Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。     

Development of silica based organic slurries for stereolithographic printing process

In this study, silica based slurries for stereolithographic printing of glass structures are developed and characterized. Stereolithography has the potential to print complex structures with high resolution. Therefore, acrylate based photocurable slurries have been developed and their viscosities are examined as a function of the solid loading. A critical shear rate can be derived, which must not be exceeded during the printing process. Therefore, rheological characterizations provide important insights into the printing process and the ability to produce samples with precise structures. Other properties such as polymerization time and curability kinetic were investigated with time dependent attenuated total reflection infrared spectroscopy (ATR-IR). Afterwards, the slurries were printed on a commercial printer operating with visible light. For debinding the printed green bodies, the decomposition temperatures were derived from thermogravimetric analysis in order to obtain stable and transparent samples.     

铜浮选专家控制系统设计与应用

针对国内某选矿厂铜浮选工艺泡沫速率不稳定,精矿品位波动大,回收率不理想等特点,设计了一套浮选专家控制系统,该系统结合泡沫影像分析技术,在线品位分析技术,PID控制与模糊逻辑控制技术。系统架构简明合理,逻辑层次清晰有效,投入运行一段时间后,在不同原矿品位前提下,都能实现稳定泡沫速率,减少精矿品位波动,提高回收率等指标优化,同时药剂添加量也有明显减少。这表明该系统运行效果良好,值得应用推广。     

The dielectric,thermal properties and crystallization mechanism of Li–Al – B–Si – O glass – Ceramic systems as a new ULTCC material

Li–Al–B–Si–O (LABS) glass-ceramics with a sintering temperature of 600 °C were studied for ultra-low temperature co-fired ceramics (ULTCC) applications. The crystal phase of LABS glass-ceramics is dendritic β-spodumene. The permittivity and dielectric loss of LABS glass-ceramics are ε_r = 5.8 and tgδ = 1.3 × 10⁻³ at 10 MHz, respectively. The coefficient of thermal expansion (CTE) of LABS glass-ceramics is 3.23 ppm/°C, which is close to that of silicon. The dielectric and thermal properties of LABS glass-ceramics are closely correlated to the degree of its crystallization. The permittivity decreases continually while the dielectric loss decreases first and slightly increases with the increasing of crystallization of β-spodumene. The CTE of LABS glass-ceramics decreases as β-spodumene crystallized from LABS glass. The crystallization kinetic and mechanism of LABS glass-ceramics indicate that the β-spodumene crystallizes in a two-dimensional interfacial growth mechanism due to the migration of Li-ions. The diffusion coefficients derived from energy-dispersive X-ray spectroscopy (EDS) results indicated that both Al and Ag electrodes have good compatibilities with ULTCC tapes, which could reduce the cost of multilayer electro-ceramic devices dramatically by using the ULTCC and base metallization.     

浮选机运输区的结构特征的测试研究

浮选机内各动力学分区的流动特征复杂。本文选取单槽容积0.2m3KYF型充气机械搅拌式浮选机为研究对象,采用PIV测试技术开展运输区的结构特征和动力学特征的研究。研究表明运输区在半个槽体的取截面内的轮廓形状整体呈现为左边为直线,右边折弯线,上下近似直线的近梯形结构,具有高度和宽度两个主要结构特征。运输区轮廓边界处的动力学特征存在明显差异。本研究加深了对浮选机运输区特征的理解,有助于通过调控运输区特征方法解决大型机械搅拌式浮选机粗粒矿物回收率低的难题。     

NH2-MCM-41的改性及其pH响应性释药的研究

采用正硅酸乙酯（TEOS）和3-氨丙基三乙氧基硅烷（APTES）通过共缩聚法合成介孔二氧化硅（MCM-41）。首先对其氨基修饰，再通过有机合成接枝—R基团（—R：—CHO、—OH、—CH₃、—COOH），制备得到Me-Ph-NH-MCM-41、OHC-Ph-NH-MCM-41、HO-Ph-NH-MCM-41、HOOC-Ph-NH-MCM-41四种不同的药物载体。利用FT-IR、Zeta电位、XRD和SEM对其结构和形貌表征，结果表明NH₂-MCM-41改性成功。以罗丹明B（RhB）为模型进行载药性能测试，并考察了此释药系统在模拟不同pH的体液下的敏感释药行为，同时探究了不同—R基团对释药的影响。结果显示，四种载体在中性条件下几乎不发生药物释放，通过改变环境体系pH可以有效控制药物释放，其释药行为可以用Korsmeyer-Peppas动力学模型来描述。实验表明，释药量：RhB@HOOC-Ph-NH-MCM-41>RhB@OHC-Ph-NH-MCM-41>RhB@HO-Ph-NH-MCM-41>RhB@Me-Ph-NH-MCM-41，不同—R基团的药物载体的pH响应性不同，其中RhB@HOOC-Ph-NH-MCM-41释药量在pH=1.2时可达57.87%，在用于药物智能控释材料方面具有一定的应用潜力。     

郴州某复杂硫化铅锌矿阶段磨浮试验研究

针对郴州某复杂硫化铅锌矿资源的性质特点,采用铅快速浮选后尾矿再磨再选的阶磨阶选工艺,较好地实现了铅锌的高效浮选回收。研究了磨矿方式、捕收剂和调整剂种类及用量等因素对该矿石浮选的影响,确定了最佳浮选条件,通过小型闭路浮选试验,得到了铅品位60.05%、回收率89.63%的铅精矿和锌品位47.01%、回收率88.14%的锌精矿。     

A mixed collector system for phosphate flotation

Flotation has been used in industry for more than a half century as the primary technique for upgrading phosphate. While the flotation of phosphate was inefficient when oleic acid was used alone as a collector, therefore a mixed collector of oleic acid (HOl), linoleic acid (LA) and linolenic acid (LNA) was employed to improve the recovery of phosphate flotation. The batch flotation results showed that the optimal composition of the mixed collector was 54 wt.% HOl, 36 wt.% LA and 10 wt.% LNA. Additionally, the effect of pH on the mixed collector application was studied while considering the surface tension, contact angle and micro-flotation. The results showed that the mixed collector should be used at a pH of 9.5. Above a pH of 9.5, the adsorption of fatty acids dimers on the apatite surface hindered phosphate flotation. The influence of the mixed collector assembly on apatite flotation was also investigated. It was demonstrated that due to its low critical micelle concentration, a sufficiently hydrophobic apatite surface could be generated at a collector concentration of 60 mg/L. In addition, zeta potential experiments suggested that collector adsorption was governed by chemisorption. FTIR and XPS spectra studies further indicated that the chemical reaction involved the carboxyl groups of fatty acids and Ca species at the apatite surface for each fatty acid in the mixed collector.