聚乳酸烟用过滤嘴制备工艺及若干基础问题的研究

本论文适应聚乳酸烟用过滤嘴工业化的需要，针对烟用过滤嘴特殊的工艺和技术要求，进行了相关问题的基础研究。 在自制模型小纺丝机上进行了小试研究。研究了干燥条件、树脂水分含量、树脂规格、添加助剂、纺丝温度、纺丝速度，后处理等对聚乳酸可纺性、纤维性能的影响，确定了中试纺丝条件。在聚丙烯烟用丝束国产线上进行了中试研究，研究了纺丝速度，牵倍，牵伸温度，松弛热定型温度和时间对聚乳酸纤维力学性能、热学性能、粘接性能、开松性能、过滤性能的影响，进一步明确了树脂规格和纺丝条件，研发出适合聚乳酸香烟滤材的粘接剂，并且初步得到了吸阻和硬度符合接烟要求的过滤嘴棒。在卷烟厂进行了过滤嘴的香烟接装实验，结果表明聚乳酸香烟过滤嘴可以满足高速接烟的需要。 在实验室和卷烟厂分别进行了聚乳酸滤材吸附/过滤性能研究：1）在实验室，进行了聚乳酸纤维对烟气中典型的烟气成分的静态吸附实验；2）在卷烟厂，对接装聚乳酸香过滤嘴的香烟进行了烟气分析和品吸。结果表明聚乳酸烟用丝束对极性和非极性烟气成分气体有较高的吸附/吸收能力，但对烟碱的吸附却很少。因而聚乳酸过滤嘴的香烟可能有自己独特的吸味风格。聚乳酸香烟过滤嘴具有同二醋酸纤维素过滤嘴相近的过滤能力，可以有效的过滤烟气中的有害物质，过滤效果优于聚丙烯。 针对聚乳酸在熔体纺丝过程中热稳定性差这一关键问题，深入系统地研究了添加有聚碳化二亚胺聚乳酸的流变学行为、热学性能、热降解行为、力学性能、酶降解行为和稳定机制。实验结果表明在聚乳酸中添加抗水解稳定剂能显著提高聚乳酸的加工热稳定性，表现为经过熔体加工后，分子量较少下降，熔融指数增加不多，力学性能基本维持不变。改性的原因是聚碳化二亚胺在加工的过程中与残留的或加工过程中形成的乳酸和/或水分子反应，消除或减少了聚乳酸的水解，阻止了乳酸对聚乳酸水解的催化作用；与聚乳酸的端羟基或端羧基发生了化学反应，从而减少了通过端基“反咬”形成丙交酯而降解的可能性，甚至将端基偶联，使分子量增大。 通过高压静电纺丝制备具有不同三醋酸甘油酯（GTA）含量的聚乳酸超细纤维毡，场发射扫描电镜、示差扫描量热仪、水接触角和力学性能测试表明，随着GTA含量的增加，纤维之间趋于粘连，形成立体网状结构，纤维毡的断裂伸长率、回弹率、拉伸强度可分别达到200%、85%、4.24MPa，比不改性的聚乳酸超细纤维毡有显著地提高。当GTA含量在40%以下时，纤维粘毡表现出超疏水特性，表面表观水接触角约在130°左右，当GTA含量高于50%，水能迅速浸润和渗入纤维毡，表观水接触角为0°。

A mechanism for enhanced photocatalytic activity of silver-loaded titanium dioxide

In this paper, silver-loaded TiO2 photocatalyst was prepared by photochemical impregnation method and characterized by transmission electron microscopy (TEM), diffuse reflectance spectra (DRS), photooxidation of phenol and photoreduction of Cr(VI). Electron paramagnetic resonance (EPR) was used to detect photoproduced paramagnetic radicals. The correlation of photocatalytic activity and photogenerated reactive species was discussed, and the mechanism of silver-loaded TiO2 for enhancement of photocatalytic activity was elucidated. The results show that deposited silver on TiO2 Surface acts as a site where electrons accumulate. The better separation between electrons and holes on the modified TiO2 surface allowed more efficiency for the oxidation and reduction reactions. The enhanced photocatalytic activity was mainly attributed to the increased amounts of O-2(.-) reactive species and surface Ti3+ reactive center on silver-loaded TiO2 photocatalyst. (C) 2004 Published by Elsevier B.V.

Synthesis and characterization of carbon black supported Pt-Ru alloy as a model catalyst for fuel cells

A set of bimetallic Pt-Ru catalysts prepared by co-impregnation of carbon black with ruthenium(III) chloride hydrate and hydrogen hexachloroplatinate(IV) hydrate were investigated by temperature-programmed reduction (TPR), chemisorption of hydrogen, transmission electron microscopy (TEM), microcalorimetry of adsorbed CO and a structure-sensitive reaction (n-hexane conversion). The results showed that the volumetric capacities for CO and H-2 adsorption is influenced in the bimetallic Pt-Ru catalysts by the formation of a Pt-Ru alloy. The n-hexane reaction revealed that the reaction mechanism for the pure Pt catalyst mainly occurs via cyclic isomerization and aromatization due to the presence of bigger Pt surface ensembles, whereas the Pt-Ru catalysts exhibited predominantly bond-shift isomerization by the diluting effect of Ru metal addition. The differential heats of CO chemisorption on Pt-Ru catalysts fell between the two monometallic Pt and Ru catalysts extremes. (C) 2004 Elsevier B.V. All rights reserved.

Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by Al-27 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Si-O-Al bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)(x)Al(OP)(4 - x) species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Si-O-Al bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by P-31 MAS NMR spectra. (C) 2004 Elsevier Inc. All rights reserved.

Studies on state and structure of noble metals in electrocatalyst made by coprecipitation method

The electrocatalysts of Pt/C, PtRu/C and Ru/C were prepared by the impregnation method. The facet characterization, the dispersion and the particle size for the catalysts were determined by means of X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy was also used to analyze the state and the valency of the noble metals. The results show that the particle size was in nanometer range and the binary metals have come into being an alloy. The platinum in the catalysts existed in zero valency. The valency of the ruthenium on the surface is different from that in the body, while the ruthenium on the surface existed in oxide-form. PtRu/C and Pt/C are of good activity to the electrooxidation of hydrogen except Ru/C. PtRu/C is more tolerant of CO than Pt/C, and CO is only adsorbed on Pt.

Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured beta-Mo2C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 degreesC. The particle sizes of beta-Mo2C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 degreesC. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO4 precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 degreesC. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors. (C) 2003 Elsevier Science Ltd. All rights reserved.

A Mossbauer study of In-Fe2O3/HZSM-5 catalysts for the selective catalytic reduction of NO by methane

The selective catalytic reduction of NO by CH4 was compared over In-Fe2O3/HZSM-5 catalysts prepared by impregnation and co-impregnation methods. It was found that the catalyst preparation method greatly affected the catalyst activity. The impregnated catalyst was very active, but the co-impregnated one showed poor activity. The In Fe2O3/HZSM-5 catalysts were investigated by Mossbauer spectroscopy. The results showed that indium cations entered into the iron oxide lattice in the co-impregnated catalyst, while the impregnated catalyst exhibited a more stable structure, when both of the catalysts were treated severely in the reaction atmosphere. Characterization by means of combined in situ temperature programmed reduction (TPR)- Mossbauer spectroscopy further revealed that the performances of the two catalysts were different in the TPR processes.

Effect of addition of Zn on the catalytic activity of a Co/HZSM-5 catalyst for the SCR of NOx with CH4

The selective catalytic reduction (SCR) of NOx by methane in the presence of excess oxygen was studied on a Zn-Co/HZSM-5 catalyst. It was found that the addition of Zn could improve effectively the selectivity of methane towards NOx reduction. When prepared by a coimpregnation method, the Zn-Co/HZSM-5 catalyst showed much higher catalytic activity than the two catalysts of a Zn/Co/HZSM-5 and Co/Zn/HZSM-5 prepared by the successive impregnation method. It is considered that there exists a cooperative effect among the Zn, Co and zeolite, which enhances the reduction of NO to NO2 reaction and the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

ZnO clusters encapsulated inside micropores of zeolites studied by UV Raman and laser-induced luminescence spectroscopies

Using microporous zeolites as host, sub-nanometric ZnO clusters were prepared in the micropores of the host by the incipient wetness impregnation method. A small amount of sub-nanometric ZnO clusters were introduced into the channels of HZSM-5 zeolite, whereas a large quantity of sub-nanometric ZnO clusters can be accommodated in the supercages of HY zeolite and no macrocrystalline ZnO exists on the extra surface of the HY material. The vibrations of the zeolite framework and ZnO were characterized by UV Raman spectroscopy. The optical properties of these ZnO clusters were studied by UV-visible absorption spectroscopy and laser-induced luminescence spectroscopy. It is found that there are strong host-guest interactions between the framework oxygen atoms of zeolite and ZnO clusters influencing the motions of the framework oxygen atoms. The interaction may be the reason why ZnO clusters are stabilized in the pores of zeolites. Different from bulk ZnO materials, these sub-nanometric ZnO clusters exhibit their absorption onset below 265 nm and show a purple luminescence band (centered at 410-445 nm) that possesses high quantum efficiency and quantum size effect. This purple luminescence band most likely originates from the coordinatively unsaturated Zn sites in sub-nanometric ZnO clusters. On the other hand, the differences in the pore structure between HZSM-5 and HY zeolites cause the absorption edge and the purple luminescence band of ZnO clusters in ZnO/HZSM-5 show a red shift in comparison with those of ZnO clusters in ZnO/HY.

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO2 thin films were fabricated. The Ag/TiO2 composite films were prepared by incorporating Ag in the pores of TiO2 films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N-2 adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy.

Esterification of acetic acid with N-butanol over the catalysts of surface hydrophobicity and lipophobicity

A series of silica-supported silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by impregnation method. The surface properties of the catalysts were studied by means of XRD, BET, NH3-TPD and the Drop Shape Analyzer (DSA) measurements. Both the surface hydrophobicity and the surface lipophobicity of HSiW/SiO2-Teflon catalysts are enhanced by means of the addition of Teflon.

Hydrogenation of phenol in scCO(2) over carbon nanofiber supported Rh catalyst

A catalyst of Rh nanoparticles supported on a carbon nanofiber, 5 wt.% Rh/CNF, with an average size of 2-3 nm has been prepared by a method of incipient wetness impregnation. The catalyst presented a high activity in the ring hydrogenation of phenol in a medium of supercritical CO2 (scCO(2)) at a low temperature of 323 K. The presence of compressed CO2 retards hydrogenation of cyclohexanone to cyclohexanol under the reaction conditions used, and this is beneficial for the formation of cyclohexanone, increasing the selectivity to cyclohexanone.

Synthesis, Spectroscopic Properties, and Stabilities of Ternary Europium Complex in SBA-15 and Periodic Mesoporous Organosilica: A Comparative Study

Ternary europium complex Eu(tta)(3)phen was covalently bonded with the general mesoporous. material SBA-15 and SBA-15-type of periodic mesoporous organosilica (PMO) material via impregnation of Eu(tta)(3)center dot 2H(2)O into phen-S15 and phen-PMO, respectively, through a ligand exchange reaction. The parent materials of phen-S15 and phen-PMO were synthesized by co-condensation of tetraethylorthosilicate (TEOS) or 1,2-bis(triethoxysilyl)ethane (BTESE) and the functionalized chelate ligand 5-(N,N-bis(3-triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as template, which were confirmed by SEM, XRD, FTIR, Si-29 CP-MAS NMR, and N-2 adsorption measurements.