Crystallography and equilibrium solubility for ammonium and potassium orthophosphites and hypophosphites

The composition and solubility properties of eight ammonium and potassium orthophosphites and hypophosphites were determined to evaluate the potential of these classes of materials for increasing the plant nutrient content of liquid fertilizers. Phase relationships for the systems (NH₄)₂O-P₂O₃-H₂O, K₂O-P₂O₃-H₂O, (NH₄)₂O-P₂O-H₂O, and K₂O-P₂O-H₂O were determined along with the crystallographic properties (X-ray and optical) of the solid phases. Toxicity and phosphite response was tested in greenhouse experiments for the compounds.     

Ni(Ⅳ)引发丙烯酸甲酯与三元尼龙接枝共聚反应的研究

以二过碘酸合镍(Ⅳ)钾〔Ni(Ⅳ)〕为氧化剂,共聚尼龙上的弱的还原基团(酰胺基)为还原剂,组成氧化还原引发体系,于碱性介质中直接在共聚尼龙分子骨架上产生接枝点,引发丙烯酸甲酯(MA)的接枝共聚合反应,获得了较高的接枝效率(可达90%以上)。探讨了引发剂浓度、单体浓度、反应温度对接枝参数的影响,结果表明:当c〔Ni(Ⅳ)〕=8×10-4mol/L,c(MA)=1 5mol/L,θ=35℃时,接枝效率和接枝百分比可达到最高值。用红外光谱、X射线衍射、扫描电镜对接枝共聚物进行了表征,提出了建立在镍(Ⅳ)还原为镍(Ⅱ)的过程为两步单电子转移的基础之上的引发机理。将所得接枝共聚物用作尼龙/聚甲基丙烯酸甲酯体系的增容剂,通过扫描电镜分析表明:该共混体系的相容性得到一定程度的改善。     

杂卤石溶解动力学

杂卤石中含丰富的钾资源,由于其化学上的难溶性和埋藏较深,尚未合理开发利用.已有研究表明,杂卤石矿层具备溶浸开采的地质基本条件.矿石中钾的溶解是杂卤石资源合理利用的技术关键.利用CaCl2水溶液为溶剂,通过测定溶浸液中钾、钙离子的浓度,考察了溶浸剂浓度、矿石粒度、温度对杂卤石表观溶解动力学过程的影响.实验条件下,矿石中钾的溶解率随粒度的降低明显升高.矿石粒度在0.149～1 mm之间,钾的溶解率可达80%以上.该溶解反应为一级反应（对CaCl₂而言）.计算实验条件下溶浸过程表观动力学速率常数,得溶解反应表观活化能为8.34 kJ•mol^-1,实验结果初步表明杂卤石溶解过程受内扩散控制,溶解动力学方程符合未反应核收缩模型,实验结论对地浸法提取钾具有理论参考意义.     

氟铝酸钾共晶铝钎剂的研究

本文研究了在不同结晶条件下制备得到的一系列KF-AlF3共晶产物。使用差热分析法(DTA)测定了这一系列产物的熔点,使用X-射线衍射仪(XRD)确定了各生成物的组成。试验表明,在反应过程中,将结晶温度控制在特定条件下有利于得到主结构为K2A1F5·H2O的氟铝酸钾共晶材料。该材料为铝及铝合金钎焊过程应用的理想状态铝钎剂。     

催化剂对沥青氧化聚合的影响

在300℃、空气条件下用硝酸钾、对甲苯磺酸两种催化剂对沥青进行氧化处理,通过软化点、甲苯不溶物含量、元素分析、红外光谱分析以及热重分析检测发现催化剂对软化点、组成、分子结构有显著影响。沥青经催化氧化后甲苯不溶物含量增加,高分子组分比例增加,低分子组比例减少,软化点升高,升高幅度达40%～100%,H/C原子比减少,苯环上的氢及侧链减少,芳环缩合程度增加。热失重表明催化剂的存在加快了沥青的氧化分解,分子侧链的断裂,从而加快氧化聚合速度。     

含盐乙醇-水-异辛醇体系液液平衡

用自制的液液平衡釜测定了乙醇-水-异辛醇体系和乙醇-水-异辛醇-氟化钾/氯化钠体系的液液平衡数据。比较了上述3种体系的乙醇在有机相和水相中的分配系数,其中含盐体系高于无盐体系,含氟化钾体系高于氯化钠体系。对所测液液平衡数据用hand方程进行关联,结果良好。     

Effect of Potassium Doping on the Catalytic Behavior of Mo–V–Sb Mixed Oxide Catalysts in the Oxidation of Propane to Acrylic Acid

Small addition of potassium to a Mo–V–Sb mixed oxide catalyst (previously prepared by hydrothermal synthesis) strongly modifies its catalytic behavior. Thus, while acetic acid is mainly observed in the K-free catalysts, acrylic acid is selectively obtained in K-doped catalysts. In this case, a selectivity to acrylic acid of about 30% is achieved at propane conversions of 30%. This catalytic behavior is apparently not due to modification of the crystalline phases in the K-doped catalysts but to the elimination of the acid sites of the undoped Mo–V–Sb mixed oxide catalyst.     

Molecular Dynamics Simulation of Rutile TiO_2 and Potassium Hexatitanate (K_3Ti_6O_(13)) Crystal

This paper presents the results of molecular dynamics (MD) simulation on the rutile titanium dioxide and potassium hexatitanate (K2O.6TiO2 or K2Ti6O13) crystal. The interaction of atoms is described by two-body central force interatomic potential, which includes Coulombic term, Gilbert-type repulsion term, van der Waals term and Morse-type potential. The optimized crystal structure of rutile TiO2 is in very good agreement with the experimental data in the literature. The present MD simulation also gives several physical properties, including volume thermal expansivity and elastic bulk modulus.     

K-doped CuO/ZnO with dual active centers of synergism for highly efficient dimethyl carbonate synthesis

The application of heterogeneous catalysts in dimethyl carbonate (DMC) synthesis from methanol is hindered by low activation efficiency of methanol to methoxy intermediates (CH₃O*), which is the key intermediate for DMC generation. Herein, a catalyst of alkali metal K anchored on the CuO/ZnO oxide is rationally designed for offering Lewis acid–base pairs as dual active centers to improve the activation efficiency of methanol. Characterizations of CO₂-TPD, NH₃-TPD, XPS, and DRIFTS revealed that the addition of Lewis base K observably boosted the dissociation of methanol and combined with Lewis acid CuO/ZnO oxide to adsorb the formed CH₃O* stably, thus synergistically promoted the transesterification. Finally, the CuO/ZnO-9%K₂O catalyst exhibited the optimal catalytic activity, achieving a high yield of 74.4% with an excellent selectivity of 98.9% for DMC at a low temperature of 90°C. The strategy of constructing Lewis acid–base pairs provides a reference for the design of heterogeneous catalysts.     

以Na2SO4介质制备镁橄榄石轻质材料的性能研究

以天然镁橄榄石和Na2SO4为原料,采用树脂作为结合剂,将原料压制成型,分别经900、1 000、1 100℃保温10 h烧后,再经过蒸馏水洗盐处理,经110℃24 h烘干后制备了镁橄榄石轻质材料。检测了试样的体积密度、显气孔率及常温耐压强度,并利用XRD、SEM及EDS分析了原料的相组成和试样的显微结构。结果表明:随着烧成温度的升高,镁橄榄石烧结程度良好,在材料中形成骨架结构;当镁橄榄石与熔盐Na2SO4的理论质量比为1 1时,熔盐与镁橄榄石反应生成的MgO具有较完整的晶体形貌,晶粒尺寸大的约5μm,小的约1μm;当镁橄榄石与熔盐Na2SO4的理论质量比为1 1.3,在1 100℃烧后,经蒸馏水洗盐处理后的试样综合性能最佳,其显气孔率为56%,体积密度为1.3 g·cm-3,耐压强度为18 MPa。