Additive manufacturing of sodalite monolith for continuous heavy metal removal from water sources

Herein,we present a simple strategy for preparing monolithic sodalite adsorbents via sequential additive manufacturing and post-treatments.In detail,the method includes(i)3D printing of cylindrical monoliths using clay as the base material;(ii)thermal activation of the 3D-printed clay monoliths by calcination(to produce reactive alumina and silica species and enable mechanical stabilization);(iii)conversion of the activated clay monoliths to hierarchical porous sodalite monoliths via hydrothermal alkaline treatment.Parametric studies on the effect of calcination temperature,alkaline concentration and hydrothermal treatment time on the property of the resulting materials(such as phase composition and morphology)at different stages of preparation was conducted.Under the optimal conditions(i.e.,calcination temperature of 850℃,NaOH concentration of 3.3 mol·L^(-1),reaction temperature of 150℃,and reaction time of 6 h),a high-quality pure sodalite monolith was obtained,which possesses a relatively high BET surface area(58 m^(2)·g^(-1))and hierarchically micro-meso-macroporous structure.In the proposed application of continuous removal of heavy metals(chromium ion as the model)from wastewater,the developed 3D-printed sodalite monolith showed excellent Cr^(3+)removal performance and fast kinetics(~98%removal efficiency within 25 cycles),which outperformed the packed bed using sodalite pellets(made by extrusion).

Transformation of Coal Gangue to Sodalite and Faujasite Using Alkali-hydrothermal Method

The coal gangue as the only source of silicon and aluminum was employed to synthesize sodalite and faujasite using hydrothermal method,which directly treated the mixture of pre-treated coal gangue and NaOH solution under hydrothermal environment.X-ray powder diffraction analysis(XRD),thermogravimetry analysis(TG)and differential thermogravimetry analysis(DTG),scanning electron microscopy(SEM),high resolution transmission electron microscopy(HRTEM),N_(2)adsorption-desorption technique,X-ray photoelectron spectroscopy(XPS),etc.were used to characterize the samples.Cd^(2+) ion was used to evaluate the heavy metal ions removal performance of the samples.The experimental results show that the coal gangue,which consists of quartz,calcium feldspar,potassium feldspar and kaolinite,can transform to sodalite and faujasite under alkali-hydrothermal condition at 150 and 180℃,respectively.The as-prepared sodalite and faujasite can effectively remove the simulated Cd2+ion wastewater and actual industrial wastewater containing As^(3+),Cd^(2+),and Cr^(3+)ions,and the good heavy metal ion removal performance of the zeolites is mainly attributed to their low Si/Al ratio and high Na+content.This alkali-hydrothermal method appears to be a simple and efficient method for transformation of coal gangue to high purity zeolites.

Recycling of Mud Derived from Backwash Wastewater Coagulation as Magnetic Sodalite Sphere for Zn^(2+) Adsorption

Herein,we reported a method to prepare magnetic sodalite sphere by using the mud from backwash wastewater after polyaluminum chloride(PAC)coagulation.The results showed that approximately 100%of Fe in the wastewater was precipitated as flocculent iron mud(FM)by adding PAC.FM was converted to spherical magnetic sodalite(FMP)with a diameter of 3μm via a facile alkali hydrothermal method without adding Al/Si resources or reductant.The product FMP had the saturated magnetization of 10.9 emu g^(-1) and high Zn^(2+)adsorption capacity of 50.6 mg g^(-1).Without coagulation with PAC,the removal rate of Fe from the wastewater was only 92.7%,and the precipitated mud(RM)was converted to irregular particles(RMP),which had weak magnetic response and low capacity of Zn^(2+)adsorption comparing with FMP.With the method,the Fe in backwash wastewater was effectively recycled,and the generated sludge was converted to well-formed sodalite sphere without generating any secondary waste.

Nanocomposite sodalite/ceramic membrane for pre-combustion CO2 capture： synthesis and morphological characterization

Carbon capture and storage （CCS） is amongst the possible options to reduce CO2 emission. In the application of CCS, CO2 capture techniques such as adsorption and membrane system have been proposed due to less energy requirement and environmental benign than the absorption process. However, membrane system has drawbacks such as poor membrane reproducibility, scale-up difficulty and high cost of the membrane supports. In this study synthesis and characterization of nanocomposite sodalite （HS）/ceramic membrane via ＂pore-plugging＂ hydrothermal synthesis （PPH） protocol for pre- combustion CO2 capture is reported. The morphology and crystallinity of the as-prepared membranes were checked with scanning electron microscopy and X-ray diffraction. Surface chemistry of the membrane was examined with Fourier Transform Infrared spectroscopy. In nanocomposite architecture membranes, zeolite crystals are embedded within the pores of the supports instead of forming thin-film layers of the zeolite crystals on the surface of the supports. Compared to the conventional in situ direct hydrothermal synthesis, membranes obtained from PPH possess higher mechanical strength and thermal stability. In addition, defect control with nanocomposite architecture membranes is possible because the zeolite crystals are embedded within the pores of the support, thereby limiting the maximum defect size to the pore size of the support. Furthermore, the nanocomposite architecture nature of the membranes safeguards the membrane from shocks or abrasion that could promote formation of defects. The aforementioned advantages of the nanocomposite architecture membranes could be beneficial in developing high performance and cost-effective membrane materials for pre-combustion CO2 capture.

NaBH₄Sodalites, Synthesized by Modified Methods: (1) Autothermal Synthesis and (2) Crossover Reaction from Gel to Melt Flow

NaBH4 sodalites were obtained by two new modified methods of crystallization: (1) autothermal synthesis and (2) crystallization with crossover from gel to melt flow in NaOH flux. Syntheses results were presented according to XRD, SEM and FTIR. Besides important features of both synthesis procedures product properties like crystal size and morphology were investigated. Spherical agglomerates of microcrystalline sodalite of composition Na7[AlSiO4]6BH4(H2O)2 were already observed after 4 h without any external heating by the autothermal procedure. Sodalites of the same average composition but in form of agglomerated nanoparticles are crystallized after very short times (2 h 30’) by the crossover reaction from gel to melt flow. Hydrogen release by heating was further studied for two selected samples with comparable composition from each synthesis procedure. Total hydrogen release by hydrolysis reaction with the internal cage water was found during heating of the autothermal product in synthetic air up to 550°C. In contrast hydrogen release from the nanocrystalline sample of crossover synthesis was not completed when heated under the same conditions. These differences were discussed in terms of crystal size and an earlier loss of the internal water from the nanocrystals of the crossover

Mesoporogen-free synthesis of hierarchical sodalite as a solid base catalyst from sub-molten salt-activated aluminosilicate

A rapid and environmentally friendly approach to synthesize hierarchical sodalite from natural aluminosilicate mineral without the involvement of any mesoporogen or post-synthesis treatment was developed.This strategy involves three important steps:the first is the depolymerization of an aluminosilicate mineral into highly reactive silicon and aluminum species with ideal meso-scale structures through activation of a sub-molten salt.The second step is the hydrolysis and condensation of the activated aluminosilicate mineral into zeolitic precursors that also have a meso-scale structure.The third is the rapid zeolitization of the zeolitic precursors through the reversed crystal growth route at room temperature and ambient pressure to form hierarchical sodalite.The physicochemical properties of the as-synthesized sodalite were systematically characterized,and the formation mechanism of the hierarchical pore structure was discussed.When used as a solid base catalyst for Knoevenagel condensation,the as-synthesized sodalite and its potassium ion-exchanged product with hierarchical micro-meso-macroporous structure both exhibited high catalytic activity and product selectivity.

Effects of Cs Doping on Structural and UV-photochromic Properties of Sodalite

The NaAlO_2,Na_2SiO_3-9H_2O,NaOH and CsOH·H_2O were used as raw materials to synthesize Cs-doped sodahte samples by a chemical synthetic approach.The effects of different Cs doping contents on structural and UV-photochromic properties of sodalite were investigated.The results suggested that the maximum doping content of Cs in sodalite was about 2.9%,and the impure phase CsAlSiO_4·H_2O arose exceeding the doping content.The lattice parameters(a and v) of sodalite decreased integrally due to the effect of hydrated Cs ions on sodalite lattice.Meanwhile,the surface morphology of Cs-doped sodalite consisted of petal shaped aggregated particles at the maximum Cs doping content,which was basically similar as pristine sodalite.In addition,the ultraviolet(UV) absorptance of the Cs-doped sodalite,compared with pure sodalite,increased about 1.3%-2.3%from 225 to 280 nm and about 1.8%-2.8%from 280 to 350 nm,respectively.

Loading single lanthanide ion into aluminum molecular rings:water-stable sodalite cage for removal of nuclear-industry anions

Based on our discovery of neutral aluminum molecular rings,we herein introduce rare earth ions into the center of the ring and reveal their structural adaptability.The resulting yoyo-like cationic macrocycles are highly adaptive to guests,creating unusual supramolecular assemblies.The first category is stacked with singly oriented rhombohedral channels,which exhibit fast and reversible solvent-triggered molecular motions and structural rearrangements.The second type of assembly is that yoyo macrocycles and guest molecules form a nested host-guest sodalite cage supramolecular structure.It is uncommon for guest molecules to be well-defined within cages although caged structures have been well-documented.Their host-guest interaction discussion reveals the self-adaptation and flexibility of the yoyo macrocycles.Considering their good water stability,we investigated their anion exchange properties.The results show that they have significant exchange capacity for KI/I_(2),ReO_(4)^(-),and MnO_(4)^(-),revealing their potential application in water purification and nuclear waste treatment.

Dissolution kinetics and removal mechanism of kaolinite in diasporic bauxite in alkali solution at atmospheric pressure

A new chemical pre-desilication process of kaolinite in diasporic bauxite in alkali solution at atmospheric pressure was proposed.The dissolution kinetics and mechanism were studied by chemical analysis,XRD and SEM.The kinetic results of dissolution process show that the kaolinite is symbiotic with diaspore but without cladding.The dissolution ratio of kaolinite is close to 100%at 100℃for 90 min.The dissolution kinetic equation is 1-(1-α)^1/3=7.88×10^6 exp[-64434/(RT)]t.With the low L/S(L/S=10:1),the dissolution ratio of kaolinite decreases to 55%.This is due to the formation of lamellar hydroxyl-sodalite(OH-SOD)which is deposited on the surface of kaolinite and hinders the further dissolution of kaolinite.Under the optimum conditions,the A/S(mass ratio of Al2 O3 to SiO2)of dissolved residues is increased to 8.55,while the A/S of the bauxite is only 4.97.

Mineral transition of desilication products precipitated in synthetic sodium aluminate solution under atmospheric pressure

The liquor concentration, mineral proportion, crystal parameters and micro morphology of various desilication products（DSPs） precipitated in silica-supersaturated sodium aluminate solution at 95 ℃ under different reaction conditions were systematically researched. The DSPs formed under atmospheric pressure comprise amorphous phase, zeolite A, zeolite and sodalite, and the DSPs concentration and crystallinity increase with the increase of initial silica concentration, initial molar ratio of caustic Na2O to Al2O3（αK） and desilication duration. Decreasing the initial silica concentration, initial αK and increasing the desilication duration can reduce the proportion of zeolite A. The zeolite and sodalite are the stable DSPs, while the precipitation of zeolite A occurs at a high silica-supersaturated state in sodium aluminate solution. The DSPs are precipitated in the form of agglomerates, but the morphologies of various DSPs are quite different. Both the molar ratios of Na2O to Al2O3 and SiO-2 to Al2O3 in DSPs increase with the increasing desilication duration, resulting in the increase of the cell volumes of various DSPs. The precipitation sequence of DSPs under atmospheric pressure is： amorphous phase→zeolite A→zeolite→sodalite.

Synthesis of Zeolite a from Natural Ca-Bentonite Using a Direct Alkali Hydrothermal Approach

Ca-bentonite can be converted into zeolites A through hydrothermal alkaline treatment by varying the synthetic parameters. This study focuses on the effect of initial Si/Al molar ratio, NaOH concentration on the type of formed zeolite A. The Ca-bentonite (China, Fuxin)were mixed with an aqueous NaOH solution, Al(OH)3 powder and hydrothermally treated at about 90 ℃,12 h. Different types of zeolites (zeolite X, P, and A),sodalite were synthesized after the treatment. Zeolites were characterized and quantified by means of XRD and SEM analysis. Zeolite A predominantly formed with 0.5≤Si/Al≤2.0 was produced and zeolite X, P formed with Si/Al>2.0 under the 2.2mol/LNaOH concentration; Sodalite was also formed under high NaOH molarities. Shape of zeolite A is show the cube by the SEM micrograph.

SiO2/Al2O3 RATIO OF HYDRATED SODIUM ALUMINOSILICATE IN ALUMINA PRODUCTION

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沸石分子筛的高效绿色合成

通过不同方法,优化Sodalite沸石的晶化过程。采用加入过硫酸钠的方法,以及不同硅铝比配比的方法,测试不同时间Sodalite沸石的晶化效果。采用X-射线衍射(XRD)表征不同时间Sodalite沸石的晶化程度。结果表明,加入过硫酸钠后,Sodalite沸石的晶化速度明显加快,且以硅铝比为0.23的配比进行晶化,可以加快Sodalite沸石的晶化。此研究对高效合成沸石分子筛具有重大意义。

Unusual Luminescence of Ca_8[Al_(12)O_(24)](WO_4)_2: Tb^(3+)

The luminescence properties of aluminate sodalite Ca8[Al12O24](WO4)2 (CAW) undoped and doped with Tb3+ are reported and discussed. At room temperature the emission of tetrahedral 2-4WO in CAW showed an abnor-mally small Stokes shift (9060 cm-1), which is related to the crystal structure of CAW. A strong absorption band in the excitation spectrum of the Tb3+-activated CAW is ascribed to the absorption of the charge transfer state Tb4+- W5+, into which the excitation resulted in the efficient emission from the 5D4 level of Tb3+, but not from the 5D3 level.