature of the aluminium reagent and composition of the product. Batch Cd2+-uptakes of AF-150 (54 mg g-1) and AH-150 (48 mg g-1) were greater than that of AN-150 (36 mg g-1) indicating that the sodalite- and tobermorite-rich products exhibited a superior affinity for Cd2+ ions. The observed Pb2+- and Cd2+-uptake capacities of the mixed-product ion-exchangers compared favourably with those of other inorganic waste-derived sorbents reported in the literature.

Synthesis of zeolites from residual diatomite using a microwave-assisted hydrothermal method.

Population growth directly affects the industrial production sector, as well as the quantities of waste generated in this sector. Diatomite is a typical example of such industrial waste and is used for the filtration of various products. With the aim of increasing its value, the present study employs this residue, following its usage in beer filtration, as a silicon source for the synthesis of zeolites. Two synthetic routes are used, namely, hydrothermal treatment with and without a pre-treatment step in a conventional microwave for 3-24 h. The results of the compositional and morphological characterization show that the use of a few minutes of microwave radiation reduces the process of zeolite synthesis to 15 h compared to the synthesis without pre-treatment, as well as reducing the production costs. The efficiency of microwave radiation is assessed with regards to solubilizing the residue, the possibility of employing a device of conventional use and the possibility of putting to use the diatomite residue, turning it into a versatile material that can be applied in several areas and process, such as industrial catalysts, the adsorption of environmental pollutants (ions and molecules) and water treatment via ion-exchange resins.

Converting loess into zeolite for heavy metal polluted soil remediation based on "soil for soil-remediation" strategy.

Both soil erosion and soil contamination pose critical environmental threats to the Chinese Loess Plateau (CLP). Green, efficient and feasible remediation technologies are highly demanded to meet these challenges. Herein we propose a unique "soil for soil-remediation" strategy to remediate the heavy metal polluted soil in CLP by converting loess into zeolite for the first time. With a simple template-free route, the natural loess can be converted into cancrinite (CAN) type of zeolite. A highly crystalline CAN was obtained via hydrothermal treatment at 240 oC for 48 h, with a precursor alkalinity of Na/(Si+Al)> 2.0. The as-synthesized CAN zeolite exhibits excellent remediation performance for Pb(II) and Cu(II) polluted soil. Plant assay experiment demonstrates that CAN can significantly restrain the uptake and accumulation of Pb(II) and Cu(II) ions in vegetables, with a high removal efficiency up to 90.7% and 81.4%, respectively. This work demonstrates a "soil for soil-remediation" strategy to utilize the natural loess for soil remediation in CLP, which paves the way for developing green and sustainable remediation eco-materials with local loess as raw materials.

Síntese hidrotérmica de zeólitas a partir de cinza volante de carvão mineral: aplicação na adsorção de íon amônio / Hydrothermal synthesis of zeolites from fly ash of mineral coal: application of ion ammonium adsorption

RESUMO A cinza volante é o principal resíduo industrial do uso de carvão mineral na geração de vapor e energia. No Brasil, são produzidas 1,4 milhão toneladas ao ano. Essas cinzas podem ser convertidas em produtos zeolíticos por tratamento hidrotérmico alcalino. Este trabalho teve como objetivo principal realizar essa conversão hidrotérmica, a fim de obter unicamente fases cristalinas zeolíticas para a adsorção de íon amônio. Realizaram-se diversas sínteses alterando o método utilizado (clássico ou de duas fases), o tempo de reação (24 ou 30 h) e a massa de NaOH. A caracterização dos produtos e da cinza (in natura e calcinada) foi realizada por difratometria de raios X, microscopia eletrônica de varredura e, em alguns casos, análises térmica diferencial e gravimétrica (ATD-TG). Os resultados demonstraram que é possível sintetizar as zeólitas hidroxissodalita e cancrinita a partir da cinza estudada. O produto obtido pelo método de duas etapas foi utilizado na adsorção de íon amônio em solução, sendo, neste processo, o modelo isotérmico de Sips o mais adequado; alcançando um valor de capacidade máxima de adsorção de 2,71 mg.g-1.

ABSTRACT Fly ash is the main industrial waste generated by coal in steam and power plans. In Brazil, 1,4 million tons are produced every year. These ashes can be converted into zeolite products by alkaline hydrothermal treatment. The main objective of this paper was to induce this reaction which produces only zeolitic crystalline phases for ammonium ion absorption. So, some syntheses were done by different hydrothermal method (classical or two stages), work time (24 or 30 h) and many NaOH bulks. The characterization of ash (in natura and calcined) and products was performed by X-ray diffraction method, scanning electron microscopy and, in some cases, differential thermal and thermogravimetric analysis The product by two stages method was used in ammonium ion absorption in solution at Sips Mathematic Model: the highest capacity of 2,71 mg.g-1.

Cancrinite from nepheline syenite (mariupolite) of the Oktiabrski massif, SE Ukraine, and its growth history.

Secondary cancrinite, (Na5.88K<0.01)∑5.88(Ca0.62 Fe0.01Mn0.01Zn<0.01 Mg<0.01)∑0.64[Si6.44Al 5.56O24](CO3)0.67(OH)0.26(F<0.01,Cl<0.01)·2.04H2O), was found as accessory component of mariupolite (albite-aegirine nepheline syenite) from the Oktiabrski massif in the Donbass (SE Ukraine). It probably crystallized from a subsolidus reaction involving nepheline (and sodalite?) and calcite dissolved in the aqueous-carbonic fluid at the maximum temperature of 930 °C, decreasing to hydrothermal conditions. It is depleted in sodium, calcium and carbon, what results in the occurrence of vacant positions at both cationic and anionic sites. Ca-deficient cancrinite crystallized from the same hydrothermal Si-undersaturated fluids enriched in the ions such as Na(+), Ca(2+), Cl(-), F(-), HCO3(-), which formed calcite, sodalite, natrolite and fluorite. It has dark-red CL colours with patchy zoning, what indicates the variable/diverse fluid composition during its formation. In the CL spectrum of cancrinite only one broad emission band at 410 nm is observed, which can be attributed to O* center (the recombination of a free electron with an O(-) hole center). The formation of secondary CO3-rich species, i.e. cancrinite and calcite in mariupolite suggests that redox conditions in the Oktiabrski massif were oxidizing at the postmagmatic stage.