Mechanism analysis of ions interaction in MgCl_2/LiCl solution and effect of lithium on ammonia precipitation products

Producing magnesium hydroxide is the basic way to utilize magnesium resources of natural brines. However, the effect of lithium on properties of product is always neglected. The interaction between ions in magnesium chloride solution containing lithium was illustrated based on the experimental results, and the effect of lithium on the crystallization of magnesium was clarified. The results of X-ray diffraction（XRD）, scanning election microscope（SEM）, Fourier transform infrared spectroscopy（FTIR）, thermogravimetry analysis（TGA） and laser particle size analysis indicate that the effect of lithium is not obvious on the crystal phase and morphology of the products. But the XRD relative intensity of（001） surface of magnesium hydroxide declines, the specific surface area reduces apparently and the additive mass of lithium affects the heat loss rates of precipitations obviously. Quantum chemical calculations on the interactional systems of Mg（H2O）2＋6 and Li（H2O）＋4 were performed using B3LYP/6-311 G basis set. The results show that when the distance of Mg2＋ and Li＋ is 7-10 , the interaction energy is high and the trend of solvation is strong, which would make hydroxide ions easier to combine with hydrogen ions in ammonia precipitation process. And the absolute value of solvation free energy reduces significantly in MgCl2 solution（1 mol/L） containing lithium ion.

The effect of the amount of ammonia on the Cu^0/Cu^+ ratio of Cu/SiO_2 catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol

The effect of the amount of precipitant ammonia on the Cu0/Cu＋ratio of Cu/Si O2 prepared by the deposition–precipitation method is investigated. Species at different preparation stages, resulted from the amount of ammonia used, are identified by the XRD and FTIR techniques. Chrysocolla together with either copper nitrate hydroxide or copper hydroxide coexist in the uncalcined catalysts. Upon calcination, the latter two species are converted to Cu O particles while chrysocolla remains. Following reduction, Cu O is transformed to metallic Cu and chrysocolla is converted to Cu2 O. The value of Cu0/Cu＋ratio can be evaluated using the peak areas in their TPR profiles. Hydrogenation of dimethyl oxalate（DMO） to ethylene glycol（EG） shows that the selectivity of EG depends on the Cu0/Cu＋ratio. Catalyst prepared with the addition of ammonia solution at n（NH3）/n（Cu2＋） = 0.9 for precipitation–deposition gains a more suitable Cu0/Cu＋ratio upon reduction and thus has a higher selectivity for EG.