造纸废水的混凝-水解-接触氧化处理技术

研究了以混凝、厌氧酸化、生物接触氧化一体化反应器处理含氯漂折护望洋兴叹，水力停留时间为15h时，整个系统CODCr、BOD5、AOX、毒性值去除率分别达88.1%、81%、98.4%、92%。混凝单元主要去除大分子氯代有机物；厌氧单元通过还原脱氯及酸性水解，使氯代有机物得到了基本的去除；好氧单元对CODCr有较高的去除率。红外光谱的分析结果表明：废水中既有木素又有纤维素和半纤维素，虽然漂白废水厌氧处理技术不如好氧处理，但厌氧、好氧联合处理可有效地提高处理效果。     

Adsorption of hydrocarbons by ZSM-5 zeolites with different SiO2/Al2O3 ratios: a combined FTIR and gravimetric study

In metal-free ZSM-5, the decrease in the concentration of Bronsted and Lewis acid sites parallels the increase in the SiO₂/Al₂O₃ ratio. In the presence of residual moisture, the adsorption of small alkanes does not markedly depend on the SiO₂/Al₂O₃ ratio in the range from 30 to 150. The acidity is more important for the adsorption of alkenes (propene) which oligomerize following adsorption. The addition of 5 wt.% of La does not significantly affect the strength of the surface acid sites but does decrease their concentration. It causes a transformation, in a part, of the Bronsted acid sites. These new centers could perhaps be assigned to LaO(OH) or La(OH)₂⁺ species which may be formed on the surface in La-containing ZSM-5. La could exchange only the strongest acidic sites without inducing large changes in their total concentration. La addition has a very small effect on the adsorption of small hydrocarbons. The exchange of the protons by Cu²⁺ decreases the concentration of Bronsted acid sites. At a sufficient loading of the ZSM-5 by Cu²⁺, i.e. at an atomic ratio Cu/Al > 1.0, the exchange can almost totally suppress the Bronsted acidity. Another effect of the ion exchange is the suppression of the adsorption capacity of small hydrocarbons due to lowered surface area and internal pore volume. The lowered available internal pore volume also limits the extent of the oligomerization of propene.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

集成橡胶SIBR臭氧老化过程的研究

本文跟踪考察了集成橡胶SIBR的臭氧老化过程,并对老化过程中微观结构及其样品表面臭氧龟裂的变化规律进行了研究。结果表明：在臭氧老化过程中SIBR分子链中双键含量减少,并且伴有羰基结构的产生。双键和羰基结构的变化趋势与丁苯橡胶SBR相似,老化后期均趋于平缓。未填充和填充SIBR产生臭氧龟裂的初裂时间均居于丁苯橡胶SBR和异戊橡胶IR之间,但是发生初裂之后,未填充和填充SIBR表面裂纹的增长速度均较慢。经臭氧老化后,SIBR的力学性能变化率均较低,由此说明,SIBR的耐臭氧老化性能优于SBR和IR。     

Butanol isomer separation using polyamide-imide/CD mixed matrix membranes via pervaporation

Mixed matrix membranes (MMMs) comprising polyamide-imide (PAI) and α-, β- or γ-cyclodextrin (CD) have been investigated experimentally and computationally for isomeric n-butanol/tert-butanol (n-BuOH/t-BuOH) separation via pervaporation. Consistent with molecular simulation, experimental results show that the CD inclusion ability and butanol discrimination ability are dependent on both CD cavity size and butanol molecular size. The PAI membrane incorporated with α-CD has the smallest cavity and has the highest discrimination ability for the n-BuOH/t-BuOH pair but with a low butanol flux. The mixed matrix membrane embedded with γ-CD has the lowest selectivity and the highest flux. The PAI/β-CD membrane has a comparable selectivity and flux, and exhibits preferential sorption and diffusion selectivity toward n-BuOH. A maximum separation factor of 1.53 with a corresponding flux of 4.4 g/m² h are obtained at an optimal β-CD loading of 15 wt%. Further increments in the CD content eventually lead to a decrease in separation performance because of CD agglomeration and severe phase separation. To better understand the influence of CD on the separation performance of mixed matrix membranes, SEM, FTIR and XRD have been employed for membrane characterizations. The effect of n-butanol/t-butanol ratio in the feed composition has also been studied. It is found that both flux and separation factor decrease with increasing n-butanol content in the feed. The decline is attributed to the change in total vapor pressure at the upstream and the mutual drag effect of isomeric butanol molecules.     

Measurement and modeling of lignin pyrolysis

Pyrolysis of lignin is one approach that has been investigated to upgrade this material into higher value products. However, there have been relatively few efforts to quantitatively model these reactions. This paper describes a methodology for modeling lignin pyrolysis which has been extensively developed for related materials like coal. The samples are characterized using pyrolysis experiments under a standard set of conditions, where the products are analyzed by Fourier Transform Infrared (FT-IR) Spectroscopy and Field Ionization Mass Spectrometry (FIMS). Solvent extraction experiments are done to determine the extractables yields and elemental analysis is done to further constrain the model.

One lignin, produced from ethanol/water extraction of mixed hardwoods, was selected for the application of this modeling approach. The model was able to qualitatively predict the tar molecular weight distributions and quantitatively predict the variations of the gas and tar evolution rates and yields with heating rate for the calibration set of experiments. The model can be improved by more precise information on lignin structure, crosslinking chemistry, and tar transport mechanisms. It also needs to be validated by simulation of pyrolysis conditions at high heating rates and/or high pressures for which data is currently not available.     

CO火焰对碳粒燃烧影响的理论分析和实验研究

建立了球坐标系下传热、传质和化学反应全耦合的碳粒燃烧数值模拟程序．在详细理论计算的配合下，通过精密设计的实验研究，用FTIR透射-发射实验测温方法成功捕捉了持续时间极短的“CO在颗粒表面被点燃而引起的颗粒高温”现象．连续膜模型的计算结果和FTIR测温实验结果表明，CO的空间反应与碳粒表面反应的相互作用及其对碳粒表面温度、总体反应速率的影响是极其复杂的．而CO能否在颗粒表面附近被点燃及其所引起的颗粒表面温度差可高达数百度．在实际煤粉火焰条件下，单膜模型和严格的连续膜模型的预报结果相差比较大，特别是对着火点及着火后某段区间内的颗粒温度的预报，是仅考虑表面氧化反应C＋1／2 O2→CO的单膜模型所无法完成的，这说明单膜模型存在较大的应用局限性．     

聚苯胺的合成、表征及气敏性能研究

用化学氧化聚合法,以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,控制反应温度,在酸性介质(无机酸和有机酸)中合成聚苯胺(PAn)。用傅里叶红外光谱(FTIR)和紫外可见光光谱(UV-Vis)对聚苯胺掺杂前后结构的变化进行了测试,讨论了酸掺杂对聚合产物结构的影响。结果表明电子的离域使聚苯胺主链结构经质子酸掺杂后形成了共轭结构。常温下,通过聚苯胺的气敏性能测试,得知有机酸掺杂的聚苯胺的气敏性能更好,其中用磺基水杨酸掺杂的聚苯胺对1000ppm氨气的灵敏度最高,达到了14.8580,具有实际应用价值。     

A study of hydrogel thermal-dynamics using Fourier transform infrared spectrometer

A rapid and reliable method was presented for studying hydrogel dynamics/kinetics. Two temperature-sensitive hydrogels, poly-N-isopropylacrylamide (poly(NIPAAm)) and the copolymer of N,N-diethylacrylamide and sodium methacrylate (molar ratio=97:3, poly(NDEAAm-co-MAA)) were synthesized. The thermal-behaviors of the gels were studied through the absorbance intensities of both swollen water and gel frame components, and the peak positions of amide band along heating/cooling pathways under dynamic Fourier transform infrared (FTIR) probing. The results showed that the lower critical solution temperature (LCST) of poly(NIPAAm) is about 33-35 °C, which is consistent with reported value of ∼34 °C. Compared to poly(NIPAAm), poly(NDEAAm-co-MAA) has relatively continuous volume phase transition, starting at ∼35 °C and a better thermal-reversibility with similar swelling and deswelling profiles over a larger temperature range (10-80 °C for poly(NDEAAm-co-MAA) vs. 10-33 °C for poly(NIPAAm)). The H-bonding water along phase transition was also studied, showing a less reversibility of poly(NIPAAm) compared to poly(NDEAAm-co-MAA). In addition, FTIR spectrometer was also used to study the volume changes of poly(NDEAAm-co-MAA) under variations in environmental salinity.     

Microscale analysis of patterning reactions via FTIR imaging: Application to intelligent hydrogel systems

A novel application of FTIR imaging for real-time characterization of patterning polymerization processes with microscale spatial resolution is presented. These methods will enable the microscale analysis of the reactions of polymeric systems with various substrates and devices. Specifically, intelligent hydrogels containing ionic groups (pH responsive) and poly(ethylene glycol) have been micropatterned onto gold surfaces, and the free-radical polymerization reaction has been characterized. It was demonstrated that differences in the reaction rates across a patterned region could be successfully resolved and characterized. This novel characterization method based on FTIR imaging will facilitate the optimization of integration processes of patterned polymeric films leading to enhanced (and reproducible) application of these materials as functional components in a variety of microdevices.