CaSO4—H3PO4—H2SO4—H2O四元系统及其应用（上）

ＣａＳＯ４－Ｈ３ＰＯ４－Ｈ２ＳＯ４－Ｈ２Ｏ四元系统是湿法磷酸领域中的主要相图，直到１９５８年才由日本学者池野亮当等人＊首先发表，而且只是其中关于ＣａＳＯ４·１２Ｈ２ＯＣａＳＯ４·２Ｈ２Ｏ转化过程部分的研究结果。７０年代中，笔者在研究半水—二水再结晶流程时发现：在温度恒定的条件下，四元系统中的ＣａＳＯ４·１２Ｈ２ＯＣａＳＯ４·２Ｈ２Ｏ转化过程的平衡点轨迹呈线性，可以用直线方程式计算有关参数，扩大了它的意义。随后，笔者在进行半水—二水再结晶流程的中试时，曾用上述计算参数控制ＣａＳＯ４·１２Ｈ２Ｏ—→ＣａＳＯ４·２Ｈ２Ｏ转化过程中二水物结晶的形成，取得满意结果。     

Effective and simple recovery of 1,3-propanediol from a fermented medium by liquid–liquid extraction system with ethanol and K_3PO_4

1,3-Propanediol,traditionally obtained from fossils,has numerous industrial applications,including use in the production of high performance polymers.The microbial production of 1,3-propanediol presents several opportunities,and the final purity grade determines its price and commercial viability.The development of novel separation technology could improve the economic viability of the bioproduction of 1,3-propanediol.Thus,we investigated salting-out extraction as a novel process for 1,3-propanediol recovery from fermentation broth.Initially,a screening for the best salt/solvent combination was conducted and then optimized using the response surface methodology.The solvents studied were methanol,ethanol,isopropanol and acetone,and the salts examined were K_2HPO_4,Na_2CO_3,K_2CO_3,(NH_4)_2SO_4,NaHPO_4,K_3PO_4 and C_6H_5NaO_7.The optimal extraction system consisted of 34 wt%K_3PO_4,28 wt% ethanol,and 38 wt% fermentation broth containing 23.0 g·L~(-1)1,3-propanediol,which gave the highest partition coefficient of 33 and recovery yield of 97%.The results demonstrated that salting-out extraction was a promising method for 1,3-propanediol recovery from fermentation broth.     

Synthesis of magnetic core-shell structure Fe3O4@MCM-41 nanoparticle by vesicles in aqueous solutions☆

In this study, magnetic core–shel structure Fe3O4@MCM-41 nanoparticles were synthesized with vesicles as soft templates. In the preparation, FeCl2 and tetraethy orthosilicate (TEOS) were selected as Fe processor and Si pre-cursor, respectively. Stable vesicles first formed in 0.03 mol·L?1 1:2 mixture of anionic surfactant sodium dode-cyl sulfate and cationic surfactant cetyltrimethyl ammonium bromide. Then, TEOS was added in the vesicle aqueous solution, leading to a highly dispersed solution. After high-temperature calcination, Fe3O4@MCM-41 nanoparticles were obtained. Their structure and morphology were characterized by Saturn Digisizer, transmis-sion electron microscope and vibrating sample magneto-meter. The results indicate that the vesicles are spherical and their size could be tuned between 20 and 50 nm. The average grain diameter of synthesize magnetic core–shel Fe3O4@MCM-41 particles is 100–150 nm and most of them are in el iptical shape. The dispersion of magnet-ic particles is very good and magnetization values are up to 33.44 emu·g?1, which are superior to that of other Fe3O4 materials reported.     

The separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ),and cadmium(Ⅱ) in a sulfate-based solution using a mixture of Versatic 10 acid and Mextral 984H

We studied the separation and recovery of copper(Ⅱ), nickel(Ⅱ), cobalt(Ⅱ), zinc(Ⅱ), and cadmium(Ⅱ) from magnesium and calcium, using synergistic solvent extraction(SSX) in a typical hydrometallurgical waste solution. A mixture of Versatic 10 acid and Mextral 984 H, diluted with Mextral DT100, was used to obtain fundamental data on p H and distribution isotherms, as well as the kinetics of extraction and stripping. We also investigated the main effects and interactions of common solvent extraction factors: the extraction p H at equilibrium, the temperature, and the extractant concentration. The synergistic effect for extracting metals was confirmed. The results showed that the addition of Mextral 984 H enhanced the separation factors of copper, nickel, cobalt,zinc, and cadmium over magnesium and calcium. Compared with Versatic 10 acid alone, for a mixture of0.5 mol·L~(-1) Versatic 10 acid/0.5 mol·L~(-1)Mextral 984 H, Δp H50 values of copper, nickel, cobalt, zinc, and cadmium were found to be N 2.0, 3.30, 2.85, 0.95, and 1.32 p H units, respectively. The Δp H_(50)(Zn–Mg)and Δp H_(50)(Zn–Ca)values were 3.27 and 2.25, respectively, indicating easy separation and recovery of copper, nickel, zinc, cobalt,and cadmium. The extraction and stripping of copper, cobalt, zinc, and cadmium were fast, with 90% of the metal transferred in 2 min. We next studied whether the metals could be stripped from the extracted liquid selectively in sequence, by using sulfuric acid at different concentrations. The influence of the molecular structure of the oxime and carboxylic acid components upon the synergistic effects was identified by numerical analysis.Excellent separation of copper, nickel, cobalt, and zinc over magnesium and calcium was achieved with this synergistic solvent extraction system.     

Synthesis of high purity Li_2CO_3 and MgCO_3·3H_2O in a homogeneous-like organic phase

Herein, three kinds of Li_2CO_3 and two kinds of MgCO_3·3H_2O crystals are easily synthesized in a homogeneouslike organic phase. The morphology and size of synthesized crystals are controllable and adjustable in the single organic phase, with the morphology of Li_2CO_3 ranging from micro-flaky, flower to nanobranch, MgCO_3·3H_2O ranging from nanosphere to nanorod. Compared with coupled reaction and solvent extraction process, of which the crystallization process occurred in the interface of two phase, our proposed method made it possible that the crystallization process occurred in the single organic phase, which resulted in better crystal morphology.Moreover, the formation mechanism of different crystal morphologies is discussed, the results showed that the crystals in micron size and nano size are involved in two crystallization mechanism, the micron particles in the form of flake and flower-like is a typical radial growth, which means that the growth occurs by diffusion around a nucleus as starting point, while the reaction model for small particles should be similar to a water-in-oil structure. As the reaction carried out, the crystal should be restricted in a constrained organic structure.     

Static magnetic field-assisted synthesis of Fe_3O_4 nanoparticles and their adsorption of Mn(Ⅱ) in aqueous solution

A facile method for synthesis of the magnetic Fe_3O_4 nanoparticles was introduced.Magnetic nanoparticles were prepared via co-precipitation method with(PMF) and without(AMF) 0.15 T static magnetic field.The effects of magnetic field on the properties of magnetic nanoparticles were studied by XRD,TEM,SEM,VSM and BET.The results showed that the magnetic field in the co-precipitation reaction process did not result in the phase change of the Fe_3O_4 nanoparticles but improved the crystallinity.The morphology of Fe_3O_4 nanoparticles was varied from random spherical particles to rod-like cluster structure.The VSM results indicated that the saturation magnetization value of the Fe_3O_4 nanoparticles was significantly improved by the magnetic field.The BET of Fe_3O_4nanoparticles prepared with the magnetic field was larger than the control by 23.5%.The batch adsorption experiments of Mn(Ⅱ) on the PMF and AMF Fe_3O_4 nanoparticles showed that the Mn(II) equilibrium capacity was increased with the pH value increased.At pH 8,the Mn(Ⅱ) adsorption capacity for the PMF and AMF Fe_3O_4 was reached at 36.81 and 28.36 mg·g~(-1),respectively.The pseudo-second-order model fitted better the kinetic models and the Freundlich model fitted isotherm model well for both PMF and AMF Fe_3O_4.The results suggested that magnetic nanoparticles prepared by the magnetic field presented a fairly good potential as an adsorbent for an efficient removal of Mn(Ⅱ) from aqueous solution.     

Synthesis of a novel organic–inorganic hybrid flame retardant based on Ca(H2PO4)2 and hexachlorocyclotriphosphazene and its performance in polyvinyl alcohol

To optimize the poor thermal stability and flammable of polyvinyl alcohol (PVA), a novel environmental-friendly organic–inorganic hybrid flame retardant Ca(H₂PO₄)₂@HCCP was successfully designed and synthesized via surface treatment technology and used to advance the flame retardancy of PVA. The thermogravimetric analysis implied that Ca(H₂PO₄)₂@HCCP can enhance significantly the thermal stability and char forming ability of PVA. Combustion results demonstrate that Ca(H₂PO₄)₂@HCCP could effectively suppress the melt dripping of PVA in the process of combustion. The presence of Ca(H₂PO₄)₂@HCCP can sharply reduce peak heat release rate and the total heat release up to 75% and 22.9%, respectively, in the microscale combustion calorimeter measurement. The results manifested that Ca(H₂PO₄)₂@HCCP could endow PVA with superior flame retardancy. Moreover, char residues analysis explained the flame retardant mechanism in condensed and gas phase, which is mainly attributed to the strong catalytic char formation, free radical trapping, and gas barrier effect. Therefore, the green flame retardant has great applications prospect in fire safety.     

Fabrication of Poly（y-glutamic acid）-coated Fe3O4 Magnetic Nanoparticles and Their Application in Heavy Metal Removal

In this study, poly（y-glutamic acid）-coated Fe3O4 magnetic nanoparticles （y-PGA/Fe304 MNPs） were successfully fabricated using the co-precipitation method. Fe3O4 MNPs were also prepared for comparison. The av erage size and specific surface area results reveal that 7-PGA/Fe304 MNPs （52.4 nm, 88.41 m2.g-1） have smaller particle size and larger specific surface area_ than Fe3O4 MNPs （62.0 nm, 76.83 mLg-1）. The y-PGA/Fe3O4 MNPs