Adsorption of fluoride by the calcium alginate embedded with Mg-Al-Ce trimetal oxides

Batch experiments were conducted to study the adsorption performance of fluorine removal by the calcium alginate (SA) embedded by the composite Mg-Al-Ce oxides (SA-CMAC). The physical and chemical properties of the SA-CMAC were characterized by XRD, SEM and XPS analysis. The optimum conditions for fluoride removal were determined and the maximum adsorption capacity was 26.12mg g^?1. The co-existing PO ₄ ^3? and CO ₃ ^2? anions in solution had more effect than the SO ₄ ^2? and NO ₃ ^- on the fluoride removal efficiency. The adsorption process of fluorine by SA-CMAC was attributed to ion exchange on the surface of the SA-CMAC. The experimental data fitted both the isotherms and Freundlich well, and the Freundlich model had a little higher correlation coefficient. As the rate determining step, the adsorption process could be best described by the pseudo-second order kinetic model followed by the intra-particle diffusion. The thermodynamic examination demonstrated that the fluoride adsorption on the SA-CMAC beads was reasonably spontaneous and exothermic. The reclaimed adsorbents still could adsorb 65% of the total fluoride in the solution after three cyclic processes using 0.01mol/L NaOH.     

Effects of co-ion initial concentration ratio on removal of Pb<Superscript>2+</Superscript> from aqueous solution by modified sugarcane bagasse

A modified sugarcane bagasse (SCB) fixed bed column was used to remove Pb²⁺ from aqueous solution. To determine the optimal condition for Pb²⁺ separation, Ca²⁺ was chosen as the model interfering ion, and effects of Ca²⁺ and Pb²⁺ initial concentration ratio (C ₀ ^Ca : C ₀ ^Pb ) on the adsorption of Pb²⁺ were investigated. Results showed that adsorption amount ratio of Ca²⁺ and Pb²⁺ (q _e ^Ca : q _e ^Pb ) had a good linear relationship with C ₀ ^Ca : C ₀ ^Pb . Mass ratio of Pb²⁺ absorbed on the modified SCB was higher than 95% at C ₀ ^Ca : C ₀ ^Pb <1.95, illustrating that Pb²⁺ could be selectively removed from aqueous solution. To verify that, simulated waste water containing co-ions of K⁺, Na⁺, Cd²⁺ and Ca²⁺ was treated, and results showed that the equilibrium amount of Pb²⁺, K⁺, Na⁺, Cd²⁺ and Ca²⁺ adsorbed was 134.14, 0.083, 0.058, 1.28, and 1.28mg g^?1, respectively, demonstrating that the modified SCB could be used to remove Pb²⁺ from aqueous solution in the investigated range.     

Kinetic modeling and dynamic simulation for the catalytic wet air oxidation of aqueous ammonia to molecular nitrogen

A kinetic model for the catalytic wet air oxidation of aqueous ammonia over Ru/TiO₂ catalyst was developed considering the consecutive reaction steps as follows: (i) formation of active oxygen sites O* by the dissociative adsorption of aqueous O₂ on the catalyst, (ii) oxidation of aqueous NH₃ by the reaction with three O* sites to produce HNO₂, (iii) aqueous phase dissociation of HNO₂ into H⁺ and NO ₂ ^? , (iv) formation of NH ₄ ⁺ by the association of NH₃ with the HNO₂-dissociated H⁺, (v) formation of N₂ by the aqueous phase reaction between NO ₂ ^? and NH ₄ ⁺ , (vi) formation of NO₃ by the reaction of NO ₂ ^? with an O* site. For each reaction step, a rate equation was derived and its kinetic parameters were optimized by experimental data fitting. Activation energies for the reactions (ii), (v), and (vi) were 123.1, 76.7, and 54.5 kJ/mol, respectively, suggesting that the oxidation reaction of aqueous NH₃ to HNO₂ was a ratedetermining step. From the simulation using the kinetic parameters determined, the initial pH adjustment of the ammonia solution proved to be critical for determining the oxidation product selectivity between desirable N₂ and undesirable NO ₃ ^? as well as the degree of oxidation conversion of ammonia.     

Removal of UO 2 2+ from aqueous solution using halloysite nanotube-Fe3O4 composite

Halloysite nanotubes (HNTs) were modified with Fe₃O₄ to form novel magnetic HNTs-Fe₃O₄ composites, and the composites were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM). The as-obtained results indicated that Fe₃O₄ nanoparticles were successfully installed on the surface of HNTs. The adsorption of UO ₂ ²⁺ on HNTs-Fe₃O₄ was investigated as a function of solid content, contact time, pH, ionic strength and temperature by batch experiments. The consequences revealed that the adsorption of UO ₂ ²⁺ onto HNTs-Fe₃O₄ was strongly dependent on pH and ionic strength. Equilibrium data fitted well with the Langmuir isotherm. The experimental results demonstrated that the adsorbents with HNTs-Fe₃O₄ had the largest adsorption capacity of 88.32 mg/g for UO ₂ ²⁺ .     

Effect of heat transfer conditions on the critical pressure of metal ignition in oxygen

Experimental data on the critical pressure of ignition of titanium alloy fragments in gaseous oxygen are analyzed. The fragments are obtained after fracture of alloy samples in the dynamic mode (p₂^*) and under natural convection conditions (p₁^*). The results are analyzed with allowance for the heat transfer coefficients from material ignition initiators under similar conditions. Based on the shape of the experimental thermograms of plate cooling, the coefficient of heat transfer from microcraters with a juvenile surface formed due to knockout of metal particles from the plate by the high-velocity flow is found: α₂ ≈ 11 kW(m² ·K). The value of α₂ is close to the value of this coefficient calculated with the use of the coefficient α₁ ≈ 5 kW/(m² · K) of heat transfer from titanium rod microfragments (with the size of the order of metal grains) formed during titanium rod fracture in oxygen under conditions of natural convection with allowance for the ratio p₂^*/p₁^*.     

Physico-chemical study of dew melon peel biochar for chromium attenuation from simulated and actual wastewaters

This work introduces a biochar as novel adsorbent prepared from the dew melon peel by pyrolysis method, and demonstrates its potential for eliminating Cr(VI) from simulated and actual wastewaters. The dew melon peel biochar (DPB) was characterized by several techniques and methodologies such as, BET, SEM, FTIR, Boehm titration, ultimate analysis, and pHzpc. DPB is a microporous material with the BET specific surface area of 196 m²/g. The effects of different parameters including pH, amount of adsorbent, Cr(VI) concentration, and mixing time on the removal of Cr(VI) from wastewater were studied. Maximum adsorption (98.6%) was observed at pH 6 and 100 mg/L metal concentration. The equilibrium adsorption was analyzed by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms. Kinetic data were evaluated by pseudo-first order, pseudo-second order, intraparticle diffusion, film diffusion (Boyd), Elovich, and Avrami models. The kinetic data were best fitted to the pseudo-second order model. The Langmuir isotherm model gives the better correlation to predict the adsorption equilibrium, with a maximum adsorption capacity of 198.7 mg/g. The thermodynamic parameters showed that the adsorption of Cr(VI) was endothermic and spontaneous. Competition between the co-existing ions of Cl^?, NO ₃ ^? , SO ₄ ^2? , PO ₄ ^3? , and HCO ₃ ^? on the adsorption process was studied. The efficacy of DPB was successfully examined by analyzing the removal of Cr(VI) from two industrial wastewaters. The results indicate that DPB is promising as an effective and economical adsorbent for Cr(VI) ions removal and could be repeatedly used with no significant loss of adsorption efficiency.     

One-pot synthesis of high fructose corn syrup directly from starch with SO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack>/USY solid catalyst

An efficient process was developed for the conversion of starch directly into high fructose corn syrup (HFCS) by using SO₄ ^2?/USY solid catalyst in water. The SO ₄ ^2? /USY catalyst was found to act as a bifunctional catalyst with high activity for both hydrolysis of starch and isomerization of glucose, achieving a one-step preparation path of HFCS from starch. An optimal HFCS yield, containing 58.34% glucose and 27.84% fructose (mass fraction), was obtained at 150 °C for only 1 h.     

Study on the Preparation and Characterization of Biodegradable Polylactide/SiO2–TiO2 Hybrids

In this study, the silicic acid produced from sodium metasilicate hydrate and titanium tetraisopropylate were chosen as the ceramic precursors for the modification of biodegradable polylactide (PLA) through an in situ sol-gel process and the melt blending method. In addition, acrylic acid grafted polylactide (PLA-g-AA) was studied as an alternative to PLA. Hybrids were characterized by Fourier transform infrared spectroscopy, ²⁹ Kumar , P. ; Badrinarayanan , M.S. ; Sastry , M. Nanocrystalline TiO₂ studied by optical, FTIR and X-ray photoelectron spectroscopy: correlation to presence of surface states . Thin Solid Films 2000 , 358 , 122 – 130 .[Crossref], [Web of Science ®] , [Google Scholar]Si solid-state nuclear magnetic resonance (NMR), thermogravimetry analysis (TGA), scanning electron microscope (SEM), and Instron mechanical tester. The result was that properties of the PLA-g-AA/SiO₂–TiO₂ hybrid were superior to those of the PLA/SiO₂–TiO₂ hybrid. This was because the carboxylic acid groups of acrylic acid acted as coordination sites for the silica-titania phase to allow the formation of stronger chemical bonds. The ²⁹ Kumar , P. ; Badrinarayanan , M.S. ; Sastry , M. Nanocrystalline TiO₂ studied by optical, FTIR and X-ray photoelectron spectroscopy: correlation to presence of surface states . Thin Solid Films 2000 , 358 , 122 – 130 .[Crossref], [Web of Science ®] , [Google Scholar]Si solid-state NMR showed that Si atoms coordinated around SiO₄ units were predominantly Q₃ and Q₄. The 10 wt.% SiO₂–TiO₂ content gave the maximum values of tensile strength and glass transition temperature in PLA/SiO₂–TiO₂ and PLA-g-AA/SiO₂–TiO₂ both because excess SiO₂–TiO₂ particles caused separation between the organic and inorganic phases.     

Structure of a biologically active binuclear palladium complex in the compound (bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium)(1,10-phenanthroline)-palladium(I)]) · tetranitrates · hydrate

The structure of a biologically active palladium complex [(1,10-phenanthroline)Pd(μ₂-2-chloroethylammoniu)] ₂ ⁴⁺ · 4NO ₃ ^? · H₂O has been determined from the diffractometric data. The compound crystallizes in the triclinic crystal system, space group of symmetry P \(\bar 1\), with the unit cell parameters a = 12.8352(8) Å, b = 14.4040(8) Å, c = 12.1668(9) Å, α = 116.16(1)°, β = 115.72(1)°, γ = 91.09(1)°, V = 1756.3 ų, Z = 2, and ρ = 1.892 g/cm³. The final reliability factor is R ₁ = 0.0351 for 7357 nonequivalent reflections with I ≥ 2σ(I), wR ₂ = 0.0970, and S = 1.044. The asymmetric part of the unit cell contains one positively charged binuclear palladium complex, four NO ₃ ^?1 anions, and one water molecule. The nanocomplexes are involved in the stacking π-π interaction by pairs: each complex forms a stacking with only one adjacent complex. The interaction between layers and inside each layer occurs through the van der Waals interactions and a three-dimensional system of hydrogen bonds, which are formed by the N ₃ ⁺ groups and water molecules.     

Performance and sludge characteristics of anammox process at moderate and low temperatures

A sequencing batch reactor (SBR) was used to investigate the performance and sludge characteristics of anammox process at moderate and low temperatures. The initial pH was 7.5 and hydraulic retention time (HRT) was 3 h. When temperature was 25-35 °C, nitrogen removal rate (NRR) fluctuated from 1.67 to 1.82 kg/m³·d. However, when temperature dropped to 15 °C, NRR suddenly decreased by 0.48 kg/m³·d. Larger activation energy was acquired at lower temperature, and it was difficult to achieve efficient nitrogen removal under low temperature. When temperature declined to 10 °C, ΔNO ₂ ^? -N/ΔNH ₄ ⁺ -N and ΔNO ₃ ^? -N/ΔNH ₄ ⁺ -N reached 1.02 and 0.27, respectively. Inhibition resulting from low temperature on anammox activity was recoverable, and the modified Boltzmann model was appropriate to analyze recovery feature of anammox process. Low temperature not only led to poor nitrogen removal, but also affected sludge size and feature.     

Surface analysis of three aluminum foils and relation to hydrogen generation capability

We have successfully generated hydrogen using aluminum foil instead of aluminum powder from the perspective of improving safety. We analyzed the surface states of three aluminum foils and correlated their surface properties with hydrogen generation capability. The surfaces of the foils were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy, and atomic force microscopy. Hydrogen generation was performed by adding Ca(OH)₂ solution to the aluminum foil in water. The TOF-SIMS results showed that the Al foils have Al₂O ₃ ^- , AlO ₂ ^- , (OH)₂AlO^-, (Al₂O₃)OH^-, and (Al₂O₃)AlO ₂ ^- and related species on their surfaces. The amount of these species on the surface of an Al foil is linearly correlated with the hydrogen generation reaction rate.     

The Symmetric and Topological Code of the Cluster Self-Assembly of the Crystal Structure of ε-Mg<Subscript>23</Subscript>Al<Subscript>30</Subscript> of K63 Nanoclusters

The geometrical and topological analysis of the crystal structure of intermetallide ε-Mg₂₃Al₃₀ (ToposPro program) with V = 3098.0 ų and space group R-3 is carried out. The symmetric and topological codes of the cluster self-assembly of the crystal structure are determined: primary chain S ₃ ¹ → microlayer S ₃ ² → microframework S ₃ ³ . A new type of nanocluster-precursor of the crystal structure, which is formed on the internal 13-atomic cluster, which represents a template and consists of two bound ridged rings Mg–Al–Mg–Al–Mg–Al with the central Mg atom, is discovered. A quasi-spherical deltahedron shell made from 50 atoms is formed on the template. The center of a K63 cluster occupies the position with the point symmetry 3? in the unit cell. There are six neighboring K63 clusters in the local environment of the K63 cluster in the layer. The basic 3D network, which characterizes the location of the gravity centers of the K63 clusters, corresponds to a hexagonal closely packed network (HCP, Mg type) with CN = 12. The localization of two Mg atoms in the pores of the framework is determined.     

On the critical displacement of excited kinetic units in liquids and glasses

The critical displacement of an atom (a group of atoms) in inorganic glasses Δr _m, which corresponds to the maximum of the interatomic attractive force, is calculated using available data on the surface tension and elastic constants. It is found that the critical atomic displacement Δr _m is close in order of magnitude to the linear dimension of the activation volume of atomic excitation v _h ^1/3 for glasses in the As-S and Ge-As-S systems with a chain structure and is considerably less than the value of v _h ^1/3 for alkali silicate glasses and glasses in the Cd-As system with a structure involving ionic sublattices. A relationship for calculating the activation volume of the atomic excitation from data on the glass transition temperature and elastic constants is derived within the model of an excited state.     

Predicting the classification characteristics of coal. Part 3. Gross calorific value of dry,ash-free coal

For 63 samples of Ukrainian, Russian, and imported coal, equations for predicting the gross calorific value Q_s^daf on the basis of the following coal characteristics are developed: W^a, O_d^daf, Q_s^af, and C_ar. The error is within the standard tolerances (σ ≤ 0.3 MJ/kg). With sufficient accuracy, Q_s^daf may be predicted from equations based on petrographic characteristics such as the vitrinite reflectance, the content of liptinitegroup minerals, and the sum of lean macerals (I + 2Sv/3). In these equations, the coefficients correspond to the heat of combustion of the vitrinite components at different metamorphic stages, the liptinite, and the lean macerals.     

Influence of reactivity of the colloidal silica on the properties of conjugate phases

The properties of hydrosols (brand Ludox) are studied by dynamic light scattering (photon correlation spectroscopy, PCS) and colorimetric analysis (formation of a colored β-silicomolybdate complex, KMK). Experimental sol samples for silicate modulus M = 50.0 and М = 3.0 M (M = [SiO₂]/[Me₂O], mol/mol) are obtained by introducing an alkali metal hydroxide (Me). According to the PCS data, the hydrodynamic radius of the sol particles (\({C_{Si{O_2}}}\)= 41.0 g/L) is r = 8.0 nm and increases with the dilution of the sol. These particles’ radii r _∞ (at \({C_{Si{O_2}}}\) → 0) for the initial sol are r _∞ = 13.8 nm and r _∞ = 16.8 nm in sols with alkali metal hydroxides (M = 50). The conjugated phase properties (silica particles and aqueous solution) were considered in the light of polycondensation and depolymerization kinetic reactions involving reactive silicate anions (HO)₃SiO^– and Si(OH)₄) on the surface of the particles and in the composition of soluble fractions. The result is the formation of surface layers of a gel-like structure. With the introduction of alkali metal hydroxides, the initial dissolution rate increases in the range from LiOH to KOH. The existence of peaks in the kinetic dependences of the active silica fractions in highly alkaline environments (M = 50 and M = 3.0) characterizes the secondary polycondensation of silicic acid in the aqueous phase, resulting in the formation of the oligo- and polymeric molecules of a linear structure.     

Structure of a biologically active binuclear palladium complex in the compound bis(bis[(μ<Subscript>2</Subscript>-2-chloroethylammonium) (1,10-phenanthroline)-palladium(I)]) · octanitrates · dihydrates

The structure of a biologically active binuclear palladium complex, namely, [(1,10-phenanthroline) Pd(μ₂-2-chloroethylammonium) ₂ ⁴⁺ · 4NO ₃ ^? · H₂O, has been determined using X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group of symmetry Cc, with the unit cell parameters a = 24.527(3) Å, b = 13.097(1) Å, c = 22.651(3) Å, β = 104.23(1)°, V = 7052(2) ų, Z = 8, and ρ = 1.88 g/cm³. The final discrepancy factor is R1 = 0.0316 for 15581 symmetrically nonequivalent reflections with I ≥ 2σ(I), wR2 = 0.0513, and GooF = 1.047. The palladium atoms reside in the oxidation state of 1+, which is rarely encountered in organometallic compounds. The asymmetric part of the unit cell contains two chemically equivalent but crystallographically independent positively charged binuclear palladium complexes, eight NO ₃ ^? anions, and two water molecules. The π-π stacking interaction between the nearest 1,10-phenanthroline rings of the neighboring layers takes place. Moreover, the interlayer and intralayer interactions occur through electrostatic interaction forces and a complex three-dimensional system of hydrogen bonds, which are formed by water molecules and N ₃ ⁺ groups.     

Synthesis and Properties in Solution of Gaussian Homo Asymmetric Polysiloxanes with a Bulky Side Group

Ring opening polymerization (ROP) of 1,3,5-tri-n-hexyl,1,3,5-trimethylcyclotrisiloxane (D ₃ ^Hexa ) and 1,3,5-tri-n-heptyl,1,3,5-trimethylcyclotrisiloxane (D ₃ ^Hepta ) was promoted by acid-treated synthetic silica–alumina to obtain Gaussian homo asymmetric polysiloxanes. M_w was above 70?kg/mol, meaning that homo asymmetric bulky side-group polysiloxane chains with high molecular weight were obtained. The material was treated in an acidic medium to improve the contents of acid sites and successfully tested as an inorganic acidic catalyst for ROP of D ₃ ^Hexa and D ₃ ^Hepta cyclosiloxanes. The samples of poly(methylhexylsiloxane) (PMHS) and poly(methylheptylsiloxane) (PMHepS) obtained were structurally characterized mainly by ²⁹Si NMR. All the experimental values including the refractive index increment (dn/dc), the second virial coefficient (A₂), the square root of the mean square radius of gyration ( $ \langle {{\text{RMS}}_{\text{radius}}}^{ 2} \rangle^{ 1/ 2} $ ), the average molecular weight (M_w), the average molecular numeral (M_n), and the weight polydispersity (M_w/M_n) were obtained using a gel permeation chromatography/light scattering (GPC/LS) coupled system. The A₂ experimental value for the two polymers (between 4 and 6.5?×?10^?4?mol/mL?g²) indicated that toluene was a good solvent. In addition, PMHS and PMHepS $ \langle {{\text{RMS}}_{\text{radius}}}^{ 2} \rangle^{ 1/ 2} $ were greater than 30?nm, indicating that larger chains of high molecular weight were obtained.     

Influence of Si species on intergrowth and anisotropic crystal growth of silicalite-1

Silicalite-1 crystals were hydrothermally synthesized from silica gels prepared under different conditions. The influence of the state of Si species in the silica gels and the concentrations of silicate ions and a template agent in the reaction sols on crystal growth of silicalite-1 was examined. The use of silica gels with a high degree of condensation of Si species resulted in the intergrowth of silicalite-1 crystals, whereas a low degree of condensation of Si species led to coffin-shaped crystals. Thus, the degree of condensation of Si species had significant influence on the intergrowth of silicalite-1 crystals. Moreover, at a low silicate concentration, silicalite-1 crystals elongated along the c-axis were obtained. With increasing silicate concentration in the reaction sols, the aspect ratio of silicalite-1 decreased. Furthermore, with decreasing the amount of N(C₃H₇) ₄ ⁺ used as a template agent, the silicalite-1 crystals became larger isotropically. Thus, the growth direction of silicalite-1 crystals was dependent on silicate ion concentration in the reaction sols, but not on N(C₃H₇) ₄ ⁺ concentration.     

Conversion of methanol into light olefins over ZSM-11 catalyst in a circulating fluidized-bed unit

Methanol conversion and the reaction pathway were investigated in a pilot-scale circulating fluidized-bed (CFB) unit over hierarchical ZSM-11 catalyst. Experimental results indicated that ZSM-11 catalyst was highly resistant to external coke due to the formation of mesopores. Elevated temperatures favored the production of propylene and butylene and decreased the yield of ethylene. Additionally, no direct relations were shown between the formation of ethylene and other products under different pressures, suggesting that ethylene was a primary product produced at the initial of the reaction. Methylation-cracking and oligomerization were verified as the main reaction pathway for the formation of C ₃ ⁺ alkenes., Methylation and oligomerization of olefins were dominated under high methanol partial pressure and consequently responsible for the production of higher olefins, while the b-scission of C ₇ ⁼ for propene and butylene, and C ₈ ⁼ for butylene were enhanced at low methanol partial pressure.     

On the mechanism of thermal decomposition of ammonium dinitramide (review)

Despite significant progress in studying thermal decomposition of ammonium dinitramide (ADN), the kinetics of the process at the level of elementary stages has not been adequately understood. The aim of this review is to summarize various published data, which are of interest for studying and simulating the processes of thermal decomposition and combustion of ADN. Considerable attention is paid to physical and chemical properties of ADN, dinitramide and its anion N(NO₂)₂^-, which play a key role in ADN decomposition. Various paths of decomposition of ADN, dinitramide, and N(NO₂)₂^- are discussed. Results illustrating alternative points of view on the decomposition process are presented.