Flotation behavior of four dodecyl tertiary amines as collectors of diaspore and kaolinite

The flotation of diaspore and kaolinite by one of a series of tertiary amines (DRN, DEN, DPN and DBN) was investigated. The tertiary amines show better floating recovery for kaolinite compared to diaspore. The maximum recovery D-value is 45% over a pH range from 3 to 8. FT-IR spectra confirm the presence of hydroxyl groups on the surface of kaolinite and diaspore. Zeta potential measurements show that the mineral surfaces are negatively charged over a wide pH range. Ionization of hydroxyl groups mainly accounts for the surface charging mechanism. The adsorption of tertiary amines onto the mineral surface is due mainly to electrostatic effects and the difference in electrostatic effect between a collector and the two minerals can explain the flotation separation. Inductive electronic and steric effects from the substituent groups result in different collecting powers for the four tertiary amines.     

Synthesis of N, N-diethyl dodecyl amine and its flotation properties on bauxite

N, N-diethyl dodecyl amine（DEN12） was synthesized from dodecyl amine, formic acid and acetic aldehyde. The collecting property of DENI2 on diaspore, kaolinite and illite was investigated by flotation test and infrared spectrum. The results show that in the presence of 2.0× 10^-4 mol/L DEN12, the recoveries of kaolinite and illite are all higher than 78% and the recovery of diaspore is 50% in the pH range of 5.5-6.0. The mass ratio of A1203 to SiO2 in concentrate obtained from separation artificial mixture is higher than 10, suggesting that DEN12 can be used as a collector to separate the aluminosilicates from diaspore in bauxite ores at the pulp pH below 8. The measurements of the infrared spectrum approve that the action between aluminosilicates and tertiary amine collector is strong electrostatic adsorption and that of diaspore is weak electrostatic adsorption.     

Asymmetric synthesis of 3β-acetoxy-17,17-ethylendioxy-15β, 16β-methylene-5-androsten-7β-ol

3β-acetoxy-17, 17-ethylendioxy-15β, 16β-methylene-5-androsten-7β-ol(I) was prepared by 3 steps from 3β-acetoxy-15β, 16β-methylene-5-androsten-17-one (II) with overall yield of 52.7%. Thus, interaction of ethylene glycol and material (II) gave 3β-acetoxy- 17, 17-ethylendioxy-15β, 16β-methylene-5-androsten (III) which was subsequently oxidated and stereoselectively reduced to produce compound(I). The normal influencing factors, such as the types of oxidants and reductives, the mole ratio of reactants, the reaction temperature, and the addition ways of reactants, in oxidation and reduction were discussed. The results show that the oxidation rate order is CrO₃-C₅H₅N (1:1, mole fraction)>CrO₃-C₅H₅N(1:2)>(C₅H₅NH)₂Cr₂O₇ in terms of the oxidant, the yield of the oxidation becomes higher with increasing the oxidant stoichiometry and raising the reaction temperature. And the optimum condition is that the reaction temperature is at 30 °C, and n(III)/n(CrO₃-C₅H₅N(1:2))=1:20. The yield of the −7β alcohol order with Li[Al(OC(CH₃)₃)₃H] (e. g. 78.6%) is more than that with NaBH₄ (e. g. 14.5%) in terms of the reductive agent and the reduction rate decreases in the course of reaction. The compound (I) is characterized by IR and MS. Foundation item: Project (1357) supported by the Excellent Young Teachers Program of the Ministry of Education of China     

Orbital Calculations of Kaolinite Surface： on Substitution of Al^3＋ for Si^4＋ in the Tetrahedral Sites

The surface properties of kaolinite were determined using density functional theory discrete variational method （DFT-DVM） and Gaussian 03 program. A SiO4 tetrahedral hexagonal ring with two A1 octahedra was chosen to model the kaolinite crystal. The total density of states of the kaolinite cluster are located near the Fermi level at both sides of the Fermi level. Both the highest occupied molecular orbit （HOMO） and the lowest unoccupied molecular orbit （LUMO） of kaolinite indicate that kaolinite system can not only readily interact with electron-acceptor species, but also readily interact with electron-donor species on the edge surface and the gibbsite layer surface, and thus, shows amphoteric behavior. Substitution of Al3^＋ for Si4＋ in the tetrahedral site linking the vacant Al3^＋ octahedra does not increase the surface chemical reactivity of kaolinite, while substitution of Al3^＋ for Si^4＋ in the tetrahedral site with the apex O linking Al3^＋ octahedra increase the surface chemical reactivity of the siloxane surface of kaolinite, especially acting as electron donors. Additionally, substitution of Al3^＋. for Si^4＋ in the tetrahedral site results in the re-balance of charges, leading to the increase of negative charge of the coordinated O atoms of the AlO4 tetrahedra, and therefore favoring the formation of ionic bonds between cations and the surface O atoms in the basal plane.     

Ethylene Polymerization by a Novel Dinuclear Heter-oligated Titanium Complex with the Ligand of （Salicylaldiminato） （β-enaminoketonato）

The condensation of acetylacetone （CH3COCH2COCH3） with benzdine （H2N-C6H4-C6H4-NH2） yielded diimine ligand 1 [HOC（Me）C（H）（Me）C=N（p-C6H4）（C6H4-p）N= C（Me）C（H）C（Me）OH）], which was converted into sodium salts. And then the sodium salts reacted with monosalicylaldiminato titanium complex 2{[3,5-di-But′2-（O）C6H2CHN（PH）]TiCl3（THF）} in dried dichloromethane to give a new benzdine-bridged binuclear complex 3{[3,5-di-Bu′-2-（O）C6H2CHN（PH）]2 [OC（Me）C（H）（Me）C=N（p-C6H4）-（C6H4-p）N=C（Me）C（H） C（Me）]Ti2Cl4}. The complex 3 was characterized by ^1HNMR and elemental analysis. In the presence of MAO（methylaluminoxane）, the complex 3 in toluene was effective to catalyze polymerization, affording moderately high catalytic activity 1.93 × 10^5 g PE/（mol.Ti.h）]and high molecular weight polyethylene [5.63× 10^5 g/moll. The high temperature gel permeation chromatography （GPC） curve of polyethylene obtained revealed a single peak, but the molecular weight distribution （MWD = 3.21） is obviously broader than that of the similar mononuclear titanium complex. The melting points of the obtained polyethylene reaches 138 ℃, indicating that the polyethylene is of high crystallinity.     

Chemieal Strueturcs and Adsorptive Behaviors of Superplastieizers on β-C2S

The chemical structures of four types of superplasticizers （SPs） and their adsorptive behaviors on β-C2S were investigated. The adsorption properties of SPs on β-C2S were measured and the relationship between the adsorption quantity and the specific surface of β-C2S was analyzed. The experimental results show that the adsorption quantity increases with the surface area increase of β-C2S, but the adsorption quantity per surface area is similar, which means that the main adsorbent is β-C2S itself. Polycarboxylic ester （PCE） showed the highest adsorption amount on β-C2S, followed by β-naphthalene sulfonates （NSF） and formaldehyde-acetone condensates sulfonates （FAS）, amino sulphonate （AS） showed the least adsorption amount on β-C2S. PCE affected the surface potential of β-C2S particles in water differently in comparison with other types of SPs. The adsorption capacity of SPs on β-C2S is determined by factors such as molecular structure, functional groups and molecular weight of SPs.     

Flotation of kaolinite and diaspore with hexadecyl dimethyl benzyl ammonium chloride

Tertiary amine was synthesized from fatty amine and formaldehyde. And then the synthesized tertiary amine was used to react with benzyl chloride to synthesize hexadecyl dimethyl benzyl ammonium chloride （1627） at ambient pressure. Using the synthesized 1627 as collector,the flotation properties of diaspore and kaolinite were investigated by single mineral and mixed mineral test. The flotation mechanism of diaspore,kaolinite and 1627 was discussed based on FTIR spectra. The results show that the mass ratio of aluminum to silicate achieves 15.02 and the recovery of alumina in concentrate is 43.07% using 1627 as a collector. The 1627 is found to be a more effective and a promising collector for reverse flotation to remove aluminum-silicate minerals from bauxite.     

Chemial Bond and Stability of Adsorption of [Au（ AsS3 ）]^2- on the Surface of Kaolinite

Density function theory and discrete variation method (DFT-DVM) were used to study the adsorption of [Au( AsS3 )]^2- on the surface of kaolinite. The correlation among structure, chemical bond and stability was discussed. Several models were selected with [ Au( AsS3)]^2- in different directions and sites. The results show that the models with gold on the edge of kaolinite basal layer contain pincerlike bond among gold and several oxygen atoms and form strong Au - 0 covalent bond, so these models are more stable than those with gold above or under the layer. The models with gold near to [ AlO2(OH)4] octahedra are more stable than those with gold near to the vacancy withont aluminium. These two stable tendencies in kaolinite- [ Au( AsS3)]^2- are stronger than that in kaolinite-Au systems. The interaction between [ Au( AsS3 )]^2- and kaolinite is stronger than that between gold and kaolinite, and this interaction is strong enough to form the surface complexes.     

从多硫化物浸金贵液和石硫合剂浸金贵液中萃取金的研究

研究了ＴＢＰ、胺类萃取剂及其混合体系从多硫化物含金贵液中萃取金的规律,考察了一些影响萃取平衡的因素．实验结果表明：ＴＢＰ与胺类萃取剂都能从碱性多硫化物介质中萃取金;在胺类萃取剂中,伯胺的萃取能力要强于叔胺的萃取能力．并对具有协萃效应的Ｎ１９２３－ＴＢＰ混合体系进行了深入研究．选择０．５ｍｏｌ／Ｌ Ｎ１９２３－０．５ｍｏｌ　ＴＢＰ／正辛烷混合体系为萃取有机相,验证其从多硫化物浸金贵液中和石硫合剂浸金贵液中萃取回收金及金铜分离的情况．结果表明：在ｐＨ〈８或ｐＨ〉１１时的碱性介质中,金与铜的分离效果很好,金的一次萃取率较高．     

Synthesis,characterization and catalytic application of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/MCM-48 in the esterification of methacrylic acid with n-butyl alcohol

A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.     

NMR research on cement clinker and its structures in early age hydration

Clinker has long been regarded as a critical factor for cement hydration and solidification.α-C2S and β-C2S in 2CaO·SiO2(C2S) phase and C3S Monoclinic 1(C3S M1) and C3S Monoclinic 3 (C3S M3) in 3CaO·SiO2 (C3S) phase were clearly recorded in the 29Si MAS NMR spectra.The content of C3S phase in the clinker deduced from the fine peak analysis coincides with the phase quantification analysis calculated by the Taylor-Bogue method based on XRF,which also accords to the statistical data in industrial production.NM...     

Synthesis of mesoporous chromium aluminophosphate (CrAlPO) via solid state reaction at low temperature

Mesoporous chromium aluminophosphate（CrAlPO）was successfully synthesized via solid state reaction（SSR）route at low temperature in the presence of a cationic surfactant cetyltrimethyl ammonium bromide（CTAB）and inorganic sources such as AlCl₃·6H₂O,CrCl₃·6H₂O and NaH₂PO₄·2H₂O.Characterizations by means of powder X-ray diffraction（XRD）,N₂ adsorption-desorption,high resolution transmission electron microscopy（HR-TEM）,scanning electron micrography（SEM）,energy dispersion spectroscopy（EDS）,thermo-gravimetry（TG）,Fourier transform infrared spectroscopy（FT-IR）,and ultraviolet visible light spectroscopy（UV-Vis）were carried out to understand both the pore characteristics and electron transition route of these obtained materials.The experimental results show that the meso-CrAlPO materials with various Cr/Al molar ratios possess a mesostructure and a specific surface area of 193 to 310 m² /g corresponding to an average pore size of 5.5 to 2.2 nm,respectively.The maxium content of Cr in meso-CrAlPO materials synthesized via SSR route can achieve 16.7wt%,being significantly higher than that of the meso-CrAlPO prepared via a conventional sol-gel route.Meanwhile,the formation mechanism of the meso-CrAlPO was also proposed.     

Biosorption mechanism of Cr （Ⅳ） onto cells of Synechococcus sp.

The biosorption mechanism of Cr （Ⅳ） ions on Synechococcus sp. biosorbent was studied by analyzing the biosorption kinetics as well as speciation change and bond formation during the biosorption process. The kinetics study shows that the adsorption process of Cr （Ⅳ） consists of a very fast stage in the first several minutes, in which more than half of the saturation adsorption is attained, and a slower stage that approximately follows the first order kinetic model, basically Freundlich isotherm models were observed. Comparative studies of FT-LR spectra of K2Cr2O7, free cells of Synechococcus sp., and Cr-bound cells of Synechococcus sp show that the speciation of chromium that binds to the cells ofSynechococcus sp. is Cr （Ⅲ）, instead of Cr （Ⅳ）, and the carboxylic, alcoholic, amido and amino groups may be involved in the binding of Cr （Ⅲ）. Integrative analyses of the surface electric potential, the effect of pH value on adsorption behavior of Cr （Ⅵ）, and the results of FT-IR show that the biosorption of Cr （Ⅵ） follows two subsequent steps, biosorption of Cr2O7 ^2- by electrostatical force at the protonated active sites and reduction of Cr2O7^2- to Cr^3＋ by the reductive groups on the surface of the biosorbents.     

Preparation of TiO2/Kaolinite Nanocomposite and Its Photocatalytical Activity

Titanium dioxide/ kaolinite nanocomposite was prepared by the sol-gel method, with layered kaolinite as a substrate and Ti （ OC4H9 ）4 as a precursor. The effects of hydrolysis, drying and calcination on the production of nanometric titanium dioxide were discussed. The optimal conditions for preparation were＂ bbtained through experiments. The 1- 10 nrn thick monolayer anatase nano TiO2 crystal was produced under the conditions as follows： hydrolyzed at 37-42 ℃ for 4 h, dried at 70-80 ℃ for 1 h, and calcined at 550-650℃ for 3 h. The rate of degradation of 40 mg/ L azo dye and 20 mg/ L acid red dye can reuch 96% and 81.45%, respectively.     

The Microstructure and Chemical Bonds of β-C2S Under the High Energy Ball Grinding Function

Using the laser granularity survey technology , logy, X-ray powder diffraction, scanning electron microscopy （SEM） and infrared spectrum anal）sis methods, we studied the microscopic structure and chemical bonds changes of β-C2 S monomineral under the high energy ball grinding function. The result indicates that, continuously under the mechanical power, β-C2 S crystal size would decrease, the micro strain and the effective Beff parameter would increase, and the amorphous phases would be presented. Furthermore, the mechanical power would cause Si-O bond broken and reorganized, the specific surface area would increase, the energy of micro-powder agglomeration vibration would be enhanced and the crystal would be disordered. Finally, β- C2 S was caused to have the mechanochemical change and the activity enhancement.     

Reaction Activity of Kaolinite Surfaces：Quantum Chemistry Calculations

The anion-kaolinite surface infractions and AuS - adsorption onto the surfaces of kaolinite were studied using the self-consistent-field discrete variation ( SCF - Xα - DV) method. Electronic structure and energies of the system of anion AuS- adsorbed on an atomic cluster of kaolinite were calculated. The results show that the systems with lower total energy are those AuS- adsorbed on the edge surfaces, which indicates that the systems of adsorption of AuS- on the edges are more stable relative to those adsorbed on the basal plane. On the other hand, bond order data suggest that significant shifting of atomic charge and the overlapping of electronic cloud between Au ( Ⅰ ) of the AuS- and the surface ions of kaolinite would take place in the systems with AuS - being adsorbed on the edges, especially at the she near A1 octahedra. Therqrore, it can be concluded that edge sites will dominate the complexation reactions of the surfaces of kaolinite, with negligible contributions from other fimctional groups on the basal plane, which are dominated by either siloxane sites in silica layers or aluminol sites in gibbsite layers.     

Hydration mechanisms of smithsonite from DFT-D calculations and MD simulations

Investigation on the mineral?water interactions is crucial for understanding the subsequent interfacial reactions. Currently, the hydration mechanisms of smithsonite are still obscure. In this paper, the adsorption of H₂O at different coverage rates on smithsonite (1 0 1) surface was innovatively investigated using density-functional theory (DFT) calculations and molecular dynamics (MD) simulations by analyzing adsorption model, interaction energy, atomic distance, density of state, electron density difference, concentration profile, radial distribution function and self-diffusion coefficient. We found that single H₂O preferred to be dissociated on smithsonite (1 0 1) surface via the interaction of surface Zn with the Ow of H₂O and H-bond between Hw of H₂O and surface Os. However, dissociation adsorption and molecular adsorption coexisted on the smithsonite surface at a high coverage rate of H₂O, and dissociation adsorption remained the main adsorption mechanism. Moreover, we found the interaction between smithsonite surface and H₂O was weakened as a function of H₂O coverage, which was because the presence of interlayer H₂O and different layers of H₂O decreased the reactivity of the smithsonite surface. The H₂O is mainly adsorbed on the smithsonite surface by forming three layers of H₂O (about 10–15 Å), with the ordering degree gradually decreasing.     

Surface organic modification of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

The surface organic modification of Fe3O4 nanoparticles with silane coupling reagent KH570 was studied. The modified and unmodified nanoparticles were characterized by FT-IR, XPS and TEM. The spectra of FT-IR and XPS revealed that KH570 was coated onto the surface of Fe3O4 nanoparticles to get Fe-O- Si bond and an organic coating layer also was formed. Fe3O4 nanoparticles were spheres partly with mean size of 18,8 nm studied by TEM, which was consistent with the result 17.9 nm calculated by Scherrer＇s equation. KH570 was adsorbed on surface and formed chemistry bond to be steric hindrance repulsion which prevented nanoparticles from reuniting. Then glycol-based Fe3O4 magnetic liquids dispersed stably was gained.     

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine system with high plating rate

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) chelating agent was researched comprehensively. The results indicate that plating rate decreases with the increase of concentration for THPED, CuSO₄ · 5H₂O and HCHO, pH value and bath temperature. The additive of K₄[Fe(CN)₆] · 3H₂O, 2, 2′-dipyridyl and polyethylene glycol(PEG) decrease plating rate and K₄[Fe(CN)₆] · 3H₂O has a bad effect on deposits quality, but 2, 2′-dipyridyl and PEG make deposits quality improve greatly. Low concentration of 2-mercaptobenzothiozole (2-MBT) increases plating rate and improves deposits quality, but decreases plating rate and worsens deposits quality when 2-MBT reaches 5 mg/L. The optimal conditions of this electroless copper plating process are that the concentration of THPED, HCHO, CuSO₄ · 5H₂O, PEG, 2, 2′-dipyridyl and 2-MBT are 16.8 g/L, 16.0 mL/L, 13.3 g/L, 0.5 g/L, 5.0 mg/L and 2.0 mg/L, respectively, pH value is 12.75, bath temperature is 30 °C. Plating rate reaches 9.54 μm/h plating for 30 min in the bath. The SEM images demonstrate that the surface of copper film is smooth and the crystal is fine. Foundation item: Project supported by Hubei Daye Nonferrous Metal Corporation of China