Acidity Modification of ZSM-5 for Methane Conversion in Co-feeding Method with MTA Reaction

Acidity plays a vital role in methane conversion by co-feeding method, which is one of the best strategies to improve the utilization and gentle the reaction conditions of methane. In this work, Zn, Ni, Mo, La, Ga, Fe and Co-impregnated ZSM-5 zeolites have been prepared with the same substitutions to variate the acidities and tested in co-aromatization of methanol with methane. It is demonstrated that the new medium-strong acid sites formed by metal and strong acid sites are the key role to activate methane in co-reaction. Zn-modified ZSM-5 catalyst is preferred to exhibit the best methane conversion of 12%, whose aromatic selectivity increases from 27.2% to 52.2% compared with that of HZSM-5. Besides, the addition of methane further improves the production of high-valued aromatics compared with methanol to aromatics (MTA) reaction.     

Mixing time of an unaligned Gibbs sampler on the square

The paper concerns a particular example of the Gibbs sampler and its mixing efficiency. Coordinates of a point are rerandomized in the unit square ${[0,1]}^2$ to approach a stationary distribution with density proportional to $exp(?A^2{(u?v)}^2)$ for $(u,v)\in {[0,1]}^2$ with some large parameter $A$.Diaconis conjectured the mixing time of this process to be $O\left(A^2\right)$ which we confirm in this paper. This improves on the currently known $O(exp\left(A^2\right))$ estimate.     

含氧化铝Zn/HZSM-5催化剂芳构化反应性能的研究

考察了在含氧化铝载体条件下,不同Zn负载量改性后HZSM-5催化剂的MTA反应性能。采用BET、XRD、PyFTIR、NH3-TPD和H2-TPR等分析手段对催化剂进行表征。实验结果表明,氧化铝载体的加入使得HZSM-5催化剂产生了介孔并且增强了Zn物种在催化剂表面的稳定性;Zn物种的加入破坏了HZSM-5分子筛的骨架结构、改变了催化剂表面酸性;此外,Zn物种的加入可以促进MTA过程脱氢反应的进行,中间产物烯烃的后续芳构化过程受到抑制;在实验的考察范围内,当Zn负载量为0.5%(质量分数)时,芳烃(C6~11)收率存在最大值21.0%(质量分数);甲醇的芳构化能力会受到生焦的抑制,然而,再生后的催化剂呈现更高的芳烃收率。     

液晶模板合成多级孔ZSM-5分子筛及其催化应用

以哌嗪基丙基甲基二甲氧基硅烷偶联剂(PZPMS)和阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为复合液晶模板,在水热条件下合成多级孔ZSM-5分子筛.采用XRD、 SEM、 BET、 XRF、 FT-IR和NH_3-TPD对催化剂的性能进行了表征.结果表明, PZPMS/CTAB复合液晶模板的加入可以减小颗粒尺寸,增加外表面积,有利于合成多级孔ZSM-5分子筛.加入液晶模板可以有效调整催化剂表面B酸与L酸量比例,改善催化剂表面酸性.对合成的催化剂样品在MTA反应中进行了催化性能测试,样品在反应中对芳烃表现出较高的选择性,催化寿命有不同程度的提高.     

Ion chromatographic separations of phosphorus species: a review

The aim of this paper is to review recent literature regarding the determination of phosphorus species by ion chromatography (IC), and describe the implementation of new developments in sample treatment and ion chromatography methodology for the analysis of these compounds. Ion-exchange methods using both carbonate/hydrogencarbonate and hydroxide selective columns in combination with self-regenerating membrane and solid-phase-based suppressors enable determination of phosphate down to ppb levels. New technology, particularly on-line electrolytic hydroxide generators and electrolytic self-regenerating suppressor devices, has allowed the use of elution gradients in both carbonate/hydrogencarbonate and hydroxide selective systems, improving sensitivity and reducing total analysis time for samples containing phosphate together with other inorganic anions. In addition to a review of these developments, optimization and application of chromatographic methods using reversed stationary phases and cationic and/or zwitterionic surfactants is also discussed.The objective of most of the IC methods developed for phosphorus species is the determination of phosphate and total phosphorus. Therefore, sample treatment and separation conditions specifically developed for this purpose are also described. In addition, application of IC to the analysis of other inorganic (reduced and condensed) and organic (phytates, alkyl phosphate, and phosphonates) phosphorus species is discussed along with methodology and relevant applications in water analysis and other miscellaneous fields.     

Soil compaction management: Reduce soil compaction using a chain-track tractor

Modern agricultural production requires research for new design and layout plans of the track-chained mover, providing a reduction in soil compaction. One of many ways to improve the efficiency of machine-tractor aggregate (MTA) use is to improve the geometry of the support part of the chain-track tractor. Flat geometry of the support part of a chain-track tractor with a semi-rigid suspension creates maximum pressure on soil with the first and last track rollers, which causes increased soil compaction. Research objective is to ensure the uniform pressure on soil from the tractor with a semi-rigid suspension by justifying the geometry of the supporting part of the track-chained mover.Based on experimental and theoretical studies a model of pressure distribution along the length of the support part was developed. Thus, the geometry of the support part of a track-chained tractor with a semi-rigid suspension was substantiated. Pressure decrease on soil and compaction reduction are achieved by changing the geometry of the support part and rational location of the tractor mass center. To achieve the elliptical geometry of the support part of a track-chained tractor with a semi-rigid suspension lower track rollers were placed at different heights.To test the formulas and to study the influence of the support part geometry, of the hitch height and the force on the hook of a track-chained tractor on soil compaction, experiments were conducted. As a model for experiment, the tractor actively used in agriculture was modernized; chain-track tractor T-170M1.03-55 with flat and elliptical caterpillar bypasses. The pressure was measured directly by pressure sensors that were placed into the ground. Soil density in the track left by a track-chained tractor mainly depends on mover pressure and the number of impacts per pass. Track-chained mover makes two impacts on soil with the flat support part. If the support part geometry is changed, the number of impacts on soil is reduced to one. To create typical working conditions for T-170M1.03-55 track-chained tractor the third and fourth support rollers should be lowered by 9.5 ± 1.5 mm, the second and fifth-by 4.5 ± 0.5 mm relatively, which leads to a decrease in the maximum pressure on soil and reduces its compaction in the track left by the mover by 15–25%.     

Electrospun poly(l‐lactide) nanofibers coated with mineral trioxide aggregate enhance odontogenic differentiation of dental pulp stem cells

A combination of bioceramics and nanofibrous scaffolds holds promising potential for inducing of mineralization in connective tissues. The aim of the present study was to investigate the attachment, proliferation and odontogenic differentiation of dental pulp stem cells (DPSC) on poly(l ‐lactide) (PLLA) nanofibers coated with mineral trioxide aggregate (MTA). Polymeric scaffolds were fabricated via the electrospinning method and their surface was coated with MTA. DPSC were isolated from dental pulp and their biological behavior was evaluated on scaffolds and the control group using MTT assay. Alkaline phosphatase (ALP) activity, biomineralization and the expression of odontogenic genes were analyzed during odontogenic differentiation. Isolated DPSC showed spindle‐shaped morphology with multi‐lineage differentiation potential and were positive for CD73, CD90 and CD105. MTA‐coated PLLA (PLLA/MTA) exhibited nanofibrous structure with average fiber diameter of 756 ± 157 nm and interconnected pores and also suitable mechanical properties. Similar to MTA, these scaffolds were shown to be biocompatible and to support the attachment and proliferation of DPSC. ALP activity transiently peaked on day 14 and was significantly higher in PLLA/MTA scaffolds than in the control groups. In addition, increasing biomineralization was observed in all groups with a higher amount in PLLA/MTA. Odontogenic‐related genes, DSPP and collagen type I showed a higher expression in PLLA/MTA on days 21 and 14, respectively. Taken together, MTA/PLLA electrospun nanofibers enhanced the odontogenic differentiation of DPSC and showed the desired characteristics of a pulp capping material.     

Optimization of ultrasound assisted-emulsification-dispersive liquid-liquid microextraction by experimental design methodologies for the determination of sulfur compounds in wines by gas chromatography-mass spectrometry

A new method was developed for analyzing sulfur compounds in the aroma of white wines using ultrasound assisted-emulsification-dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry detection. In the present work, the analytical method for simultaneous determination of seven sulfur compounds (methylmercaptoacetate, methyl(methylthio)acetate, 2-methylthioethanol, 3-methylthiopropanol, 3-methylthiohexanol, 4-methylthio-4-methyl-2-pentanone and hexanethiol) is reported. Parameters that affect the efficiency of the methodology such as extracting and dispersing solvents, sample volume, ion strength, cavitation time and centrifugation time were investigated using a fractionated factorial 2^6-1 (R = V) screening design. Then, the factors presenting significant positive effects on the analytical response (extracting volume, ion strength, cavitation time and centrifugation time) were considered in a further central composite design to optimize the operational conditions for the ultrasound assisted-emulsification-dispersive liquid-liquid microextraction procedure. Additionally, multiple response simultaneous optimization by using the desirability function was used to find the optimum experimental conditions. The best results were obtained using pH sample 4.25, extractant volume 150 μL, ionic strength 8.75% NaCl, cavitation time 20 s and centrifugation time 50 s. The use of the optimized ultrasound assisted-emulsification-dispersive liquid-liquid microextraction technique allowed to obtain the best extraction results with the minimum interference from other substances from the matrix, and it allowed to quantify the analytes in white wine samples by calibration graphs. Recoveries ranging from 91.99% to 125.87% for all sulfur compounds proved the accuracy of the proposed method in white wine samples. Method detection limits were in the range of 0.36-1.67 ng mL⁻¹ and limits of quantitation were between 0.63 and 3.02 ng mL⁻¹ for sulfur compounds in white wine samples. The proposed methodology was successfully applied for the determination concentrations of sulfur compounds in different commercial Chardonnay wine samples from Mendoza, Argentine.     

Sensing colorimetric approaches based on gold and silver nanoparticles aggregation: Chemical creativity behind the assay. A review

Localized surface plasmon resonance (LSPR) is one of the most remarkable features of gold nanoparticles (Au NPs) and silver nanoparticles (Ag NPs). Due to these inherent optical properties, colloidal solutions of Au and Ag NPs have high extinction coefficients and different colour in the visible region of the spectrum when they are well-spaced in comparison with when they are aggregated. Therefore, a well-designed chemical interaction between the analyte and NPs surroundings leads to a change of colour (red to blue for Au NPs and yellow to brown for Ag NPs from well-spaced to aggregated ones, respectively) allowing the visual detection of the target analyte.