香兰素基非离子表面活性剂的动态表面张力与气/液界面吸附行为

通过最大气泡压力法测定香兰素基聚氧乙烯醚(VAEO)的动态表面张力,利用Word-Tordai方程研究其在气/液界面的吸附行为。结果表明,质量浓度低于临界胶束浓度(cmc)时,VAEO在吸附前期为扩散控制吸附,在吸附后期为混合动力控制吸附;质量浓度大于cmc时,为混合动力控制吸附,胶束不影响吸附行为。VAEO_(10)和VAEO_(20)的扩散系数D的数量级为10~(-11)m~2/s,比文献报道的壬基酚聚氧乙烯醚(NPEO_9)低一个数量级。     

Hyperbranched Polyethylenimine Modified Waste Fiberboard Activated Carbon for Enhanced Adsorption of Hexavalent Chromium

The objective of this work is to prepare a hyperbranched polyethylenimine (HBPEI) grafted activated carbon obtained from waste fiberboard for effectively removing Cr(VI) from aqueous solution. The waste fiberboard activated carbon (WFAC) was modified by HBPEI and cross-linked with glutaraldehyde (GA). The optimal modified conditions were as follows: HBPEI molecular weight 10,000 g/mol, HBPEI/WFAC (w/w) 0.5, GA concentration 0.25%, reaction time 60 min. Both pristine WFAC and HBPEI–WFAC were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET), Scanning electronic microscopy (SEM), and Roman spectra. XPS data showed the obvious increase in nitrogen (from 0.72% to 6.65%) after modification. The results of FTIR and XPS suggested that HBPEI was chemically bonded onto the WFAC by the glutaraldehyde (GA) between the amine groups of WFAC and that of HBPEI. HBPEI was also probably grafted onto WFAC through the intermolecular interaction between the carboxylate groups of WFAC and the amine groups of HBPEI. However, the BET surface area of modified WFAC declined slightly (about 200 m²/g). The I_D/I_G of modified WFAC decreased from 0.92 to 0.82, which indicated that the modification process had no significant effect on the graphitization of activated carbon. The adsorption property onto HBPEI–WFAC and the factors containing contact time, pH value, and Cr(VI) concentration were also investigated. Analysis of the Cr(VI) adsorption data was well simulated by the pseudo-second-order kinetic model and Langmuir adsorption isotherm model, and maximum Cr(VI) uptake of HBPEI–WFAC was 500 mg/g.     

Study of the catalytic combustion of lean hydrogen-air mixtures in a monolith reactor

This paper presents an experimental study of catalytic hydrogen combustion that used commercial catalysts containing Pt in a honeycomb monolith reactor in a plug flow configuration. The emphasis is on determining global kinetics in the case of low hydrogen content. Measurements of the temperature and composition of the reaction product at the outlet in the steady state condition at the different initial compositions of hydrogen and total volumetric feed rates were performed. The conversion of hydrogen was determined in parallel to the composition of the reaction product at the outlet using GC as well as by means of the thermodynamic approach using material and energy balances. The influence of the flow rate and initial molar fraction of hydrogen on hydrogen conversion is shown. A kinetic expression of the Arrhenius type is proposed with the reaction first order in hydrogen and zero order in oxygen for the overall process of the oxidation of hydrogen in lean hydrogen-air mixtures. The determined activation energy was in good agreement with the desorption activation energy for O₂ from graphene-covered Pt(111) surfaces using temperature-programmed desorption. This result shows transport-limitations for heterogeneous hydrogen conversion in catalytic hydrogen combustion.     

Drying kinetics of poplar lumber during periodic hot-press drying

The drying kinetics of poplar lumber was experimentally investigated as a function of drying temperature (115, 135, 160, 185 and 205°C) during a periodic hot-press-drying process. Poplar lumber was dried under contact (compression ratio of 10%) and high-press states (compression ratio of 44%). Compared with the contact-state, the high-press-state showed higher drying rate and higher efficiency of removing free water than bound water in wood. Eight mathematical models from the literature were established to analyze the drying behavior. The Weibull model, with an average determination coefficient R² of 0.9958, fitted well for all applied drying conditions. The scale parameter decreased with increasing drying temperature and was lower for high-press-state drying compared with that for contact-state drying. Moisture diffusivity and activation energy were calculated according to the Weibull model. Diffusivity increased with increasing drying temperature, with the average value of 1.734?×?10^?6 and 3.313?×?10^?6?m²/s and activation energy of 34.79 and 32.85?kJ/mol for contact-state drying and high-press-state drying, respectively. Hot-press drying created an M-shaped curve of density distribution, with high density at the two surface regions gradually decreasing toward the core region. The contact state-dried wood showed increased density near the wood surface. Both average density and peak density improved in the case of high-press-state-dried wood. Furthermore, the hydrophilic index of wood for high-press-state drying was lower than that of the contact-state drying, and the opposite was true regarding crystallinity index. The hygroscopicity of high-press-dried poplar decreased with lower equilibrium moisture content and higher moisture excluding efficiency, compared with contact-state-dried poplar. The rapid, high-quality drying of poplar lumber through periodic hot-press was more potentially achieved by the high-press-state compared with contact-state drying.     

Densification mechanism during reactive hot pressing of B4C-ZrO2 mixtures

The densification behaviors of pure B₄C and B₄C-ZrO₂ mixtures were compared during hot pressing. The results showed that in-situ formed ZrB₂ effectively enhanced the densification process of B₄C-ZrO₂ mixtures, more significantly during the intermediate stage. Within the relative density ranging from 0.75 to 0.90, the B₄C-15?wt%ZrO₂ mixture (B15Z) achieved the maximum densification rate as twice much as that of pure B₄C. The stress exponent n>3 indicated plastic deformation was the dominant densification mechanism of B15Z. The viscosities of plastic flow were evaluated using Murray-Rodger-William equation and the viscosity of B15Z was only a quarter of that in pure B₄C. The sintering activation energy was calculated to be 305.9?kJ/mol for pure B₄C and 197?kJ/mol for B15Z, respectively. It was proposed that the lower viscosity of plastic flow and activation energy accelerated the sliding and propagating motions of plastic flow, by which underlain the enhanced densification behaviors of B₄C-ZrO₂ mixtures.     

Comparative study of surface properties of Mg-substituted hydroxyapatite bioceramic microspheres

Mg-substituted hydroxyapatite (HAp) bioceramic microspheres were prepared by spray drying and subsequent processing at 1173, 1273 and 1373 K. Influence of various Mg substitution levels (up to 0.84 ± 0.10 wt%) on physicochemical properties of the HAp bioceramic microspheres was evaluated. Obtained results were used for the elucidation of the compositional and structural characteristics of the microspheres in conjunction with adsorption of protein, namely, bovine serum albumin (BSA). The primary difference among the microspheres processed at various temperature was the presence or absence of the micropores (<2 nm in diameter) and mesopores (between 2 and 50 nm). Presence of the micro- and mesopores resulted in higher specific surface area (SSA), enhanced solubility, i.e., ion release, and, accordingly, increase in the amount of BSA adsorbed on the microspheres. Furthermore, the BSA adsorption capacity of the microspheres decreased with increasing Mg content despite of higher SSA.     

Isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide composites with different ordered structure

The effects of ordered structure on isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide (iPP/GO) composites were studied using differential scanning calorimetry. The ordered structure status was controlled by tuning the fusion temperature (T_f). The results showed that depending on the variation of crystallization rate, the whole T_f range could be divided into three regions: Region I (T_f > 179 °C), Region II (170 °C ≤ T_f ≤ 179 °C) and Region III (T_f < 170 °C). As T_f decreased from Region I to Region III, the crystallization rate would increase substantially at two transition points, due to the variation of the ordered structure status. Calculation of Avrami exponent n indicated that the ordered structure induced the formation of two‐dimensional growing crystallites rather than three‐dimensional growing crystallites. Moreover, in the case of isothermal crystallization, the ordered structure effect (OSE) can also greatly increase the relative content of β‐phase (β_c). In Region II, OSE took place, resulting in evident increase of β_c, achieving 92.4% at maximum. The variation of the isothermal crystallization temperature (T_iso) had little influence on the T_f range (Region II) of the OSE. The higher T_f in Region II was more favorable for the formation of higher β_c. The ordered structure was favorable for the improvement of the nucleating efficiency of β‐nucleating agent (β‐NE), and was more effective for the improvement of lower β‐NE. © 2018 Society of Chemical Industry     

In vitro model to assess the adsorption of oral veterinary drugs to mycotoxin binders in a feed- and aflatoxin B1-containing buffered matrix

Mycotoxin binders are feed additives which are mixed in the feed to adsorb mycotoxins and thereby reducing their toxic effects on animals. Interactions with orally administered veterinary medicinal products, such as antimicrobials or coccidiostats, have been reported previously. This paper describes an in vitro model to screen the interaction between mycotoxin binders and veterinary drugs with respect to the non-specific binding of drugs. It is designed as a static setup using a single concentration of drug and binder in a feed-containing or a feed-plus-mycotoxin-containing matrix, buffered at different pH values. The model was applied to two frequently used antimicrobials in veterinary medicine, doxycycline (DOX) and tylosin (TYL), one major mycotoxin, aflatoxin B1 (AFB1), and four mycotoxin binders. Proportions of feed, DOX or TYL, AFB1, and binder are equivalent to the in vivo situation for broiler chickens, while pH and volume of the buffer are representative of the gastrointestinal tract of chickens. A substantial binding of DOX (~ 88%) and TYL (~ 66%) to the feed-matrix was observed. For the mycotoxin binders, similar results were obtained for DOX and TYL; more specifically up to an inclusion rate of 20 g binder/kg feed, no significant binding was demonstrated, determined as the free concentration of DOX and TYL. A single exception was noticed for TYL and one specific bentonite-based mycotoxin binder, for which no significant interaction could be demonstrated up to 10 g binder/kg but there was an effect at 20 g/kg. In all cases, there was no competition between the tested drugs DOX or TYL and the mycotoxin AFB1 for binding to the bentonite-based mycotoxin binder.     

Simulation of integrated novel PSA/EHP/C process for high-pressure hydrogen recovery from Coke Oven Gas

This paper introduces a novel Coke Oven Gas (COG) hydrogen purification/compression system based on the technologies of Pressure Swing Adsorption (PSA) and Electrochemical Hydrogen Purification and Compression (EHP/C). As the EHP/C tolerates O₂, N₂ and CH₄ impurities, PSA can be utilized solely for CO and CO₂ removal (other COG impurities were not considered in this work). A relaxation of PSA hydrogen purity could significantly enhance its recovery rate. In this study, the suitability of traditional hydrogen PSA as part of the hybrid PSA/EHP/C approach was investigated. Aspen Adsorption and Matlab were used to model the PSA and EHP/C systems, respectively. The effect of adsorption pressure, purge-to-feed-ratio (P/F-ratio) and adsorption time within cycle on PSA performance is reported. This study found that breakthrough of non-detrimental components is typically accompanied with poisonous CO. Hence, the CO removal with traditional H₂-PSA resulted into high purity product. In a two-bed PSA, 36.3% of hydrogen was recovered at 99.9988% purity and 0.18 ppm CO. Subsequently, as a result, the EHP/C purification capability was merely utilized, but polished this hydrogen to >99.999% purity. Simultaneously, hydrogen was isothermally compressed to 20 MPa, consuming a marginal 2.42 kWh/kg. Compared to mechanical compression, this is 31.6% more energy efficient. Recovering hydrogen from by-product COG was found to save 0.5 kg CO₂/kg H₂ compared to hydrogen produced from natural gas. Conventional hydrogen PSA, utilizing 70% Activated Carbon and 30% Molecular Sieve 5A, was found not to be effective to target the removal of CO specifically. To increase synergy between PSA and EHP/C, the PSA requires adequate design and operation using appropriate adsorbents and cycle steps to target elimination of CO. An increased EHP/C catalyst tolerance for CO also contributes to higher flexibility.     

燃油选择性吸附脱硫的多孔材料研究进展

吸附脱硫技术具有操作条件温和、节能、不改变燃油品质和成本低等特点而备受关注。针对噻吩类难脱除硫化物的深度脱除和转化问题，综述了近年来应用多孔吸附材料选择性吸附超深度脱除燃油中噻吩类硫化物的作用机理及最新研究进展。重点分析了分子筛、金属有机骨架、多孔炭材料、复合材料等不同吸附剂的研究现状，并探讨了各种吸附材料的吸附机理、改性方式和优缺点。本文指出分子筛因优异的热稳定性、高比表面积、均一的孔道结构、低成本和易于工业化等特点，是目前最具优势的吸附剂材料。未来研究应着重阐明吸附机理、提高合成便捷性、脱硫性能以及再生能力，更全面系统的研究将为开发具有理想选择性和再生能力的高效吸附剂奠定基础。